Resist composition and method for producing resist pattern

Abstract

To provide a resist composition from which a resist pattern having good CD uniformity (CDU) can be produced.SOLUTION: The resist composition contains: a resin containing a structural unit represented by formula (a2-A) and a structural unit having an acid-labile group; and a salt represented by formula (I). [In the formula (I), Q1 and Q2 each represent an F atom or a perfluoroalkyl group; X1 and X2 each represent -CO-O-, -O-CO- or the like; L1 represents a linear alkanediyl group; R3' represents an alicyclic hydrocarbon group; the alicyclic hydrocarbon group does not have an alkyl group; the alicyclic hydrocarbon group has one or more substituents, or one or more -CH2- groups contained in the alicyclic hydrocarbon group are substituted with -O-, -S- or the like; and Z+ represents an organic cation.]SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Patent Document 1 describes a resin having a structural unit derived from a compound represented by the following formula, and a polymer having a structural unit derived from a compound represented by the following formula: The resist composition contains a salt represented by the following formula as an acid generator: TIFF2025134963000001.tif59132 [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-16794 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). TIFF2025134963000002.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 bond to 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.] TIFF2025134963000003.tif22131 [In formula (I), Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a methyl group. R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, or a perfluorinated group having 1 to 6 carbon atoms. represents an orthoalkyl group. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R 1 and R 2 are mutual may be the same or different. X 1 and X 2 are each independently *-CO-O-, *-O-CO-, *-O-CO- represents O- or *-O-, and * represents C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) and R 1 and represents the binding site of L 1 represents an alkanediyl group having 1 to 12 carbon atoms. 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. Z + represents an organic cation. [2]R 3 an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent (the alicyclic hydrocarbon -CH2- contained in the hydrogen hydride group is replaced by -O-, -S-, -SO2- or -CO-. or an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent. The resist composition according to [1]. [3]L 1 is a linear alkanediyl group having 2 to 12 carbon atoms [1] or [2] A resist composition according to claim 1. [4] 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 [3 10. The resist composition according to claim 9, wherein TIFF2025134963000004.tif4291 [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently -O- or -O-(CH2) k1 -CO-O- In this case, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a4 and Ra5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, represents a hydrocarbon group of the formula: m1 represents an integer of 0 to 14. n1 represents an integer of 0 to 10. n1' represents an integer of 0 to 3. [5] 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 [4], [6] (1) A process for applying the resist composition according to any one of [1] to [5] 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. [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 For those which can have both structures, either one is acceptable. It means a group in which two or more of the indicated groups are bonded, and the valence of these groups changes appropriately depending on the bonding form. "Derived from" or "derived from" refers to a polymerizable C=C This means that the bond becomes a -CC- group by polymerization. When stereoisomers exist, all Includes stereoisomers. 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)> 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 a51The 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.

[0010] * -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-OA a52 -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.

[0011] 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.

[0012] 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—.

[0013] 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.

[0014] 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.

[0015] 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 structural unit 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 ( a2-2-1), a structural unit represented by formula (a2-2-3), or a structural unit represented by formula (a In the structural unit represented by (a2-A), R a50 Equivalent to It is preferable that the structural unit is a structural unit in which a methyl group is substituted with a hydrogen atom. TIFF2025134963000005.tif42166

[0016] 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 %. 65 mol %, and even more preferably 20 to 65 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.

[0017] 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).

[0018] <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. TIFF2025134963000006.tif1989[In formula (1), R a1 , R a2 and R a3 are each independently an alkyl group having 1 to 8 carbon atoms. , an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a group combining these, or R a1 and R a2 are bonded to each other and together with the carbon atoms to which they are bonded form alicyclic hydrocarbons having 3 to 20 carbon atoms. Form a group. ma and na each independently represent 0 or 1, and at least one of ma and na represents 1. * denotes a binding site.] TIFF2025134963000007.tif2171[In formula (2), R a1’ and R a2’ are each independently a hydrogen atom or a group having 1 to 12 carbon atoms, represents a hydrocarbon group, and R a3’ represents a hydrocarbon group having 1 to 20 carbon atoms, or R a2’ and R a3’ are bonded to each other to form, together with the carbon atoms to which they are bonded and X, a heterocyclic group having 3 to 20 carbon atoms. The —CH2— contained in the hydrocarbon group and the heterocyclic group is replaced with —O— or —S—. It may be replaced. X represents an oxygen atom or a sulfur atom. na' represents 0 or 1. * represents a bond.]

[0019] R a1 , R a2 and R a3 Examples of the alkyl group in the formula (I) include a methyl group, an ethyl group, a propyl group, Examples include a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. R a1 , R a2 and R a3 The alicyclic hydrocarbon group in may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, and a cyclohexyl group. cycloalkyl groups such as butyl and cyclooctyl groups. Examples of the substituent include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following group ( * represents a bond.) etc. a1 ~R a3 The number of carbon atoms in the alicyclic hydrocarbon group is preferably Usually 3 to 16. TIFF2025134963000008.tif9147 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 The alicyclic hydrocarbon group preferably has 3 carbon atoms. ~12. * indicates the bonding site with -O-. TIFF2025134963000009.tif30139

