salt

Abstract

To provide a salt capable of providing a resist composition from which a resist pattern having good CD uniformity (CDU) can be produced.SOLUTION: The salt is represented by formula (IA). [In the formula (IA), R1 and R2 each independently represent a hydrogen atom, a hydroxy group or a C1-12 hydrocarbon group, and -CH2- contained in the hydrocarbon group may be substituted with -O- or -CO-; m and n each independently represent 1 or 2; when m is 2, two R2's are the same or different from each other; when n is 2, two R1's are the same or different from each other; Ar1 represents an optionally substituted naphthyl group; X0' represents a single bond, -O- or -S-; Q1 and Q2 each independently represent a fluorine atom or a C1-6 perfluoroalkyl group; and R3A represents a C3-6 branched alkyl group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to salts. [Background technology]

[0002] Patent Document 1 describes a resin having a structural unit represented by the following formula and a polymer having any of the following formulas: Resist compositions containing these salts as acid generators are also described. TIFF2025188278000001.tif62132 Patent Document 2 describes a method for producing a resin having a structural unit represented by the following formula and a salt represented by the following formula with an acid. Resist compositions containing it as a generator are also described. TIFF2025188278000002.tif34149 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-153432 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-113450 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention provides a resist pattern having better CD than a resist pattern formed from the above resist composition. To provide a resist composition capable of producing a resist pattern with uniformity (CDU) The goal is to: [Means for solving the problem]

[0005] The present invention includes the following inventions. [1] Resin containing a structural unit represented by formula (a2-A) and a structural unit having an acid labile group and a resist composition containing the salt represented by formula (I). TIFF2025188278000003.tif4654[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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms 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 - represents -R a50 is 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, multiple R in Numbers a51 may be the same or different from each other.] TIFF2025188278000004.tif36104 [In formula (I), R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 12 carbon atoms. The hydrocarbon group represents a hydrocarbon group, and -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-. It's fine. m and n each independently represent 1 or 2. When m is 2, two R 1 is the same or Differently, when n is 2, two R 2 are the same or different. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X 0 represents a single bond, -CH2-, -O- or -S-. Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. Represents a group. R 3 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and The -CH2- contained in the hydroxyl group may be replaced by -O-, -S-, -SO2- or -CO-. stomach.] [2] Ar is a phenyl group which may have an alkyl group having 1 to 8 carbon atoms or a phenyl group which may have an alkyl group having 1 to 8 carbon atoms a naphthyl group which may have an alkyl group represented by the formula: The resist composition according to [1], wherein each of the groups may be replaced by —O— or —CO—. . [3]R 3 an alkyl group having 1 to 12 carbon atoms or an alkyl group having 3 to 16 carbon atoms which may have a substituent an alicyclic hydrocarbon group (wherein -CH2- contained in the alicyclic hydrocarbon group is -O- or -CO- The resist composition according to [1] or [2], wherein [4]R 1 and R 2 is a hydrogen atom, and n and m are 2. The resist composition according to claim 1. [5] The structural unit having an acid labile group is a structural unit represented by formula (a1-1) and a structural unit represented by formula (a 1-2) is at least one selected from the group consisting of structural units represented by [1] to [4 10. The resist composition according to claim 9, wherein TIFF2025188278000005.tif4496 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O represents -, 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 are each independently an alkyl group having 1 to 8 carbon atoms, a It represents an alicyclic hydrocarbon group or a group formed by combining these groups. m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [6] A salt that generates an acid weaker in acidity than the acid generated from the salt represented by formula (I) is further provided. The resist composition according to any one of [1] to [5], [7] (1) A process for applying the resist composition according to any one of [1] to [6] onto a substrate. The course, (2) 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. [8] A salt represented by formula (IA). TIFF2025188278000006.tif36106[In formula (IA), R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 12 carbon atoms. The hydrocarbon group represents a hydrocarbon group, and -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-. It's fine. m and n each independently represent 1 or 2. When m is 2, two R 1 is the same or Differently, when n is 2, two R 2 are the same or different. Ar 1 represents a naphthyl group which may have a substituent. X 0 represents a single bond, -CH2-, -O- or -S-. Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. Represents a group. R 3A represents a branched alkyl group having 3 to 6 carbon atoms.] [9] A salt represented by formula (IB). TIFF2025188278000007.tif36106[In formula (IB), R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 12 carbon atoms. The hydrocarbon group represents a hydrocarbon group, and -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-. It's fine. m and n each independently represent 1 or 2. When m is 2, two R 1 is the same or Differently, when n is 2, two R 2 are the same or different. Ar 2 represents a phenyl group which may have a substituent. X 02 represents a single bond or -CH2-. Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. Represents a group. R 3B represents a branched alkyl group having 3 to 6 carbon atoms.] [Effects of the Invention]

[0006] By using the resist composition of the present invention, it is possible to obtain a resist with good CD uniformity (CDU). A pattern can be manufactured. DETAILED DESCRIPTION OF THE INVENTION

[0007] 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 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 "at least one of" "CH2=C(CH3)-CO-" or "CH2=CH-C When a structural unit having "O-" is exemplified, structural units having both groups are also exemplified. In addition, in the groups described in this specification, a linear structure and a branched structure are If a compound can have both structures, either structure is acceptable. "Derived from" or "derived from" means that the molecule is The term "combined" refers to the formation of a -CC- group by polymerization of a polymerizable C=C bond. The term "group" means a group in which two or more of the exemplified groups are bonded together, and the valence of the group varies depending on the bonding form. This may be changed as appropriate. In this specification, the term "solid content of the resist composition" refers to the amount of the solid content of the resist composition that is the remaining amount of the resist composition. This refers to the total of all components excluding the solvent (E) described below.

[0008] [Resist Composition] The resist composition of the present invention comprises a compound having a structural unit represented by formula (a2-A) and an acid labile group. A resin containing a structural unit represented by formula (I) (hereinafter, sometimes referred to as resin (A)) It contains a salt (hereinafter sometimes referred to as "salt (I)") that is The resist composition may also contain a quencher (hereinafter referred to as "quencher (C)"). It is preferable that the liquid contains a solvent (hereinafter sometimes referred to as "solvent (E)") and / or a solvent (hereinafter sometimes referred to as "solvent (E)"). .

[0009] <Resin (A)> Resin (A) is a structural unit represented by formula (a2-A) (hereinafter referred to as "structural unit (a2-A)"). (sometimes referred to as "inventory"). <Structural unit (a2-A)> TIFF2025188278000008.tif4654[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 hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms 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 - represents -R a50 is 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, multiple R in Numbers a51 may be the same or different from each other.]

[0010] In formula (a2-A), R a50 The halogen atoms in the Examples of the fluorine atom include a fluorine atom and a bromine atom. R a50 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-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, phenyl group 2,2,3,3-tetrafluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 3-pentafluoropropyl group, propyl group, perfluorobutyl group, 1,1,2,2, 3,3,4,4-octafluorobutyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 2,2,3,3,4,4-hexafluoro 2,2,3,3,4,4,4-Heptafluorobutyl group, butyl group, pentafluorobutyl group fluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropane butyl group, 2-(perfluorobutyl)ethyl group, 2,2,3,3,4,4,5,5,5- Nonafluoropentyl group, pentyl group, hexyl group, 1,1,2,2,3,3,4,4, 5,5-decafluorohexyl group, 2,2,3,3,4,4,5,5,6,6-decafluoro Orohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohe Examples of the alkyl group include a perfluorohexyl group and a perfluorohexyl group. R a50 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is more preferably an ethyl group, and even more 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, or the like. 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 isopropyl ... Examples 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 methyl group is more preferred. A hydroxy group is more preferred. R a51 The alkylcarbonyl group in the formula (I) includes an acetyl group, a propionyl group, and a butyl group. Examples thereof include an aryl group. R a51 The alkylcarbonyloxy group in the formula (I) is an acetyloxy group, a propionyloxy group, or Examples of such groups include an aryloxy group and a butyryloxy group. R a51 is preferably a methyl group.

[0011] * -X a51 -(A a52 -X a52 ) nb -As * -O-, * -CO-O-, * -OC O-, * -CO-OA a52 -CO-O-, * -O-CO-A a52 -O-, * -OA a52 -CO-O-, * -CO-OAa52 -O-CO-, * -O-CO-A a52 -O-CO-, Among them, * -CO-O-, * -CO-OA a52 -CO-O- or * - Office Automation a52 -CO-O- is preferred.

[0012] 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.

[0013] A a50 is a single bond, * -CO-O- or * -CO-OA a52 -CO-O- Preferably, a single bond, * -CO-O- or * -CO-O-CH2-CO-O- More preferably, a single bond or * More preferably, it is —CO—O—.

[0014] mb is preferably 0, 1 or 2, more preferably 0 or 1, and particularly preferably 0. The hydroxy group is preferably bonded to the o- or p-position of the benzene ring, and more preferably to the p-position. It is more preferable to combine them.

[0015] Examples of the structural unit (a2-A) include those described in JP-A-2010-204634 and JP-A-2012- Examples of structural units include those derived from monomers described in Japanese Patent Publication No. 12577.

[0016] The structural unit (a2-A) is represented by the formulas (a2-2-1) to (a2-2-6). The structural units and the structural units represented by formulas (a2-2-1) to (a2-2-6) R in structural unit (a2-A) a50 The structure in which the methyl group corresponding to 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 Preferably, the structural unit has a corresponding methyl group substituted for a hydrogen atom. TIFF2025188278000009.tif42166

[0017] The content of the structural unit (a2-A) in the resin (A) is preferably 5% by weight based on the total amount of the structural units. The content is preferably from 10 to 80 mol %, more preferably from 10 to 70 mol %, and even more preferably from 15 to 180 mol %. It is preferably 60 mol %, and even more preferably 20 to 55 mol %. The structural unit (a2-A) can be prepared by, for example, polymerizing the structural unit (a1-4) and then reacting the polymer with p-toluenesulfonyl ether. It can be incorporated into the resin (A) by treating it with an acid such as enesulfonic acid. After polymerization using acetoxystyrene, etc., tetramethylammonium hydroxide, etc. By treating with an alkali, the structural unit (a2-A) can be incorporated into the resin (A). can.

[0018] The resin (A) contains a structural unit having an acid labile group (hereinafter, sometimes referred to as "structural unit (a1)"). Here, the acid labile group includes a group having a leaving group, which is released upon contact with an acid. By "hydrophilic group" is meant a group that forms a hydrophilic group (for example, a hydroxy group or a carboxy group).

[0019] <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. TIFF2025188278000010.tif1989 [In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. R represents a cyclic group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these groups; a1 Reach BiR a2 are bonded to each other and, together with the carbon atoms to which they are bonded, are non-aromatic carbon atoms having 3 to 20 carbon atoms. Forms a hydrogen chloride ring. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF2025188278000011.tif2171[In formula (2), R a1’ and R a2’ are each independently a hydrogen atom or a group having 1 to 1 carbon atoms, represents a hydrocarbon group of 2, and R 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 atoms to which they are bonded and X, form a group having 3 to 20 carbon atoms. A heterocyclic ring is formed, and -CH2- contained in the hydrocarbon group and the heterocyclic ring is -O- or -S- may be replaced by . X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * denotes a binding site.]

[0020] R a1 , R a2 and R a3 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a propyl group. Examples of the alkyl group include an alkyl 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 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: (* indicates a bonding site.) a1 , R a2 and R a3 Alicyclic carbonization of The hydrogen group preferably has 3 to 16 carbon atoms. TIFF2025188278000012.tif11150 Examples of the group 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-C(R a1 )(R a2 )(R a3 ) includes the following rings. The non-aromatic hydrocarbon ring is preferably a carbon The numbers are 3 to 12. * indicates the bonding site with -O-. TIFF2025188278000013.tif31139

[0021] R a1’ , R a2’ and R a3’ The hydrocarbon group in the Examples of the alkyl group include a hydroxyl group, 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 Examples include: Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as 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, 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 with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. An aryl-cycloalkyl group is exemplified. R a2’ and R a3’ are bonded to each other and together with the carbon atoms to which they are bonded and X, When forming a ring, -C(R a1’ )(R a2’ )-XR a3’ Examples of rings include the following: * indicates a binding site. TIFF2025188278000014.tif19130R a1’ and R a2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0022] Examples of the group (1) include the following groups. In formula (1), R a1 , 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 preferred. In formula (1), R a1 , R a2 However, together with the carbon atoms to which they are bonded, they form adamannes Forms a methyl 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, and R a3 Adama A group in which ma=0 and na=1. Specific examples of the group (1) include the following: * represents a binding site. TIFF2025188278000015.tif73154

[0023] Specific examples of group (2) include the following groups: * represents a binding site. TIFF2025188278000016.tif62148

[0024] 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.

[0025] Among the (meth)acrylic monomers having an acid labile group, those having 5 to 20 carbon atoms are preferred. Examples of the compound having a bulky structure such as an alicyclic hydrocarbon group include: 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.

[0026] 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)) or a structural unit represented by the formula ( a1-2) (hereinafter, sometimes 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. TIFF2025188278000017.tif46148 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or -O-(CH2) k1 - represents CO-O-, k1 represents an integer of 1 to 7, and * represents the bonding site with -CO-. represent. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04are each independently an alkyl group having 1 to 8 carbon atoms, 18 alicyclic hydrocarbon groups or groups combining these groups. R a6 and R a7 are each independently an alkyl group having 1 to 8 carbon atoms, a 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.

[0027] 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 alkyl groups, alicyclic hydrocarbon groups, and As a group combining these, R in group (1) a1 , R a2 and R a3 The same groups as those listed in Examples include: 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 group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. do. R a6 and R a7The 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. The alkyl group is an isopropyl group or an isopropyl group. R a02 , R a03 , R a04 , R a6 and R a7 The number of carbon atoms in the alicyclic hydrocarbon group is preferably It is 5 to 12, and more preferably 5 to 10. The group in which an alkyl group and an alicyclic hydrocarbon group are combined is The total number of carbon atoms in combination with the group is preferably 18 or less. R a02 and R a03 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl The alkyl group is an alkyl group or an ethyl group. R a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon having 5 to 12 carbon atoms. group, more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. be. R a6 and R a7 are each independently 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. group or an isopropyl 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.

