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

Abstract

To provide a salt which allows a resist pattern having good CD uniformity (CDU) to be produced, and a resist composition containing the same.SOLUTION: The salt is represented by formula (I) [where Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group; R1 and R2 each represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group; z represents an integer of 0-6; X1 and X2 each represent -CO-O-, -O-CO-, -O-CO-O- or -O-; L1 represents a single bond or a substituted / unsubstituted hydrocarbon group; A1 represents an optionally substituted lactone ring; L2 represents a single bond or an alkanediyl group; R3 represents an aliphatic hydrocarbon group having an iodine atom, wherein a hydrogen atom contained in the group may be substituted with a fluorine atom or an alkyl group; and Z+ represents an organic cation].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a salt for an acid generator used in the fine processing of semiconductors, an acid generator containing the salt, and a resist The present invention relates to a resist composition and a method for producing a resist pattern. [Background technology]

[0002] Patent Document 1 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. TIFF2025000705000001.tif2761

[0003] Patent Document 2 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. TIFF2025000705000002.tif2871

[0004] Patent Document 3 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. TIFF2025000705000003.tif2770

[0005] Patent Document 4 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. TIFF2025000705000004.tif2793

[0006] Patent Document 5 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is described. JPEG2025000705000005.jpg2854

[0007] Patent Document 5 describes a salt represented by the following formula and a resist composition containing the salt as an acid generator. The composition is also described. TIFF2025000705000006.tif4156 [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2009-191054 A [Patent Document 2] JP 2011-046694 A [Patent Document 3] JP 2011-126869 A [Patent Document 4] JP 2017-019997 A [Patent Document 5] JP 2018-025789 A Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention provides a resist pattern having a higher CD uniformity than the resist pattern formed using the above resist composition. The salt provides a resist pattern having excellent uniformity (CDU). [Means for solving the problem]

[0010] The present invention includes the following inventions. [1] A salt represented by formula (I). TIFF2025000705000007.tif23139 [In formula (I), Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms; It represents a aryl group. R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom, or a perfluorinated group having 1 to 6 carbon atoms. represents an orthoalkyl group. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R 1 and R2 are mutual may be the same or different. X 1 and X 2 are each independently *-CO-O-, *-O-CO-, *-O-CO- represents O- or *-O-, and * represents C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) and the joint Represents rank. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, The -CH2- in the hydrogen group is replaced with -O-, -S-, -SO2- or -CO-. It may be possible. A 1 represents a lactone ring having 3 to 36 carbon atoms which may have a substituent. L 2 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R 3 represents a hydrocarbon group having 1 to 18 carbon atoms and an iodine atom, The hydrogen atom may be replaced by a fluorine atom or an alkyl group having 1 to 6 carbon atoms. The --CH2-- contained in the alkyl group may be replaced by --O-- or --CO--. Z + represents an organic cation. [2]A 1 is a norbornane lactone ring. [3] L 2 The salt according to [1] or [2], wherein is a single bond. [4]R 3 is a group represented by formula (R3-1), salt. TIFF2025000705000008.tif2771[In formula (R3-1), L 3 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. m3 represents an integer of 1 to 5. R 4 represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group contains - CH2- may be replaced by -O- or -CO-. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 are the same They may be the same or different. * is X 2 represents the binding site for [5] An acid generator comprising the salt according to any one of [1] to [4]. [6] A resist composition comprising the acid generator according to [5] and a resin having an acid labile group. [7] The resin having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1- 2) The residue according to [6], which contains at least one selected from the group consisting of structural units represented by Store composition. TIFF2025000705000009.tif4189 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or *-O-(CH2) k1 -CO-O k1 represents an integer of 1 to 7, and * represents a bonding site 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, It represents an alicyclic hydrocarbon group or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [8] The resin having an acid labile group is a resin containing a structural unit represented by formula (a2-A): The resist composition according to [6] or [7]. TIFF2025000705000010.tif4449[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or a group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group represented by the formula: R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or * -X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined represents the bonding site with the carbon atom. 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 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.] [9] The composition further contains a salt that generates an acid having a weaker acidity than the acid generated from the acid generator. The resist composition according to any one of items 6] to [8].

[10] (1) A resist composition according to any one of [6] to [9] is applied onto a substrate. process, (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A method for producing a resist pattern, comprising the step of developing the composition layer after heating. Effect of the Invention

[0011] By using the resist composition of the present invention, it is possible to produce a resist with good CD uniformity (CDU). A pattern can be manufactured. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In this specification, the term "(meth)acrylic monomer" refers to a monomer having a structure such as "CH2=CH-CO-" Monomers having the structure "CH2=C(CH3)-CO-" and monomers having the structure "CH2=C(CH3)-CO-" Similarly, "(meth)acrylate" and "(Meth)acrylic acid" refers to a compound selected from the group consisting of acrylate and methacrylate. "At least one selected from the group consisting of acrylic acid and methacrylic acid" and "at least one selected from the group consisting of acrylic acid and methacrylic acid "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also included. In addition, in the groups described in this specification, straight chain structures and branched structures are For those which can have both structures, either one is acceptable. The valence of the groups may vary depending on the bond type. "Derived from" or "derived from" refers to a polymerizable C=C This means that the bond is polymerized to become a -CC- group. When stereoisomers exist, all Includes stereoisomers. In this specification, the term "solid content of a resist composition" refers to the fraction of the total amount of the resist composition that is This refers to the total of all components excluding the solvent (E) described below.

[0013] <Salt represented by formula (I)> The present invention relates to a salt represented by formula (I) (hereinafter sometimes referred to as "salt (I)"). In salt (I), the side with a negative charge is called an anion (I) and the side with a positive charge is called a cationic salt (I). It is sometimes called "On(I)". TIFF2025000705000011.tif23139 [In formula (I), all symbols have the same meanings as defined above.]

[0014] Q 1 , Q 2 , R 1 and R 2 The perfluoroalkyl group is preferably a trifluoromethyl group. , perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro Fluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Examples include a perfluoropentyl group and a perfluorohexyl group. Q 1 and Q 2 are each independently preferably a trifluoromethyl group or a fluorine atom. and more preferably a fluorine atom. R 1 and R 2 are each independently preferably a hydrogen atom or a fluorine atom. It is preferred that z is 0 or 1.

[0015] X 1 are each independently *-CO-O-, *-O-CO-, or *-O-CO-O- It is preferable that *-CO-O- or *-O-CO-O-(* is C(R 1 )(R 2 ) Or C(Q 1 )(Q 2 ) is more preferred.

[0016] L 1 The divalent hydrocarbon group represented by the formula (I) is a divalent chain hydrocarbon group such as an alkanediyl group. group, a monocyclic or polycyclic divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group, A group combining two or more of these groups (e.g., an alicyclic hydrocarbon group and an alkanediyl group) A divalent hydrocarbon group formed from a group consisting of a cyclic alkyl group and a cyclic alkyl group may also be used. Examples of the alkanediyl group include a methylene group, an ethylene group, and a 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 group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,1 2-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, Pentadecane-1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,16-diyl group linear alkanediyl groups such as alkane-1,17-diyl groups; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and branched alkanediyl groups such as 2-methylbutane-1,4-diyl group. The monocyclic or polycyclic divalent alicyclic saturated hydrocarbon group is preferably cyclobutane-1,3-dicyclic. Cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclo A monocyclic divalent alicyclic group such as a cycloalkanediyl group, e.g., a cyclooctane-1,5-diyl group. Saturated hydrocarbon groups; and Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups are included. The alkanediyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms. More preferably, it is 1 to 6, and even more preferably, it is 1 to 4. The carbon number of the group is preferably 3 to 18, more preferably 3 to 16, and further preferably Usually it is 3 to 12. The divalent aromatic hydrocarbon group includes a phenylene group, a naphthylene group, an anthrylene group, a biphenyl group, Examples of aromatic hydrocarbon groups include arylene groups such as a phenylene group and a phenanthrylene group. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14 carbon atoms. and more preferably 6 to 10. The group consisting of two or more groups is a combination of an alicyclic saturated hydrocarbon group and an alkanediyl group. and a group combining an aromatic hydrocarbon group and an alkanediyl group. Examples of the group combining an alicyclic saturated hydrocarbon group and an alkanediyl group include -2 cycloaliphatic saturated hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent cycloaliphatic saturated Alicyclic saturated hydrocarbon group, alkanediyl group, -alkanediyl group, divalent saturated alicyclic hydrocarbon group --etc. Examples of the group combining an aromatic hydrocarbon group and an alkanediyl group include a -2-valent Aromatic hydrocarbon group-alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group -alkanediyl group-, -alkanediyl group-divalent aromatic hydrocarbon group-, etc. . L 1The -CH2- contained in the divalent hydrocarbon group having 1 to 28 carbon atoms is -O-, -S-, It may be replaced by -SO2- or -CO-. L 1 The -CH2- contained in the hydrocarbon group having 1 to 28 carbon atoms represented by the formula: When it is replaced with -SO2- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms is

[0017] L 1 The substituents which may be contained in the alkyl group include a hydroxy group, a carboxy group, a halogen atom, a silyl group, and the like. Ano group, alkyl group having 1 to 12 carbon atoms, 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; Examples of the alkyl group include an alkylcarbonyloxy group and a combination thereof. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl Examples of the alkyl group include an aryl group and a nonyl group. Examples of the alkoxy group having 1 to 12 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a butyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl oxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group etc. Alkoxycarbonyl groups having 2 to 13 carbon atoms, alkylcarbonyl groups having 2 to 13 carbon atoms, and the alkylcarbonyloxy group having 2 to 13 carbon atoms is the above-mentioned alkyl or alkoxy group. The aryl group represents a group having a carbonyl group or a carbonyloxy group bonded to the aryl group. Examples of the alkoxycarbonyl group having 2 to 13 carbon atoms include a methoxycarbonyl group, an ethoxy carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 13 carbon atoms. Examples of the aryl group include an acetyl group, a propionyl group, and a butyryl group, and the like. The alkylcarbonyloxy group of 3 is an acetyloxy group, a propionyloxy group, butyryloxy group and the like.

[0018] The substituent is preferably an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or a halogen atom. Preferably, it is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and more preferably, it is methyl. It is more preferably a group or a fluorine atom.

[0019] L 1 is a single bond, an alkanediyl group having 1 to 4 carbon atoms (provided that the alkanediyl group does not include The -CH2- may be replaced by -O- or -CO-. An alicyclic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group is not -O-, -S -, -SO2- or -CO- may be substituted. Aromatic hydrocarbon groups having 6 to 18 carbon atoms, alkanediyl groups having 1 to 4 carbon atoms and fatty acids having 3 to 18 carbon atoms. A group formed by combining with a cyclic hydrocarbon group (provided that the -CH2 - may be replaced by -O- or -CO-, and - contained in the alicyclic hydrocarbon group CH2- may be replaced by -O-, -S-, -SO2- or -CO-; The alkanediyl group has 1 to 4 carbon atoms and an aromatic carbon atom having 6 to 18 carbon atoms which may have a substituent. A group formed by combining with a hydrogen group (provided that the -CH2- contained in the alkanediyl group is - It is preferable that the alkyl group is a single bond, a carbon number of which may be replaced by -O- or -CO-. an alkanediyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms (provided that the alicyclic hydrocarbon The -CH2- contained in the radical may be replaced by -O- or -CO-. A phenylene group which may have a group, an alkanediyl group having 1 to 4 carbon atoms, and an alicyclic group having 3 to 12 carbon atoms. A group formed by combining with a cyclic hydrocarbon group (provided that the -CH2 - may be replaced by -O- or -CO-; or an alkanediyl group having 1 to 4 carbon atoms. A group formed by combining an alkane group and an optionally substituted phenylene group (provided that the alkane The -CH2- contained in the diyl group may be replaced with -O- or -CO-. More preferably, it is a single bond, an alkanediyl group having 1 to 4 carbon atoms, an adamantanediyl group, an alkyl group, a phenylene group which may have a fluorine atom, an alkanediyl group having 1 to 4 carbon atoms, and A group formed by combining an alkanediyl group with an alkanediyl group (provided that the -CH 2- may be replaced by -O- or -CO-; or an alkane having 1 to 4 carbon atoms. A group formed by combining a diyl group and a phenylene group which may have a fluorine atom (provided that the The -CH2- in the glycandiyl group may be replaced by -O- or -CO-. It is even more preferable that L 1 It is even more preferred that is a single bond.

[0020] A 1 The lactone ring having 3 to 36 carbon atoms represented by the formula: It represents a ring in which -CH2-CH2- in a simple ring is replaced with -CO-O-. For example, Examples of the ring include those represented by the following formula: TIFF2025000705000012.tif49120A 1 As the ring, the ring represented by the following formula is more preferable. TIFF2025000705000013.tif2485A 1 As the ring, a norbornane lactone ring represented by the following formula is more preferable. TIFF2025000705000014.tif2451

[0021] A 1 The substituents which may be possessed by L 1 The substituents which may be included in do.

[0022] A 1 The substituent that may be possessed by the alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a 4 is preferably a hydroxyalkyl group, a carboxy group, a cyano group, or a halogen atom. Preferably, the alkyl group has 1 to 4 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, or a halogen atom. More preferably, it is a hydroxy group, a cyano group, or a halogen atom. It is.

[0023] L 2 Examples of the alkanediyl group having 1 to 6 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group linear alkanediyl groups such as hexane-1,6-diyl group; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group Examples include: L 2 is preferably a single bond.

[0024] X 2 is preferably *-CO-O-, *-O-CO-O- or *-O-, -CO-O- or *-O-CO-O- (* is L 2 It is preferable that the binding site is This is more preferable.

[0025] R 3 As the hydrocarbon group having 1 to 18 carbon atoms and an iodine atom represented by the formula (I), an aliphatic hydrocarbon group is Hydrogen groups (chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, etc. and alicyclic hydrocarbon groups) At least one hydrogen atom contained in a substituted or unsubstituted alkyl group, an aromatic hydrocarbon group, or a group consisting of a combination of these groups One of the groups is replaced by an iodine atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 12 carbon atoms. Preferably, it is 1 to 9, more preferably 1 to 6, and even more preferably 1 to 4. be. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, and a butenyl group. isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples of such groups include an octynyl group, an isooctynyl group, and a nonenyl group. Examples of the alkynyl group include an ethynyl group, a propynyl group, an isopropynyl group, a butynyl group, isobutynyl group, tert-butynyl group, pentynyl group, hexynyl group, octynyl group, Examples thereof include a nonynyl group. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, a cyclobutyl group, or a cyclopropyl group. Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to It is preferably 18, more preferably 3 to 16, and further preferably 3 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of aromatic hydrocarbon groups include aryl groups such as phenanthryl and fluorenyl. The prime number is preferably 6 to 18, more preferably 6 to 14, and even more preferably The aromatic hydrocarbon group is a phenyl group, a naphthyl group, and an anthryl group. is preferred, with a phenyl group and a naphthyl group being more preferred, and a phenyl group being even more preferred.