[0020] R a1’ , R a2’ and R a3’ The hydrocarbon group in the formula (I) may be an alkyl group, an alicyclic hydrocarbon group, or the like. groups, aromatic hydrocarbon groups, and groups formed by combining these groups. . The alkyl group and the alicyclic hydrocarbon group are represented by R a1 , R a2 and R a3 The same groups as those listed in It can be obtained. 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 group), aralkyl group (e.g., benzyl group), alkyl group Aromatic hydrocarbon groups (p-methylphenyl group, p-tert-butylphenyl group, tolyl group) , xylyl group, cumenyl group, mesityl group, 2,6-diethylphenyl group, 2-methyl-6 -ethylphenyl group, etc.), aromatic hydrocarbon groups with alicyclic hydrocarbon groups (p-cyclohexyl phenyl group, p-adamantylphenyl group, etc.), aryl-cycloalkyl group (phenyl cyclohexyl group, etc.). R a2’ and R a3’ are bonded to each other and form a heterocyclic group together with the carbon atoms to which they are bonded and X. When forming -C(R a1’ )(R a2’ )-XR a3’ Examples of the group include the following: * indicates the bond position. TIFF2025134963000010.tif19130R a1’ and Ra2’ At least one of these is preferably a hydrogen atom. na' is preferably 0.

[0021] 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 na= 1. The group is preferably a tert-butoxycarbonyl group. 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. TIFF2025134963000011.tif74158

[0022] Specific examples of group (2) include the following groups: * represents a binding site. TIFF2025134963000012.tif67153

[0023] 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.

[0024] 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.

[0025] 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. TIFF2025134963000013.tif42137 [In formula (a1-0), formula (a1-1) and formula (a1-2), L a01 , L a1 and L a2 are each independently -O- or * -O-(CH2) k1 -CO represents —O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a01 , R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a02 , R a03 and R a04 are 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 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic group having 3 to 18 carbon atoms, represents a hydrocarbon group of the formula: 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.

[0026] 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 -CO- O- (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 the like Examples of the group formed by combining these include R a1 ~R a3 Examples of the groups include the same groups as those listed in the above. 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 a7 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably More preferably, it is a methyl group, an ethyl group, or an isopropyl group, and even more preferably, it is an ethyl group. Or an isopropyl group. R a02 , R a03 and R a04 The alicyclic hydrocarbon group preferably has 5 to 12 carbon atoms, More preferably, it is 5 to 10. The group 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 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably methyl group, an ethyl group, or an isopropyl group, and more preferably an ethyl group or an isopropyl group. is. 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.

[0027] 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 Methionine equivalent The structural units of the formula (a1-0-1) to the formula (a1-0) are examples of the structural units in which a methyl group is replaced with a hydrogen atom. -10) is preferred. TIFF2025134963000014.tif65159

[0028] 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 Equivalent to Structural units in which the methyl group is replaced with a hydrogen atom are preferred, and those represented by the formulas (a1-1-1) to ( A structural unit represented by any one of a1-1-4) is more preferred. TIFF2025134963000015.tif43119

[0029] 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. TIFF2025134963000016.tif36155

[0030] When the resin (A) contains the structural unit (a1-0), the total structural units of the resin (A) are It is usually 5 to 60 mol %, preferably 5 to 50 mol %, more preferably 10 to 40 It is in mole percent. 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 95 mol % based on the total structural units of the resin (A), and preferably It is preferably 15 to 90 mol %, more preferably 20 to 85 mol %, and even more preferably Preferably, it is 25 to 80 mol %, and even more preferably, it is 30 to 75 mol %.

[0031] 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)"). TIFF2025134963000017.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.]

[0032] R a32 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 a33Examples 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 a35 and 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: TIFF2025134963000018.tif10151Aromatic 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.

[0033] 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. Ra34 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.

[0034] 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 In accordance with A structural unit in which the corresponding hydrogen atom is replaced by a methyl group is preferred, and a structural unit represented by the formula (a 1-4-1) to (a1-4-5), and structural units represented by formula (a1-4-10) Examples include: TIFF2025134963000019.tif68157

[0035] 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 10 to 95 mol %, more preferably 15 to 90 mol %, based on the total of the units. It is more preferable that the content is 20 to 85 mol %, and even more preferable that the content is 20 to 70 mol %. It is even more preferable that the content is 20 to 60 mol %, and it is particularly preferable that the content is 20 to 60 mol %.

[0036] 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. TIFF2025134963000020.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.

[0037] 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—.

[0038] 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. TIFF2025134963000021.tif32133

[0039] 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.

[0040] Further, examples of the structural unit (a1) include the following structural units. TIFF2025134963000022.tif30162

[0041] 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.

[0042] Resin (A) is a copolymer consisting of only structural units (a2-A) and structural units (a1). or may contain one or more structural units other than the structural unit (a2-A) and the structural unit (a1). The structural unit other than the structural unit (a2-A) and the structural unit (a1) may be a copolymer. The structural unit may be a structural unit having a halogen atom other than a structural unit having an acid labile group. structural unit (hereinafter sometimes referred to as "structural unit (a4)"), a structural unit not having an acid labile group (hereinafter sometimes referred to as "structural unit (s)"), a structural unit having a non-leaving hydrocarbon group (hereinafter (hereinafter sometimes referred to as "structural unit (a5)"), a structural unit that decomposes upon exposure to generate acid (hereinafter sometimes referred to as "structural unit (II)"), and other monomers known in the art. Examples include structural units derived from When the resin (A) contains a structural unit represented by the formula (a4) and / or (a5) described below ( Hereinafter, this may be referred to as "resin (AX)"). The content of I) is preferably 5 to 75% by weight based on the total amount of all structural units of the resin (X) of the present invention. % by mole, more preferably 10 to 70 mol %, and further preferably 10 to 65 mol %. % by mole, and particularly preferably 10 to 60 mol %.