[0028] 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 in which a methyl group is replaced with a hydrogen atom include those represented by the formula (a1-0-1) to the formula (a1- 0-10) are preferred. TIFF2025188278000018.tif65159

[0029] 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 -1-4) and R in the structural unit (a1-1) a4 In accordance with Structural units in which the corresponding methyl group is replaced with a hydrogen atom are preferred, and those represented by the formulae (a1-1-1) to (a1-1-2) are A structural unit represented by any one of (a1-1-4) is more preferred. TIFF2025188278000019.tif43119

[0030] The structural unit (a1-2) is any one of the structural units represented by formula (a1-2-1) to formula (a1-2-6). and R in the structural unit (a1-2) a5 The methyl group corresponding to Examples of structural units in which atoms are replaced include those represented by formula (a1-2-2), formula (a1-2-5), and A structural unit represented by any one of the formulas (a1-2-6) is preferred. TIFF2025188278000020.tif36156

[0031] When the resin (A) contains the structural unit (a1-0), its content is determined based on the total structural units of the resin (A). It is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably The content is usually 10 to 40 mol %. When the resin (A) contains the structural unit (a1-1) and / or the structural unit (a1-2), The total content of these is usually 10 to 90 mol % based on the total structural units of the resin (A), and preferably It is preferably 15 to 85 mol %, more preferably 20 to 80 mol %, and even more preferably Preferably, it is 20 to 75 mol %, and even more preferably, it is 20 to 70 mol %.

[0032] The structural unit (a1) having the group (2) is represented by the formula (a1-4). Examples of such structural units include those (hereinafter, may be referred to as "structural unit (a1-4)"). TIFF2025188278000021.tif4070[In formula (a1-4), R a32 is a hydrogen atom, a halogen atom, or a C1 group optionally having a halogen atom Represents an alkyl group of 1 to 6. R a33 is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a Alkoxy group, alkylcarbonyl group having 2 to 4 carbon atoms, alkylcarbonyl group having 2 to 4 carbon atoms 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.]

[0033] Ra32 and R a33 The alkyl group in the formula (I) is a methyl group, an ethyl group, a propyl group, an iso ... Examples of the alkyl group include a propyl group, a butyl group, a pentyl group, and a hexyl group. An alkyl group having 1 to 4 prime numbers is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is Even more preferable. 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. ethyl group, difluoromethyl group, methyl group, perfluoroethyl group, 2,2,2-trifluoromethyl group perfluoroethyl group, 1,1,2,2-tetrafluoroethyl group, ethyl group, perfluoropropyl group propyl group, 2,2,3,3,3-pentafluoropropyl group, propyl group, perfluoropropyl group butyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, butyl group, perfluorobutyl group 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, Examples of the alkyl group include an ethyl 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, and the like. Among them, alkoxy groups having 1 to 4 carbon atoms are particularly preferred. A methoxy group or an ethoxy group is more 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. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Examples thereof include a thyryloxy group. R a34 , R a35and R a36 The hydrocarbon group in the formula (I) may be 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 methyl group. Examples include a sil group, a heptyl group, and an octyl group. The alicyclic hydrocarbon group may be either monocyclic or polycyclic. Examples of the cyclopentyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthalene, butyl group, adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include: TIFF2025188278000022.tif11151Aromatic hydrocarbon groups include phenyl, naphthyl, anthryl, biphenyl, Examples include aryl groups such as 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, 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 with alicyclic hydrocarbon groups (p-cyclohexane adamantylphenyl group, p-adamantylphenyl group, phenylcyclohexyl group, etc. In particular, R a36 As for carbon number 1 to 18, 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 groups include groups formed by combining these.

[0034] In formula (a1-4), R a32 is preferably a hydrogen atom. R a33 As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferred, and a methoxy group and an ethoxy group are also preferred. 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, a Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 18 carbon atoms, or combinations thereof More preferably, it is a group formed by an alkyl group having 1 to 18 carbon atoms, a group formed by an alkyl group having 3 to 1 carbon atoms, R is an alicyclic aliphatic hydrocarbon group having 8 carbon atoms or an aralkyl group having 7 to 18 carbon atoms. a36 in The alkyl group and the alicyclic hydrocarbon group are preferably unsubstituted. a36 Fragrance in The aromatic hydrocarbon group is preferably an aromatic ring having an aryloxy group having 6 to 10 carbon atoms. -OC(R a34 )(R a35 )-OR a36 is an acid (e.g. p-toluenesulfonic acid), it is eliminated to form a hydroxy group.

[0035] Examples of the structural unit (a1-4) include those described in JP-A-2010-204646. The structural units derived from the monomers of formula (a1-4-1) to formula (a1-4-2) are preferred. -4-12) and R in the structural unit (a1-4) a32 to The structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred, and more preferred is a structural unit represented by the formula ( a1-4-1) to (a1-4-5), and (a1-4-10) are structural units respectively represented by the formulas Rankings include: TIFF2025188278000023.tif69157

[0036] When the resin (A) contains the structural unit (a1-4), the content thereof is determined based on the total structure of the resin (A). It is preferably 3 to 80 mol %, more preferably 5 to 75 mol %, based on the total of the units. More preferably, the content is 7 to 70 mol %, and even more preferably, 7 to 65 mol %. It is even more preferable that the content is 10 to 60 mol %.

[0037] The structural unit derived from a (meth)acrylic monomer having the group (2) includes a structural unit represented by the formula (a1 -5) (hereinafter sometimes referred to as "structural unit (a1-5)") can be. TIFF2025188278000024.tif4558 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 a halogen atom. Z a1 is a single bond or -(CH2) h3 -CO-L 54 -, and h3 is 1 to 4 represents an integer, and * represents L 51 represents the binding site 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.

[0038] Examples of halogen atoms include fluorine atoms and chlorine atoms, with fluorine atoms 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, and an ethyl group. group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, fluoro group Examples of such groups include a trifluoromethyl group and a 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 Among these, it is preferred that one is —O— and the other is —S—. s1 is preferably 1. s1' is preferably an integer of 0 to 2. Z a1 is preferably a single bond or —CH2—CO—O—.

[0039] Examples of the structural unit (a1-5) include those described in JP-A-2010-61117. Among them, structural units derived from the monomers of formula (a1-5-1) to formula (a1-5- 4), and the structural units represented by formula (a1-5-1) or formula (a1-5-2) are preferred. ) is more preferred. TIFF2025188278000025.tif32133

[0040] When the resin (A) contains the structural unit (a1-5), the content thereof is determined based on the total structure of the resin (A). The content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and more preferably 5 to 40 mol %, based on the unit. % by mole is more preferable, and 5 to 30 mol % is even more preferable.

[0041] Further, examples of the structural unit (a1) include the following structural units. TIFF2025188278000026.tif31162

[0042] When the resin (A) contains structural units such as those of (a1-3-1) to (a1-3-7) The content thereof is preferably 10 to 95 mol % based on the total structural units of the resin (A), and more preferably 15 to 95 mol %. More preferably, the content is 20 to 90 mol %, even more preferably, 20 to 85 mol %, and 20 to 70 mol %. It is even more preferable, and 20 to 60 mol % is particularly preferable.

[0043] Further, examples of the structural unit (a1) include the following structural units. TIFF2025188278000027.tif58108When resin (A) contains structural units such as (a1-6-1) to (a1-6-3) The content thereof is preferably 10 to 60 mol % based on the total structural units of the resin (A), and more preferably 15 to 60 mol %. More preferably, the content is 20 to 55 mol %, even more preferably, 20 to 50 mol %, and 20 to 45 mol %. It is even more preferable, and 20 to 40 mol % is particularly preferable.

[0044] Resin (A) is a copolymer consisting of only structural units (a2-A) and structural units (a1). Alternatively, the structural unit (a2-A), the structural unit (a1), and the structural unit (a2-A) may be present. and one or more structural units other than the structural unit (a1). Examples of structural units other than the unit (a2-A) and the structural unit (a1) include the acid-modified hydroxyl groups described below. Structural units that do not have stable groups (hereinafter sometimes referred to as "structural units (s)"), A structural unit having a halogen atom other than the structural unit having a halogen atom (hereinafter referred to as "structural unit") (a4)"), a structural unit having no acid labile group (hereinafter referred to as "structural unit (s)") "), a structural unit having a non-leaving hydrocarbon group (hereinafter referred to as "structural unit (a5)" (hereinafter referred to as "structural unit (II)"), and a structural unit that decomposes upon exposure to generate an acid. )), structural units derived from other monomers known in the art, etc. It can be obtained.

[0045] <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 without 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 not having an 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, This can improve the resolution of the resist pattern and the adhesion to the substrate.

[0046] <Structural unit (a2)> The hydroxy group contained in the structural unit (a2) may be an alcoholic hydroxy group. The structural unit (a2) may contain one type alone or two or more types. That's fine.

[0047] The structural unit (a2) having an alcoholic hydroxy group includes a structural unit represented by the formula ( a2-1) (hereinafter referred to as "structural unit (a2-1)") Examples include: TIFF2025188278000028.tif4158 formula (a2-1), L a3 is -O- or *-O-(CH2) k2 represents -CO-O-, k2 represents an integer of 1 to 7. * represents the bonding site with —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 between 0 and 10.

[0048] In equation (a2-1), L a3 is 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.

[0049] 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 examples. ) is preferred, and a structural unit represented by any one of the formulas (a2-1-1) to (a2-1-4) The structural unit represented by formula (a2-1-1) or formula (a2-1- The structural unit represented by 3) is more preferred. TIFF2025188278000029.tif53147

[0050] When the resin (A) contains the structural unit (a2-1), its content is determined based on the total amount of all structural units in the resin (A). It is usually 1 to 45 mol %, preferably 1 to 40 mol %, more preferably It is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, and even more preferably The content is usually 2 to 25 mol %.

[0051] <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 condensed ring of a monocyclic lactone ring with another ring. Preferably, the ring is 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:

[0052] The structural unit (a3) ​​is preferably a structural unit 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. TIFF2025188278000030.tif52164 [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 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-La9 -O- vinegar. L a8 and L a9 each independently represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bonding site with the carbonyl group. R a18 , R a19 and R a20 each independently represents a hydrogen atom or a methyl group. R a24 is an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or represents a halogen atom. X a3 represents -CH2- or an oxygen atom. R a21 represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms. R a22 , R a23 and R a25 are each independently a carboxy group, a cyano group or a carbon atom. It 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.]

[0053] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group Examples of alkyl groups include: Ra24 The halogen atoms in the formula (I) include fluorine, chlorine, bromine and iodine. Examples include atoms. 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. Preferably, the alkyl group has 1 to 4 carbon atoms, and more preferably, the 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 include a methyl group and a triiodomethyl group.

[0054] L a8 and L a9 The alkanediyl group in the formula (I) is a methylene group, an ethylene group, a propane group, or a methyl 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, pentaerythritol Examples include 2-methylbutane-1,4-diyl group and 2-methylbutane-1,4-diyl group.

[0055] 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 any of 1 to 4 groups each of which is an integer, more preferably -O- and *-O-CH2-CO-O-, and 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 methyl group. p1, q1, and r1 each independently represent an integer of preferably 0 to 2, More preferably, it is 0 or 1.

[0056] In formula (a3-4), R a24 is 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 a 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)'. TIFF2025188278000031.tif3845(in the formula, R a24 , L a7 has the same meaning as above.)

[0057] The structural unit (a3) ​​may be a monomer described in JP-A-2010-204646. , the monomers described in JP-A-2000-122294, and JP-A-2012-41274 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 formula (a3-1) to formula (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. TIFF2025188278000032.tif115165

[0058] 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). It is usually 5 to 70 mol %, preferably 5 to 60 mol %, more preferably The content is usually 7 to 50 mol %. In addition, the structural unit (a3-1), the structural unit (a3-2), the structural unit (a3-3) or the structural unit (a3-4) The content of the units (a3-4) is 5 to 60 moles per total structural units of the resin (A). % by mole, more preferably 5 to 50 mol %, and even more preferably 7 to 40 mol %.

[0059] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025188278000033.tif2860[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 halogen atom, The —CH2— contained in the radical may be replaced by —O— or —CO—. R42 The saturated hydrocarbon group represented by the formula (I) is a chain saturated hydrocarbon group and a monocyclic or polycyclic alicyclic saturated hydrocarbon group. Examples of the hydrocarbon group include hydrocarbon groups and groups formed by combining these groups.

[0060] 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 a decyl group, a heptadecyl group, and an octadecyl group. 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 aliphatic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic saturated hydrocarbon groups. TIFF2025188278000034.tif11146 The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more alicyclic saturated hydrocarbon groups. -alkanediyl group-alicyclic saturated hydrocarbon group, -alicyclic saturated hydrocarbon group-alkanediyl group Examples include an -alkanediyl group, -alicyclic saturated hydrocarbon group, and -alkyl group.

[0061] The structural unit (a4) may be a structural unit represented by formula (a4-0), a structural unit represented by formula (a4-1), and a structural unit represented by formula (a4-4). TIFF2025188278000035.tif4146[In formula (a4-0), R 54 represents a hydrogen atom or a methyl group. L 4a represents a single bond or an alkanediyl group having 1 to 4 carbon atoms. L 3ais a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 64 represents a hydrogen atom or a fluorine atom.

[0062] L 4a The alkanediyl group in the formula (I) includes a methylene group, an ethylene group, a propane-1, linear alkanediyl groups such as butane-1,3-diyl and butane-1,4-diyl; -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 is a diyl group.

[0063] L 3a The perfluoroalkanediyl group in Fluoroethylene group, perfluoroethylfluoromethylene group, perfluoropropane- 1,3-diyl group, perfluoropropane-1,2-diyl group, perfluoropropane- 2,2-diyl group, perfluorobutane-1,4-diyl group, perfluorobutane-2, 2-diyl group, perfluorobutane-1,2-diyl group, perfluoropentane-1,5 -diyl group, perfluoropentane-2,2-diyl group, perfluoropentane-3,3 -diyl group, perfluorohexane-1,6-diyl group, perfluorohexane-2,2 -diyl group, perfluorohexane-3,3-diyl group, perfluoroheptane-1,7 -diyl group, perfluoroheptane-2,2-diyl group, perfluoroheptane-3,4 -diyl group, perfluoroheptane-4,4-diyl group, perfluorooctane-1,8 -diyl group, perfluorooctane-2,2-diyl group, perfluorooctane-3,3 -diyl group, perfluorooctane-4,4-diyl group, and the like. L 3a The perfluorocycloalkanediyl group in perfluorocyclopentanediyl group, perfluorocycloheptanediyl group yl group, perfluoroadamantanediyl group, and the like.