[0026] The combined groups are: Alicyclic hydrocarbon groups and chain hydrocarbons such as alkyl groups, alkenyl groups and / or alkynyl groups a group combining an aromatic hydrocarbon group with an alkyl group, an alkenyl group and / or an aryl group; Groups that combine chain hydrocarbon groups such as quinyl groups, and groups that combine alicyclic hydrocarbon groups with aromatic hydrocarbon groups In addition, the combined group may be an alicyclic hydrocarbon group, an aryl group, or a cyclic group. Chain hydrocarbon groups such as alkyl groups, alkenyl groups, alkynyl groups, and aromatic hydrocarbon groups are Two or more of each may be combined. The combined groups are: Alicyclic hydrocarbon groups such as adamantylmethyl group and cyclohexylmethyl group - chain hydrocarbons base-*, Chain hydrocarbon groups such as methyladamantyl groups - alicyclic hydrocarbon groups - * Aromatic hydrocarbons such as tolyl, xylyl, and cyclohexylphenyl groups elementary group-*, Methylcyclohexylmethyl group and other chain hydrocarbon groups - alicyclic hydrocarbon groups - chain hydrocarbons base-*, Aromatic hydrocarbon groups such as benzyl groups - chain hydrocarbon groups -* Aromatic hydrocarbon groups - Aromatic hydrocarbon groups - Aromatic hydrocarbon groups -* etc. Here, * is X 2 represents the bonding position with

[0027] R 3 A hydrocarbon group having 1 to 18 carbon atoms and an iodine atom represented by the formula: The hydrogen atom may be replaced by a fluorine atom or an alkyl group having 1 to 6 carbon atoms. The --CH2-- contained in the alkyl group may be replaced by --O-- or --CO--. ) is preferably a group represented by formula (R3-1). TIFF2025000705000015.tif2771[In formula (R3-1), L 3 represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. m3 represents an integer of 1 to 5. R 4 represents a fluorine atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group contains - CH2- may be replaced by -O- or -CO-. m4 represents an integer of 0 to 4, and when m4 is 2 or more, a plurality of R 4 are the same They may be the same or different. * is X 2represents the binding site for

[0028] L 3 Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane group, -1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexa linear alkanediyl groups such as alkane-1,6-diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group Examples include: L 3 is preferably a single bond or an alkanediyl group having 1 to 3 carbon atoms, More preferably, it is a bond or a methylene group.

[0029] R 4 Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. propyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, etc. The number of carbon atoms in the alkyl group is preferably 1 to 4, and more preferably Usually it is 1 to 3. R 4 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is preferred. m4 is an integer of 0 to 3, and preferably 0 to 2.

[0030] Examples of the anion in the salt (I) include the anions represented by the following formulae (Ia-1) to (Ia-26) Among them, the anions represented by the formulas (Ia-1) to (Ia-7) and (I a-12), formula (Ia-15) and formula (Ia-22) are preferred, and anions represented by the formula ( Ia-1) ~ Formula (Ia-5), Formula (Ia-12), Formula (Ia-15), Formula (Ia-22) Anions represented by the following formula are more preferred. TIFF2025000705000016.tif139131

[0031] TIFF2025000705000017.tif222138

[0032] Z + The organic cations include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are and organic iodonium cations are preferred, with arylsulfonium cations being more preferred. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter , and may be referred to as "cation (b2-1)" etc. depending on the formula number.

[0033] TIFF2025000705000018.tif77115In equations (b2-1) to (b2-4), R b4 ~R b6 each independently represents a chain hydrocarbon group having 1 to 30 carbon atoms, It represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 36 carbon atoms, and the chain hydrocarbon group The hydrogen atoms contained in the alkyl group are hydroxyl groups, alkoxy groups having 1 to 12 carbon atoms, and fatty acids having 3 to 12 carbon atoms. The alicyclic group may be substituted with a cyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. The hydrogen atoms contained in the hydrocarbon group are halogen atoms, aliphatic hydrocarbon groups having 1 to 18 carbon atoms, may be substituted with an alkylcarbonyl group having 2 to 4 carbon atoms or a glycidyloxy group. The hydrogen atom contained in the aromatic hydrocarbon group is replaced by a halogen atom, a hydroxyl group, or a C1 It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 each independently represents a hydroxyl group or 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 0 to 5. When m2 is 2 or more, multiple R b7 may be the same or different, and when n2 is 2 or more, R in Numbers b8 may be the same or different. R b9 and R b10 each independently represents a chain hydrocarbon group having 1 to 36 carbon atoms or a chain hydrocarbon group having 3 to 4 carbon atoms, Represents 36 alicyclic hydrocarbon groups. R b9 and R b10 are bonded together to form a ring with the sulfur atom to which they are attached The -CH2- contained in the ring may be replaced with -O-, -S- or -CO-. Good too. R b11 is a hydrogen atom, a chain hydrocarbon group having 1 to 36 carbon atoms, an alicyclic hydrocarbon group having 3 to 36 carbon atoms, It represents a hydrogen group or an aromatic hydrocarbon group having 6 to 18 carbon atoms. Rb12 represents a chain hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or It represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, and the hydrogen atoms contained in the chain hydrocarbon group are It may be substituted with an aromatic hydrocarbon group having a prime number of 6 to 18, and the aromatic hydrocarbon group The hydrogen atom is preferably an alkoxy group having 1 to 12 carbon atoms or an alkylcarbonyl group having 1 to 12 carbon atoms. It may be substituted with an oxy group. R b11 and R b12 means that they are bonded together to form a ring including the -CH-CO- to which they are attached. The -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. This is also possible. R b13 ~R b18 each independently represents a hydroxyl group or 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 an integer of 0 to 5. q2 and r2 each independently represent an integer of 0 to 4. u2 represents 0 or 1. When o2 is 2 or more, multiple R b13 are the same or different, and when p2 is 2 or more, multiple R b14 are the same or different, and when q2 is 2 or more, multiple R b15 are the same or different, r2 When is 2 or more, multiple R b16 are the same or different, and when s2 is 2 or more, multiple R b17 teeth Identical or different, when t2 is 2 or more, multiple R b18 are the same or different.

[0034] The aliphatic hydrocarbon group refers to 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, and a butyl group. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of the alkyl group is 2-ethylhexyl. In particular, R b9 ~R b12 The chain hydrocarbon group preferably has 1 to 12 carbon atoms. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. cycloalkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl groups. Examples of polycyclic alicyclic hydrocarbon groups include decahydronaphthyl and adamantyl groups. , norbornyl group, and the following groups. TIFF2025000705000019.tif10158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms.

[0035] Examples of alicyclic hydrocarbon groups in which hydrogen atoms are replaced by aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl, dimethylcyclohexyl, 2-methyladamantan-2-yl, 2-ethyl 2-Isopropyladamantan-2-yl group, methylnor Examples of the alkyl group include a bornyl group and an isobornyl group. In the alicyclic hydrocarbon group, the total number of carbon atoms in the alicyclic hydrocarbon group and the aliphatic hydrocarbon group is preferably Preferably, it is 20 or less.

[0036] Examples of the aromatic hydrocarbon group include a phenyl group, a biphenyl group, a naphthyl group, and a phenanthryl group. The aromatic hydrocarbon group may be an open-chain hydrocarbon group or an alicyclic hydrocarbon group. Examples of the aromatic hydrocarbon group having a chain hydrocarbon group include a tolyl group, Xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group Examples of the phenyl group include a 2,6-diethylphenyl group and a 2-methyl-6-ethylphenyl group. As an aromatic hydrocarbon group having an alicyclic hydrocarbon group, a p-cyclohexylphenyl group is used. Examples thereof include a p-adamantylphenyl group. In addition, when the aromatic hydrocarbon group has a chain hydrocarbon group or an alicyclic hydrocarbon group, A chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples of the alkyl group include aryl groups. Examples of the chain hydrocarbon group in which a hydrogen atom is replaced by an aromatic hydrocarbon group include a benzyl group, a phenoxy group, and the like. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples of such groups include aralkyl groups.

[0037] The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be done. Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. The alkylcarbonyloxy group includes a methylcarbonyloxy group, an ethylcarbonyloxy group, and an ethyl Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group Si group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples thereof include an oxy group and a 2-ethylhexylcarbonyloxy group.

[0038] R b4 and R b5 and form a ring together with the sulfur atom to which they are attached: The ring may be any of monocyclic, polycyclic, aromatic, non-aromatic, saturated and unsaturated. The ring may be one having 3 to 18 carbon atoms, and preferably one having 4 to 18 carbon atoms. The ring containing a sulfur atom may be a 3- to 12-membered ring, preferably a 3- to 7-membered ring. Examples of the ring include the following rings, where * represents the bond position. TIFF2025000705000020.tif25144

[0039] R b9 and R b10 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. Preferably, it is a 3- to 7-membered ring. For example, a thiolane-1-ium ring (tetrahydrothio ophenium ring), thian-1-ium ring, 1,4-oxathiane-4-ium ring, etc. Can be obtained. R b11 and R b12 The ring formed by combining with may be monocyclic, polycyclic, aromatic or non-aromatic. The ring may be either a saturated or unsaturated ring. Examples of the ring include a 3-membered ring to a 12-membered ring. and preferably a 3- to 7-membered ring. Oxocycloheptane ring, oxocyclohexane ring , oxonorbornane ring, oxoadamantane ring, etc.

[0040] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025000705000021.tif79158

[0041] TIFF2025000705000022.tif74143

[0042] Examples of the cation (b2-2) include the following cations. TIFF2025000705000023.tif18127

[0043] Examples of the cation (b2-3) include the following cations. TIFF2025000705000024.tif26140

[0044] Examples of the cation (b2-4) include the following cations. TIFF2025000705000025.tif85164

[0045] The salt (I) is a combination of the above-mentioned anions and the above-mentioned organic cations, which are optionally The salt (I) is preferably a salt represented by the formula (Ia-1) to the formula (Ia-7) an anion represented by any one of formula (Ia-12), formula (Ia-15), and formula (Ia-22) A combination of an amine and a cation (b2-1), a cation (b2-2) or a cation (b2-3). Examples include:

[0046] Examples of the salt (I) include the salts shown in Table 1. In the following table, each symbol represents the above-mentioned The symbols are attached to the structures representing anions and cations. For example, salt (I-1) is a salt represented by the formula (I a-1) and a cation represented by formula (b2-c-1) It has the following taste and represents the salts shown below. TIFF2025000705000026.tif32111 [Table 1] TIFF2025000705000028.tif223154 TIFF2025000705000029.tif223154 TIFF2025000705000030.tif223154 TIFF2025000705000031.tif234157

[0047] Among them, salt (I) includes salts (I-1) to (I-7), salt (I-12), and salt (I-15). ~Salt (I-21), Salt (I-26), Salt (I-29) ~Salt (I-35), Salt (I-40) , salt (I-43) ~ salt (I-49), salt (I-54), salt (I-57) ~ salt (I-63) , salt (I-68), salt (I-71) ~ salt (I-77), salt (I-82), salt (I-85) ~Salt (I-91), Salt (I-96), Salt (I-99), Salt (I-106), Salt (I-11 1), salt (I-118), salt (I-123), salt (I-130), salt (I-135), salt (I-142), salt (I-147), salt (I-154), salt (I-159), salt (I-1 66), salt (I-171), and salt (I-178).

[0048] <Method for producing salt (I)> In the salt (I), X 1 However, *-CO-O-(* is C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) (a salt represented by formula (I1)) is, for example, a salt represented by the formula The salt represented by (I1-a) is reacted with carbonyldiimidazole in a solvent, and then With a compound represented by formula (I1-b), TIFF2025000705000032.tif56151 (wherein all symbols have the same meanings as above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0049] Examples of the salt represented by formula (I1-a) include the salts represented by the following formula: Manufactured by the method described in JP-A-08-127367 and JP-A-2011-046694 It is possible. TIFF2025000705000033.tif37141

[0050] In the compound represented by formula (I1-b), X 2 But *-X 2b -O-(X 2b is simply Represents a bond, a carbonyl group, or *-O-CO-**. * represents L 2 * represents the binding site. The symbol * represents a bonding site with an oxygen atom. The compound represented by formula (I1-c1) is dissolved in carbonyldiimidazole. After reacting in a reaction agent, the compound is further reacted with a compound represented by formula (I1-d1). It can be manufactured as follows. TIFF2025000705000034.tif25147 (wherein all symbols have the same meanings as above.) Solvents for this reaction include chloroform, acetonitrile, and the like. Examples of the compound represented by formula (I1-c1) include compounds represented by the following formula: It is easily available on the market. TIFF2025000705000035.tif2060

[0051] Examples of the compound represented by formula (I1-d1) include compounds represented by the following formula: It is easily available on the market. TIFF2025000705000036.tif1960

[0052] The compound represented by formula (I1-b1) can be, for example, a compound represented by formula (I1-c1) and a compound represented by formula (I1-d2) in the presence of a base in a solvent to produce It can also be constructed. TIFF2025000705000037.tif20146 (wherein all symbols have the same meanings as above. X b represents a halogen atom .) The solvent for this reaction is dimethylformamide, tetrahydrofuran, chloroform, etc. Examples of the solvent include formaldehyde and acetonitrile. The base in this reaction is potassium carbonate, potassium iodide, triethylamine, Examples thereof include pyridine. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0053] Examples of the compound represented by formula (I1-d2) include compounds represented by the following formula: It is easily available on the market. TIFF2025000705000038.tif20113

[0054] In the compound represented by formula (I1-b), X 2 However, *-O-CO-(* is L 2 With The compound represented by formula (I1-b3) can be, for example, a compound represented by formula A compound represented by formula (I1-c1) and a compound represented by formula (I1-d3) are reacted in the presence of a base. Alternatively, the compound can be produced by reacting the compound in a solvent. TIFF2025000705000039.tif24147 (wherein all symbols have the same meanings as above.) The solvent for this reaction is dimethylformamide, tetrahydrofuran, chloroform, etc. Examples of the solvent include formaldehyde and acetonitrile. The base in this reaction is triethylamine, pyridine, dimethylaminopyridine. Examples include The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0055] Examples of the compound represented by formula (I1-d3) include compounds represented by the following formula: It is easily available on the market. TIFF2025000705000040.tif1826

[0056] In the salt (I), X 1 However, *-O-CO-(* is C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) (a salt represented by formula (I2)) is, for example, a salt represented by the formula The compound represented by (I2-b) is reacted with carbonyldiimidazole in a solvent, and then Furthermore, it can be prepared by reacting with a salt represented by formula (I2-a). TIFF2025000705000041.tif57124 (wherein all symbols have the same meanings as above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0057] Examples of the salt represented by formula (I2-a) include the salts represented by the following formula: It can be produced by the method described in Publication No. 12-193170. TIFF2025000705000042.tif2742

[0058] The compound represented by formula (I2-b) includes the compound represented by the following formula: It is easily available from the market and can be easily produced by known methods. . TIFF2025000705000043.tif25107

[0059] In the salt (I), X 1 However, *-O-CO-O-(* is C(R 1 )(R 2 ) or C( Q 1 )(Q 2 ) (salt represented by formula (I3)) can be, for example, After reacting the salt represented by formula (I2-a) with carbonyldiimidazole in a solvent, Furthermore, it can be produced by reacting with a compound represented by formula (I1-b) . TIFF2025000705000044.tif58149 (wherein all symbols have the same meanings as defined above.) Solvents for this reaction include chloroform, acetonitrile, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0060] In the salt (I), X 1 However, *-O-(* is C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) (a salt represented by formula (I4)) can be, for example, a salt represented by formula (I2 -a) is reacted with a compound represented by formula (I1-b) in a solvent in the presence of a base. It can be produced by TIFF2025000705000045.tif46142 (wherein all symbols have the same meanings as above.) The base in this reaction includes potassium hydroxide and the like. The solvents used in this reaction are chloroform, acetonitrile, and tetrahydrofuran. , dimethylformamide, and the like. The reaction temperature is usually 5° C. to 80° C., and the reaction time is usually 0.5 hours to 24 hours.