[0043] <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.

[0044] <Structural unit (a2)> The hydroxy group of the structural unit (a2) may be an alcoholic hydroxy group or a phenolic hydroxy group. It may also be a hydroxyl group. When a resist pattern is produced from the resist composition of the present invention, KrF is used as the exposure light source. High energy rays such as excimer laser (248 nm), electron beam, or EUV (extreme ultraviolet) are used. In this case, the structural unit (a2) may be a structural unit having a phenolic hydroxy group ( It is preferable to use a2). In addition, it is also preferable to use an ArF excimer laser (193 nm) or the like. In this case, the structural unit (a2) may be a structural unit (a2) having an alcoholic hydroxy group. ) is preferred, and it is more preferred to use the structural unit (a2-1) described below. As a2), one kind may be contained alone, or two or more kinds may be contained.

[0045] 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: TIFF2025134963000023.tif3955 formula (a2-1), L a3is -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.

[0046] 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.

[0047] 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. TIFF2025134963000024.tif54149

[0048] 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 1 to 20 mol %, and even more preferably The content is usually 1 to 10 mol %.

[0049] <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:

[0050] 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. TIFF2025134963000025.tif51161 [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-L a9 -O- vinegar. L a8and 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.]

[0051] R a21 , R a22 , R a23 and R a25 The aliphatic hydrocarbon group in butyl, sec-butyl and tert-butyl groups. Examples include alkyl groups such as t-butyl groups. R a24 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.

[0052] 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.

[0053] 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.

[0054] 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)'. TIFF2025134963000026.tif4051(in the formula, R a24 , L a7 has the same meaning as above.)

[0055] 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 Structural units that replace elementary atoms are preferred. TIFF2025134963000027.tif117167

[0056] 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 10 to 65 mol %, more preferably The content is preferably 10 to 60 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 5 to 20 mol %.

[0057] <Structural unit (a4)> Examples of the structural unit (a4) include the following structural units. TIFF2025134963000028.tif2859[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—. R 42 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.

[0058] 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. TIFF2025134963000029.tif10146 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.

[0059] 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). TIFF2025134963000030.tif4248[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 3a is a perfluoroalkanediyl group having 1 to 8 carbon atoms or a perfluoroalkanediyl group having 3 to 12 carbon atoms. represents a fluorocycloalkanediyl group. R 64 represents a hydrogen atom or a fluorine atom.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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. TIFF2025134963000031.tif95166

[0064] TIFF2025134963000032.tif4866[In formula (a4-1), R a41 represents a hydrogen atom or a methyl group. R a42 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, 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 a41 and R a42 At least one of the following is a substituent: It contains a halogen atom (preferably a fluorine atom). TIFF2025134963000033.tif1487 [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 ]

[0065] 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.

[0066] 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. TIFF2025134963000034.tif11160The 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 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.

[0067] 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. TIFF2025134963000035.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.

[0068] A a45 The 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): TIFF2025134963000036.tif11160The 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.

[0069] 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.

[0070] 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). TIFF2025134963000037.tif872[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.]

[0071] A a46 The 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 Aa 47 is more preferably a cyclohexyl group or an adamantyl group.

[0072] 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). TIFF2025134963000038.tif14160

[0073] 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.

[0074] 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.

[0075] 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 TIFF2025134963000039.tif46140

[0076] 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: TIFF2025134963000040.tif93135

[0077] TIFF2025134963000041.tif132150

[0078] 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). TIFF2025134963000042.tif4156[In formula (a4-2), Rf5 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.]

[0079] 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.

[0080] 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.

[0081] TIFF2025134963000043.tif5671[In formula (a4-3), R f7 represents a hydrogen atom or a methyl group. L 5 represents an alkanediyl group having 1 to 6 carbon atoms. A f13 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom. vinegar. X f12 represents *-O-CO- or *-CO-O- (* represents A f13 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.

[0082] L 5 The alkanediyl group in a41 The same as those exemplified for the alkanediyl group The following groups are mentioned:

[0083] 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.

[0084] 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.

[0085] In formula (a4-3), L 5 is preferably an ethylene group. A f13 The 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 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.

[0086] Examples of the structural unit represented by formula (a4-3) include the structural units represented by formula (a4-1'-1) to formula (a 4-1'-11) are structural units represented by the following formulas. 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.

[0087] The structural unit (a4) also includes a structural unit represented by formula (a4-4). TIFF2025134963000044.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.]

[0088] 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 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.

[0089] 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.

[0090] 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. TIFF2025134963000045.tif87160

[0091] 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.

[0092] <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): . TIFF2025134963000046.tif3454[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—.

[0093] 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.

[0094] L 55The 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.

[0095] 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. TIFF2025134963000047.tif18165 formula (L1-1), X x1 represents *-O-CO- or *-CO-O- (* represents L X1 ) . L x1 represents a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. L x2 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 15 carbon atoms. However, L x1 and L x2 The total number of carbon atoms is 16 or less. In formula (L1-2), L x3 represents a divalent aliphatic saturated hydrocarbon group having 1 to 17 carbon atoms. L x4represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 16 carbon atoms. However, 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.

[0096] 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.