[0064] L 4a is preferably a single bond, a methylene group or an ethylene group, more preferably a single bond, bond, a methylene group. L 3a is preferably a perfluoroalkanediyl group having 1 to 6 carbon atoms, more preferably or a perfluoroalkanediyl group having 1 to 3 carbon atoms.

[0065] The structural unit (a4-0) may be the following structural unit or a structural unit ( a4-0) in R 54 The structural unit in which the methyl group corresponding to can be. TIFF2025188278000036.tif95166

[0066] TIFF2025188278000037.tif4967[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 with -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 a41and R a42 At least one of the The group has a halogen atom (preferably a fluorine atom). TIFF2025188278000038.tif1488 [In formula (a-g1), s represents 0 or 1. A a42 and A a44 are each independently a divalent group having 1 to 5 carbon atoms which may have a substituent. Represents a saturated hydrocarbon group. A a43 represents a single bond or a divalent saturated hydrocarbon group having 1 to 5 carbon atoms which may have a substituent. Represents. X a41 and X a42 are each independently -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. * indicates the binding site, and the * on the right is -O-CO-R a42 ]

[0067] R a42 The saturated hydrocarbon group in the formula (I) includes a chain hydrocarbon group and a monocyclic or polycyclic saturated alicyclic group. and groups formed by combining these.

[0068] Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadecyl group, hexa Examples include a decyl group, a heptadecyl group, and an octadecyl group. Examples of the monocyclic or polycyclic saturated alicyclic hydrocarbon group include a cyclopentyl group and a cyclohexyl group. cycloalkyl groups such as cycloheptyl and cyclooctyl groups; decahydronaphthyl groups; Polycyclic aliphatic groups such as adamantyl group, norbornyl group, and the following groups (* indicates a bonding site): Examples include cyclic hydrocarbon groups. TIFF2025188278000039.tif10160The group formed by the combination may include one or more alkyl groups or one or more alkanedi groups. and groups formed by combining an alkyl group with one or more saturated alicyclic hydrocarbon groups. -alkanediyl group-saturated alicyclic hydrocarbon group, -saturated alicyclic hydrocarbon group-alkanediyl group Examples include an alkyl group, -alkanediyl group-saturated alicyclic hydrocarbon group-alkyl group, and the like.

[0069] R a42 The substituents of the formula (a-g3) include 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 include a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom. TIFF2025188278000040.tif855[In formula (a-g3), X a43 represents an oxygen atom, a carbonyl group, *-O-CO- or *-CO-O-. A a45 represents a saturated hydrocarbon group having 1 to 17 carbon atoms which may have a halogen atom. * denotes R a42 represents the binding site with However, R a42 -X a43 -A a45 In R a42 If A does not have a halogen atom, a4 5 represents a saturated hydrocarbon group having 1 to 17 carbon atoms and at least one halogen atom.

[0070] A a45The saturated hydrocarbon group in the formula (I) is a methyl group, an ethyl group, a propyl group, or a butyl group. , pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, pentadeca Alkyl groups such as silyl, hexadecyl, heptadecyl, and octadecyl groups; Monocyclic groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups alicyclic hydrocarbon groups; and decahydronaphthyl groups, adamantyl groups, norbornyl groups, and and polycyclic and alicyclic hydrocarbon groups such as the following groups (* represents a bonding site): TIFF2025188278000041.tif10160The 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. -alkanediyl group-alicyclic hydrocarbon group, -alicyclic hydrocarbon group-alkyl group, -alkanediyl group-alicyclic hydrocarbon group Examples include a candiyl group-alicyclic hydrocarbon group-alkyl group.

[0071] 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) 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. It is preferably a saturated hydrocarbon group having a fluorocarbon group, more preferably a perfluoroalkyl 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 fluoro groups include perfluoromethyl, perfluoroethyl, and perfluoropropyl groups. , perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoro Examples of perfluorocycloalkyl groups include perfluoroheptyl and perfluorooctyl groups. Examples of the cyclohexyl group include a perfluorocyclohexyl group. R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), g3) and 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.

[0072] R a42 is a saturated hydrocarbon group having a group represented by formula (a-g3), R a42 Yes, More preferred is a group represented by formula (a-g2). TIFF2025188278000042.tif772[In formula (a-g2), A a46 represents 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 The binding site represent.). A a47 represents a saturated 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 the bonding site with the carbonyl group.]

[0073] A a46The saturated hydrocarbon group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. A a47 The saturated hydrocarbon group preferably has 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and A a 47 is more preferably a cyclohexyl group or an adamantyl group.

[0074] A preferred structure of the group represented by formula (a-g2) is the following structure (* indicates a carbonyl group): (This is the binding site for ATP). TIFF2025188278000043.tif14160

[0075] A a41 The alkanediyl group in the formula (I) includes 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 2-methylbutane-1,4-diyl. do. A a41 The substituents in the alkanediyl group represented by the formula (I) include a hydroxy group and an alkanediyl group having 1 to 10 carbon atoms. Examples of the alkoxy group include alkoxy groups of 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.

[0076] A in the group represented by formula (a-g1) a42 , A a43 and A a44 represents the divalent saturated hydrocarbon The element groups include linear or branched alkanediyl groups and monocyclic divalent alicyclic saturated hydrocarbon groups. and a divalent alicyclic saturated hydrocarbon group. Examples of the divalent saturated hydrocarbon groups include methylene groups, ethylene groups, polypropylene groups, and the like. propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, 1-methylpropane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2- Examples include a methylpropane-1,2-diyl group. A a42 , A a43 and A a44 The substituent of the divalent saturated hydrocarbon group represented by is a hydroxy group. and alkoxy groups having 1 to 6 carbon atoms. Preferably, s is 0.

[0077] 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: ** indicates the binding site, and ** indicates -O-CO-R a42 This is the binding site for TIFF2025188278000044.tif46140

[0078] The structural unit represented by formula (a4-1) includes the following structural units and 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: TIFF2025188278000045.tif93135

[0079] TIFF2025188278000046.tif132150

[0080] The structural unit represented by formula (a4-1) includes a structural unit represented by formula (a4-2) and Examples of the structural unit include those represented by formula (a4-3). TIFF2025188278000047.tif4460[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, and —C 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 maximum total carbon number is 21.]

[0081] L 44 The alkanediyl group having 1 to 6 carbon atoms is A a41 The same groups as those exemplified in can be. R f6 The saturated hydrocarbon group of R 42 Examples of the groups include the same groups as those exemplified in L 44 The alkanediyl group in the formula (I) is preferably an alkanediyl group having 2 to 4 carbon atoms. An ethylene group is more preferred.

[0082] Examples of the structural unit represented by formula (a4-2) include those represented by formula (a4-1-1) to formula (a4 -1-11) are structural units represented by the structural unit (a4-2). 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 is one of the structural units.

[0083] TIFF2025188278000048.tif6076[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5represents 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 represents the binding site 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 a molecule is limited to 20.

[0084] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned:

[0085] A f13 The divalent saturated hydrocarbon group optionally having a fluorine atom in or a divalent chain saturated hydrocarbon group which may have a fluorine atom and a divalent chain saturated hydrocarbon group which may have a fluorine atom It is a divalent alicyclic saturated hydrocarbon group, more preferably a perfluoroalkanediyl group. It is a aryl group. The divalent chain saturated hydrocarbon group which may have a fluorine atom includes a methylene group, an ethylene group, alkanediyl groups such as ethylene, propanediyl, butanediyl, and pentanediyl groups; ;Difluoromethylene group, perfluoroethylene group, perfluoropropanediyl group, perfluoroalkanes such as perfluorobutanediyl and perfluoropentanediyl groups Examples thereof include a diyl group. The divalent alicyclic saturated hydrocarbon group which may have a fluorine atom may be either monocyclic or polycyclic. The monocyclic group may be a cyclohexanediyl group or a perfluorocyclohexane group. Examples of the polycyclic group include an adamantanediyl group, a norbornanediyl group, and the like. Examples thereof include a nandiyl group and a perfluoroadamantanediyl group.

[0086] A f14 The saturated hydrocarbon group and the saturated hydrocarbon group which may have a fluorine atom are 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 groups, cyclopropylmethyl groups, cyclopropyl groups , cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, perfluorocyclohexyl group xyl group, adamantyl group, adamantylmethyl group, adamantyldimethyl group, norbornyl group norbornyl group, norbornylmethyl group, perfluoroadamantyl group, perfluoroadamantine A methyl group is preferred.

[0087] In formula (a4-3), L 5 is preferably an ethylene group. A f13The divalent saturated hydrocarbon group is a divalent chain saturated hydrocarbon group having 1 to 6 carbon atoms and a carbon A group containing a divalent alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms is preferred, and a divalent chain having 2 to 3 carbon atoms is preferred. Saturated hydrocarbon groups of the formula are more preferred. A f14 The saturated hydrocarbon group is a chain saturated hydrocarbon group having 3 to 12 carbon atoms and a A group containing an alicyclic saturated hydrocarbon group such as the above is preferred, and a chain saturated hydrocarbon group having 3 to 10 carbon atoms and A group containing an alicyclic saturated hydrocarbon group having 3 to 10 carbon atoms is more preferred. f14 teeth , preferably a group containing an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms, more preferably Cyclopropylmethyl group, cyclopentyl group, cyclohexyl group, norbornyl group and a It is a damantyl group.

[0088] Examples of the structural unit represented by formula (a4-3) include those represented by formula (a4-1'-1) to formula (a 4-1'-11) are structural units represented by the following formulas. KerR f7 The 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.

[0089] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF2025188278000049.tif4466[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.]

[0090] R f22 The saturated hydrocarbon group of R a42 Examples include the saturated hydrocarbon groups represented by the following formula: .R f22 is an alkyl group having 1 to 10 carbon atoms and having a fluorine atom, or a carbon atom having a fluorine atom An alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms and a fluorine atom is preferred. An alkyl group is more preferred, and an alkyl group having 1 to 6 carbon atoms and a fluorine atom is even more preferred. It's nice.

[0091] In formula (a4-4), A f21 As -(CH2) j1 - is preferred, and ethylene A group or a methylene group is more preferred, and a methylene group is even more preferred.

[0092] Examples of the structural unit represented by formula (a4-4) include the following structural units and In the structural unit represented by R in the structural unit (a4-4) f21 The methyl group corresponding to Examples of structural units include those in which hydrogen atoms are replaced. TIFF2025188278000050.tif86160

[0093] 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.

[0094] <Structural unit (a5)> The non-leaving hydrocarbon group contained in the structural unit (a5) may be a straight-chain, branched or cyclic hydrocarbon group. Among these, 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): . TIFF2025188278000051.tif3352[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 may be replaced with —O— or —CO—.

[0095] 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 cyclopentyl group, and a cyclopentyl group. Examples of the polycyclic alicyclic hydrocarbon group include: , an adamantyl group, and a norbornyl group. Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an isopropyl group. Propyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group Examples of alkyl groups 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.

[0096] L 55 The divalent saturated hydrocarbon group in the above is a divalent chain saturated hydrocarbon group and a divalent fatty acid group. Examples 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 propanediol group. alkanediyl groups such as butanediyl, pentanediyl, and the like. The divalent alicyclic saturated hydrocarbon group may be either monocyclic or polycyclic. Examples of saturated hydrocarbon groups include cyclopentanediyl and cyclohexanediyl groups. Examples of the polycyclic divalent alicyclic saturated hydrocarbon group include an adatom group. Examples include a mantanediyl group and a norbornanediyl group.

[0097] L 55 The -CH2- contained in the divalent saturated hydrocarbon group represented by is replaced by -O- or -CO-. Examples of the substituted groups include groups represented by formulae (L1-1) to (L1-4). In the following formula, * and ** each represent a bonding site, and * represents a bonding site with an oxygen atom. TIFF2025188278000052.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L x1 represents the binding site with ). L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L 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 are each independently 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 W x1 The total number of carbon atoms is 15 or less.

[0098] 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 Preferably, it is a methylene group or an ethylene group. L x7 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms. L x8 is preferably a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably 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.

[0099] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025188278000053.tif53135

[0100] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025188278000054.tif23130

[0101] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025188278000055.tif15147

[0102] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025188278000056.tif26114

[0103] L 55 is preferably a single bond or a group represented by formula (L1-1).

[0104] The structural unit (a5-1) includes the structural units shown below and the structural units ( R in a5-1) 51 The structural unit in which the methyl group corresponding to can be. TIFF2025188278000057.tif77157

[0105] TIFF2025188278000058.tif39160When the resin (A) has the structural unit (a5), its content is determined based on the total structural units of the 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.

[0106] <Structural unit (II)> The resin (A) further contains a structural unit that decomposes upon exposure to generate an acid (hereinafter, “structural unit”). The structural unit (II) may include, for example, Examples of the structural units include those described in JP-A-2016-79235, and those having a sulfonyl group in the side chain. A structural unit having a carboxylate group or a carboxylate group and an organic cation, or a sulfonate group in a side chain A structural unit having an aryl group and an organic anion is preferred.

[0107] A structural unit having a sulfonate group or a carboxylate group and an organic cation in the side chain is preferably a structural unit represented by formula (II-2-A'). TIFF2025188278000059.tif3189 [In formula (II-2-A'), X III3represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the saturated hydrocarbon group The -CH2- contained in the saturated carbon 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 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 group having 1 carbon atom which may have a halogen atom Represents an alkyl group of 1 to 6. ZA + represents an organic cation.

[0108] R III3 The halogen atom represented by the formula (I) includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples include uran atoms. 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 Examples include the same things. 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, and the like. , 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 Examples thereof include a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like. do. A x1 Examples of the perfluoroalkyl group having 1 to 6 carbon atoms which may be substituted include trifluoroalkyl groups. Fluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroiso Propyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group Examples of the alkyl group include a perfluoropentyl group, a perfluorohexyl group, and the like.

[0109] X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched hydrocarbon group. 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; butane-1,3-diyl; 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentaerythritol Branched alkanediyl groups such as 2-methylbutane-1,4-diyl group, 2-methylbutane-1,4-diyl group ru radical; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane -1,4-diyl group, cycloalkanediyl group such as cyclooctane-1,5-diyl group, etc. a divalent monocyclic alicyclic saturated hydrocarbon radical; Norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1 Divalent polycyclic alicyclic saturated hydrocarbons such as 2,5-diyl group, adamantane-2,6-diyl group, etc. groups, etc.