[0061] <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.

[0062] 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) The anion of the onium salt is typically a sulfonate anion. ion, sulfonylimide anion, sulfonylmethide anion, etc.

[0063] Examples of the acid generator (B) include those described in JP-A-63-26653 and JP-A-55-164824. JP-A-62-69263, JP-A-63-146038, JP-A-63-163452 , JP-A-62-153853, JP-A-63-146029, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate an acid when exposed to radiation, such as those described in US Pat. No. 5,312,712, can be used. In addition, a compound produced by a known method may be used. The acid generator (B) may be a compound containing two or more kinds of compounds. They may also be used in combination.

[0064] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)"). TIFF2025000705000046.tif2963[In formula (B1), Q b1 and Q b2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents an alkyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, The -CH2- contained therein may be replaced with -O- or -CO-, and the divalent saturated carbon atom A hydrogen atom contained in the hydride group may be substituted with a fluorine atom or a hydroxy group. Y is a methyl group which may have a substituent or a substituted group having 3 to 1 carbon atoms. 8, and -CH2- contained in the alicyclic hydrocarbon group is -O-, - It may be replaced by S(O)2- or -CO-. Z1 + represents an organic cation.

[0065] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) is a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Examples include a fluoropentyl group and a perfluorohexyl group. Q b1 and Q b2 each independently represents a fluorine atom or a trifluoromethyl group; and more preferably, both of them are fluorine atoms.

[0066] L b1 The divalent saturated hydrocarbon group in the formula (I) is a linear alkanediyl group, a branched alkanediyl group, candiyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may also be a group formed by combining two or more of the following. 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- Linear alkanediyl groups such as diyl groups; Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group branched alkanediyl groups such as 2-methylbutane-1,4-diyl group; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa Cycloalkanediyl groups such as cyclohexene-1,4-diyl group and cyclooctane-1,5-diyl group a monocyclic divalent alicyclic saturated hydrocarbon group, Norbornane-1,4-diyl group, Norbornane-2,5-diyl group, Adamantane- Polycyclic divalent alicyclic saturated carbons such as 1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like.

[0067] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, the groups represented by the formulae (b1-1) to (b1-3) and their components are also included. In the exemplary groups represented by formulae (b1-4) to (b1-11), * represents a bond to -Y. Represents the hand.

[0068] TIFF2025000705000047.tif26118[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the 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, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. L b7represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group may be substituted with fluorine atoms or hydroxy groups, and the saturated The --CH2-- contained in the hydrocarbon group may be replaced by --O-- or --CO--. However, L b6 and L b7 The total number of carbon atoms is 23 or less. * and ** represent binding sites, and * represents the binding site with Y.]

[0069] In the groups represented by formulae (b1-1) to (b1-3), the saturated hydrocarbon group When -CH2- is replaced by -O- or -CO-, the number of carbon atoms before the replacement is The number of carbon atoms in the hydrocarbon group. As the divalent saturated hydrocarbon group, L b1 The divalent saturated hydrocarbon groups are the same as those mentioned above. can be.

[0070] 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, The hydrogen atom contained in the hydrogen group may be substituted with 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, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms. L b7 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. In the divalent saturated hydrocarbon group, -CH2- is replaced with -O- or -CO-. This is also fine.

[0071] L b1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0072] The group represented by formula (b1-1) is preferably any of the groups represented by formulas (b1-4) to (b1-8). Examples of such groups include those mentioned above. TIFF2025000705000048.tif48120[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom or a hydroxy group. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The contained --CH2-- 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, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b9 and L b10 The total number of carbon atoms is 20 or less. 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, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b11 and L b12 The total number of carbon atoms is 21 or less. 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, The --CH2-- contained in the 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, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b13 ~L b15 The total number of carbon atoms is 19 or less. In formula (b1-8), L b16 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the formula 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, The hydrogen atoms contained in the hydrocarbon group may be substituted with fluorine atoms or hydroxy groups. . However, L b16 ~L b18 The total number of carbon atoms is 19 or less. * and ** represent binding sites, and * represents the binding site with Y.]

[0073] 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. Lb10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, more preferably More preferably, it is 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 b15 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, more preferably More preferably, it is 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 More preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0074] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), Examples of the groups include those represented by the following formula: TIFF2025000705000049.tif23139[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b19 and L b20 The total number of carbon atoms is 23 or less. In formula (b1-10), L b21 represents a single bond or a divalent saturated hydrocarbon group having 1 to 21 carbon atoms, A 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, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b21 , L b22 and L b23 The total number of carbon atoms is 21 or less. In formula (b1-11), L b24 represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b25 represents a divalent saturated hydrocarbon group having 1 to 21 carbon atoms. L b26represents a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The -CH2- contained in the alkylcarbonyloxy group may be -O- or -CO-, and the hydrogen atom contained in the alkylcarbonyloxy group may be replaced by The atom may be substituted with a hydroxy group. However, L b24 , L b25 and L b26 The total number of carbon atoms is 21 or less. * and ** represent binding sites, and * represents the binding site with Y.]

[0075] In addition, in the groups represented by formulae (b1-9) to (b1-11), When a hydrogen atom in a hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is regarded as the number of carbon atoms of the saturated hydrocarbon group.

[0076] The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0077] Examples of the group represented by formula (b1-4) include the following. TIFF2025000705000050.tif16151 (* and ** represent binding sites, * represents the binding site with Y.)

[0078] Examples of the group represented by formula (b1-5) include the following. TIFF2025000705000051.tif72149 (* and ** represent binding sites, * represents the binding site with Y.)

[0079] Examples of the group represented by formula (b1-6) include the following. TIFF2025000705000052.tif53149 (* and ** represent binding sites, * represents the binding site with Y.)

[0080] Examples of the group represented by formula (b1-7) include the following. TIFF2025000705000053.tif67159 (* and ** represent binding sites, * represents the binding site with Y.)

[0081] Examples of the group represented by formula (b1-8) include the following. TIFF2025000705000054.tif23150 (* and ** represent binding sites, * represents the binding site with Y.)

[0082] Examples of the group represented by formula (b1-2) include the following. TIFF2025000705000055.tif30160 (* and ** represent binding sites, * represents the binding site with Y.)

[0083] Examples of the group represented by formula (b1-9) include the following. TIFF2025000705000056.tif44137 (* and ** represent binding sites, * represents the binding site with Y.)

[0084] Examples of the group represented by formula (b1-10) include the following. TIFF2025000705000057.tif88158 (* and ** represent binding sites, * represents the binding site with Y.)

[0085] Examples of the group represented by formula (b1-11) include the following. TIFF2025000705000058.tif81158 (* and ** represent binding sites, * represents the binding site with Y.)

[0086] The alicyclic hydrocarbon group represented by Y includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y38). Examples of the group include a group represented by the formula (Y38). The -CH2- contained in the alicyclic hydrocarbon group represented by Y is -O-, -S(O)2- or - When the group is replaced by CO-, the number of the CO- may be one or more. Examples of the groups include those represented by the formulae (Y12) to (Y35) and (Y39) to (Y41). can be.

[0087] The alicyclic hydrocarbon group represented by TIFF2025000705000059.tif85166Y is preferably a group represented by the formula (Y1) to the formula (Y20), the formula (Y21) to the formula (Y22) Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39) to formula (Y41) and more preferably a group represented by formula (Y11), formula (Y15), or formula (Y16) ), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y 39) or (Y40), and more preferably a group represented by formula (Y11), formula (Y1 5), formula (Y20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula ( Y39) or a group represented by formula (Y40). The alicyclic hydrocarbon group represented by Y is represented by the formula (Y28) to the formula (Y35), the formula (Y39) to the formula (Y In the case of a spiro ring containing an oxygen atom such as 40), the alkanediyl between the two oxygen atoms is The group preferably has one or more fluorine atoms. In the candiyl group, the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom. It is preferable that

[0088] The substituent of the methyl group represented by Y is a halogen atom, a hydroxyl group, a methyl group having 3 to 1 carbon atoms, 6 alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, glycidyloxy groups, -( CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 group (in the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, to 18 aromatic hydrocarbon groups or combinations thereof, The -CH2- contained in the hydrocarbon group is replaced by -O-, -SO2- or -CO-. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be The atom may be replaced by a hydroxy group or a fluorine atom. ja is any one of 0 to 4. It represents any one of the integers. The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms which may be substituted with an aryloxy group; an alicyclic group having 3 to 16 carbon atoms; Hydrocarbon groups, alkoxy groups having 1 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms, carbon Aralkyl groups having 7 to 21 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms, and glycidyloxy groups. , -(CH2) ja -CO-OR b1 Group or -(CH2) ja -O-CO-R b1 Base( In the formula, R b1 is an alkyl group having 1 to 16 carbon atoms, an alicyclic hydrocarbon group having 3 to 16 carbon atoms, The alkyl group and the aromatic hydrocarbon group each having 6 to 18 carbon atoms or a combination thereof are represented by the formula: The -CH2- contained in the alicyclic hydrocarbon group is replaced by -O-, -SO2- or -CO-. The alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be different from each other. The hydrogen atom may be replaced by a hydroxy group or a fluorine atom. It represents any integer of the above.)

[0089] Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexane group, and a cyclohexane group. Cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples of the alkyl group include a carbonyl group and an adamantyl group. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, and the like. Examples of the aromatic hydrocarbon group include aryl groups such as an alkyl group and an aryl group such as a phenyl group and a phenanthryl group. It may have a hydrocarbon group or an alicyclic hydrocarbon group, and may have a chain hydrocarbon group having 1 to 18 carbon atoms. Aromatic hydrocarbon groups (tolyl, xylyl, cumenyl, mesityl, p-methyl Phenyl group, p-ethylphenyl group, p-tert-butylphenyl group, 2,6-diethyl phenyl group, 2-methyl-6-ethylphenyl group, etc.), and alicyclic carbons having 3 to 18 carbon atoms. Aromatic hydrocarbon groups having a hydride group (p-cyclohexylphenyl group, p-adamantyl phenyl group, etc. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromoalkyl 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. Examples of alkyl groups substituted with hydroxy groups include hydroxymethyl groups, hydroxy Examples of such groups include hydroxyalkyl groups such as an ethyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, aryloxy, hexyloxy, heptyloxy, octyloxy, decyloxy and dodecyloxy groups. The aralkyl group includes a benzyl group, a phenethyl group, a phenylpropyl group, a naphthyl group, and the like. Examples of the alkyl group include ethyl and naphthylethyl groups. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0090] Y includes the following: TIFF2025000705000060.tif140163

[0091] Y is preferably an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent. More preferably, it is an adamantyl group which may have a substituent. The -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. Y is more preferably an adamantyl group, a hydroxyadamantyl group, group, an oxoadamantyl group, or a group represented by the following formula: TIFF2025000705000061.tif59161

[0092] The anion in the salt represented by formula (B1) is represented by the formulas (B1-A-1) to (B1- A-55) (hereinafter, "anion (B1-A-1), etc." according to the formula number) Formula (B1-A-1) to Formula (B1-A-4), Formula (B1 -A-9), formula (B1-A-10), formula (B1-A-24) ~ formula (B1-A-33), formula (B1-A-36) ~ Formula (B1-A-40), Formula (B1-A-47) ~ Formula (B1-A-5 5) is more preferable.

[0093] TIFF2025000705000062.tif54135

[0094] TIFF2025000705000063.tif48137

[0095] TIFF2025000705000064.tif27136

[0096] TIFF2025000705000065.tif121158

[0097] TIFF2025000705000066.tif65151

[0098] TIFF2025000705000067.tif94146

[0099] TIFF2025000705000068.tif74133

[0100] TIFF2025000705000069.tif115164 Here R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is preferably a methyl group or an ethyl group. i8 is, for example, an aliphatic hydrocarbon having 1 to 12 carbon atoms. a group, preferably an alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 to 12 carbon atoms, or More preferably, the group formed by combining these is a methyl group, an ethyl group, or a cyclohexyl group. It is a silyl group or an adamantyl group. A4 is a single bond or an alkanediyl having 1 to 4 carbon atoms. It is based on Q b1 and Q b2 has the same meaning as above. Specific examples of the anion in the salt represented by formula (B1) include those described in JP-A-2010-20 Examples of the anions include those described in US Pat. No. 4,646.

[0101] Preferred anions in the salt represented by formula (B1) include those represented by formulae (B1a-1) to (B1a-2) B1a-34) are examples of anions represented by the formula: TIFF2025000705000070.tif120148

[0102] TIFF2025000705000071.tif92145

[0103] TIFF2025000705000072.tif144162

[0104] Among them, the compounds represented by formulae (B1a-1) to (B1a-3) and (B1a-7) to (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 30) is preferably an anion represented by any one of the following:

[0105] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and and organic phosphonium cations. The cation Z in the salt (I) is + The same thing as Some examples include:

[0106] The acid generator (B) is a combination of the above-mentioned anion and the above-mentioned organic cation. The acid generator (B) is preferably a compound represented by the formula (B1a-1) to Formula (B1a-3), Formula (B1a-7) to Formula (B1a-16), Formula (B1a-18), Formula (B1a-19), an aniline represented by any one of formulas (B1a-22) to (B1a-34) A combination of on and the cation (b2-1) or the cation (b2-3) is also included.