[0097] Examples of the group represented by formula (L1-1) include the divalent groups shown below. TIFF2025134963000048.tif53136

[0098] Examples of the group represented by formula (L1-2) include the divalent groups shown below. TIFF2025134963000049.tif23130

[0099] Examples of the group represented by formula (L1-3) include the divalent groups shown below. TIFF2025134963000050.tif15147

[0100] Examples of the group represented by formula (L1-4) include the divalent groups shown below. TIFF2025134963000051.tif26114

[0101] L 55is preferably a single bond or a group represented by formula (L1-1).

[0102] 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. TIFF2025134963000052.tif77157

[0103] TIFF2025134963000053.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.

[0104] <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.

[0105] 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'). TIFF2025134963000054.tif3189 [In formula (II-2-A'), X III3 represents a divalent saturated hydrocarbon group having 1 to 18 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 group are replaced by halogen atoms, alkyl groups having 1 to 10 carbon atoms which may have halogen atoms. 6 may be substituted with an alkyl group or a hydroxy group. A x1 represents an alkanediyl group having 1 to 8 carbon atoms, and the hydrogen atoms contained in the alkanediyl group The atom may be substituted with a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. . RA - represents a sulfonate group or a carboxylate group. R III3 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: ZA + represents an organic cation.

[0106] R III3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R III3 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and 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 and which is represented by Examples include: A x1 Examples of the alkanediyl group having 1 to 8 carbon atoms represented by the formula (I) include a methylene group, an ethylene group, Propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group , hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4-diyl group yl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, etc. . A x1 Examples of the optionally substituted perfluoroalkyl group having 1 to 6 carbon atoms include: Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoro Isopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert -butyl group, perfluoropentyl group, perfluorohexyl group, and the like. X III3 The divalent saturated hydrocarbon group having 1 to 18 carbon atoms represented by the formula (I) is a straight-chain or branched alkyl group. and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. It may also be a combination. 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 cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohetane-1,3-diyl group, Cycloalkanediyl groups such as cyclohexan-1,4-diyl group and cyclooctane-1,5-diyl group norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane Divalent polycyclic alicyclic saturated carbons such as benzophenone-1,5-diyl and adamantane-2,6-diyl groups Examples thereof include a hydrogen hydride group. -CH2- in saturated hydrocarbon groups is replaced with -O-, -S- or -CO- Examples of such groups include divalent groups represented by 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 formulas, * and ** represent bonding positions, is A X1 represents the bonding position with TIFF2025134963000055.tif145161

[0107] 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.

[0108] ZA + The organic cation represented by the formula (I) may be the same as the cation represented by the formula (I) described below. Examples include:

[0109] The structural unit represented by formula (II-2-A') is a structural unit represented by formula (II-2-A) It is preferable that: TIFF2025134963000056.tif38108 [In formula (II-2-A), R III3 , X III3 and ZA + has the same meaning as above. z2A represents an integer of 0 to 6. R III2 and R III4 are each independently a hydrogen atom, a fluorine atom, or a phenyl group having 1 to 6 carbon atoms. When z2A is 2 or more, multiple R III2 and R III4 are mutually They may be the same or different. Q a and Q b are each independently a fluorine atom or a perfluoroalkane having 1 to 6 carbon atoms. represents a alkyl group.] R III2 , R III4 , Q a and Q b and a perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: As for the aforementioned Q b1 The perfluoroalkyl group having 1 to 6 carbon atoms represented by the formula: It can be obtained.

[0110] 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 . TIFF2025134963000057.tif5576 [In formula (II-2-A-1), R III2 , R III3 , R III4 , Q a , Q b and ZA + has the same meaning as above. R III5 represents a saturated hydrocarbon group having 1 to 12 carbon atoms. z2A1 represents an integer of 0 to 6. X I2 represents a divalent saturated hydrocarbon group having 1 to 11 carbon atoms, and -CH2- may be replaced by -O-, -S- or -CO-, and the saturated hydrocarbon A hydrogen atom contained in the group may be substituted with a halogen atom or a hydroxy group. 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, a propane group, and a propyl group. propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl methyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl groups. Examples include straight-chain or branched alkyl groups such as a decyl group. X I2 As the divalent saturated hydrocarbon group represented by X III3 Divalent saturated hydrocarbons represented by The same groups as those mentioned above can be mentioned.

[0111] The structural unit represented by formula (II-2-A-1) is preferably a structural unit represented by formula (II-2-A-2). More preferred are structural units in which TIFF2025134963000058.tif5287 [In formula (II-2-A-2), R III3 , R III5 and ZA + has the same meaning as above. mA and nA each independently represent 1 or 2.]

[0112] 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. TIFF2025134963000059.tif86163

[0113] 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. TIFF2025134963000060.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 Reach BiR II3 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R II4 is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. represents an alkyl group. A - represents an organic anion. R II1 Examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by the formula (I) include a phenylene group and and naphthylene groups. R II2 and R II3 Examples of the hydrocarbon group represented by the formula (I) include an alkyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and aromatic hydrocarbon groups and groups formed by combining these groups. R a1’ , R a2’ and R a3’ The hydrocarbon groups are the same as those in the above. R II4 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Atoms and the like can be mentioned. R II4 The alkyl group having 1 to 6 carbon atoms which may have a halogen atom and is represented by the formula: , R a8The same as an alkyl group having 1 to 6 carbon atoms which may have a halogen atom and which is represented by Examples include: A II1 Examples of the divalent linking group represented by the formula (I) include a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. The -CH2- contained in the divalent saturated hydrocarbon group may be -O-, -S- or Specifically, X may be replaced with -CO-. III3 2 of carbon atoms 1 to 18 represented by The examples of the saturated hydrocarbon groups include the same as those of the 4-valent saturated hydrocarbon groups.