[0110] -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of the divalent groups 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 each of the preceding groups is 17 or less. In the following formula, * and ** represent binding sites. * is A x1 represents the binding site with TIFF2025188278000060.tif145161

[0111] X 3 represents a divalent saturated hydrocarbon group having 1 to 16 carbon atoms. X 4 represents a divalent saturated hydrocarbon group having 1 to 15 carbon atoms. X 5 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms. X 6 represents a divalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 7 represents a trivalent saturated hydrocarbon group having 1 to 14 carbon atoms. X 8 represents a divalent saturated hydrocarbon group having 1 to 13 carbon atoms.

[0112] ZA + Examples of the organic cation represented by the formula include organic onium cations, organic sulfonium cations, and the like. Thione, organic iodonium cation, organic ammonium cation, benzothiazolium cation Among these, organic sulfonium cations are preferred. Preferred are iodonium cations and organic iodonium cations, and arylsulfonium cations. More preferably, the compound represented by any one of formulas (b2-1) to (b2-4) is (hereinafter, depending on the formula number, it may be referred to as "cation (b2-1)" etc.) can be.

[0113] TIFF2025188278000061.tif69104In equations (b2-1) to (b2-4), R b4 ~R b6 are each independently a chain hydrocarbon group having 1 to 30 carbon atoms, a chain hydrocarbon group having 3 to 36 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 with 1 to 12 carbon atoms, and alkyl groups with 3 to 12 carbon atoms. It 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 atoms contained in the aromatic hydrocarbon group are replaced by halogen atoms, hydroxy groups, or groups having 1 carbon atom. It may be substituted with up to 12 alkoxy groups. R b4 and R b5 are bonded to each other and form a ring with the sulfur atom to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. good. R b7 and R b8 are each independently a hydroxy 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 are each independently 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 to each other and form a ring with the sulfur atom to which they are attached -CH2- contained in the ring may be replaced by -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. R b12 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 6 to 18 prime numbers, 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 are bonded to each other to form a ring including the -CH-CO- to which they are attached. -CH2- contained in the ring may be replaced by -O-, -S- or -CO-. It is also possible. R b13 ~R b18 are each independently a hydroxy 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.

[0114] 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. group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group and An example of an alkyl group is a 2-ethylhexyl group. 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, and a monocyclic alicyclic hydrocarbon group may be 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. TIFF2025188278000062.tif11158 In particular, R b9 ~R b12The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms.

[0115] Examples of alicyclic hydrocarbon groups in which hydrogen atoms are substituted with aliphatic hydrocarbon groups include methylcyclohexane. cyclohexyl group, dimethylcyclohexyl group, 2-methyladamantan-2-yl group, 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 1. Preferably it is 20 or less.

[0116] 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 a chain hydrocarbon group or an alicyclic hydrocarbon group. It may have a hydrocarbon group, and an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, xylyl group, etc.) phenyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic carbons Aromatic hydrocarbon groups containing hydrogen hydride groups (p-cyclohexylphenyl group, p-adamantyl The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. When a hydrocarbon group is contained, it is a chain hydrocarbon group having 1 to 18 carbon atoms and an alicyclic hydrocarbon group having 3 to 18 carbon atoms. Hydrocarbon groups of the formula are preferred. Examples of aromatic hydrocarbon groups in which hydrogen atoms are substituted with alkoxy groups include p-methoxyphenyl. Examples thereof include a methyl group. Examples of the chain hydrocarbon group in which a hydrogen atom is substituted with an aromatic hydrocarbon group include a benzyl group, a phenyl group, and a phenyl group. ethyl group, phenylpropyl group, trityl group, naphthylmethyl group, naphthylethyl group, etc. Examples include aralkyl groups.

[0117] The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group 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 atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alkylcarbonyloxy group include a methylcarbonyloxy group and an ethylcarbonyloxy group. Oxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group butylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group silyl group, pentylcarbonyloxy group, hexylcarbonyloxy group, octylcarbonyl Examples include an oxy group and a 2-ethylhexylcarbonyloxy group.

[0118] R b4 and R b5 and bond together with the sulfur atom to which they are attached to form a ring The ring may be monocyclic, polycyclic, aromatic, non-aromatic, saturated or unsaturated. The ring may have 3 to 18 carbon atoms, and preferably has 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 include the rings shown below, where * represents a binding site. TIFF2025188278000063.tif24142

[0119] R b9 and R b10 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. 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 thiolan-1-ium ring (tetrahydrothio) thiophenium ring), thian-1-ium ring, 1,4-oxathian-4-ium ring, etc. It can be obtained. R b11 and R b12 The ring formed by combining and can be monocyclic, polycyclic, aromatic, or non-aromatic. The ring may be either saturated or unsaturated. 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.

[0120] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025188278000064.tif153158

[0121] Examples of the cation (b2-2) include the following cations. TIFF2025188278000065.tif18130

[0122] Examples of the cation (b2-3) include the following cations. TIFF2025188278000066.tif25129

[0123] Examples of the cation (b2-4) include the following cations. TIFF2025188278000067.tif84167

[0124] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: JPEG2025188278000068.jpg38108 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z represents an integer of 0 to 6; R III2 and R III4 are each independently a hydrogen atom, a fluorine atom, or a group having 1 carbon atom represents a perfluoroalkyl group having a number of 1 to 6, and when z is 2 or more, a plurality of R III2 and R II I4 may be the same or different from each other. Q a and Q b are each independently a fluorine atom or a perfluoroalkane having 1 to 6 carbon atoms. represents a alkyl group.]

[0125] R III2 , R III4 , Q a and Q b Perfluoroalkyl groups having 1 to 6 carbon atoms, represented by As the aryl group, the Q group described below b1 The same as the perfluoroalkyl group having 1 to 6 carbon atoms represented by Examples include:

[0126] 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 . TIFF2025188278000069.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b , z and ZA + has the same meaning as above represent. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and the saturated hydrocarbon group -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon The hydrogen atoms contained in the alkyl group may be substituted with halogen atoms or hydroxy groups.

[0127] R III5 Examples of the saturated hydrocarbon group having 1 to 12 carbon atoms represented by the formula include a methyl group, an ethyl group, and , 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 groups. X I2 As the divalent saturated hydrocarbon group represented by X III3 Divalent saturated carbon represented by The same as the hydrogen chloride group can be mentioned.

[0128] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). The structural unit is preferably TIFF2025188278000070.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. m and n each independently represent 1 or 2.

[0129] 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 atom 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 WO 2012 / 050015. ZA + represents an organic cation. TIFF2025188278000071.tif86163

[0130] The structural unit having a sulfonio group and an organic anion in the side chain is represented by formula (II-1-1): It is preferable that the structural unit is a structural unit that can be formed by the above-mentioned method. TIFF2025188278000072.tif3381 [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 to each other to form a ring with the sulfur atom to which they are attached. That's fine. R II4 is a hydrogen atom, a halogen atom, or a group having 1 to 10 carbon atoms which may have a halogen atom 6 represents an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group. 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. Examples of the alkyl group and the alicyclic hydrocarbon group include the same as those described above. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a biphenyl group, Examples include aryl groups such as a phenanthryl group. The combined group may be a group in which the above-mentioned alkyl group and alicyclic hydrocarbon group are combined. , aralkyl groups such as benzyl groups, aromatic hydrocarbon groups having alkyl groups (p-methylphenyl nyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.), alicyclic carbon Aromatic hydrocarbon groups containing hydrogen hydride groups (p-cyclohexylphenyl group, p-adamantyl phenyl group, phenylcyclohexyl group, and other aryl-cycloalkyl groups. can be. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodide atom. Examples 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, represented by 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 may be -O-, -S- or may be replaced by -CO-. Specifically, X III3 The number of carbon atoms is 1 to 1 Examples thereof include the same divalent saturated hydrocarbon groups as those of 8.

[0131] The structural unit containing a cation in formula (II-1-1) includes the structural units represented by the following formulas: BiR II4 The group corresponding to the methyl group in the formula (1) is a hydrogen atom, a fluorine atom, trifluoromethyl, etc. Examples include replaced structural units. TIFF2025188278000073.tif84130

[0132] A - Examples of the organic anion represented by the formula include a sulfonate anion, a sulfonylimide anion, and Examples include sulfonylmethide anions, carboxylic acid anions, and the like. - is expressed as The organic anion is preferably a sulfonate anion, and examples of the sulfonate anion include those described below. Examples of the anion include the anion represented by formula (B1).

[0133] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025188278000074.tif43135

[0134] Examples of sulfonylmethide anions include the following: TIFF2025188278000075.tif28123

[0135] Examples of carboxylate anions include the following: TIFF2025188278000076.tif51152

[0136] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025188278000077.tif88149

[0137] When the structural unit (II) is contained in the resin (A), the content of the structural unit (II) is It is preferably 1 to 20 mol %, more preferably 2 to 30 mol %, based on the total structural units of the fat (A). It is 15 mol %, and more preferably 3 to 10 mol %.

[0138] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0139] The resin (A) is preferably a resin composed of the structural unit (a2-A) and the structural unit (a1). , that is, a copolymer of the monomer (a2-A) and the monomer (a1) and the structural unit (a2 -A) and the structural unit (a1) and the structural unit (s), that is, a resin comprising the monomer (a2 -A) and a copolymer of monomer (a1) and monomer (s). The structural unit (a1) is preferably a structural unit (a1-6), a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2), a structural unit (a1-3), a structural unit (a1-4), a structural unit (a1-5), a structural unit (a1-6), a structural unit (a1-0), a structural unit (a1-1), a structural unit (a1-2), a structural unit (a1-3), a structural unit (a1-4), a The unit (a1-1) and the structural unit (a1-2) (preferably a cyclohexyl group, and a cyclohexyl group) and more preferably, Preferably, the structural unit (a1-1) and the structural unit (a1-2) (preferably a cyclohexyl group) and the structural unit having a cyclopentyl group) More preferably, there are at least two types. 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 at least one selected from the structural unit (a2-1). The structural unit (a3) ​​is preferably a structural unit represented by formula (a3-1), a structural unit represented by formula (a3 -2) and a structural unit represented by formula (a3-4), At least one of these is

[0140] The structural units constituting the resin (A) may be used singly or in combination of two or more. Instead, monomers that lead to these structural units are used in known polymerization methods (for example, radical polymerization methods). The content of each structural unit contained in the resin (A) can be determined by the following procedure. It 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 this specification, the weight average molecular weight is 1,000 or less, and more preferably 15,000 or less. The molecular weight is determined by gel permeation chromatography under the conditions described in the examples. is.

[0141] <Resins other than Resin (A)> The resist composition of the present invention may further contain a resin other than the resin (A). Examples of resins other than the resin (A) include those containing the structural unit (a4) or the structural unit (a5). a resin (hereinafter sometimes referred to as resin (X)) having a structural unit represented by formula (a2-A): and a resin containing a structural unit having an acid labile group (hereinafter referred to as resin (AY) (There are some examples.)

[0142] As the resin (X), a resin containing the structural unit (a4) is particularly preferred. In resin (X), the content of structural unit (a4) is the sum of all structural units in resin (X). It is preferably 30 mol % or more, more preferably 40 mol % or more. It is more preferable that the content is 45 mol % or more. The structural units that the resin (X) and the resin (AY) may further have include the structural unit ( a1), structural unit (a2), structural unit (a3) ​​and structures derived from other known monomers Among them, the resin (X) contains the structural unit (a4) and / or the structural unit (a It is preferable that the resin consists of only 5).

[0143] The structural units constituting the resin (X) and the resin (AY) may be of one type or a combination of two or more types. The monomers from which these structural units are derived may be used in the form of a copolymer, and the copolymer may be polymerized by a known polymerization method (e.g., polymerization of a copolymer). The content of each structural unit in resin (X) is can be adjusted by the amount of monomer used in the polymerization. The weight average molecular weight of the resin (X) and the resin (AY) is preferably 6, 000 or more (more preferably 7,000 or more), 80,000 or less (more preferably 60 The weight average molecular weight of the resin (X) and the resin (AY) is measured by The same as in the case of fat (A).

[0144] When the resist composition of the present invention contains resin (AY), the content thereof is 10% by weight of resin (A). 0 parts by mass, usually 1 to 2500 parts by mass (more preferably 10 to 1000 parts by mass) is. Furthermore, when the resist composition contains resin (X), the content of resin (X) is 100 mass % of resin (A). parts, preferably 1 to 60 parts by mass, more preferably 1 to 50 parts by mass, It is more preferably 1 to 40 parts by mass, and particularly preferably 1 to 30 parts by mass. The amount is preferably 1 to 8 parts by mass.

[0145] The content of resin (A) in the resist composition is 8% by weight 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 of the solid content of the resist composition. The content is preferably 90% by mass or more and more preferably 99% by mass or less. The solid content of the product and the resin content relative to it are measured by liquid chromatography or gas chromatography. It can be measured by known analytical means such as graphy.

[0146] <Salt represented by formula (I)> The resist composition of the present invention contains a salt represented by formula (I) (hereinafter, sometimes referred to as "salt (I)"). Contains TIFF2025188278000078.tif36106 [In formula (I), R 1 and R 2 are each independently a hydrogen atom, a hydroxyl group, or a hydrocarbon having 1 to 12 carbon atoms. The hydrocarbon group represents a hydrocarbon group, and -CH2- contained in the hydrocarbon group is replaced by -O- or -CO-. It's fine. m and n each independently represent 1 or 2. When m is 2, two R 1 is the same or Differently, when n is 2, two R 2 are the same or different. Ar represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. X 0 represents a single bond, -CH2-, -O- or -S-. Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. Represents a group. R 3 represents a hydrocarbon group having 1 to 18 carbon atoms which may have a substituent, and The -CH2- contained in the hydroxyl group may be replaced by -O-, -S-, -SO2- or -CO-. stomach.] 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 It is sometimes called "On(I)".