[0107] The acid generator (B) is preferably one represented by formula (B1-1) to formula (B1-48), Among them, those containing an arylsulfonium cation are preferred. Formula (B1-1) ~ Formula (B1-3), Formula (B1-5) ~ Formula (B1-7), Formula (B1-11) ~Formula (B1-14), Formula (B1-20) ~Formula (B1-26), Formula (B1-29), Formula (B Those represented by formulas (B1-31) to (B1-48) are particularly preferred. TIFF2025000705000073.tif119149

[0108] JPEG2025000705000074.jpg77147

[0109] JPEG2025000705000075.jpg147147

[0110] JPEG2025000705000076.jpg61154

[0111] TIFF2025000705000077.tif108143

[0112] In the case where the acid generator contains a salt (I) and an acid generator (B), the salt (I) and the acid generator (B) The ratio of the contents of the salt (I):acid generator (B) (mass ratio; salt (I):acid generator (B)) is usually 1:99 to 99:1. The ratio is preferably 2:98 to 98:2, and more preferably 5:95 to 95:5. , more preferably 10:90 to 90:10, and particularly preferably 15:85 to 85: It is 15. In the resist composition of the present invention, the total content of the acid generator is 00 parts by mass, preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less.

[0113] <Resist Composition> The resist composition of the present invention comprises an acid generator containing a salt (I) and a resin having an acid labile group (hereinafter Here, the "acid labile group" refers to a group that is eliminated by When the structural unit is contacted with an acid, the leaving group is eliminated, and the structural unit becomes a hydrophilic group (e.g., a hydroxyl group). It means a group that converts into a structural unit having a silyl group or a carboxy group. The resist composition of the present invention generates an acid having a weaker acidity than the acid generated from the acid generator. It may contain a quencher such as a salt (hereinafter referred to as "quencher (C)"). It is preferable that the ink contains a solvent (hereinafter, sometimes referred to as "solvent (E)").

[0114] <Resin (A)> Resin (A) contains a structural unit having an acid labile group (hereinafter sometimes referred to as “structural unit (a1)”). The resin (A) may further contain a structural unit other than the structural unit (a1). As the structural unit other than the structural unit (a1), a structural unit not having an acid labile group ( (hereinafter sometimes referred to as "structural unit (s)"), structural unit (a1) and structural unit (s) other than (for example, a structural unit having a halogen atom described later (hereinafter referred to as "structural unit (a4) "), a structural unit having a non-leaving hydrocarbon group described below (hereinafter referred to as a "structural unit ( a5) and other structural units derived from monomers known in the art etc.

[0115] <Structural unit (a1)> The structural unit (a1) is 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 a group represented by formula (1) (hereinafter, also referred to as group (1)). ) and / or a group represented by formula (2) (hereinafter also referred to as group (2)) is preferred. TIFF2025000705000078.tif2397[In formula (1), R a1 , R a2 and R a3 each independently represents an alkyl group having 1 to 8 carbon atoms , an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a combination thereof, or R a1 and R a2 are bonded together with the carbon atoms to which they are bonded to form alicyclic hydrocarbons having 3 to 20 carbon atoms. Form a group. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * represents a bond.] TIFF2025000705000079.tif2379[In formula (2), R a1’ and R a2’ each independently represents a hydrogen atom or a group having 1 to 1 carbon atoms R represents a hydrocarbon group of a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ Reach BiR a3’ are bonded to each other and, together with the carbon atom to which they are bonded and X, A heterocyclic group is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic group is -O- or - May be replaced with S-. X represents an oxygen atom or a sulfur atom. na′ represents 0 or 1. * represents a bond.]

[0116] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, Examples of the alkyl group include an aryl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, Examples of cycloalkyl groups include cycloheptyl and cyclooctyl groups. Examples of the hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups: (* represents a bond.) a1 , R a2 and R a3 Alicyclic hydrocarbons The radical preferably has 3 to 16 carbon atoms. TIFF2025000705000080.tif23114 Examples of groups combining an alkyl group and an alicyclic hydrocarbon group include methylcyclohexane. xyl group, dimethylcyclohexyl group, methylnorbornyl group, cyclohexylmethyl group , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, etc. do. Preferably, ma is 0 and na is 1. R a1 and R a2 When they are bonded to each other to form an alicyclic hydrocarbon group, -C(R a1 )(R a2 )(R a3 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * represents a bond to -O-. TIFF2025000705000081.tif31136

[0117] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a fluorine atom, an aromatic hydrocarbon group, and a group formed by combining these groups. can be done. The alkyl group and the alicyclic hydrocarbon group are R a1 , R a2 and R a3 The same groups as those listed in The following are some of the reasons. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples of the aryl group include a phenanthryl group and the like. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl group), aralkyl group (e.g., benzyl group), alkyl group Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group) , xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6 -ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl cyclophenyl group, p-adamantylphenyl group, etc.), alicyclic carbons having aromatic hydrocarbon groups Hydrogen groups (such as phenylcyclohexyl groups) 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, When forming a ring group, -C(R a1’ )(R a2’ )-XR a3’ Examples of the group include the following: * represents a bond. TIFF2025000705000082.tif21142R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0118] Examples of the group (1) include the following groups. In formula (1), Ra1 , R a2 and R a3 is an alkyl group, ma=0, and n A group where a=1. As the group, a tert-butoxycarbonyl group is preferable. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamantane. Forming a ethyl 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 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following groups. * represents a bond. TIFF2025000705000083.tif77166

[0119] Specific examples of the group (2) include the following groups. * represents a bond. TIFF2025000705000084.tif79164

[0120] The monomer (a1) is preferably a monomer having an acid labile group and an ethylenically unsaturated bond. More preferably, it is a (meth)acrylic monomer having an acid labile group.

[0121] Of the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of such a bulky structure include those having an alicyclic hydrocarbon group. A resin (A) having a structural unit derived from a monomer (a1) having the above structure is used in a resist composition. This can improve the resolution of the resist pattern.

[0122] As a structural unit derived from a (meth)acrylic monomer having a group (1), 0) (hereinafter, may be referred to as structural unit (a1-0)), -1) (hereinafter, may be referred to as structural unit (a1-1)) and a structural unit represented by the formula ( a1-2) (hereinafter, may be referred to as structural unit (a1-2)). Preferably, the structural unit (a1-1) is selected from the group consisting of the structural unit (a1-2) These may be used alone or in combination of two or more. They may be used in combination. TIFF2025000705000085.tif44146 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 each independently represents -O- or * -O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to -CO-. vinegar. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 each independently represents an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or combinations thereof. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, It represents an alicyclic hydrocarbon group or a group formed by combining these. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

[0123] R a01 , R a4 and R a5 is preferably a methyl group. L a01 , L a1 and L a2 is preferably an oxygen atom or *-O-(CH2) k01 -C OO- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom. R a02 , R a03 , R a04 , R a6 and R a7 The alkyl group, alicyclic hydrocarbon group, and As a group combining these, R in formula (1) a1 ~R a3 The same groups as those listed in can be. R a02 , R a03 , and R a04 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. A methyl group or an ethyl group is more preferable, and a methyl group is even more preferable. do. R a6 and R a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. It is a propyl group or an isopropyl group. R a02 , R a03 and R a04 The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms. More preferably, it is 5 to 10. The group consisting of a combination of an alkyl group and an alicyclic hydrocarbon group is It is preferred that the total number of carbon atoms in combination with the group is 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl It is a phenyl group or an ethyl 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. is preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably Preferably, the alkyl group is a ethyl group, an ethyl group, or an isopropyl group, more preferably an ethyl group or an isopropyl group. It is a aryl group. m1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1 is preferably an integer of 0 to 3, and more preferably 0 or 1. n1' is preferably 0 or 1.

[0124] Examples of the structural unit (a1-0) include those represented by the formulae (a1-0-1) to (a1-0-12): and R in the structural unit (a1-0) a01 The equivalent The structural units represented by the formula (a1-0-1) to the formula (a1- 0-10) are preferred. TIFF2025000705000086.tif66158

[0125] Examples of the structural unit (a1-1) include those described in JP-A-2010-204646. Among them, structural units derived from the monomers of formula (a1-1-1) to formula (a1-1-2) are included. -1-4) and R in the structural unit (a1-1) a4 In accordance with The structural units represented by the formulae (a1-1-1) to (a1-1-2) are preferably those in which the corresponding methyl groups are replaced by hydrogen atoms. A structural unit represented by any one of (a1-1-4) is more preferred. TIFF2025000705000087.tif44114

[0126] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to (a1-2-6). R in the structural unit (a1-2) a5 The methyl group corresponding to The structural units are represented by the formula (a1-2-2), the formula (a1-2-5), and A structural unit represented by any one of the formulas (a1-2-6) is preferred. TIFF2025000705000088.tif36161

[0127] Resin (A) is a structural unit (a1-0) and / or a structural unit (a1-1) and / or a structural unit When the unit (a1-2) is included, the total content of these units relative to the total structural units of the resin (A) is: It is usually 10 to 95 mol %, preferably 15 to 90 mol %, and more preferably 20 to 95 mol %. 85 mol %, more preferably 25 to 80 mol %, and even more preferably 3 It is 0 to 5 mol %.

[0128] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of the structural unit include a structural unit (hereinafter sometimes referred to as "structural unit (a1-4)"). TIFF2025000705000089.tif3867[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1-6 alkyl group which may have a halogen atom represents an alkyl group represented by the formula: R a33 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. la represents an integer of 0 to 4. When la is 2 or more, a plurality of R a33 are mutual may be the same or different. 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 combined with each other and These form a divalent hydrocarbon group having 2 to 20 carbon atoms together with the -CO- to which they are bonded, and the hydrocarbon The -CH2- contained in the alkyl group and the divalent hydrocarbon group is replaced by -O- or -S-. That's fine.]

[0129] R a32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the alkyl group include propyl, butyl, pentyl and hexyl groups. An alkyl group having 1 to 4 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferred. R a32 and R a33 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. Examples include: Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom include trifluoromethyl. group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoro Ethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluorobutyl group group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoro 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an alkyl group, a hexyl group, and a perfluorohexyl group. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is preferred, and a methoxy group is even more preferred. . Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. can be. The alkylcarbonyloxy group includes an acetyloxy group, a propionyloxy group, a bromooxy group, Examples thereof include a thyloxy group. R a34 , R a35 and R a36 The hydrocarbon group in the formula (I) is an alkyl group or an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups combining these. The alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a hexyl group. Examples include a silyl group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the aryl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, The following groups (* indicates a bonding site): Some examples include: TIFF2025000705000090.tif10151 Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples of the aryl group include a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. (e.g., cycloalkylalkyl groups), aralkyl groups such as benzyl groups, and alkyl groups. Aromatic hydrocarbon groups (p-methylphenyl, p-tert-butylphenyl, tolyl group, xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl- 6-ethylphenyl group, etc.), aromatic hydrocarbon groups having alicyclic hydrocarbon groups (p-cyclohexyl p-adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for the carbon number 1-18, an alkyl group, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or Examples of the groups include groups formed by combining these.

[0130] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. is more preferred, and a methoxy group is even more preferred. la is preferably 0 or 1, and more preferably 0. R a34 is preferably a hydrogen atom. R a35 is preferably an alkyl group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms, more preferably More preferably, it is 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.

[0131] -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid) and is eliminated to form a hydroxyl group.

[0132] 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. -4-12) and R in the structural unit (a1-4) a32 To A structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred. Examples of the structural units include those represented by formulas (a1-4-1) to (a1-4-10). TIFF2025000705000091.tif68158

[0133] When the resin (A) has the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total of the structural units. It is more preferable that the content is 10 to 40 mol %.

[0134] The structural unit derived from a (meth)acrylic monomer having the group (2) is represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can also be mentioned. can be. TIFF2025000705000092.tif4354 formula (a1-5), R a8 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom. Represents an acetylene atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, h3 is 1 to 4 represents an integer, and * represents L 51 Represents a bond with . L 51 , L 52 , L 53 and L 54 each independently represents -O- or -S-. s1 represents an integer of 1 to 3. s1' represents an integer of 0 to 3.

[0135] Examples of the halogen atom include a fluorine atom and a chlorine atom, with a fluorine atom being 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, Propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoromethyl group Examples of the alkyl group include the ethyl group and the trifluoromethyl group. In formula (a1-5), R a8 is a hydrogen atom, a methyl group, or a trifluoromethyl group. preferable. L 51 is preferably an oxygen atom. L 52 and L 53 Of these, it is preferred that one is -O- and the other is -S-. It is preferable that s1 is 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or -CH2-CO-O-.

[0136] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers represented by the formula (a1-5-1) to the formula (a1-5- 4), and the structural units represented by the formula (a1-5-1) or the formula (a1-5-2) are preferred. ) is more preferred. TIFF2025000705000093.tif33139

[0137] When the resin (A) has the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content of the copolymer is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0138] Examples of the structural unit (a1) include a structural unit represented by the formula (a1-0X) (hereinafter, This is sometimes called the structural unit (a1-0X). TIFF2025000705000094.tif3961[In formula (a1-0X), R x1 represents a hydrogen atom or a methyl group. R x2 and R x3 each independently represents a saturated hydrocarbon group having 1 to 6 carbon atoms. Ar x1 represents an aromatic hydrocarbon group having 6 to 36 carbon atoms.]

[0139] R x2 and R x3 The saturated hydrocarbon group includes an alkyl group, an alicyclic hydrocarbon group, and the like. and the like. The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. do. The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group Examples of the aryl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples include:

[0140] Ar x1 Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the aryl groups include those having 6 to 36 prime numbers. The aromatic hydrocarbon group preferably has 6 to 24 carbon atoms, more preferably 6 to 1 8, and more preferably a phenyl group.

[0141] Ar x1 is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably Preferably, the aryl group is a phenyl group or a naphthyl group, and more preferably, a phenyl group. R x1 , R x2 and R x3 are each preferably independently a methyl group or an ethyl group. A methyl group is preferable.

[0142] The structural unit (a1-0X) may be any of the structural units and structural units (a1-0X) shown below. R in x1 Examples of compounds in which the methyl group corresponding to the structure is replaced with a hydrogen atom include: The unit (a1-0X) is a structural unit (a1-0X-1) to a structural unit (a1-0X-3). It is preferable that TIFF2025000705000095.tif33161

[0143] When the resin (A) has the structural unit (a1-0X), the content of the structural unit (a1-0X) in the resin (A) is It is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, based on the total monomers in the copolymer. It is more preferable that the content is 10 to 40 mol %, and further more preferable that the content is 10 to 40 mol %. The resin (A) may contain two or more types of the structural unit (a1-0X).

[0144] Further, examples of the structural unit (a1) include the following structural units. TIFF2025000705000096.tif30167

[0145] When the resin (A) contains the above structural unit, the content of the structural unit is The content is preferably 5 to 60 mol %, more preferably 5 to 50 mol %, and even more preferably 10 to 40 mol %. More preferred.

[0146] Structural unit(s) The structural unit (s) is a monomer that does not have an acid labile group (hereinafter referred to as "monomer (s)"). The monomer from which the structural unit (s) is derived is an acid-inhibiting monomer known in the resist field. Monomers that do not have stabilizing groups can be used. The structural unit (s) preferably has a hydroxy group or a lactone ring. A structural unit having an oxy group and no acid labile group (hereinafter referred to as "structural unit (a2)") and / or a structural unit having a lactone ring and no acid labile group (hereinafter referred to as "structural unit" When a resin having the structural unit (a3) ​​is used in the resist composition of the present invention, For example, the resolution of the resist pattern and the adhesion to the substrate can be improved.