[0114] 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, a trifluoromethyl group, etc. Examples include replaced structural units. TIFF2025134963000061.tif85130

[0115] 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 the sulfonate anion is preferably a sulfonate anion as described below. More preferably, it is an anion contained in the salt represented by formula (B1).

[0116] A - Examples of the sulfonylimide anion represented by the formula (I) include the following. TIFF2025134963000062.tif43135

[0117] Examples of sulfonylmethide anions include the following: TIFF2025134963000063.tif29123

[0118] Examples of carboxylate anions include the following: TIFF2025134963000064.tif42154

[0119] Examples of the structural unit represented by formula (II-1-1) include the structural units represented by the following formula: can be done. TIFF2025134963000065.tif90154

[0120] 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 %.

[0121] The resin (A) may have structural units other than the above-mentioned structural units. The moieties include structural units known in the art.

[0122] 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 (a1-0), a structural unit (a1-1) and a structural unit (a1-2). The structural unit (a1-2) (preferably the structure having a cyclohexyl group and a cyclopentyl group) The structural unit (a1-) is preferably at least one selected from the group consisting of 1) and structural unit (a1-2) (preferably a cyclohexyl group and a cyclopentyl group) and more preferably at least one selected from the group consisting of the structural units 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

[0123] 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.

[0124] <Resins other than Resin (A)> The resist composition of the present invention may contain a resin other than the resin (A) in combination. Examples of 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.)

[0125] 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).

[0126] 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).

[0127] 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.

[0128] 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.

[0129] <Salt represented by formula (I)> The resist composition of the present invention may be referred to as a salt represented by formula (I) (hereinafter, "salt I"). ) contains. 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)". TIFF2025134963000066.tif21126 [In formula (I), Q 1 and Q 2 are each independently a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. represents a methyl group. R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, or a perfluorinated group having 1 to 6 carbon atoms. represents an orthoalkyl group. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R 1 and R 2 are mutual may be the same or different. X 1 and X 2 are each independently *-CO-O-, *-O-CO-, *-O-CO- represents O- or *-O-, and * represents C(R 1 )(R 2 ) or C(Q 1 )(Q 2 ) and R 1 and represents the binding site of L 1 represents an alkanediyl group having 1 to 12 carbon atoms. 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. Z + represents an organic cation.

[0130] Q 1 , Q 2 , R 1 and R 2 The perfluoroalkyl group is a trifluoromethyl group. , perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisopropyl group Fluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, Examples include a perfluoropentyl group and a perfluorohexyl group. Q 1 and Q 2 are each independently preferably a trifluoromethyl group or a fluorine atom. and more preferably a fluorine atom. R 1 and R 2are each independently preferably a hydrogen atom or a fluorine atom. Preferably, z is 0 or 1.

[0131] X 1 and X 2 *-CO-O- or *-O-CO-O-(* is C(R 1 )(R 2 )also is C(Q 1 )(Q 2 ) and R 1 It is preferable that the bond is

[0132] L 1 Examples of the alkanediyl group represented by the formula (I) include a methylene group, an ethylene group, a propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1 ,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane- 1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group a linear alkanediyl group of the decane-1,12-diyl group; and Ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group group, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane- 1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group and branched alkanediyl groups such as a 2-methylbutane-1,4-diyl group.

[0133] L 1 is preferably a linear alkanediyl group having 2 to 12 carbon atoms, and , butane-1,4-diyl group, hexane-1,6-diyl group, octane-1,8-diyl group It is more preferred that the aryl group is a decane-1,10-diyl group, or a dodecane-1,12-diyl group. It's nice.

[0134] R 3 Examples of the hydrocarbon group represented by the formula (I) include chain hydrocarbon groups such as alkyl groups, alicyclic hydrocarbon groups, etc. groups, aromatic hydrocarbon groups, and groups formed by combining these groups. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, Isobutyl group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, etc. The alkyl group preferably has 1 to 12 carbon atoms, and more preferably has 1 to 12 carbon atoms. Preferably, it is 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. be. The alicyclic hydrocarbon group may be any of monocyclic, polycyclic and spirocyclic groups, and may be saturated or unsaturated. The alicyclic hydrocarbon group may be a cyclopropyl group, a cyclobutyl group, ... Cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group group, monocyclic cycloalkyl groups such as cyclododecyl group, norbornyl group, adamantyl group, etc. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 3 to 100. It is preferably 16, more preferably 3 to 12, and even more preferably 3 to 10. The aromatic hydrocarbon group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl group, and Examples of the alkyl group include aryl groups such as anthryl, anthryl, phenanthryl, and binaphthyl. The aromatic hydrocarbon group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. do. The group comprising a combination of an alkyl group, an alicyclic hydrocarbon group and / or an aromatic hydrocarbon group includes an alicyclic hydrocarbon group. A group that combines a cyclic hydrocarbon group with an alkyl group (e.g., an alicyclic hydrocarbon group-alkane Diyl group, alkyl group, alicyclic hydrocarbon group, alkanediyl group, alkyl group, alicyclic hydrocarbon groups, etc.), groups combining alkyl groups and aromatic hydrocarbon groups (e.g., alkyl Group-aromatic hydrocarbon group-, aromatic hydrocarbon group-alkanediyl group-, alkyl group-aromatic Hydrocarbon groups (alkanediyl groups, etc.), alicyclic hydrocarbon groups and aromatic hydrocarbon groups Combined groups (e.g., alicyclic hydrocarbon group-aromatic hydrocarbon group, aromatic hydrocarbon group-alicyclic Hydrocarbon groups such as -. Aromatic hydrocarbon groups -alkanediyl groups-* include alkanediyl groups such as benzyl and phenethyl groups. Examples include ralkyl groups. Examples of alkyl groups - aromatic hydrocarbon groups - include tolyl, xylyl, and cumenyl groups. Examples include: 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 (-1-methyl-yl)-1-methylethyl. 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 aromatic hydrocarbon groups - alicyclic hydrocarbon groups - include phenylcyclohexyl groups. It can be obtained. Examples of alicyclic hydrocarbon groups - aromatic hydrocarbon groups - include cyclohexylphenyl groups. In the above groups, * represents X 2 represents the binding site with In addition, in the combination, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and chain hydrocarbon groups and two or more of each may be combined. 2 It may be bound to stomach.