[0147] In formula (I), examples of the aromatic hydrocarbon group of Ar include a phenyl group and a naphthyl group. It can be obtained. The substituent of the aromatic hydrocarbon group of Ar is an alkyl group having 1 to 16 carbon atoms (the -CH2- in the alkyl group may be replaced by -O- or -CO-), Examples of the alkyl group include halogen atoms, cyano groups, and groups in which two or more of these groups are combined. 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 8 carbon atoms, and more preferably Usually it is 1 to 4. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of alkyl groups in which -CH2- is replaced with -O- or -CO- include: Hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), carbo Xyl group (a group in which the -CH2-CH2- in an ethyl group is replaced with -O-CO-) an alkoxy group having 1 to 15 carbon atoms (-CH2- contained in an alkyl group having 2 to 16 carbon atoms); is replaced by -O-), alkoxycarbonyl groups having 2 to 15 carbon atoms (groups having 3 to (a group in which -CH2-CH2- in the alkyl group of 16 is replaced with -O-CO-), Alkylcarbonyl group having 2 to 16 carbon atoms (-C contained in alkyl group having 2 to 16 carbon atoms) a group in which H2- is replaced by -CO-), an alkylcarbonyloxy group having 2 to 15 carbon atoms (-CH2-CH2- in alkyl groups with 3 to 16 carbon atoms is replaced with -CO-O-) and groups in which two or more of these groups are combined. The alkoxy group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like. hexyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy Examples of the alkyl group include an alkyloxy group, a decyloxy group, and an undecyloxy group. The alkoxycarbonyl group, alkylcarbonyl group and alkylcarbonyloxy group are A carbonyl group or a carbonyloxy group is bonded to the alkyl group or the alkoxy group. Represents a group. The alkoxycarbonyl group includes a methoxycarbonyl group, an ethoxycarbonyl group, a bromine group, a methyl ... Examples of the alkylcarbonyl group include an acetyl group, a propyl group, and the like. The alkylcarbonyloxy group includes acetyl, ... Examples thereof include an oxy group, a propionyloxy group, and a butyryloxy group. The substituent is an alkyl group having 1 to 12 carbon atoms (the —CH2— contained in the alkyl group is , which may be replaced by —O— or —CO—) or a fluorine atom. an alkyl group having 1 to 8 carbon atoms (wherein —CH2— contained in the alkyl group is —O— or —CO—); -) or a fluorine atom is more preferred.

[0148] R 1 and R 2 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group (an alkyl group, an alkane ... chain hydrocarbon groups such as alkyl groups, alkynyl groups, and alicyclic hydrocarbon groups), aromatic hydrocarbon groups, and and groups formed by combining these. The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl groups. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples include an n-undecyl group and an n-dodecyl group. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples 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 either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group may be Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl ... cyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, cyclodecyl group Examples of the polycyclic alicyclic hydrocarbon group include a cycloalkyl group such as a decacyclic group. Examples include a hydronaphthyl group, an adamantyl group, a norbornyl group, and an isobornyl group. do. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthryl group. In the case of a combined group, the above groups may be groups with different valences (alkanediyl group, alkanediyl group, etc.). cycloalkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) Good too. The group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group is (for example, aralkyl groups), and alicyclic hydrocarbon groups and chain hydrocarbon groups. and a group combining (for example, an alicyclic hydrocarbon group, an alkanediyl group, an alkyl group, Alicyclic hydrocarbon groups -*) are included. * indicates the bonding site. Examples of the aralkyl group include a benzyl group and a phenethyl group. Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 and cycloalkylalkyl groups such as (-yl)ethyl groups. Examples of alkyl groups - alicyclic hydrocarbon groups - include methylcyclohexyl, dimethylcyclohexyl, a cycloalkyl group having an alkyl group such as a 2-hexyl group or a 2-alkyladamantan-2-yl group Examples thereof include alkyl groups. Examples of groups in which -CH2- in a hydrocarbon group is replaced with -O- or -CO- include: Alkoxy groups such as methoxy, ethoxy, and butoxy groups, cyclohexyloxy groups, cyclohexyloxy groups, cycloalkoxy groups such as a cyclohexylmethoxy group, alkylcarbonyl groups such as an acetyl group, alkoxycarbonyl groups such as methoxycarbonyl groups, alkylcarbonyl groups such as acetyloxy groups, alkoxycarbonyloxy groups such as benzoyloxy groups and butoxycarbonyloxy groups; Examples of the hydrocarbon group include aromatic hydrocarbon groups such as an aryloxy group and a carbonyloxy group. When -CH2- in the formula is replaced by -O- or -CO-, the number of such replacements may be at least one. It can be 2 or more.

[0149] Ar is a phenyl group which may have an alkyl group having 1 to 12 carbon atoms or A naphthyl group which may have an alkyl group (provided that the -CH2- contained in the alkyl group is - It is preferable that the carbon number is 1 to 8. A phenyl group which may have an alkyl group or a naphtha group which may have an alkyl group having 1 to 8 carbon atoms a methyl group (provided that -CH2- contained in the alkyl group is replaced by -O- or -CO-) It is more preferable that the alkyl group has 1 to 4 carbon atoms. Phenyl group, alkoxy group having 1 to 6 carbon atoms, or alkoxyalkanediyl group having 2 to 5 carbon atoms A naphthyl group which may have an oxy group is more preferred. m is 1 or 2, and is preferably 2. n is 1 or 2, and is preferably 2. At least one of m and n is preferably 2, and both are more preferably 2. n+m is preferably 3 or 4. R 1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and It is more preferable to do so. R 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and It is more preferable to do so. R 1 and R 2 and are preferably both hydrogen atoms. X 0 is preferably a single bond, -CH2-, or -O-, and is preferably -CH2-, or - O- is more preferred.

[0150] Q 1 and Q 2 Examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoro Ethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoropentyl group Examples of the alkyl group include a butyl group and a perfluorohexyl group. Q 1and Q 2 are each independently preferably a fluorine atom or a trifluoromethyl group, Fluorine atoms are more preferred. 1 and Q 2 and more preferably, both are fluorine atoms. .

[0151] R 3 The hydrocarbon group represented by the formula (I) is an aliphatic hydrocarbon group (an alkyl group, an alkenyl group, chain hydrocarbon groups such as alkynyl groups and alicyclic hydrocarbon groups), aromatic hydrocarbon groups and Examples of the group include a group formed by combining The alkyl group includes methyl, ethyl, n-propyl, isopropyl, and n-butyl groups. butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, Examples include an n-undecyl group and an n-dodecyl group. Examples of the alkenyl group include an ethenyl group, a propenyl group, an isopropenyl group, a butenyl group, isobutenyl group, tert-butenyl group, pentenyl group, hexenyl group, heptenyl group, Examples 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 either monocyclic or polycyclic, and a monocyclic alicyclic hydrocarbon group may be Examples of the hydrogen group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl ... cyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group, cyclodecyl group Examples of the polycyclic alicyclic hydrocarbon group include a cycloalkyl group such as a decacyclic group. Examples include a hydronaphthyl group, an adamantyl group, a norbornyl group, and an isobornyl group. Specifically, the alicyclic hydrocarbon group includes those represented by the formulae (Y1) to (Y11) and (Y36) to (Y37). Examples of the group include a group represented by formula (Y38). When it is replaced by -, -S-, -SO2- or -CO-, the number of them may be one. Such groups include those represented by formula (Y12) to formula (Y35) and formula (Y39): -A group represented by formula (Y41) is exemplified. TIFF2025188278000079.tif87165 Examples of aromatic hydrocarbon groups include a phenyl group, naphthyl group, and anthryl group. In the case of a combined group, the above groups may be groups with different valences (alkanediyl group, alkanediyl group, etc.). cycloalkanetriyl group, cycloalkanediyl group, cycloalkanetriyl group, etc.) Good too. The group formed by combining an aromatic hydrocarbon group and a chain hydrocarbon group is (for example, aralkyl groups), and alicyclic hydrocarbon groups and chain hydrocarbon groups. and a group combining (for example, an alicyclic hydrocarbon group, an alkanediyl group, and an alkyl The * indicates the bonding site. Examples of the aralkyl group include a benzyl group and a phenethyl group. Alicyclic hydrocarbon groups - alkanediyl groups - * include cyclohexylmethyl groups, cyclohexylmethyl groups, Hexylethyl group, 1-(adamantan-1-yl)methyl group, 1-(adamantan-1 and cycloalkylalkyl groups such as (-yl)ethyl groups. Examples of alkyl groups - alicyclic hydrocarbon groups - include methylcyclohexyl, dimethylcyclohexyl, a cycloalkyl group having an alkyl group such as a 2-hexyl group or a 2-alkyladamantan-2-yl group Examples thereof include alkyl groups. Examples of groups in which -CH2- in a hydrocarbon group is replaced with -O- or -CO- include: Alkoxy groups such as methoxy, ethoxy, and butoxy groups, cyclohexyloxy groups, cyclohexyloxy groups, cycloalkoxy groups such as a cyclohexylmethoxy group, alkylcarbonyl groups such as an acetyl group, alkoxycarbonyl groups such as methoxycarbonyl groups, alkylcarbonyl groups such as acetyloxy groups, alkoxycarbonyloxy groups such as benzoyloxy groups and butoxycarbonyloxy groups; Examples of the hydrocarbon group include aromatic hydrocarbon groups such as an aryloxy group and a carbonyloxy group. -CH2- contained in the formula is replaced by -O-, -S-, -S(O)2- or -CO-. In particular, the number of the alicyclic hydrocarbon group may be one or more. Examples of the group in which —CH— is replaced by —O—, —S—, —S(O)— or —CO— include: Examples thereof include groups represented by formulae (Y12) to (Y35) and (Y39) to (Y41).

[0152] R 3 The substituents of the hydrocarbon group include halogen atoms, cyano groups, and groups having 1 to 12 carbon atoms. The alkyl group, hydroxy group (-CH2- in the methyl group is replaced with -O-) a carboxyl group (the -CH2-CH2- contained in the ethyl group is substituted with -O-CO-) substituted groups), alkoxy groups having 1 to 12 carbon atoms (groups contained in alkyl groups having 2 to 13 carbon atoms) (a group in which -CH2- is replaced with -O-), alkoxycarbonyl having 2 to 13 carbon atoms The -CH2-CH2- contained in the alkyl group (having 3 to 14 carbon atoms) is replaced with -O-CO-. alkylcarbonyl groups having 2 to 13 carbon atoms (among alkyl groups having 2 to 13 carbon atoms) (a group in which -CH2- in the above is replaced with -CO-), alkylcarbonyl groups having 2 to 13 carbon atoms A bonyloxy group (-CH2-CH2- contained in an alkyl group having 3 to 14 carbon atoms) is replaced with -CO -O- substituted), and groups in which two or more of these groups are combined. do. Examples of these substituents include the same groups as the substituents of Ar. The substituent is preferably a fluorine atom, a hydroxy group, or an alkyl group having 1 to 12 carbon atoms. It is preferably a fluorine atom, a hydroxy group or an alkyl group having 1 to 6 carbon atoms. More preferable. R 3 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent (the alkyl group The —CH2— contained in may be replaced by —O— or —CO—, an alicyclic hydrocarbon group having 3 to 16 carbon atoms that may be present (the —CH 2- may be replaced by -O- or -CO-) or alkyl having 1 to 6 carbon atoms a group formed by combining a group and an alicyclic hydrocarbon group having 3 to 12 carbon atoms (the alkyl group and the alicyclic hydrocarbon group) The cyclic hydrocarbon group may have a substituent, and the alkyl group and the alicyclic hydrocarbon group may have a substituent. The —CH2— may be replaced by —O— or —CO—. or an alkyl group having 1 to 12 carbon atoms which may have a substituent (-C contained in the alkyl group H2- may be replaced by -O- or -CO-. an alicyclic hydrocarbon group having 3 to 16 carbon atoms (the —CH2— contained in the alicyclic hydrocarbon group is —O - or -CO-), and more preferably has 1 to 12 carbon atoms. an alkyl group or an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have a substituent (the alicyclic hydrocarbon The —CH2— contained in the hydrogen hydride group may be replaced by —O— or —CO—. More preferably, it is a branched alkyl group having 3 to 12 carbon atoms, or a fluorine atom or a hydrochloride. an alicyclic hydrocarbon group having 3 to 16 carbon atoms which may have an oxy group (the alicyclic hydrocarbon group The -CH2- may be replaced by -O- or -CO-. or a branched alkyl group having 3 to 6 carbon atoms, or a carbon atom having a fluorine atom or a hydroxy group An alicyclic hydrocarbon group having 5 to 16 prime numbers (-CH2- contained in the alicyclic hydrocarbon group is -O- or -CO-, and even more preferably isopropyl. group, t-butyl group, or alicyclic group having 5 to 16 carbon atoms and a fluorine atom or a hydroxy group Hydrocarbon group (-CH2- contained in the alicyclic hydrocarbon group is replaced with -O- or -CO-) It is okay to know.)

[0153] The salt (I) is a salt represented by formula (IA) (hereinafter sometimes referred to as "salt (IA)"). Examples include: TIFF2025188278000080.tif36106[In formula (IA), R 1 , R 2 , m, n, X 0 , Q 1 and Q 2 is synonymous with the above. Ar 1 represents a naphthyl group which may have a substituent. R 3A represents a branched alkyl group having 3 to 6 carbon atoms.] Ar 1 Examples of the substituent on the naphthyl group of are the same as the substituent on Ar. Ar 1is a naphthyl group which may have an alkyl group having 1 to 12 carbon atoms (provided that the alkyl -CH2- contained in the group may be replaced by -O- or -CO-. and a naphthyl group which may have an alkyl group having 1 to 8 carbon atoms (provided that the alkyl -CH2- contained in the group may be replaced by -O- or -CO-. More preferably, the alkoxy group has 1 to 6 carbon atoms or the alkoxyalkane has 2 to 5 carbon atoms. A naphthyl group which may have a diyloxy group is more preferred. R 3A is preferably an isopropyl group or a t-butyl group, and more preferably a t-butyl group. It is more preferable to do so.

[0154] The salt (I) may be a salt represented by the formula (IB) (hereinafter referred to as "salt (IB)"). (There are also some) TIFF2025188278000081.tif36106[In formula (IB), R 1 , R 2 , m, n, Q 1 and Q 2 is synonymous with the above. Ar 2 represents a phenyl group which may have a substituent. X 02 represents a single bond or -CH2-. R 3B represents a branched alkyl group having 3 to 6 carbon atoms.] Ar 2 Examples of the substituent on the phenyl group of are the same as the substituent on Ar. Ar 2 is a phenyl group which may have an alkyl group having 1 to 12 carbon atoms (provided that the alkyl -CH2- contained in the group may be replaced by -O- or -CO-. and a phenyl group which may have an alkyl group having 1 to 8 carbon atoms (provided that the alkyl -CH2- contained in the group may be replaced by -O- or -CO-. It is more preferable that the alkyl group is a phenyl group which may have an alkyl group having 1 to 4 carbon atoms. More preferable. X 0 is preferably -CH2-. R 3B is preferably an isopropyl group or a t-butyl group, and more preferably a t-butyl group. It is more preferable to do so.