[0147] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a carboxylic hydroxy group. When a resist pattern is produced from the resist composition of the present invention, the exposure light source is KrF Using high energy rays such as excimer laser (248 nm), electron beam or EUV (extreme ultraviolet light) In this case, the structural unit (a2) is a structural unit having a phenolic hydroxy group ( a2) is preferred, and it is more preferred to use the structural unit (a2-A) described below. When using an ArF excimer laser (193 nm) or the like, the structural unit (a2) is The structural unit (a2) having an alcoholic hydroxy group is preferred, and the structural unit (a2) described below is It is more preferable to use the structural unit (a2) alone. It may contain two or more kinds.

[0148] In the structural unit (a2), the structural unit having a phenolic hydroxy group is represented by the formula (a 2-A) (hereinafter sometimes referred to as "structural unit (a2-A)") is can be done. TIFF2025000705000097.tif5360[In formula (a2-A), R a50 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group. R a51 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, Alkoxy groups, alkylcarbonyl groups having 2 to 4 carbon atoms, alkylcarbonyl groups having 2 to 4 carbon atoms It represents an acryloyloxy group, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 -(A a52 -X a52 ) nb - stands for -R. a50 Combined It represents the bond to the carbon atom. A a52 each independently 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 0 to 4. When mb is an integer of 2 or more, R in Numbers a51 may be the same or different.]

[0149] R a50 Examples of the halogen atom in the formula (I) include a fluorine atom, a chlorine atom, and a bromine atom. can be. R a50 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom is, for example, tri Fluoromethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2 -Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoroethyl group 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group, Fluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group Examples of the alkyl group include ethyl, pentyl, hexyl and perfluorohexyl groups. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or is more preferably an ethyl group, and further preferably a hydrogen atom or a methyl group. R a51 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples of the butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group are listed below. can be done. R a51 The alkoxy group in the formula (I) is a methoxy group, an ethoxy group, a propoxy group, an iso Examples of the group include a propoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxy group having 1 to 4 carbon atoms is preferred, a methoxy group or an ethoxy group is more preferred, and a methoxy group or an ethoxy group is more preferred. A toxyl group is more preferred. R a51 The alkylcarbonyl group in the formula (I) is an acetyl group, a propionyl group, or a butyl group. Examples of the alkyl group include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, Examples of the alkyl groups include an alkyloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0150] *-X a51 -(A a52 -X a52 ) nb - includes *-O-, *-CO-O-, *-OC O-, *-CO-OA a52 -CO-O-, *-O-CO-A a52 -O-, *-OA a52 -CO-O-, *-CO-OA a52 -O-CO-, *-O-CO-A a52 -O-CO-, Among them, *-CO-O- and *-CO-OA are the most common. a52 -CO-O- or *- Office Automation a52 -CO-O- is preferred.

[0151] Examples of the alkanediyl group include a methylene group, an ethylene group, and 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-methylpropane-1, 3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and and 2-methylbutane-1,4-diyl group. A a52 is preferably a methylene group or an ethylene group.

[0152] A a50 is a single bond, *-CO-O- or *-CO-OA a52 -CO-O- Preferably, it is a single bond, *-CO-O- or *-CO-O-CH2-CO-O-. A single bond or *--CO--O-- is more preferable, and a single bond or *--CO--O-- is even more preferable.

[0153] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the ortho or para position of the benzene ring, and more preferably to the para position. It is more preferred to bind to

[0154] The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). In the structural units and the structural units represented by formulae (a2-2-1) to (a2-2-6), R in structural unit (a2-A) a50 The structure in which the methyl group corresponding to is replaced by a hydrogen atom The structural unit (a2-A) is a structural unit represented by the formula (a2-2-1): A structural unit represented by formula (a2-2-3), a structural unit represented by formula (a2-2-6) and a structural unit represented by formula (a2-2-7) A structural unit represented by formula (a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula ( In the structural unit represented by a2-2-6), R in the structural unit (a2-A) a50 To It is preferable that the corresponding methyl group is substituted with a hydrogen atom. TIFF2025000705000098.tif42166

[0155] Content of structural unit (a2-A) when structural unit (a2-A) is contained in resin (A) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, based on all structural units. % by mole, more preferably 15 to 65 mol %, and even more preferably 20 to 65 mol %. It is 65 mol%. The structural unit (a2-A) can be prepared, for example, by polymerization of the structural unit (a1-4) followed by p-toluenesulfonyl chloride. It can be incorporated into the resin (A) by treating it with an acid such as benzenesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating the resin with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0156] In the structural unit (a2), the structural unit having an alcoholic hydroxy group is represented by the formula ( a2-1) (hereinafter sometimes referred to as "structural unit (a2-1)") Some examples include: TIFF2025000705000099.tif4159 formula (a2-1), L a3 is -O- or * -O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents a bond to -CO-. R a14 represents a hydrogen atom or a methyl group. R a15 and R a16 each independently represents a hydrogen atom, a methyl group, or a hydroxy group. o1 represents an integer of 0 to 10.

[0157] In formula (a2-1), L a3is preferably -O-, -O-(CH2) f1 -CO-O- (wherein f1 represents an integer of 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 an integer of 0 to 3, and more preferably 0 or 1.

[0158] Examples of the structural unit (a2-1) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a2-1-1) to formula (a2-1-6) are included. ), and the structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) is preferred. A structural unit represented by any one of the formulas (a2-1-1) or (a2-1- The structural unit represented by 3) is more preferred. TIFF2025000705000100.tif54148

[0159] When the resin (A) contains the structural unit (a2-1), the content of the structural unit (a2-1) is determined based on the total amount of the structural units of the resin (A). The amount is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0160] <Structural unit (a3)> The lactone ring contained in the structural unit (a3) ​​is a β-propiolactone ring, a γ-butyrolactone ring, or It may be a monocyclic ring such as a lactone ring or a δ-valerolactone ring, or a condensation ring of a monocyclic lactone ring with another ring. It may be a γ-butyrolactone ring, an adamantane lactone ring, or a γ -Bridged ring containing a butyrolactone ring structure (for example, a structural unit represented by the following formula (a3-2)) Examples include:

[0161] The structural unit (a3) ​​is preferably represented by the formula (a3-1), the formula (a3-2), the formula (a3-3), or a structural unit represented by formula (a3-4). One of these may be contained alone, Two or more types may be contained. TIFF2025000705000101.tif51159 [In formula (a3-1), formula (a3-2), formula (a3-3) and formula (a3-4), L a4 , L a5 and L a6 are each independently -O- or *-O-(CH2) k3 - It represents a group represented by CO-O- (k3 represents an integer of any of 1 to 7). L a7 , -O-, *-OL a8 -O-, *-OL a8 -CO-O-, *-OL a8 -CO-OL a9 -CO-O- or *-OL a8 -O-CO-L a9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond 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 a halogen atom. Represents an 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 carbon atom; Represents an aliphatic hydrocarbon group having 1 to 4 prime numbers. p1 represents an integer of 0 to 5. q1 represents an integer of 0 to 3. r1 represents an integer of 0 to 3. w1 represents an integer of 0 to 8. When p1, q1, r1 and / or w1 are 2 or more, multiple R a21 , R a22 , R a2 3 and / or R a25 may be the same or different.]

[0162] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in propyl, isopropyl, butyl, sec-butyl and tert-butyl groups Examples of alkyl groups include the following. R a24 The halogen atom in the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Atoms include: R a24 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group, etc. Of these, preferred is an alkyl group having 1 to 4 carbon atoms, and more preferred is a methyl group. or an ethyl group. R a24 Examples of the alkyl group having a halogen atom in the formula (I) include a trifluoromethyl group, Perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group, perfluorohexyl group, trichloromethyl group, tribromomethyl group Examples of the alkyl group include an alkyl group, a triiodomethyl group, and a triiodomethyl group. L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a proline group, Pan-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pe hexane-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, pentamethylpropane Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0163] In formulas (a3-1) to (a3-3), L a4 ~L a6 are each independently preferred or -O- or *-O-(CH2) k3 In -CO-O-, k3 is 1 to 4 More preferably, -O- and *-O-CH2-CO-O- are also preferred. An oxygen atom is preferred. R a18 ~R a21 is preferably a methyl group. R a22 and R a23 are each independently preferably a carboxy group, a cyano group or a methyl group. It is a ethyl group. p1, q1 and r1 each independently represent an integer of preferably 0 to 2; More preferably, it is 0 or 1.

[0164] In formula (a3-4), R a24is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably It is 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 *-OL a8 -CO-O-, more preferably -O-, -O-CH2-CO-O- or -O-C2H4-CO-O-. w1 is preferably an integer of 0 to 2, and more preferably 0 or 1. In particular, the formula (a3-4) is preferably the formula (a3-4)'. TIFF2025000705000102.tif4048 (in the formula, R a24 , L a7 has the same meaning as above.)

[0165] As the structural unit (a3), a monomer described in JP-A-2010-204646 can be used. , Monomers described in JP 2000-122294 A, and JP 2012-41274 A Examples of the structural unit (a3) ​​include structural units derived from the monomers described in the above publication. , 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 2), and in the structural unit, the structural unit represented by any one of the formulas (a3-1) to (a3-2) R in a3-4) a18 , R a19 , R a20 and R a24 The methyl group corresponding to Atom-substituted structural units are preferred. TIFF2025000705000103.tif115165

[0166] When the resin (A) contains the structural unit (a3), the total content of the structural unit (a3) ​​is the total content of all structural units of the resin (A). The amount is usually 1 to 70 mol %, preferably 1 to 65 mol %, more preferably The content is usually 1 to 60 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit The content of the units (a3-4) is 1 to 60 moieties relative to the total structural units of the resin (A). % by mole is preferable, 1 to 50 mol % is more preferable, and 1 to 50 mol % is even more preferable.

[0167] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025000705000104.tif2968[In formula (a4), R 41 represents a hydrogen atom or a methyl group. R 42 represents a saturated hydrocarbon group having 1 to 24 carbon atoms and containing a fluorine atom, The -CH2- contained in the group may be replaced with -O- or -CO-. R 42 The saturated hydrocarbon group represented by the formula (I) is a chain hydrocarbon group and a monocyclic or polycyclic alicyclic hydrocarbon group. groups, as well as groups formed by combining these groups.

[0168] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, decyl, dodecyl, pentadecyl, hexa Examples include decyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Cycloalkyl groups such as cycloheptyl and cyclooctyl; decahydronaphthyl, adipyl, Polycyclic alicyclic carbons such as manthyl group, norbornyl group, and the following groups (* represents a bond): Examples of the aryl group include aryl groups. TIFF2025000705000105.tif10158 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic hydrocarbon groups. In particular, -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples thereof include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0169] The structural unit (a4) may be any of the following: a4-3) and at least one structure selected from the group consisting of formula (a4-4) Units include: TIFF2025000705000106.tif4155[In formula (a4-0), R 5a 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 is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 6a represents a hydrogen atom or a fluorine atom.

[0170] L 4a The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,4-diyl group, ethane-1,1 -diyl group, propane-1,2-diyl group, butane-1,3-diyl group, 2-methylpropane Branched alkanes such as pan-1,3-diyl and 2-methylpropane-1,2-diyl groups An example of such a group is a diyl group.

[0171] L 3a The perfluoroalkanediyl group in the formula (I) is a difluoromethylene group, Fluoroethylene group, perfluoropropane-1,1-diyl group, perfluoropropane -1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane -2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2 ,2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1, 5-diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3, 3-diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2, 2-diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1, 7-diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3, 4-diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1, 8-diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3, 3-diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in xanediyl group, perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0172] L 4a is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond, a methylene group. L 3ais preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0173] The structural unit (a4-0) may be any of the structural units shown below and the structural units ( a4-0) in R 5a The structural unit in which the methyl group corresponding to the can be done. TIFF2025000705000107.tif97165

[0174] TIFF2025000705000108.tif4264[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, The --CH2-- contained in the 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 the formula (ag 1), where A a41 and R a42 At least one of the The group has a halogen atom (preferably a fluorine atom). TIFF2025000705000109.tif1383 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 each independently represents a divalent alkyl group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 is a divalent aliphatic hydrocarbon having 1 to 5 carbon atoms which may have a single bond or a substituent. Represents a group. X a41 and X a42each independently represents -O-, -CO-, -CO-O-, or -O-CO - represents. However, A a42 , A a43 , A a44 , X a41 and X a42 The total number of carbon atoms is 7 or less. * is a bond, and the * on the right is -O-CO-R a42 It is a combination with .

[0175] R a42 The saturated hydrocarbon group in the formula (I) is preferably a chain saturated hydrocarbon group or a monocyclic or polycyclic alicyclic and groups formed by combining these. do.

[0176] Examples of the chain saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, heptyl group, Examples include xadecyl, heptadecyl and octadecyl groups. Examples of the monocyclic or polycyclic alicyclic saturated hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups, Polycyclic alicyclic rings such as adamantyl group, norbornyl group, and the following groups (* represents a bond): Saturated hydrocarbon groups of the formula: TIFF2025000705000110.tif10158 The group formed by the combination may be one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an aryl group with one or more alicyclic saturated hydrocarbon groups. Examples of the saturated alicyclic hydrocarbon group include -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkyl Examples of the alkyl group include an aryl group, an alkanediyl group, an alicyclic saturated hydrocarbon group, and an alkyl group.

[0177] R a42 The substituents of the formula (a-g3) are halogen atoms and groups represented by the formula (a-g3). The halogen atom may be at least one selected from the group consisting of fluorine atom, Examples of the atom include a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. TIFF2025000705000111.tif752[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO-, or *-CO-O-. A a45 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . * stands for R a42 It represents a bond with . However, R a42 -X a43 -A a45 In R a42 When A does not have a halogen atom, a4 5 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom .

[0178] A a45 The aliphatic hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, a butyl group, group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, penta Alkyl groups such as decyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups alicyclic hydrocarbon radicals; and Decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bond): Examples of the polycyclic alicyclic hydrocarbon group include the polycyclic alicyclic hydrocarbon groups. TIFF2025000705000112.tif10158

[0179] R a42 is preferably a saturated hydrocarbon group which may have a halogen atom, and / or a saturated hydrocarbon group having a group represented by formula (a-g3) is preferably This is more preferable. R a42 When is a saturated hydrocarbon group having a halogen atom, it is preferably a saturated hydrocarbon group having a fluorine atom. More preferably, it is a saturated hydrocarbon group having a fluoroalkyl group or a perfluorosilyl group. Preferably, the alkyl group is a chloroalkyl group, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms. Particularly preferred is a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a perfluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro perfluorooctyl and perfluoroheptyl groups. Examples of the aryl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3), including the number of carbon atoms contained in the group represented by R a42 The total number of carbon atoms is preferably 15 or less. When the alkyl group has a group represented by formula (a-g3) as a substituent, The number is preferably one.