[0135] R 3 -CH2- contained in the hydrocarbon group represented by the formula: May be replaced by O2-. R 3 The -CH2- contained in the hydrocarbon group represented by If replaced with O-, -S-, -CO- or -SO2-, the number of carbon atoms before replacement is the number of carbon atoms in the hydrocarbon group.

[0136] Examples of groups in which -CH2- in a hydrocarbon group is replaced with -O- or -CO- include: Hydroxy group (a group in which -CH2- in a methyl group is replaced with -O-), carbo an oxy group (an ethyl group in which -CH2-CH2- is replaced with -O-CO-); Alkoxy group having 1 to 17 carbon atoms (-CH2- contained in alkyl group having 2 to 18 carbon atoms) , -O- substituted), alkoxycarbonyl group having 2 to 17 carbon atoms (groups having 3 to 1 (a group in which -CH2-CH2- in the alkyl group of 8 is replaced with -O-CO-), Alkylcarbonyl groups with 2 to 18 carbon atoms (-CH contained in alkyl groups with 2 to 18 carbon atoms) 2- is replaced by -CO-), alkylcarbonyloxy group having 2 to 17 carbon atoms ( -CH2-CH2- in the alkyl group having 3 to 18 carbon atoms is replaced with -CO-O- a cycloalkoxy group having 3 to 17 carbon atoms, such as a cyclohexyloxy group; cycloalkylalkoxy groups having 4 to 17 carbon atoms, such as butoxycarbonyl groups, alkoxycarbonyloxy groups having 2 to 16 carbon atoms, such as benzoyloxy groups, Examples thereof include an aromatic hydrocarbon group having 7 to 17 carbon atoms-carbonyloxy group. Examples of the alkoxy group having 1 to 17 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a bromine group, and a methyl group. hexyloxy, pentyloxy, hexyloxy, octyloxy, 2-ethylhexyl Examples of such groups include a hydroxyl group, a nonyloxy group, a decyloxy group, and an undecyloxy group. The number of carbon atoms in the alkoxy group is preferably 1 to 11, more preferably 1 to 6, and The most preferred range is 1 to 4. Alkoxycarbonyl groups having 2 to 17 carbon atoms, alkylcarbonyl groups having 2 to 18 carbon atoms, and and the alkylcarbonyloxy group having 2 to 17 carbon atoms is the alkyl or alkoxy group described above. represents a group in which a carbonyl group or a carbonyloxy group is bonded to a group. Examples of the alkoxycarbonyl group having 2 to 17 carbon atoms include a methoxycarbonyl group, an ethoxy group, and carbonyl group, butoxycarbonyl group, etc., and alkylcarbonyl groups having 2 to 18 carbon atoms. Examples of the alkyl group include an acetyl group, a propionyl group, and a butyryl group, and the alkyl group has 2 to 1 carbon atoms. Examples of the alkylcarbonyloxy group of 7 include an acetyloxy group, a propionyloxy group, The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 6. The alkyl group is 11, more preferably 2 to 6, and further preferably 2 to 4. The carbonyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 4. It is 1, more preferably 2 to 6, and further preferably 2 to 4. Alicyclic hydrocarbon groups or -CH2- contained in alicyclic hydrocarbon groups are -O-, -S-, -C Specific examples of the group substituted with O- or -SO2- include the groups represented by formulae (Y1) to (Y41): Preferred are groups represented by formula (Y1) to formula (Y20), formula (Y26), formula (Y27), (Y30), (Y31), (Y39) to (Y41) More preferably, the formula (Y11), the formula (Y15), the formula (Y16), the formula (Y 20), formula (Y26), formula (Y27), formula (Y30), formula (Y31), formula (Y39), or A group represented by formula (Y40), more preferably a group represented by formula (Y11), formula (Y15), formula (Y20), Formula (Y26), Formula (Y27), Formula (Y30), Formula (Y31), Formula (Y39) Or a group represented by formula (Y40). TIFF2025134963000067.tif80157