[0155] The cation of the salt (I) is represented by the following formulas (Ic-1) to (Ic-40). Examples of cations include: TIFF2025188278000082.tif208134

[0156] TIFF2025188278000083.tif164121

[0157] Among them, formulas (Ic-1) to (Ic-15), formulas (Ic-21) to (Ic Cations represented by formula (Ic-1), formula (Ic-4), formula (Ic-5), formula (Ic-6), formula (Ic-7), formula (Ic-8), formula (Ic-9), formula (Ic-10), formula (Ic-11), formula (Ic-12), formula (Ic-13), formula (Ic-14), formula (Ic-15), formula (Ic-16), formula (Ic-17), formula (Ic-18), formula ( -c-5), formula (Ic-6), formula (Ic-7), formula (Ic-9), formula (Ic-1) 1), Formula (Ic-14), Formula (Ic-21), Formula (Ic-23), Formula (Ic-2) 6), cations represented by formula (Ic-28), formula (Ic-31), and formula (Ic-33) Formula (Ic-1), Formula (Ic-5), Formula (Ic-6), Formula (Ic-7), Formula (Ic-8), Formula (Ic-9), Formula (Ic-10), Formula (Ic-11), Formula (Ic-12), Formula (Ic-13), Formula (Ic-14), Formula (Ic-15), Formula (Ic-16), Formula (Ic-17), Formula (Ic-18), Formula (Ic-19), Formula (Ic- (Ic-7), Formula (Ic-11), Formula (Ic-23) and Formula (Ic-28) Cations are even more preferred.

[0158] The anion of the salt (I) may be any of the anions represented by the following formulae (Ia-1) to (Ia-12). Nion et al. TIFF2025188278000084.tif118165

[0159] The salt (I) is a combination of an anion and a cation. These anions and cations are: Specific examples of the salt (I) include the salts of the above cations (I) and Examples of the salt (I) include salts in any combination with the anion (I). Specific examples of the salt (I) are shown in the table below. In the table below, each symbol is attached to the structure representing the anion (I) or cation (I) described above. For example, the salt (I-1) is a compound having an anion represented by the formula (Ia-1) and a compound represented by the formula It is a salt formed with a cation represented by (Ic-1), and is the salt shown below. TIFF2025188278000085.tif3579 [Table 1] TIFF2025188278000087.tif223154 TIFF2025188278000088.tif223154 TIFF2025188278000089.tif223154 TIFF2025188278000090.tif249160

[0160] Among them, salt (I) is salt (I-1) to salt (I-6), salt (I-11) to salt (I-18) , Salt (I-23) ~ Salt (I-30), Salt (I-35) ~ Salt (I-42), Salt (I-47) ~Salt (I-54), Salt (I-59) ~Salt (I-66), Salt (I-71) ~Salt (I-78) , Salt (I-83) ~ Salt (I-90), Salt (I-95) ~ Salt (I-102), Salt (I-10 7) ~ Salt (I-114), Salt (I-119) ~ Salt (I-126), Salt (I-131) ~ Salt (I-138), salt (I-143), salt (I-147), salt (I-145) ~ salt (I-1 50), Salt (I-155) ~ Salt (I-162), Salt (I-167) ~ Salt (I-174), Salt (I-179) ~ Salt (I-186), Salt (I-191) ~ Salt (I-198), Salt (I- 203), and salt (I-204).

[0161] <Method for producing salt (I)> Salt (I) can be prepared by reacting a salt represented by formula (Ia) with a salt represented by formula (Ib) in a solvent. Salt (IA) and salt (IB) can also be produced by the same method. It can be produced by the method. TIFF2025188278000091.tif70117 (wherein all symbols have the same meanings as above). R A , R B and R C R each independently represents a hydrocarbon group having 1 to 12 carbon atoms. D is hydrogen represents an atom or a hydrocarbon group having 1 to 12 carbon atoms. Examples of solvents used in this reaction include chloroform, acetonitrile, and ion-exchanged water. It can be obtained. The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0162] Examples of the salt represented by formula (Ia) include the salt represented by the following formula: They are readily available and can be easily synthesized by known methods. TIFF2025188278000092.tif63138 Examples of the salt represented by formula (Ib) include the salt represented by the following formula: They are readily available and can be easily synthesized by known methods. TIFF2025188278000093.tif57160

[0163] The salt represented by formula (Ia) can be prepared, for example, by reacting a compound represented by formula (Ic) with a compound represented by formula (Id) in the presence of phosphorus pentoxide and methanesulfonic acid. It can be manufactured more efficiently. TIFF2025188278000094.tif46154 (wherein all symbols have the same meanings as defined above.) The reaction temperature is usually 0° C. to 80° C., and the reaction time is usually 0.5 to 24 hours.

[0164] Examples of the compound represented by formula (Ic) include the compounds represented by the following formula: and is readily available on the market. TIFF2025188278000095.tif32132

[0165] Examples of the compound represented by formula (Id) include the compounds represented by the following formula: and is readily available on the market. TIFF2025188278000096.tif2070

[0166] The salt (I) functions as an acid generator in the resist composition. The composition may contain one type or two or more types.

[0167] <Acid generator (B)> The resist composition of the present invention may contain, in addition to the salt (I), an acid generator known in the resist field (hereinafter referred to as The acid generator (B) may contain an acid generator (B) alone. They may be used singly or in combination of two or more.

[0168] 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., disulfones, ketones Examples of ionic acid generators include ionic acid generators such as ionic acid generators (sulfones, sulfonyldiazomethanes, etc.). Onium salts containing ammonium cations (e.g., diazonium salts, phosphonium salts, sulfonium salts) Typical examples of onium salts include sulfonate anions. anion, sulfonylimide anion, sulfonylmethide anion, etc.

[0169] Examples of the acid generator (B) include those disclosed in JP-A-63-26653 and JP-A-55-164824; JP 62-69263, JP 63-146038, JP 63-163452 , JP 62-153853 A, JP 63-146029 A, U.S. Pat. No. 3,779, 778, U.S. Pat. No. 3,849,137, German Patent No. 3914407, European Patent No. Compounds that generate acids when exposed to radiation, such as those described in US Pat. No. 126,712, can be used. In addition, compounds produced by known methods may be used. The acid generator (B) may be a mixture of two or more compounds. They may also be used in combination.

[0170] The acid generator (B) is preferably a fluorine-containing acid generator, more preferably a compound represented by the formula (B1): (hereinafter, may be referred to as "acid generator (B1)", excluding salt (I).) is. TIFF2025188278000097.tif2863[In formula (B1), Q b1 and Q b2 are each independently 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, and the divalent saturated hydrocarbon group The contained —CH2— may be replaced by —O— or —CO—, and the divalent saturated carbon The hydrogen atoms contained in the hydrogen hydride group may be substituted with fluorine atoms or hydroxy groups. Y is a methyl group which may have a substituent or a C3-C1 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.

[0171] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) includes a trifluoromethyl group, a pentafluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a fluoropentyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. and more preferably, both are fluorine atoms.

[0172] L b1The divalent saturated hydrocarbon group in candiyl group, and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups, and these 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 groups; Cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexa cycloalkanediyl groups such as cyclohexene-1,4-diyl and cyclooctane-1,5-diyl 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 Examples include a hydrogen group.

[0173] L b1-CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group may be, for example, a group represented by any one of formulas (b1-1) to (b1-3). In addition, groups represented by formula (b1-1) to formula (b1-3) and their components are exemplified. In the exemplary groups represented by formulae (b1-4) to (b1-11), * and ** represent bonds. * represents a bond to -Y.

[0174] TIFF2025188278000098.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 with -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 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 with -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 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 b7 represents 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 with -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0175] 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.

[0176] L b2 is preferably a single bond. L b3 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b4 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms, and the divalent saturated hydrocarbon The hydrogen atoms contained in the hydrogen group may be substituted with fluorine atoms. 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. The —CH2— contained in the divalent saturated hydrocarbon group is replaced with —O— or —CO—. That's fine.

[0177] L b1 -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).

[0178] The group represented by formula (b1-1) includes those represented by formulas (b1-4) to (b1-8), respectively. Examples of such groups include: TIFF2025188278000099.tif49120[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, and the divalent saturated hydrocarbon group 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 with -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 with -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.

[0179] L b8is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, 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.

[0180] The group represented by formula (b1-3) is represented by formulas (b1-9) to (b1-11), respectively. Examples include groups represented by the following formula: TIFF2025188278000100.tif23140 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 replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group 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 replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group 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 b26 represents 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 replaced by —O—. or -CO-, and the hydrogen contained in the alkylcarbonyloxy group 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.

[0181] In addition, in the groups represented by formula (b1-9) to formula (b1-11), saturated When a hydrogen atom contained in a mono- or di-hydrocarbon group is substituted with an alkylcarbonyloxy group, The number of carbon atoms before substitution is the number of carbon atoms of the saturated hydrocarbon group.

[0182] Examples of the alkylcarbonyloxy group include an acetyloxy group, a propionyloxy group, a bromide group, and a bromine group. Thyryloxy group, cyclohexylcarbonyloxy group, adamantylcarbonyloxy group etc.

[0183] Examples of the group represented by formula (b1-4) include the following. TIFF2025188278000101.tif16154

[0184] Examples of the group represented by formula (b1-5) include the following. TIFF2025188278000102.tif64141

[0185] Examples of the group represented by formula (b1-6) include the following. TIFF2025188278000103.tif39149

[0186] Examples of the group represented by formula (b1-7) include the following. TIFF2025188278000104.tif62153

[0187] Examples of the group represented by formula (b1-8) include the following. TIFF2025188278000105.tif23150

[0188] Examples of the group represented by formula (b1-2) include the following. TIFF2025188278000106.tif31161

[0189] Examples of the group represented by formula (b1-9) include the following. TIFF2025188278000107.tif44137

[0190] Examples of the group represented by formula (b1-10) include the following. TIFF2025188278000108.tif87156

[0191] Examples of the group represented by formula (b1-11) include the following. TIFF2025188278000109.tif84164

[0192] The alicyclic hydrocarbon group represented by Y includes those represented by formula (Y1) to formula (Y11), formula (Y36) to formula (Y37) Examples include a group represented by formula (Y38). The —CH2— contained in the alicyclic hydrocarbon group represented by Y is —O—, —S(O)2— or — When the group is replaced with CO-, the number of CO- may be one or more. Examples thereof include groups represented by formulae (Y12) to (Y35) and (Y39) to (Y41). can be.

[0193] The alicyclic hydrocarbon group represented by TIFF2025188278000110.tif77149Y is preferably a group represented by formula (Y1) to formula (Y20), formula ( 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 a group represented by formula (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 selected from the group consisting of the formulae (Y28) to (Y35), the formulae (Y39) to (Y In the case of a spiro ring containing an oxygen atom such as 40), an alkanediyl group between the two oxygen atoms is used. 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 to have

[0194] 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, or 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, a represents an aromatic hydrocarbon group of 0 to 18 or a group combining these; The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group represents an integer. , -S(O)2- or -CO-, and the alkyl group, the alicyclic carbon The hydrogen atom contained in the hydrogen group and the aromatic hydrocarbon group is substituted with a hydroxy group or a fluorine atom. It may be replaced.) The substituent of the alicyclic hydrocarbon group represented by Y is a halogen atom, a hydroxy group, a hydroxyl group ... an alkyl group having 1 to 12 carbon atoms which may be substituted with an alkyl 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, a carbon atom, represents an aromatic hydrocarbon group having a prime number of 6 to 18 or a group combining these groups; The —CH2— contained in the alkyl group and the alicyclic hydrocarbon group represents any one of the following integers: The alkyl group, the alicyclic group, and the cycloalkyl group may be replaced by -O-, -S(O)2-, or -CO-. The hydrogen atoms contained in the hydrocarbon group and the aromatic hydrocarbon group may be substituted by hydroxy groups or fluorine atoms. It may be replaced by a child.)

[0195] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Examples of the alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclohexyl group. cyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, Examples include a carboxyl 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 aromatic hydrocarbon groups include aryl groups such as an alkyl group and a phenanthryl group. The aromatic hydrocarbon group may have a hydrocarbon group or an alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a chain hydrocarbon group. The hydrogen group includes tolyl, xylyl, cumenyl, mesityl, and p-ethylphenyl. group, p-tert-butylphenyl group, 2,6-diethylphenyl group, 2-methyl-6- Examples of aromatic hydrocarbon groups having an alicyclic hydrocarbon group include: Examples include a p-adamantylphenyl group and a p-cyclohexylphenyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a bromine 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 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, and the like. hydroxyl group, hexyloxy group, heptyloxy group, octyloxy group, decyloxy group and dodecyloxy groups. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and the like. Examples include an ethyl group and a naphthylethyl group. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, and a butyryl group. etc.

[0196] Examples of Y include the following: TIFF2025188278000111.tif86145

[0197] TIFF2025188278000112.tif105138

[0198] 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, and the alicyclic hydrocarbon group or -CH2- constituting the adamantyl group is replaced with -CO-, -S(O)2- or -CO-. Y is more preferably an adamantyl group or a hydroxyadamantyl group. group, an oxoadamantyl group, or a group represented by the following formula: TIFF2025188278000113.tif58160

[0199] The sulfonate anion in the salt represented by formula (B1) includes those represented by formula (B1-A-1) to Anions represented by formula (B1-A-55) (hereinafter referred to as "anions (B1-A)" according to the formula number) -1) and the like are preferred, and the formulas (B1-A-1) to (B1-A-4) are , 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 (B 1-A-55) is more preferred.

[0200] TIFF2025188278000114.tif112143

[0201] TIFF2025188278000115.tif100165

[0202] TIFF2025188278000116.tif120145

[0203] TIFF2025188278000117.tif106140

[0204] TIFF2025188278000118.tif140157

[0205] where R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably R is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms. Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or more preferably a methyl group, an ethyl group, a cyclohexyl group, L is a methyl group or an adamantyl group. A4 is a single bond or an alkanediyl group having 1 to 4 carbon atoms Q b1 and Q b2 has the same meaning as above. Specific examples of the sulfonate anion in the salt represented by formula (B1) include those described in JP-A-2002-200344. Examples of the anions include those described in Japanese Patent Publication No. 10-204646.