[0180] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferably, it is a group represented by formula (a-g2). TIFF2025000705000113.tif874[In formula (a-g2), A a46represents a divalent saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. represent. X a44 represents **-O-CO- or **-CO-O- (** represents A a46 Represents the bond with vinegar.). A a47 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. . However, A a46 , A a47 and X a44 The total number of carbon atoms in A is 18 or less. a46 and A a47 of At least one of them has at least one halogen atom. * indicates a bond to the carbonyl group.

[0181] A a46 The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms. A a47 The aliphatic hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms. A a47 is more preferably a cyclohexyl group or an adamantyl group.

[0182] A preferred structure of the group represented by formula (a-g2) is the following structure (* represents a carbonyl group). (It is a combination with ). TIFF2025000705000114.tif13167

[0183] A a41 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 linear alkanediyl groups such as propane-1,2-diyl, butane-1,6-diyl; ,3-diyl group, 2-methylpropane-1,2-diyl group, 1-methylbutane-1,4- and branched alkanediyl groups such as 2-methylbutane-1,4-diyl and the like. do. A a41 The substituents in the alkanediyl group represented by the formula (I) are a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups represented by the formula (6). A a41 is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably It is preferably an alkanediyl group having 2 to 4 carbon atoms, and more preferably an ethylene group.

[0184] A in the group represented by formula (a-g1) a42 , A a43 and A a44 The bivalent saturation represented by The hydrocarbon group may be a straight-chain or branched alkanediyl group or a monocyclic or polycyclic divalent alicyclic group. By combining a divalent hydrocarbon group with an alkanediyl group and a divalent alicyclic hydrocarbon group, Specifically, a methylene group, an ethylene group, a propane-1 ,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methyl Propane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane Examples thereof include a pan-1,2-diyl group. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is hydroxyl. Examples of the alkoxy group include an alkoxy group and an alkoxy group having 1 to 6 carbon atoms. It is preferred that s is 0.

[0185] In the group represented by formula (a-g1), X a42 is -O-, -CO-, -CO-O- or Examples of the -O-CO- group include the following groups. In the following examples, * and Each ** represents a bond, and ** is -O-CO-R. a42 It is a combination with. TIFF2025000705000115.tif48153

[0186] The structural unit represented by formula (a4-1) includes the structural units shown below and the structural units shown below. R in the structural unit represented by formula (a4-1) a41 A methyl group corresponding to Examples of structural units that have been replaced include: TIFF2025000705000116.tif100142

[0187] TIFF2025000705000117.tif122140

[0188] As the structural unit represented by formula (a4-1), a structural unit represented by formula (a4-2) is preferred. I wish. TIFF2025000705000118.tif3151[In formula (a4-2), R f5 represents a hydrogen atom or a methyl group. L 44 represents an alkanediyl group having 1 to 6 carbon atoms, H2- may be replaced by -O- or -CO-. R f6 represents a saturated hydrocarbon group having 1 to 20 carbon atoms and containing a fluorine atom. However, L 44 and R f6 The total number of carbon atoms in the molecule is limited to 21.

[0189] L 44 The alkanediyl group of A a41 Examples of the groups include the same groups as those exemplified in the above. R f6 The saturated hydrocarbon group of R a42 Examples of the groups include the same groups as those exemplified in the above. L 44The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms. An ethylene group is more preferred.

[0190] Examples of the structural unit represented by formula (a4-2) include the structural units represented by formulae (a4-1-1) to (a4 -1-11) are structural units represented by the following formulas. R f5 The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-2). It can be mentioned as a structural unit.

[0191] TIFF2025000705000119.tif5164[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. vinegar. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 It represents a bond with .) . A f14 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may contain a fluorine atom. However, A f13 and A f14 At least one of L has a fluorine atom. 5 , A f13 and A f14 The total number of carbon atoms in the molecule is limited to 20.

[0192] L 5 The alkanediyl group in a41 Examples of alkanediyl groups are The same groups as those shown below can be mentioned.

[0193] A f13The divalent saturated hydrocarbon group which may have a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a It is preferably a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkane dialkyl group. It is a aryl group. Examples of the divalent chain hydrocarbon group which may have a fluorine atom include a methylene group, an ethylene alkanediyl groups such as propanediyl, butanediyl and pentanediyl groups; Fluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoro perfluoroalkanediyl groups such as perfluorobutanediyl and perfluoropentanediyl groups Examples of the alkyl group include aryl groups. The divalent alicyclic hydrocarbon group which may have a fluorine atom may be either a monocyclic or a polycyclic group. Examples of the monocyclic group include a cyclohexanediyl group and a perfluorocyclohexa Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. diyl group, perfluoroadamantanediyl group, and the like.

[0194] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are represented by R a42 in The same groups as those exemplified above can be mentioned. Among them, trifluoromethyl group, difluoromethyl group, ethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoroethyl group, 1,1 ,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group, 2,2,3, 3,3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2, 2,3,3,4,4-octafluorobutyl group, butyl group, perfluoropentyl group, 2 ,2,3,3,4,4,5,5,5-nonafluoropentyl group, pentyl group, hexyl group , perfluorohexyl group, heptyl group, perfluoroheptyl group, octyl group and perfluorohexyl group. Fluorinated alkyl groups such as fluorooctyl group, cyclopropylmethyl group, cyclopropyl group , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group, norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantyl group A methyl group and the like are preferred.

[0195] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The divalent saturated hydrocarbon group is a divalent chain hydrocarbon group having 1 to 6 carbon atoms and a divalent chain hydrocarbon group having 3 A group containing a divalent alicyclic hydrocarbon group having from 1 to 12 carbon atoms is preferred, and a divalent chain hydrocarbon group having from 2 to 3 carbon atoms is preferred. A base is more preferred. A f14 The saturated hydrocarbon group is a chain hydrocarbon group having 3 to 12 carbon atoms and an aliphatic hydrocarbon group having 3 to 12 carbon atoms. Groups containing cyclic hydrocarbon groups are preferred, and chain hydrocarbon groups having 3 to 10 carbon atoms and groups containing 3 to 1 More preferred is a group containing an alicyclic hydrocarbon group of A f14 is preferably carbon It is a group containing an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and more preferably, cyclopropylmethyl. groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups.

[0196] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formula (a4-1'-1) to formula (a 4-1´-11) are structural units represented by the following formulas. R f7The structural unit in which the corresponding methyl group is replaced by a hydrogen atom is also represented by formula (a4-3). It is one of the structural units that can be mentioned.

[0197] The structural unit (a4) also includes a structural unit represented by the formula (a4-4). TIFF2025000705000120.tif4162[In formula (a4-4), R f21 represents a hydrogen atom or a methyl group. A f21 is -(CH2) j1 -, -(CH2) j2 -O-(CH2) j3 -or-(CH2) j4 - CO-O-(CH2) j5 - represents. j1 to j5 each independently represent an integer of 1 to 6. R f22 represents a saturated hydrocarbon group having 1 to 10 carbon atoms and containing a fluorine atom.]

[0198] R f22 The saturated hydrocarbon group of R a42 The saturated hydrocarbon group may be the same as that represented by the following formula: R f22 represents an alkyl group having 1 to 10 carbon atoms and a fluorine atom, or a carbon An alicyclic hydrocarbon group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms and a fluorine atom is preferred. A fluorine atom-containing alkyl group having 1 to 6 carbon atoms is more preferred.

[0199] In formula (a4-4), A f21 As an example, -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0200] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by the formula (a4-4), R f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced by hydrogen atoms. TIFF2025000705000121.tif87160

[0201] When the resin (A) has the structural unit (a4), its content is determined based on the total structural units of the resin (A). The ratio is preferably 1 to 20 mol %, more preferably 2 to 15 mol %, and more preferably 3 to 10 mol %. % is more preferred.

[0202] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) is a straight-chain, branched or cyclic hydrocarbon group. Among them, the structural unit (a5) is preferably a group having an alicyclic hydrocarbon group. The group is preferred. Examples of the structural unit (a5) include a structural unit represented by the formula (a5-1): . TIFF2025000705000122.tif3971[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-.

[0203] 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.

[0204] L 55 The 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.

[0205] 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 bond, and * represents a bond to an oxygen atom. TIFF2025000705000123.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 It represents a bond 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 x4 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, L x3 and L x4 The total number of carbon atoms is 17 or less. 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 represents a single bond or a divalent aliphatic saturated carbon atom having 1 to 14 carbon atoms; Represents a hydrogen group. However, L x5 , L x6 and L x7 The total number of carbon atoms is 15 or less. In formula (L1-4), L x8 and L x9 represents 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, L x8 , L x9 and Wx1 The total number of carbon atoms is 15 or less.

[0206] L x1 is preferably a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably It is 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 Preferably, it is 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 It is 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 is preferred. 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 Preferably, it is 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 Preferably, it is 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.

[0207] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025000705000124.tif23135

[0208] TIFF2025000705000125.tif33117

[0209] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025000705000126.tif23131

[0210] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025000705000127.tif15147

[0211] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025000705000128.tif26114

[0212] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0213] The structural unit (a5-1) may be any of the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to the can be. TIFF2025000705000129.tif74150

[0214] TIFF2025000705000130.tif36153When resin (A) has the structural unit (a5), its content is the total of all structural units of resin (A). The ratio is preferably 1 to 30 mol %, more preferably 2 to 20 mol %, and more preferably 3 to 15 mol %. % is more preferred.

[0215] <Structural unit (II)> The resin (A) further includes a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit The structural unit (II) may specifically include is a structural unit described in JP 2016-79235 A, and has a sulfonate group in the side chain. or a structural unit having a carboxylate group and an organic cation, or a sulfonio group on the side chain and an organic anion.

[0216] The structural unit having a sulfonate group or a carboxylate group in the side chain is represented by the formula (II-2 -A') is preferably a structural unit represented by the formula: TIFF2025000705000131.tif36104[In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, The -CH2- contained in the saturated carbon atom may be replaced by -O-, -S- or -CO-. The hydrogen atom contained in the hydrogen hydride group is a halogen atom, a carbon number which may have a halogen atom It may be substituted with 1 to 6 alkyl groups or hydroxy groups. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the water contained in the alkanediyl group The nitrogen atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. stomach. RA - represents a sulfonate group or a carboxylate group. R III3 is a hydrogen atom, a halogen atom, or a carbon atom having 1 Represents an alkyl group of 1 to 6. Z.A. + represents an organic cation.

[0217] R III3Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include an uran atom. R III3 The alkyl group having 1 to 6 carbon atoms and optionally having a halogen atom is represented by the formula: R a8 The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by the formula: Examples include the following. A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, , propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group group, hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group Examples of the aryl group include pentane-1,4-diyl group and 2-methylbutane-1,4-diyl group. do. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert -butyl group, perfluoropentyl group, perfluorohexyl group, and the like. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may be a combination of the above. Specifically, methylene group, ethylene group, propane-1,3-diyl group, propane-1, 2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Linear alkanediyl groups such as decane-1,12-diyl group; butane-1,3-diyl group; 2-Methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentamethylpropane Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexanone-1,4-diyl group and cyclooctane-1,5-diyl group norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic alicyclic saturated carbons such as cyclohexyl-1,5-diyl and adamantane-2,6-diyl groups Hydrogen groups and the like. A saturated hydrocarbon group in which -CH2- has been replaced with -O-, -S- or -CO- Examples of the divalent group include those represented by the formulae (X1) to (X53). The -CH2- contained in the saturated hydrocarbon group is replaced with -O-, -S- or -CO-. The number of carbon atoms in front of each is 17 or less. In the following formula, * represents A x1 Represents a bond with . TIFF2025000705000132.tif145158

[0218] 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. X6 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.

[0219] ZA in formula (II-2-A') + is the cation Z in salt (I). + The same thing was mentioned. Can be obtained.

[0220] The structural unit represented by the formula (II-2-A') is a structural unit represented by the formula (II-2-A) It is preferable that: TIFF2025000705000133.tif38109 [In formula (II-2-A), R III3 , X III3 and Z.A. + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 each independently represents a hydrogen atom, a fluorine atom, or a carbon atom represents a perfluoroalkyl group having a number of 1 to 6; when z2A is 2 or more, multiple R III2 and R III4 may be the same as or different from each other. Q a and Q b each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents the alkyl group. R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by the formula: The Q group is b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: The following are some of the reasons.

[0221] The structural unit represented by formula (II-2-A) is a structural unit represented by formula (II-2-A-1). It is preferable that the position is 1. TIFF2025000705000134.tif5578 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and Z.A. + has the same meaning as above . R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, The -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon may be The hydrogen atoms contained in the radicals may be substituted with halogen atoms or hydroxy groups. R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, and the like. , propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and and dodecyl group. X I2 As the divalent saturated hydrocarbon group represented by the formula: III3 Divalent saturated carbon represented by The same as the hydride group can be mentioned.

[0222] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). More preferred are structural units in which TIFF2025000705000135.tif5288 [In formula (II-2-A-2), RIII3 , R III5 and Z.A. + has the same meaning as above. m and n each independently represent 1 or 2.

[0223] Examples of the structural unit represented by formula (II-2-A') include the following structural units, R III3 The group corresponding to the methyl group is a hydrogen atom, a halogen atom (e.g., a fluorine atom) or a halogen An alkyl group having 1 to 6 carbon atoms which may have one or more atoms (for example, a trifluoromethyl group, etc.) and structural units described in International Publication No. 2012 / 050015. It can be done. + represents an organic cation. TIFF2025000705000136.tif86163

[0224] The structural unit having a sulfonio group and an organic anion in the side chain is represented by the formula (II-1-1): It is preferable that the structural unit is a structural unit that is TIFF2025000705000137.tif3791 [In formula (II-1-1), 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 represents a hydrocarbon group having 1 to 18 carbon atoms; R II2 and R II3 are bonded together to form a ring with the sulfur atom to which they are attached. This is also fine. R II4 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom represents an alkyl group. A - represents an organic anion. R II1As the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I), a phenylene group is preferable. and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group and an alicyclic hydrocarbon group. , aromatic hydrocarbon groups, and groups formed by combining these groups. R II4 The halogen atom represented by the formula (I) is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of such atoms include elementary atoms. R II4 As an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, represented by is R a8 The same as the alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by the formula: Some examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated carbon atom having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group is -O-, -S- or may be replaced by -CO-. Specifically, X III3 The carbon number is 1 to 1 Examples of the divalent saturated hydrocarbon group include the same as those in 8.

[0225] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formula: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF2025000705000138.tif84130

[0226] A - As the organic anion represented by the formula (I), a sulfonate anion, a sulfonylimide anion, Examples of the anion include sulfonylmethide anion and carboxylate anion. -Represented by The organic anion is preferably a sulfonate anion. More preferably, it is an anion contained in the salt represented by formula (B1).