[0137] R 3 The substituents of the hydrocarbon group represented by the formula (I) include halogen atoms, hydroxy groups (methyl groups), a group in which -CH2- is replaced with -O-), a cyano group, an alkyl group having 1 to 12 carbon atoms alkyl group, carboxy group (-CH2-CH2- contained in the ethyl group is substituted with -O-CO-) substituted), an alkoxy group having 1 to 12 carbon atoms (a group in which -CH2- in the alkyl group is , -O- substituted), alkoxycarbonyl group having 2 to 13 carbon atoms (in alkyl group (a group in which -CH2-CH2- in the formula is replaced with -O-CO-), Alkylcarbonyl group (a group in which -CH2- in an alkyl group is replaced with -CO-) ), alkylcarbonyloxy groups having 2 to 13 carbon atoms (-CH2- contained in the alkyl group) (groups in which -CH2- is replaced by -CO-O-) and combinations of two or more of these groups Examples of such groups include: Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. do. Alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, alkoxy groups having 2 to 13 carbon atoms an alkylcarbonyl group having 2 to 13 carbon atoms and an alkoxycarbonyl group having 2 to 13 carbon atoms; Examples of the alkylcarbonyloxy group include the same groups as those described above.

[0138] R 3 The hydrocarbon group having 1 to 18 carbon atoms and optionally having a substituent, represented by the following formula (I), is preferably a group represented by the following formula (I): An alkyl group having 1 to 6 carbon atoms which may have a substituent (-CH2- contained in the alkyl group) may be replaced by -O- or -CO-), a carbon atom which may have a substituent an alicyclic hydrocarbon group having a number of 3 to 18 (-CH2- contained in the alicyclic hydrocarbon group is -O-, may be replaced by -S-, -SO2- or -CO-.) or has a substituent The aromatic hydrocarbon group having 6 to 18 carbon atoms is preferable, and an adamantyl group, a hydroxyl group, Hydroxyadamantyl group, adamantanone group, adamantane lactone ring group, norbornane a lactone ring group, a group represented by the following formula, or a phenyl group which may have a halogen atom: , more preferably an adamantyl group, a hydroxyadamantyl group, an adamantanone group, The group is a group represented by the following formula or a phenyl group which may have a halogen atom. TIFF2025134963000068.tif1823

[0139] Examples of the anion in the salt (I) include the anions represented by the following formulae (Ia-1) to (Ia-28) Among them, anions represented by formula (Ia-1) to formula (Ia-12), formula ( Anions represented by formula (Ia-18) and formula (Ia-19) are preferred, and anions represented by formula (Ia-1) to formula ( Anions represented by formula (Ia-10), formula (Ia-18) and formula (Ia-19) are more preferred. . TIFF2025134963000069.tif170157

[0140] TIFF2025134963000070.tif185157

[0141] Z + The organic cations include organic onium cations, organic sulfonium cations, Organic iodonium cations, organic ammonium cations, benzothiazolium cations and Among these, organic sulfonium cations are and organic iodonium cations are preferred, with arylsulfonium cations being more preferred. Specifically, the cation represented by any one of formulas (b2-1) to (b2-4) (hereinafter , and may be referred to as "cation (b2-1)" etc. depending on the formula number.

[0142] TIFF2025134963000071.tif46168In 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.

[0143] 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. TIFF2025134963000072.tif11158 In particular, R b9 ~R b12 The alicyclic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably has 4 to 12 carbon atoms.

[0144] 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.

[0145] Examples of aromatic hydrocarbon groups include phenyl, biphenyl, naphthyl, and phenanthryl groups. The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. It may have a group, and an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, xylyl group, group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group , 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and alicyclic carbon Aromatic hydrocarbon groups containing hydrogen groups (p-cyclohexylphenyl group, p-adamantylphenyl group) In addition, the aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. When the alkyl group has a hydrocarbon group, 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 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.

[0146] 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.

[0147] 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. TIFF2025134963000073.tif23144

[0148] 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.

[0149] Among the cations (b2-1) to (b2-4), the cation (b2 -1). Examples of the cation (b2-1) include the following cations. TIFF2025134963000074.tif104147

[0150] TIFF2025134963000075.tif31120

[0151] Examples of the cation (b2-2) include the following cations. TIFF2025134963000076.tif16130

[0152] Examples of the cation (b2-3) include the following cations. TIFF2025134963000077.tif24126

[0153] Examples of the cation (b2-4) include the following cations. TIFF2025134963000078.tif82164

[0154] The salt (I) is a combination of the above-mentioned anion and the above-mentioned organic cation, which are optionally The salt (I) is preferably a salt represented by the formula (Ia-1) to the formula (Ia-9): and a cation (b2-1) or a cation (b2-3). A combination is possible.

[0155] Examples of the salt (I) include salts listed in Table 1. In the table below, each symbol represents the above-mentioned The symbols attached to the structures representing anions and cations are shown. For example, salt (I-1) is a salt represented by the formula (I a-1) and a cation represented by formula (b2-c-1). It tastes like the salt shown below. TIFF2025134963000079.tif31111

[0156] [Table 1] TIFF2025134963000081.tif223154 TIFF2025134963000082.tif223154 TIFF2025134963000083.tif223154 TIFF2025134963000084.tif104154

[0157] Among them, salt (I) is salt (I-1) to salt (I-12), salt (I-18) to salt (I-19). ), Salt (I-25) ~ Salt (I-36), Salt (I-49) ~ Salt (I-60), Salt (I-73 ) ~ Salt (I-84), Salt (I-90) ~ Salt (I-91), Salt (I-97) ~ Salt (I-10 8), Salt (I-121) ~ Salt (I-132), Salt (I-145) ~ Salt (I-156) It is preferable that

[0158] <Acid generator> The acid generator of the present invention is an acid generator containing one kind of salt (I). Alternatively, two or more types of salt (I) may be contained. In addition to the salt (I), the acid generator of the present invention may also include acid generators known in the resist field (hereinafter referred to as "acid generators"). The acid generator (B) may be used alone. Alternatively, two or more of them may be used in combination.