[0206] The sulfonate anion in the salt represented by formula (B1) is preferably a sulfonate anion represented by formula (B1a- Examples of the anions include those represented by formulas (1) to (B1a-34). TIFF2025188278000119.tif146140

[0207] TIFF2025188278000120.tif62141

[0208] TIFF2025188278000121.tif142153

[0209] Among them, the compounds represented by formula (B1a-1) to formula (B1a-3) and formula (B1a-7) to formula (B1a- 16), formula (B1a-18), formula (B1a-19), formula (B1a-22) ~ formula (B1a- 34) is preferred.

[0210] Z1 + Examples of the organic cation include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations, and Among these, organic sulfonium cations are Preferred are iodonium and organic iodonium cations, and more preferred are arylsulfonium cations. It's nice. Z1 in formula (B1) + is an organic group in the structural unit represented by formula (II-2-A'). On ZA + The same can be mentioned.

[0211] 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) ~ Formula (B1a-16), Formula (B1a-18), Formula ( B1a-19), an anion represented by any one of formulas (B1a-22) to (B1a-34) Examples of the combination include a combination of an anion and a cation (b2-1) or a cation (b2-3).

[0212] The acid generator (B) is preferably a compound 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 (1-31) to (B1-48) are particularly preferred. TIFF2025188278000122.tif62150

[0213] TIFF2025188278000123.tif72164

[0214] TIFF2025188278000124.tif79152

[0215] TIFF2025188278000125.tif126150

[0216] TIFF2025188278000126.tif95148

[0217] TIFF2025188278000127.tif150149

[0218] When the acid generator contains a salt (I) and an acid generator (B), the salt (I) and the acid generator (B) The ratio of the salt (I):acid generator (B) content (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 1 / 100 of the above-mentioned resin (A). 00 parts by mass, preferably 1 part by mass or more and 45 parts by mass or less, more preferably 1 part by mass The content is preferably from 3 to 35 parts by mass, more preferably from 3 to 35 parts by mass.

[0219] <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 by, for example, liquid chromatography or gas chromatography. It can be measured by known analytical means such as chromatography. The solvent (E) may be ethyl cellosolve acetate, methyl cellosolve acetate, or Glycol ether esters such as propylene glycol monomethyl ether acetate ; Glycol ethers such as propylene glycol monomethyl ether; Ethyl lactate, acetic acid esters such as butyl acetate, amyl acetate and ethyl pyruvate; acetone, methyl isobutyl esters; ketones such as cyclohexanone, 2-heptanone, and cyclohexanone; γ-butyrolactone; cyclic esters; etc. One type of solvent (E) may be used alone, Two or more types may be used.

[0220] <Quencher (C)> The quencher (C) is a basic nitrogen-containing organic compound and an acid generated from the acid generator (B). The quencher (C) content is The amount is preferably about 0.01 to 15% by mass based on the solid content of the resist composition. , and more preferably about 0.01 to 10 mass %, and more preferably about 0.01 to 5 mass %. It is more preferable that the content is about 0.1 to 3 mass %. 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, Amines include secondary amines and tertiary amines. Amines include 1-naphthylamine, 2-naphthylamine, aniline, and 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, Ethyldibutylamine diamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine , ethyldioctylamine, ethyldinonylamine, ethyldidecylamine, dicyclohexane 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, pyridine 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 Examples include phenanthroline, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc., preferably diisopropylaniline, and more preferably 2,6-diisopropylaniline. Examples of the ammonium salt include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, etc. The acidity of a 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). A salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-39502, and JP-A-2011-191745. Preferably, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (carbo

[0221] The acidity of a salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The acid generated from the acid generator (B) A salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) is a salt in which the acid dissociation constant of the acid generated from the salt is usually -3 < pKa, preferably -1 < pKa < 7, and more preferably 0 < pKa < 5. Examples of the salt that generates an acid with a lower acidity than the acid generated from the acid generator (B) include salts represented by the following formula, salts represented by formula (D) described in JP-A-2015-147926 (hereinafter sometimes referred to as "weak acid inner 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, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (carbo Sometimes referred to as "weak acid inner salt (D)"). Examples include salts described in JP-A-2012-72109 and JP-A-2011-191745. Preferably, it is a salt that generates a carboxylic acid with a lower acidity than the acid generated from the acid generator (B) (carbo ​​​​​​​​A salt having a phosphate anion, more preferably a weak acid inner salt (D). TIFF2025188278000128.tif89165

[0222] Examples of the weak acid inner salt (D) include the following salts. TIFF2025188278000129.tif72165

[0223] <Other ingredients> The resist composition of the present invention may contain components other than the above-mentioned components (hereinafter referred to as "other components") as needed. It may contain other ingredients (F). The resist composition may contain additives known in the resist field, such as sensitizers, dissolution inhibitors, surfactants, stabilizers, etc. Agents, dyes, etc. can be used.

[0224] <Preparation of Resist Composition> The resist composition of the present invention comprises a salt (I), a resin (A), an acid generator (B), and, if necessary, Depending on the resin (A) used, a resin other than the resin (A), a solvent (E), a quencher (C) and its The composition can be prepared by mixing the other component (F) in any order. The temperature during mixing is not limited to 10 to 40°C, depending on the type of resin, etc. An appropriate temperature can be selected depending on the solubility of the compound in the solvent (E), etc. The mixing time is Depending on the mixing temperature, an appropriate time can be selected from 0.5 to 24 hours. The mixing means is not particularly limited, and stirring and mixing or the like can be used. After mixing the components, filter the mixture using a filter with a pore size of approximately 0.003 to 0.2 μm. It is preferable that

[0225] <Method for producing a 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) 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 is included. To apply the resist composition to the 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. 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. The heating time is preferably 10 to 180 seconds. The pressure during this process is 1 to 1.0 x 10 5 It is preferable that the pressure is about Pa. The resulting 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 laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm) Laser light emitted from a solid-state laser light source (YAG or semiconductor laser, etc.) Those that convert 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". The 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. The composition layer after exposure is subjected to a heat treatment (or The heating temperature is usually about 50 to 200°C, preferably The temperature is usually around 70 to 150°C. The composition layer after heating is usually developed using a developing device and a developing solution. Examples of methods include the dip method, paddle method, spray method, and 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. 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 a type of alkaline water used in this field. Any solution is acceptable. For example, tetramethylammonium hydroxide or (2-hydroxy Examples include an aqueous solution 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 removed. It is preferable to remove it. When a negative resist pattern is produced from the resist composition of the present invention, a developer A developer containing an organic solvent (hereinafter sometimes referred to as an "organic developer") is used. The organic solvents contained in organic developers include ketones such as 2-hexanone and 2-heptanone. Glycol ether solvents such as propylene glycol monomethyl ether acetate Ester solvents such as butyl acetate; propylene glycol monomethyl ether, etc. Glycol ether solvents; amide solvents such as N,N-dimethylacetamide; anisole and aromatic hydrocarbon solvents such as the above. 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 more preferably 95% by mass or more and 100% by mass or less, and more preferably substantially only an organic solvent. More preferable. Among them, organic developers include developers 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 more preferable that the mixture is qualitatively only butyl acetate and / or 2-heptanone. The organic developer may contain a surfactant. The water content may be less than 100%. During development, development is stopped by replacing the organic developer with a different type of solvent. Good too. After development, the resist pattern is preferably washed with a rinse solution. There are no particular limitations as long as the solvent does not dissolve the resist pattern, and solvents containing general organic solvents are also usable. A solvent can be used, preferably an alcohol solvent or an ester solvent. After cleaning, it is preferable to remove the rinse liquid remaining on the substrate and the pattern.

[0226] <Application> The resist composition of the present invention is a resist composition for exposure to KrF excimer laser, ArF excimer laser, Resist composition for exposure to ultraviolet laser, resist composition for exposure to electron beam (EB) or EU resist compositions for V exposure, particularly resist compositions for electron beam (EB) exposure or EUV exposure The composition is suitable as a resist composition for semiconductors and is useful for microfabrication of semiconductors. [Example]

[0227] The present invention will be explained 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 ent). In the examples, the value of this molecular ion peak is indicated by "MASS."

[0228] Example 1: Synthesis of salt represented by formula (I-37) TIFF2025188278000130.tif62124 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.72 parts of the compound represented by formula (I-37-b) was added over 5 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. After adding the salt and neutralizing, a solution containing the salt represented by formula (I-37-c) was obtained. -37-c), 4.00 parts of a salt represented by formula (I-1-d) and A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue. The mixture was stirred and filtered to obtain 4.02 parts of the salt represented by formula (I-37). MASS(ESI(+)Spectrum):M + 259.1 MASS(ESI(-)Spectrum):M - 245.0

[0229] Example 2: Synthesis of salt represented by formula (I-49) TIFF2025188278000131.tif64115 Add 0.91 parts of diphosphorus pentoxide to 9.07 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.20 parts of the compound represented by formula (I-2-a), and the After that, the mixture was cooled to 5°C, and 1.74 parts of the compound represented by formula (I-37-b) was added over 5 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 11 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. After adding the salt and neutralizing, a solution containing the salt represented by formula (I-49-c) was obtained. -49-c), 4.04 parts of a salt represented by formula (I-1-d) and The mixture was added with 20.21 parts of chloroform, stirred at 23°C for 18 hours, and then separated into layers. To the organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was repeated five times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the obtained residue. The mixture was added, stirred, and filtered to obtain 3.76 parts of the salt represented by formula (I-49). MASS(ESI(+)Spectrum):M + 273.1 MASS(ESI(-)Spectrum):M - 245.0

[0230] Example 3: Synthesis of salt represented by formula (I-145) TIFF2025188278000132.tif34123 33.79 parts of a salt represented by formula (I-145-c), 35 parts of a salt represented by formula (I-1-d) 140 parts of chloroform and 70 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23°C for 2 hours. To the resulting organic layer, 70 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was carried out five times. The obtained organic layer was concentrated, and the obtained residue was treated with tert-butyl methyl methacrylate. Add 150 parts of ethyl ether, stir, and filter to obtain the compound represented by formula (I-145). 39.27 parts of the salt were obtained. MASS(ESI(+)Spectrum):M + 235.2 MASS(ESI(-)Spectrum):M - 245.0

[0231] Synthesis Example 1: Synthesis of a salt represented by formula (I-147) TIFF2025188278000133.tif34130 7.33 parts of a salt represented by formula (I-145-c), 7 parts of a salt represented by formula (I-147-d) 0.50 parts of chloroform, 37.50 parts of 5% oxalic acid aqueous solution, and 2 After stirring at 3°C ​​for 2 hours, the mixture was separated. To the obtained organic layer, 18.75 parts of ion-exchanged water was added. The mixture was stirred and separated. This washing with water was repeated five times. The obtained organic layer was concentrated. 60 parts of tert-butyl methyl ether was added to the mixture, stirred, and filtered to obtain a solution of the formula ( 9.07 parts of the salt represented by formula I-147) were obtained. MASS(ESI(+)Spectrum):M + 235.2 MASS(ESI(-)Spectrum):M - 323.1

[0232] Synthesis Example 2: Synthesis of a salt represented by formula (I-48) TIFF2025188278000134.tif64117 10.92 parts of methanesulfonic acid was added to 1.09 parts of phosphorus pentoxide, and the mixture was incubated at 23°C for 30 minutes. To the resulting mixture was added 2.43 parts of the compound represented by formula (I-1-a), and the mixture was stirred. Then, the mixture was cooled to 5°C, and 2.11 parts of the compound represented by formula (I-37-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to 5°C, 12 parts of ion-exchanged water was added, and then 5 parts of 28% aqueous ammonia solution was added. By adding 1 part of the hexane and neutralizing the mixture, a solution containing a salt represented by formula (I-37-c) was obtained. A solution containing a salt represented by formula (I-37-c) is treated with a salt represented by formula (I-12-d) 5.19 A mixed solution of 15 parts of acetic acid and 15 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer, 15 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was repeated five times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the obtained residue. The mixture was added, stirred, and filtered to obtain 5.18 parts of the salt represented by formula (I-48). MASS(ESI(+)Spectrum):M+ 259.1 MASS(ESI(-)Spectrum):M - 271.1

[0233] Synthesis Example 3: Synthesis of a salt represented by formula (I-39) TIFF2025188278000135.tif63119 Add 0.90 parts of diphosphorus pentoxide to 8.97 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.72 parts of the compound represented by formula (I-37-b) was added over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to 5°C, 10 parts of ion-exchanged water was added, followed by 5 parts of 28% aqueous ammonia. was added and neutralized to obtain a solution containing a salt represented by formula (I-37-c). I-37-c) into a solution containing 4.30 parts of a salt represented by formula (I-3-d) and A mixed solution of 22 parts of chloroform and 22 parts of toluene was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer, 22 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was repeated five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue. The mixture was stirred and filtered to obtain 4.73 parts of the salt represented by the formula (I-39). MASS(ESI(+)Spectrum):M + 259.1 MASS(ESI(-)Spectrum):M - 323.1

[0234] Example 4: Synthesis of salt represented by formula (I-1) TIFF2025188278000136.tif64113 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 4.00 parts of a salt represented by formula (I-1-d) and chloroform A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 3.89 parts of the salt represented by formula (I-1). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 245.0

[0235] Synthesis Example 4: Synthesis of a salt represented by formula (I-121) TIFF2025188278000137.tif38121 33.98 parts of a salt represented by formula (I-121-c), 35 parts of a salt represented by formula (I-1-d) 140 parts of chloroform and 70 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23°C for 2 hours. To the resulting organic layer, 70 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was carried out five times. The obtained organic layer was concentrated, and the obtained residue was treated with tert-butyl methyl methacrylate. Add 150 parts of ethyl ether, stir, and filter to obtain the compound represented by formula (I-121). 39.55 parts of the salt were obtained. MASS(ESI(+)Spectrum):M + 237.1 MASS(ESI(-)Spectrum):M - 245.0