[0227] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025000705000139.tif43135

[0228] Examples of sulfonylmethide anions include the following: TIFF2025000705000140.tif29123

[0229] Examples of carboxylate anions include the following: TIFF2025000705000141.tif51153

[0230] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025000705000142.tif161141

[0231] When the resin (A) contains the structural unit (II), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 4 mol %, based on the total structural units of the oil (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0232] The resin (A) may have structural units other than the above-mentioned structural units. The positions include structural units known in the art.

[0233] The resin (A) is preferably a resin composed of the structural unit (a1) and the structural unit (s). . The structural unit (a1) is preferably a structural unit (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably a cyclohexyl group or a structural unit having a cyclopentyl group) At least one selected from the group consisting of structural units, more preferably at least two It is. The structural unit (s) is preferably selected from the group consisting of the structural unit (a2) and the structural unit (a3). The structural unit (a2) is preferably represented by the formula (a2-A): The structural unit (a3) ​​is preferably a structural unit represented by the formula (a2-1). or a structural unit represented by formula (a3-1), a structural unit represented by formula (a3-2) and a structural unit represented by formula (a3-3) a3-4) is at least one selected from the group consisting of structural units represented by the following formula:

[0234] Each structural unit constituting the resin (A) may be used alone or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (e.g., radical polymerization methods). The content of each structural unit in the resin (A) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (A) is preferably 2,000 or more (more preferably 2,500 or more). 00 or more, more preferably 3,000 or more), 50,000 or less (more preferably 30 In the present specification, the weight average molecular weight is preferably 1,000 or less, and more preferably 15,000 or less. The molecular weight is a value determined by gel permeation chromatography under the conditions described in the Examples. It is.

[0235] <Resins other than resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of the resin other than the resin (A) include a resin containing the structural unit (a4) or the structural unit (a5). (hereinafter, may be referred to as resin (X)).

[0236] As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of the structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 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. X) is preferably a resin consisting of only the structural unit (a4) and / or the structural unit (a5). It is preferable that the resin is composed only of the structural unit (a4).

[0237] Each structural unit constituting the resin (X) may be used alone or in combination of two or more kinds. Using monomers that derive these structural units, a known polymerization method (e.g., radical polymerization method) is performed. The content of each structural unit in the resin (X) can be determined by the following procedure. This can be adjusted by the amount of monomer used. The weight average molecular weight of the resin (X) is preferably 6,000 or more (more preferably 7,000 or more). 0 or more) and 80,000 or less (more preferably 60,000 or less). The method for measuring the weight average molecular weight is the same as in the case of resin (A). Furthermore, when the resist composition contains resin (X), the content of resin (X) is parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, More preferably, the content is 1 to 40 parts by mass, and particularly preferably, the content is 1 to 30 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0238] The content of the resin (A) in the resist composition is 8 to 100% based on the solid content of the resist composition. It is preferably 0% by mass or more and 99% by mass or less, and more preferably 90% by mass or more and 99% by mass or less. In addition, when a resin other than the resin (A) is contained, the resin (A) and the resin other than the resin (A) are preferably mixed. The total content of the resin is 80% by mass or more and 99% by mass or less based on the solid content of the resist composition. It is preferable that the content is 90% by mass or less, and more preferable that the content is 90% by mass or more and 99% by mass or less. In the present specification, the term "solid content of the resist composition" refers to the amount of the solvent (E The solid content of the resist composition and the resin content The rate is measured by known analytical means such as liquid chromatography or gas chromatography. It is possible.

[0239] <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.

[0240] 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.

[0241] <Quencher (C)> The quencher (C) may be a basic nitrogen-containing organic compound or an acid generator (B). The resist composition may be a salt that generates an acid weaker in acidity than the acid generated by the quencher. When the resist composition contains the quencher (C), the content of the quencher (C) is determined based on the solid content of the resist composition. As a standard, the content is preferably about 0.01 to 15% by mass, and more preferably about 0.1 to 10% by mass. It is more preferable to do so. Examples of basic nitrogen-containing organic compounds include amines and ammonium salts. The amines include aliphatic amines and aromatic amines. The aliphatic amines include primary Amines include secondary amines and tertiary amines.

[0242] Amines include 1-naphthylamine, 2-naphthylamine, aniline, diisopropylamine, aniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline Phosphorus, N,N-dimethylaniline, diphenylamine, hexylamine, heptylamine , octylamine, nonylamine, decylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine amine, triethylamine, trimethylamine, tripropylamine, tributylamine, Tripentylamine, trihexylamine, triheptylamine, trioctylamine, Trinonylamine, tridecylamine, methyldibutylamine, methyldipentylamine , methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, Methyldioctylamine, Methyldinonylamine, Methyldidecylamine, Ethyldibutyrate diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexylamine xylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropylamine Propanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine amine, 4,4'-diamino-1,2-diphenylethane, 4,4'-diamino-3,3' -Dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane 2,2'-methylenebisaniline, imidazole, 4-methylimidazole, pyridinium 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 disulfide amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, preferred are aromatic amines such as diisopropylaniline, and more preferred are aromatic amines such as diisopropylaniline. Examples include 2,6-diisopropylaniline.

[0243] Ammonium salts include tetramethylammonium hydroxide, tetraisopropyl Lithium ammonium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline and the like are mentioned.

[0244] 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). An acid with a lower acidity than the acid generated from the acid generator (B) The salt that generates is a salt with an acid dissociation constant of the acid generated from the salt usually -3 < pKa, preferably is a salt of -1 < pKa < 7, more preferably a salt of 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 salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter, may be referred to as " weak acid intramolecular salt (D)"), and salts described in JP-A-2012-229206 , JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. Preferably, as the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B), 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, a weak acid intramolecular salt (D). TIFF2025000705000143.tif113146

[0245] Examples of the weak acid intramolecular salt (D) include the following salts. TIFF2025000705000144.tif95144

[0246] <Other Ingredients> The resist composition of the present invention may further contain components other than the above-mentioned components (hereinafter referred to as “other components”) as necessary. (F)) may be contained. There are no particular limitations on other components (F). However, additives known in the resist art, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc., may be used. Agents, dyes, etc. can be used.

[0247] Preparation of Resist Composition The resist composition of the present invention comprises a salt (I) and a resin (A), and, if necessary, an acid generator. Agent (B), resin other than resin (A), solvent (E), quencher (C) and other components ( F). The order of mixing is arbitrary and is not particularly limited. The temperature during mixing ranges from 10 to 40°C, depending on the type of resin, solvent, etc. The appropriate temperature can be selected depending on the solubility of the mixture in E). The mixing time depends on the mixing temperature. Depending on the situation, an appropriate time can be selected from 0.5 to 24 hours. There is no limitation on the type of the mixture, and stirring and mixing can be used. After mixing the components, filter the mixture using a filter with a pore size of about 0.003 to 0.2 μm. It is preferable that

[0248] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) 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) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) A step of developing the composition layer after heating.

[0249] To apply the resist composition onto a substrate, a commonly used device such as a spin coater is used. The substrate can be an inorganic substrate such as a silicon wafer. Before applying the resist composition, the substrate may be cleaned, and an anti-reflection film or the like may be formed on the substrate. It may be possible.

[0250] The composition after coating is dried to remove the solvent and form a composition layer. For example, the solvent can be evaporated using a heating device such as a hot plate (prebaking). The heating temperature is 50 to 200°C. It is preferable that the heating time is 10 to 180 seconds. The pressure during the process is 1 to 1.0×10 5 It is preferable that the pressure is about Pa.

[0251] The obtained composition layer is usually exposed using an exposure machine. The exposure light source may be a KrF excimer laser (wavelength 248 nm), an ArF excimer Lasers in the ultraviolet range such as F2 excimer laser (wavelength 157 nm) and F2 laser (wavelength 193 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert the wavelength and emit harmonic laser light in the far ultraviolet or vacuum ultraviolet range, electron beams, Various types of light sources can be used, such as those that irradiate ultraviolet light (EUV). In this case, the irradiation of these radiations is sometimes collectively called "exposure". Exposure is usually carried out through a mask corresponding to the desired pattern. In the case of lines, exposure may be performed by direct writing without using a mask.

[0252] The composition layer after exposure is subjected to a heat treatment (so-called heat treatment) in order to promote the deprotection reaction of the acid labile group. The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150 degrees Celsius.

[0253] The composition layer after heating is usually developed using a developing device and a developing solution. Examples of the method include the dip method, the paddle method, the spray method, and the dynamic dispense method. The development temperature is preferably, for example, 5 to 60° C., and the development time is, for example, 5 The time is preferably 300 seconds or less. By selecting the type of developer as follows: Either a positive resist pattern or a negative resist pattern can be produced.

[0254] When a positive resist pattern is produced from the resist composition of the present invention, a developer An alkaline developer is used. The alkaline developer is any of the various alkaline solutions used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples of the aqueous solution ... ethyl)trimethylammonium hydroxide (commonly known as choline) include aqueous solutions of ethyl)trimethylammonium hydroxide (commonly known as choline). The alkaline developer may contain a surfactant. After development, the resist pattern is washed with ultrapure water, and then the water remaining on the substrate and pattern is It is preferable to remove it.

[0255] When a negative resist pattern is produced from the resist composition of the present invention, A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers are ketones such as 2-hexanone and 2-heptanone. Solvents; glycol ether ethers such as propylene glycol monomethyl ether acetate Steryl solvents; ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and the like aromatic hydrocarbon solvents. In the organic developer, the content of the organic solvent is preferably 90% by mass or more and 100% by mass or less, The content is preferably from 95% by mass to 100% by mass, and more preferably substantially only an organic solvent. More preferred. Among them, organic developers include those containing butyl acetate and / or 2-heptanone. In the organic developer, the total content of butyl acetate and 2-heptanone is preferably 50% by mass. Preferably, the content is 90% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less. It is even more preferable that the components are qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 10%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too.

[0256] It is preferable to wash the resist pattern after development with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and any solvent containing a general organic solvent may be used. Any suitable solvent may be used, preferably an alcohol or ester solvent. After cleaning, it is preferable to remove any rinsing liquid remaining on the substrate and the pattern.

[0257] <Application> The resist composition of the present invention is a resist composition for exposure to a KrF excimer laser, Resist composition for exposure to ximer laser, resist composition for exposure to electron beam (EB) or EU A resist composition for V exposure, particularly a resist composition for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductor microfabrication. EXAMPLES

[0258] The present invention will be described in more detail with reference to examples. "%" and "parts" are by weight unless otherwise specified. The weight average molecular weight is a value determined by gel permeation chromatography. The analytical conditions for gel permeation chromatography are as follows: Column: TSKgel Multipore HXL-M x 3 + guard column (Tosoh Corporation) Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Detector: RI detector Column temperature: 40℃ Injection volume: 100μl Molecular weight standard: Standard polystyrene (Tosoh Corporation) The structure of the compound was determined by mass spectrometry (LC: Agilent 1100, MASS: Agilent The molecular ion peak was measured using a LC / MSD (manufactured by Entec). In the examples, the value of this molecular ion peak is indicated as "MASS."

[0259] Example 1: Synthesis of a salt represented by formula (I-1) JPEG2025000705000145.jpg351594 parts of the compound represented by formula (I-1-a), 8 parts of dimethylformamide, 1 part of potassium carbonate 0.39 parts of potassium iodide and 1.68 parts of potassium iodide were mixed and stirred at 23°C for 30 minutes, and then the resulting mixture was mixed with a solution of the compound of the formula (I 5.99 parts of the compound represented by -1-b) and 110 parts of chloroform were added, and then 2 The mixture was stirred at 3° C. for 18 hours. 30 parts of ion-exchanged water was added to the reaction mixture obtained, and the mixture was stirred at 23° C. for 18 hours. After stirring for 30 minutes, the organic layer was separated and extracted. After stirring at 23° C. for 30 minutes, the organic layer was separated and separated. The organic layer was concentrated, and the concentrated mixture was purified by column chromatography. (Silica gel 60N (spherical, neutral) 100-210 μm; manufactured by Kanto Chemical Co., Ltd., Developing solvent: n-heptane / ethyl acetate = 1 / 1) to obtain the compound represented by formula (I-1-c). The yield was 7.13 parts of the compound represented by the formula: JPEG2025000705000146.jpg41165 5 parts of the salt represented by formula (I-1-e) and 20 parts of chloroform were mixed and incubated at 23°C for 30 minutes. After stirring for 1 hour, 1.94 parts of the compound represented by formula (I-1-f) was added, and the temperature was raised to 50° C. The mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was diluted with a compound represented by formula (I-1-c): 5.67 parts were added and stirred at 50° C. for 5 hours. The resulting reaction mixture was cooled to 23° C. After that, 70 parts of chloroform and 25 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. The organic layer was separated and the organic layer was taken out. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was diluted with 23 parts of ion-exchanged water. After stirring at ℃ for 30 minutes, the organic layer was separated and taken out. This water washing procedure was repeated three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and the organic layer was taken out. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was diluted with 23 parts of ion-exchanged water. After stirring at ℃ for 30 minutes, the organic layer was separated and taken out. This water washing procedure was repeated three times. The obtained organic layer was concentrated, and the concentrated residue was treated with 2 parts of acetonitrile and tert-butyl methyl ether. Add 30 parts of ethyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 4.98 parts of the salt represented by the formula (I-1) was obtained.

[0260] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 570.9

[0261] Example 2: Synthesis of a salt represented by formula (I-3) JPEG2025000705000147.jpg351594 parts of the compound represented by formula (I-1-a), 8 parts of dimethylformamide, 1 part of potassium carbonate 0.39 parts of potassium iodide and 1.68 parts of potassium iodide were mixed and stirred at 23°C for 30 minutes, and then the resulting mixture was mixed with a solution of the compound of the formula (I -3-b) 11.07 parts of the compound represented by the formula (1) and 110 parts of chloroform were added, and then The mixture was stirred at 23° C. for 18 hours. 30 parts of ion-exchanged water was added to the reaction mixture, and the mixture was stirred at 23° C. After stirring for 30 minutes at 40° C., the organic layer was separated and separated. After stirring at 23° C. for 30 minutes, the organic layer was separated and washed with water. The operation was repeated three times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60 N (spherical, neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / vinegar Compound 1 represented by formula (I-3-c) was obtained by fractionation using ethyl acetate (ethyl acetate / ethyl acetate=1 / 1). 0.44 parts were obtained. JPEG2025000705000148.jpg40163 5 parts of the salt represented by formula (I-1-e) and 20 parts of chloroform were mixed and incubated at 23°C for 30 minutes. After stirring for 1 hour, 1.94 parts of the compound represented by formula (I-1-f) was added, and the temperature was raised to 50° C. The mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was added with a compound represented by formula (I-3-c) 9.12 parts were added and stirred at 50°C for 5 hours. The resulting reaction mixture was cooled to 23°C. After that, 70 parts of chloroform and 25 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. The organic layer was separated and the organic layer was taken out. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was diluted with 23 parts of ion-exchanged water. After stirring at ℃ for 30 minutes, the organic layer was separated and taken out. This water washing procedure was repeated three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was separated and the organic layer was taken out. 25 parts of ion-exchanged water was added to the obtained organic layer, and the mixture was diluted with 23 parts of ion-exchanged water. After stirring at ℃ for 30 minutes, the organic layer was separated and taken out. This water washing procedure was repeated three times. The obtained organic layer was concentrated, and the concentrated residue was treated with 2 parts of acetonitrile and tert-butyl methyl ether. Add 30 parts of ethyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 4.98 parts of the salt represented by the formula (I-3) was obtained.

[0262] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 822.7

[0263] Example 3: Synthesis of a salt represented by formula (I-12) JPEG2025000705000149.jpg44153 3.96 parts of the compound represented by formula (I-1-a) and 20 parts of chloroform were mixed, and 2 After stirring at 3° C. for 30 minutes, 3.57 parts of the compound represented by formula (I-1-f) was added, and the mixture was stirred for 5 After heating to 0° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50° C. for 5 hours. After cooling to 3°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring for 10 minutes, the organic layer was separated and separated. After stirring at 23°C for 30 minutes, the organic layer was separated and the water washing procedure was repeated. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring for 10 minutes, the organic layer was separated and separated. After stirring at 23°C for 30 minutes, the organic layer was separated and the water washing procedure was repeated. The organic layer was concentrated, and the concentrated mixture was passed through a column (silica gel 60N (spheres) (state, neutral) 100-210 μm; Kanto Chemical Co., Ltd., developing solvent: n-heptane / ethyl acetate Compound 12 represented by formula (I-12-c) was obtained by fractionation using a cyclohexane distillation column (1 / 1). We got 19 copies. JPEG2025000705000150.jpg41160 5 parts of the salt represented by formula (I-1-e) and 20 parts of chloroform were mixed and incubated at 23°C for 30 minutes. After stirring for 1 hour, 1.94 parts of the compound represented by formula (I-1-f) was added, and the temperature was raised to 50° C. The mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was added with a compound represented by formula (I-12-c) The mixture was stirred at 50° C. for 5 hours. The reaction mixture was cooled to 23° C. After that, 70 parts of chloroform and 25 parts of ion-exchanged water were added and stirred at 23° C. for 30 minutes. Then, the organic layer was separated and separated. 25 parts of ion-exchanged water was added to the obtained organic layer, and After stirring at 3°C ​​for 30 minutes, the organic layer was separated and washed three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. Then, the organic layer was separated and separated. 25 parts of ion-exchanged water was added to the obtained organic layer, and After stirring at 3°C ​​for 30 minutes, the organic layer was separated and washed three times. The obtained organic layer was concentrated, and the concentrated residue was mixed with 2 parts of acetonitrile and tert-butyl ether. Add 30 parts of ethyl ether, stir at 23°C for 30 minutes, remove the supernatant, and concentrate. As a result, 4.69 parts of the salt represented by the formula (I-12) was obtained.

[0264] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 808.7

[0265] Example 4: Synthesis of a salt represented by formula (I-29) JPEG2025000705000151.jpg37165 5.21 parts of the salt represented by formula (I-29-e) and 20 parts of chloroform were mixed and heated at 23°C. After stirring for 30 minutes at 50° C., 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was heated to 50° C. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50°C for 5 hours. After cooling at 40°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the resulting organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 2 parts of acetonitrile and tert-butyl ether. 30 parts of ethyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed. By concentrating, 4.14 parts of the salt represented by the formula (I-29) was obtained.

[0266] MASS(ESI(+)Spectrum):M + 281.1 MASS(ESI(-)Spectrum):M - 570.9

[0267] Example 5: Synthesis of a salt represented by formula (I-40) JPEG2025000705000152.jpg39167 5.21 parts of the salt represented by formula (I-29-e) and 20 parts of chloroform were mixed and heated at 23°C. After stirring for 30 minutes at 50° C., 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was heated to 50° C. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50° C. for 5 hours. After cooling to 30°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The organic layer obtained was concentrated, and the concentrated residue was diluted with 2 parts of acetonitrile and tert- 30 parts of butyl methyl ether was added, and the mixture was stirred at 23°C for 30 minutes, after which the supernatant was removed. The mixture was concentrated to obtain 3.96 parts of a salt represented by the formula (I-40).

[0268] MASS(ESI(+)Spectrum):M + 281.1 MASS(ESI(-)Spectrum):M - 808.7

[0269] Example 6: Synthesis of salt represented by formula (I-106) JPEG2025000705000153.jpg39167 4.84 parts of the salt represented by formula (I-106-e) and 20 parts of chloroform were mixed, and the mixture was cooled to 23°C. After stirring at 50° C. for 30 minutes, 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was cooled to 50° C. for 30 minutes. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50° C. for 5 hours. After cooling to 30°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether (3 0 parts of the mixture was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to give 4.79 parts of the salt represented by the formula (I-106) were obtained.

[0270] MASS(ESI(+)Spectrum):M + 263.1 MASS(ESI(-)Spectrum):M - 601.0

[0271] Example 7: Synthesis of a salt represented by formula (I-43) JPEG2025000705000154.jpg40164 5.62 parts of the salt represented by formula (I-43-e) and 20 parts of chloroform were mixed and heated at 23°C. After stirring for 30 minutes at 50° C., 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was heated to 50° C. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50°C for 5 hours. After cooling at 40°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the resulting organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The obtained organic layer was concentrated, and the concentrated residue was diluted with 30 mL of tert-butyl methyl ether. After stirring at 23°C for 30 minutes, the supernatant was removed and the mixture was concentrated to obtain the product with the formula: 4.43 parts of the salt represented by (I-43) were obtained.

[0272] MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 570.9

[0273] Example 8: Synthesis of a salt represented by formula (I-130) JPEG2025000705000155.jpg35164 5.05 parts of the salt represented by formula (I-130-e) and 20 parts of chloroform were mixed, and the mixture was cooled to 23°C. After stirring at 50° C. for 30 minutes, 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was cooled to 50° C. for 30 minutes. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50° C. for 5 hours. After cooling to 30°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether (3 0 parts of the mixture was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to give 4.88 parts of the salt represented by the formula (I-130) were obtained.

[0274] MASS(ESI(+)Spectrum):M + 281.1 MASS(ESI(-)Spectrum):M - 601.0

[0275] Example 9: Synthesis of a salt represented by formula (I-142) JPEG2025000705000156.jpg40166 5.46 parts of the salt represented by formula (I-142-e) and 20 parts of chloroform were mixed, and the mixture was cooled to 23°C. After stirring at 50° C. for 30 minutes, 1.94 parts of the compound represented by formula (I-1-f) was added, and the mixture was cooled to 50° C. for 30 minutes. After heating to 50° C., the mixture was stirred at 50° C. for 2 hours. The resulting reaction mixture was stirred at 50° C. for 5 hours. After cooling to 30°C, 70 parts of chloroform and 25 parts of ion-exchanged water were added and the mixture was stirred at 23°C for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. To the obtained organic layer, 15 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23° C. for 30 minutes. After stirring, the mixture was separated to separate the organic layer. 25 parts of ion-exchanged water was added to the resulting organic layer. After stirring at 23°C for 30 minutes, the organic layer was separated and washed three times. The organic layer was concentrated, and the concentrated residue was diluted with tert-butyl methyl ether (3 0 parts of the mixture was added, and the mixture was stirred at 23°C for 30 minutes. The supernatant was then removed and the mixture was concentrated to give 5.01 parts of the salt represented by the formula (I-142) were obtained.

[0276] MASS(ESI(+)Spectrum):M + 317.1 MASS(ESI(-)Spectrum):M - 601.0

[0277] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. depending on their formula numbers. TIFF2025000705000157.tif3578

[0278] Synthesis Example 1 [Synthesis of Resin A1] As the monomer, monomer (a1-4-2), monomer (a1-1-3) and monomer (a1-2-6) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1 -3):monomer (a1-2-6) in a ratio of 38:24:38. Further, this monomer mixture was mixed with 1.5 times by mass of methyl ether based on the total mass of all monomers. Isobutyl ketone was mixed in the mixture. Azobisisobutyronite was added as an initiator to the mixture. Add 7 mol% of propylene to the total number of moles of all monomers, and heat the mixture at 85°C. The polymerization was carried out by heating at 40° C. for about 5 hours. After that, the polymerization reaction solution was diluted with p-toluenesulfone The acid solution was added, and the mixture was stirred for 6 hours, and then separated. The obtained organic layer was diluted with a large amount of n-heptane. The resin was precipitated by pouring it into a flask, and then filtered and collected to obtain a resin with a weight-average molecular weight of approximately 5.3 × 10 3 Resin A1 (copolymer) was obtained in a yield of 78%. This resin A1 has the following structural units: This is what we do. TIFF2025000705000158.tif29126

[0279] Synthesis Example 2 [Synthesis of Resin A2] As the monomers, monomer (a1-4-2) and monomer (a1-2-6) were used. The molar ratio of monomer (a1-4-2):monomer (a1-2-6) was 38:62. The monomer mixture is mixed so that the total weight of all the monomers is equal to the total weight of the monomers. 1.5 times by mass of methyl isobutyl ketone was mixed into the obtained mixture. Azobisisobutyronitrile was added at 7 mol% based on the total moles of all monomers. The mixture was then heated at 85°C for about 5 hours to carry out polymerization. An aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours, and then separated. The resin was precipitated by pouring it into a large amount of n-heptane, and then filtered and collected to obtain the weight average The amount of molecules is about 5.4 x 10 3 Resin A2 (copolymer) was obtained in a yield of 89%. has the following structural unit: TIFF2025000705000159.tif2886

[0280] <Preparation of resist composition> As shown in Table 2, the following components were mixed, and the resulting mixture was passed through a fluorine-containing filter with a pore size of 0.2 μm. The mixture was filtered through a resin filter to prepare a resist composition. [Table 2]

[0281] <Resin> A1, A2: Resin A1, Resin A2 <Salt (I)> I-1: A salt represented by formula (I-1) I-3: A salt represented by formula (I-3) I-12: A salt represented by formula (I-12) I-29: A salt represented by formula (I-29) I-40: A salt represented by the formula (I-40) I-43: A salt represented by formula (I-43) I-106: A salt represented by the formula (I-106) I-130: A salt represented by the formula (I-130) I-142: A salt represented by the formula (I-142) <Acid generator> IX-1: TIFF2025000705000161.tif2760IX-2: TIFF2025000705000162.tif2768IX-3: TIFF2025000705000163.tif2768IX-4: TIFF2025000705000164.tif2791IX-5: TIFF2025000705000165.tif2650IX-6: TIFF2025000705000166.tif3953<Quencher(C)> C1: TIFF2025000705000167.tif4347<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-Butyrolactone 5 parts

[0282] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer is heated on a direct hot plate with hexamethyldisilazane. The silicon wafer was treated at 90° C. for 60 seconds. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked for 60 seconds at the temperature shown in the "PB" column of Table 2 to form a composition layer. The composition layer formed on the wafer was then subjected to an electron beam lithography machine (ELS-F1 manufactured by Elionix Co., Ltd.). The exposure dose was gradually changed to form a contact hole pattern. (Hole pitch 40 nm / hole diameter 17 nm) was directly written. After exposure, post-exposure was performed for 60 seconds on a hot plate at the temperature shown in the "PEB" column of Table 2. The jar was baked and then immersed in 2.38% tetramethylammonium hydroxide aqueous solution. A resist pattern was obtained by puddle development in a solution for 60 seconds.

[0283] In the resist pattern obtained after development, the exposure value was set so that the hole diameter was 17 nm. The amount was taken as the effective sensitivity.

[0284] <CD Uniformity (CDU) Evaluation> In terms of 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. Among those within the same wafer, the standard deviation was determined with the average hole diameters of the patterns formed with a hole diameter of 17 nm measured at 400 locations as the population. The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm). The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm).

[0285]

Table 3

Industrial Applicability

[0286] Since the resist composition of the present invention can obtain a resist pattern having good CD uniformity (CDU), it is suitable for fine processing of semiconductors and is extremely useful industrially. Since the resist composition of the present invention can obtain a resist pattern having good CD uniformity (CDU), it is suitable for fine processing of semiconductors and is extremely useful industrially.

Claims

1. A salt represented by formula (I): [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 an integer of 0 to 6, and when z is 2 or more, a plurality of R １ and R ２ may be the same or different from each other. X 1 and X ２ each independently represents *-CO-O-, *-O-CO-, *-O-CO-O-, or *-O-, and * represents C(R １ ) (R ２ ) or C(Q １ ) (Q ２ ) binding site. L 1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -SO ２ It may be replaced by --or --CO--. A １ represents a lactone ring having 3 to 36 carbon atoms which may have a substituent. L ２ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. R ３ represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an iodine atom, a hydrogen atom contained in the aliphatic hydrocarbon group may be replaced by a fluorine atom or an alkyl group having 1 to 6 carbon atoms, and the —CH 2 - may be replaced by -O- or -CO-. Z ＋ represents an organic cation.

2. A １ The salt according to claim 1, wherein is a norbornane lactone ring.

3. L 2 The salt according to claim 1 or 2, wherein is a single bond.

4. R ３ a chain hydrocarbon group having 1 to 12 carbon atoms and containing an iodine atom, an alicyclic hydrocarbon group having 3 to 12 carbon atoms and containing an iodine atom, or a group in which an alicyclic hydrocarbon group having 3 to 12 carbon atoms and containing an iodine atom is combined with a chain hydrocarbon group having 1 to 6 carbon atoms (a hydrogen atom contained in the chain hydrocarbon group or the alicyclic hydrocarbon group may be replaced by a fluorine atom or an alkyl group having 1 to 6 carbon atoms, and a —CH 2 The salt according to any one of claims 1 to 3, wherein - may be replaced by -O- or -CO-.

5. An acid generator comprising the salt according to any one of claims 1 to 4.

6. A resist composition comprising the acid generator according to claim 5 and a resin having an acid labile group.

7. 7. The resist composition according to claim 6, wherein the resin having an acid labile group comprises at least one member 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 are each independently -O- or *-O-(CH ２ ) ｋ１ represents --CO--O--, k1 represents an integer of 1 to 7, and * represents the bonding site 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 alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3.

8. 8. The resist composition according to claim 6, wherein the resin having an acid labile group is a resin containing a structural unit represented by formula (a2-A). [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 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 is a single bond or *-X a51 - (A a52 -X a52 ) nｂ -, * is -R a50 Combined represents the bonding site with the carbon atom. 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 0 to 4. When mb is an integer of 2 or more, a plurality of R a51 may be the same or different.

9. 9. The resist composition according to claim 6, further comprising a salt capable of generating an acid having a weaker acidity than the acid generated from the acid generator.

10. (1) A step of applying the resist composition according to any one of claims 6 to 9 onto a substrate; (2) A step of drying the applied composition to form a composition layer; (3) exposing the composition layer to light; (4) heating the composition layer after exposure; and (5) developing the composition layer after heating; A method for producing a resist pattern comprising the steps of:

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