[0236] Synthesis Example 5: Synthesis of a salt represented by formula (I-75) TIFF2025188278000138.tif70121 Add 0.90 parts of diphosphorus pentoxide to 8.97 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.52 parts of the compound represented by formula (I-75-b) was added over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to 5°C, 10 parts of ion-exchanged water was added, followed by 5 parts of 28% aqueous ammonia. was added and neutralized to obtain a solution containing a salt represented by formula (I-75-c). I-75-c) into a solution containing 4.30 parts of a salt represented by formula (I-3-d) and A mixed solution of 22 parts of chloroform and 22 parts of toluene was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer, 22 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was repeated five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue. The mixture was stirred and filtered to obtain 4.12 parts of the salt represented by the formula (I-75). MASS(ESI(+)Spectrum):M + 245.1 MASS(ESI(-)Spectrum):M - 323.1

[0237] Synthesis Example 6: Synthesis of a salt represented by formula (I-83) TIFF2025188278000139.tif62117 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.52 parts of the compound represented by formula (I-75-b) was added over 5 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. After adding the salt and neutralizing, a solution containing the salt represented by formula (I-75-c) was obtained. -75-c), 3.57 parts of a salt represented by formula (I-11-d) and A mixed solution of 20 parts of chloroform and 20 parts of toluene was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer, 20 parts of ion-exchanged water was added, and the mixture was stirred and separated. This water washing was repeated five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue. The mixture was stirred and filtered to obtain 2.19 parts of the salt represented by the formula (I-83). MASS(ESI(+)Spectrum):M + 245.1 MASS(ESI(-)Spectrum):M - 203.0

[0238] Example 5: Synthesis of salt represented by formula (I-2) TIFF2025188278000140.tif64113 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 3.86 parts of a salt represented by formula (I-2-d) and chloroform A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 3.12 parts of the salt represented by formula (I-2). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 231.0

[0239] Synthesis Example 7: Synthesis of a salt represented by formula (I-3) TIFF2025188278000141.tif72115 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 1-c), 4.31 parts of a salt represented by formula (I-3-d) and chloro A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 4.09 parts of the salt represented by formula (I-3). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 323.1

[0240] Synthesis Example 8: Synthesis of a salt represented by formula (I-4) TIFF2025188278000142.tif72119 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 1-c), 4.47 parts of a salt represented by formula (I-4-d) and chloroform A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 3.69 parts of the salt represented by formula (I-4). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M- 339.1

[0241] Synthesis Example 9: Synthesis of a salt represented by formula (I-5) TIFF2025188278000143.tif73118 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 1-c), 4.45 parts of a salt represented by formula (I-5-d) and chloroform A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 4.24 parts of the salt represented by formula (I-4). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 337.1

[0242] Synthesis Example 10: Synthesis of a salt represented by formula (I-6) TIFF2025188278000144.tif72123 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.00 parts of the compound represented by formula (I-1-a), and the After that, the mixture was cooled to 5°C, and 1.75 parts of the compound represented by formula (I-1-b) was added thereto over 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to ° C., 10 parts of ion-exchanged water was added, and then 5 parts of a 28% aqueous ammonia solution was added. By adding and neutralizing, a solution containing a salt represented by formula (I-1-c) was obtained. 1-c), 6.05 parts of a salt represented by formula (I-6-d) and chloro A mixed solution of 20 parts of chloroform was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. 20 parts of ion-exchanged water was added to the layer, and the mixture was stirred and separated. This water washing was carried out five times. The organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the resulting residue and stirred. The mixture was filtered to obtain 4.61 parts of the salt represented by formula (I-6). MASS(ESI(+)Spectrum):M + 261.1 MASS(ESI(-)Spectrum):M - 481.1

[0243] Example 6: Synthesis of salt represented by formula (I-193) TIFF2025188278000145.tif83115 Add 0.90 parts of diphosphorus pentoxide to 4.49 parts of methanesulfonic acid and stir at 23°C for 30 minutes. To the resulting mixture was added 2.73 parts of the compound represented by formula (I-193-a), Thereafter, the mixture was cooled to 5°C, and 1.75 parts of a compound represented by formula (I-1-b) was added thereto over a period of 20 minutes. After stirring at 5°C for 20 minutes, the mixture was further stirred at 23°C for 4 hours. After cooling to 5°C, 10 parts of ion-exchanged water was added, and then 5 parts of 28% aqueous ammonia solution was added. The solution was neutralized by adding 1 part of the hexane and obtained a solution containing the salt represented by formula (I-193-c). 4.00 parts of a salt represented by formula (I-1-d) to a solution containing a salt represented by formula (I-1-c). A mixed solution of 20 parts of chloroform and 20 parts of toluene was added, and the mixture was stirred at 23°C for 18 hours, followed by separation. To the organic layer was added 20 parts of ion-exchanged water, and the mixture was stirred and separated. This water washing was repeated five times. The obtained organic layer was concentrated, and 30 parts of tert-butyl methyl ether was added to the obtained residue. The mixture was stirred and filtered to obtain 3.92 parts of the salt represented by the formula (I-193). MASS(ESI(+)Spectrum):M + 319.1 MASS(ESI(-)Spectrum):M - 245.0

[0244] Resin synthesis The compounds (monomers) used in the synthesis of resin (A) are shown below. are referred to as "monomer (a1-1-3)" etc. according to their formula numbers. TIFF2025188278000146.tif79164

[0245] Synthesis Example 11 [Synthesis of Resin A1] As the monomers, the monomer (a1-4-2), the monomer (a1-1-3) and the 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, Furthermore, this monomer mixture was mixed with 1.5 times by mass of methyl methyl ester based on the total mass of all monomers. Isobutyl ketone was mixed in the resulting mixture, and azobisisobutyronite was added as an initiator. The amount of methyl acrylate was 7 mol % based on the total number of moles of all monomers. The polymerization was carried out by heating at 40°C for about 5 hours. An aqueous acid solution was added, and the mixture was stirred for 6 hours, followed by separation. 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) having the following structural units was obtained in a yield of 78%. This is what we do. TIFF2025188278000147.tif29126

[0246] Synthesis Example 12 [Synthesis of Resin A2] As the monomers, the monomer (a1-4-2) and the monomer (a1-2-6) were used. The molar ratio of monomer (a1-4-2):monomer (a1-2-6) was 38:62. Further, to this monomer mixture, 1.5 times by mass of methyl isobutyl ketone was mixed with the resulting mixture. Azobisisobutyronitrile was added at 7 mol% relative to the total moles of all monomers. The mixture was then heated at 85°C for approximately 5 hours to carry out polymerization. An aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred for 6 hours, followed by separation of the resulting organic layer. The resin was poured into a large amount of n-heptane to precipitate, and then filtered and recovered to obtain a weight average The molecular weight is approximately 5.4 x 10 3 Resin A2 (copolymer) was obtained in a yield of 89%. has the following structural unit: TIFF2025188278000148.tif2887

[0247] Synthesis Example 13 [Synthesis of Resin A3] As the monomer, the monomer (a1-4-2), the monomer (a1-6-1) and the monomer (a3-2-1) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-x ): Monomer (a3-2-1)) were mixed in a ratio of 38:31:31, and then Then, 1.5 times by mass of methyl isopropyl alcohol was added to this monomer mixture based on the total mass of all monomers. The resulting mixture was mixed with azobisisobutyronitrile as an initiator. was added so that the amount was 7 mol% relative to the total number of moles of all monomers, and the mixture was heated at 85°C for approximately Polymerization was carried out by heating for 5 hours. After that, p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution. The solution was added, and the mixture was stirred for 6 hours, followed by separation. The obtained organic layer was poured into a large amount of n-heptane. The resin was precipitated, filtered, and collected to obtain a polymer with a weight-average molecular weight of approximately 5.9 × 10 3 Yes Resin A3 (copolymer) was obtained in a yield of 88%. This resin A3 has the following structural units: It is something. TIFF2025188278000149.tif49133

[0248] Synthesis Example 14 [Synthesis of Resin A4] As the monomer, monomer (a1-4-2), monomer (a1-1-2), monomer ( a1-2-5), monomer (a2-1-1) and monomer (a3-1-1), Molar ratio [monomer (a1-4-2):monomer (a1-1-2):monomer (a1-2- 5): Monomer (a2-1-1): Monomer (a3-1-1) The monomer mixture was mixed in a ratio of 0:13, and the total amount of all monomers was then added to the monomer mixture. Methyl isobutyl ketone was added in an amount of 1.5 times by mass relative to the mass of the resulting mixture. As an initiator, 7 mol of azobisisobutyronitrile was used relative to the total number of moles of all monomers. %, and the mixture was heated at 85°C for about 5 hours to carry out polymerization. A p-toluenesulfonic acid aqueous solution was added to the polymerization reaction solution, and the mixture was stirred for 6 hours, followed by separation. The organic layer was poured into a large amount of n-heptane to precipitate the resin, which was then filtered and collected. , weight-average molecular weight is about 5.5 × 10 3 Resin A4 (copolymer) was obtained in a yield of 85%. This resin A4 has the following structural units: TIFF2025188278000150.tif34164

[0249] Synthesis Example 15 [Synthesis of Resin AX1] As the monomers, the monomer (a1-6-1) and the monomer (a3-2-1) were used. The molar ratio of monomer (a1-x):monomer (a3-2-1) is 50:50. Mix as shown above, and add propylene glycol monomethyl ether acetate in an amount 1.5 times the total amount of monomers. acetate was added to form a solution. Azobisisobutyronitrile and methyl ... and azobis(2,4-dimethylvaleronitrile) in an amount of 1.5 ml each based on the total amount of monomers. 4.5 mol% and 4.5 mol% of acetic acid were added, and the mixture was heated at 75°C for about 5 hours. The mixture was poured into a large amount of a mixed solvent of methanol and water to precipitate the resin, which was then filtered. The obtained resin is added to a methanol / water mixed solvent, repulped, and then filtered. The preparation procedure was repeated twice to obtain a weight-average molecular weight of 5.7 × 10 3 Resin AX1 was obtained in a yield of 78%. Resin AX1 has the following structural units: TIFF2025188278000151.tif49105

[0250] Synthesis Example 16 [Synthesis of Resin AX2] As the monomers, monomer (a1-1-2), monomer (a1-2-5), monomer ( Monomer (a2-1-1) and monomer (a3-1-1) were used, and the molar ratio [monomer (a1-1 -2): Monomer (a1-2-5): Monomer (a2-1-1): Monomer (a3-1- 1)) was mixed in a ratio of 5:42:32:21, and a protease agent 1.5 times the total amount of monomers was added. Propylene glycol monomethyl ether acetate was added to prepare a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) as initiators ) were added in an amount of 1.5 mol % and 4.5 mol % based on the total amount of monomers, respectively, and these were mixed for 7 The mixture was heated at 5°C for about 5 hours. The resulting reaction mixture was poured into a large amount of a mixed solvent of methanol and water. The resin was precipitated with ethanol and filtered. The resin was added to a methanol / water mixed solvent. The product was purified twice by adding cellulose, repulping, and filtering, resulting in a weight-average molecular weight of 5.7 x 1 0 3 Resin AX2 was obtained in a yield of 77%. This resin AX2 has the following structural units: is. TIFF2025188278000152.tif34144

[0251] <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]

[0252] <Resin> A1 to A4, AX1, AX2: Resin A1 to Resin A4, Resin AX1, Resin AX2 <Salt (I)> I-1: A salt represented by formula (I-1) I-2: A salt represented by formula (I-2) I-3: A salt represented by formula (I-3) I-4: Salt represented by formula (I-4) I-5: A salt represented by formula (I-5) I-6: Salt represented by formula (I-6) I-37: A salt represented by formula (I-37) I-39: A salt represented by formula (I-39) I-48: A salt represented by formula (I-48) I-49: A salt represented by formula (I-49) I-75: A salt represented by formula (I-75) I-83: ​​A salt represented by formula (I-83) I-121: A salt represented by formula (I-121) I-145: A salt represented by the formula (I-145) I-147: A salt represented by formula (I-147) I-193: A salt represented by the formula (I-193) <Quencher (C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025188278000154.tif3546<solvent> Propylene glycol monomethyl ether acetate 400 parts Propylene glycol monomethyl ether 100 parts γ-butyrolactone 5 parts

[0253] (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 using a resist composition. The layer was spin-coated to a thickness of 0.04 μm. The substrate was prebaked on the sheet 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 subjected to electron beam lithography using an electron beam lithography machine (ELS-F1 manufactured by Elionix Co., Ltd.). Using "25 125 keV", the exposure dose was changed stepwise to directly draw a contact hole pattern (hole pitch 40 nm / hole diameter 17 nm). After exposure, post-exposure bake was performed on a hot plate at the temperature shown in the "PEB" column of Table 2 for 60 seconds, followed by paddle development in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 60 seconds to obtain a resist pattern.

[0254] In the resist pattern obtained after development, the exposure dose at which the formed hole diameter became 17 nm was defined as the effective sensitivity.

[0255] <CD Uniformity (CDU) Evaluation> At the effective sensitivity, the hole diameter of the pattern formed with a hole diameter of 17 nm was measured 24 times for each hole, and the average value was defined as the average hole diameter of one hole. The average hole diameter of the pattern formed with a hole diameter of 17 nm within the same wafer was measured at 400 locations and used as the population to calculate the standard deviation. The results are shown in Table 3. The numerical values in the table indicate the standard deviation (nm). [[ID=##]]

Table 3

Industrial Applicability

[0256] The resist composition of the present invention can obtain a resist pattern having good CD uniformity (CDU), and thus is suitable for semiconductor microfabrication and is extremely useful industrially. <##>

Claims

1. A salt represented by formula (IA): [In formula (IA), R 1 and R 2 each independently represents a hydrogen atom, a hydroxy group, or a hydrocarbon group having 1 to 12 carbon atoms, and —CH 2 - may be replaced by -O- or -CO-. m and n each independently represent 1 or 2; When m is 2, two R 2 are the same or different, and when n is 2, two R 1 are the same or different. Ar １ represents a naphthyl group which may have a substituent. X ０’ represents a single bond, —O— or —S—. Q 1 and Q 2 each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R ３Ａ represents a branched alkyl group having 3 to 6 carbon atoms.

2. Ar １ is a naphthyl group which may have an alkyl group having 1 to 8 carbon atoms (provided that the —CH ２ The salt according to claim 1, wherein - may be replaced by -O- or -CO-.

3. R １ and R ２ 3. The salt according to claim 1 or 2, wherein is a hydrogen atom, and n and m are 2.

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