[0159] 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.

[0160] Examples of the acid generator (B) include those disclosed in JP-A-63-26653 and JP-A-55-164824; JP-A-62-69263, JP-A-63-146038, JP-A-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.

[0161] 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. TIFF2025134963000085.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 a methyl group. L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, and the divalent saturated hydrocarbon group The -CH2- contained in the carboxylic acid may be replaced by -O- or -CO-, and the divalent saturated carbon atom The hydrogen atom contained in the hydrogen group may be substituted with a fluorine atom or a hydroxy group. 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-. Z + represents an organic cation.

[0162] Q b1 and Q b2 The perfluoroalkyl group represented by the formula (I) includes a trifluoromethyl group, a perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoro butyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples include a perfluoropentyl group and a perfluorohexyl group. Q b1 and Q b2 are each independently a fluorine atom or a trifluoromethyl group. It is preferable that both are fluorine atoms.

[0163] L b1 The divalent saturated hydrocarbon group in and monocyclic or polycyclic divalent alicyclic saturated hydrocarbon groups. A group formed by combining two or more of these may also be used. Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1 ,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1 ,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, Tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane- 1,15-diyl group, hexadecane-1,16-diyl group and heptadecane-1,17- 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.

[0164] L b1 The -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, the groups represented by formulae (b1-1) to (b1-3) and their specific examples are In the examples of groups represented by formulae (b1-4) to (b1-11), * and ** represent bonding sites. * represents the bond to -Y.

[0165] TIFF2025134963000086.tif21105[In formula (b1-1), L b2 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b3 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group may be replaced by -O- or -CO-. However, L b2 and L b3 The total number of carbon atoms is 22 or less. In formula (b1-2), L b4 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms. L b5 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in the saturated carbon may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group may be replaced by -O- or -CO-. However, L b4 and L b5 The total number of carbon atoms is 22 or less. In formula (b1-3), L b6 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. L b7 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the saturated carbon may be substituted with fluorine atoms or hydroxy groups. The -CH2- contained in the hydrogen hydride group may be replaced by -O- or -CO-. However, L b6 and L b7 The total number of carbon atoms is 23 or less.

[0166] 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 of do. 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 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 hydrogen hydride 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, A hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom or a hydroxy group, The -CH2- contained in the divalent saturated hydrocarbon group is replaced with -O- or -CO-. Good too. L 1 The -CH2- contained in the divalent saturated hydrocarbon group represented by the formula: The substituted group is preferably a group represented by formula (b1-1) or formula (b1-3).

[0167] Examples of formula (b1-1) include groups represented by formulas (b1-4) to (b1-8). It can be obtained. TIFF2025134963000087.tif41107[In formula (b1-4), L b8 represents a single bond or a divalent saturated hydrocarbon group having 1 to 22 carbon atoms, The hydrogen atoms contained in may be substituted with fluorine atoms or hydroxy groups. In formula (b1-5), L b9 represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the divalent saturated hydrocarbon group The -CH2- contained therein 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 hydrogen hydride 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 hydrogen hydride 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 hydrogen hydride 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 hydrogen hydride 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, and the divalent saturated hydrocarbon group The contained -CH2- may be replaced by -O- or -CO-. L b17 represents a divalent saturated hydrocarbon group having 1 to 18 carbon atoms. L b18 represents a single bond or a divalent saturated hydrocarbon group having 1 to 17 carbon atoms, The hydrogen atoms contained in the hydrogen hydride 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. L b8 is preferably a divalent saturated hydrocarbon group having 1 to 4 carbon atoms. L b9 is preferably a divalent saturated hydrocarbon group having 1 to 8 carbon atoms. L b10 is preferably a single bond or a divalent saturated hydrocarbon group having 1 to 19 carbon atoms, and more preferably 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 b14is 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, and more preferably 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, and more preferably Preferably, it is a single bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms.

[0168] 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: TIFF2025134963000088.tif21127[In formula (b1-9), L b19 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, A hydrogen atom contained in the group may be substituted with a fluorine atom. L b20 represents a single bond or a divalent saturated hydrocarbon group having 1 to 23 carbon atoms, The hydrogen atoms contained in the group are substituted with fluorine atoms, hydroxy groups, or alkylcarbonyloxy groups. The —CH2— contained in the alkylcarbonyloxy group may be 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 b21represents 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.

[0169] 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. 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.

[0170] Examples of the group represented by formula (b1-4) include the following. TIFF2025134963000089.tif16138 (* and ** represent binding sites, * represents the binding site with Y.)

[0171] Examples of the group represented by formula (b1-5) include the following. TIFF2025134963000090.tif59138 (* and ** represent binding sites, * represents the binding site with Y.)

[0172] Examples of the group represented by formula (b1-6) include the following. TIFF2025134963000091.tif28163 (* and ** represent binding sites, * represents the binding site with Y.)

[0173] Examples of the group represented by formula (b1-7) include the following. TIFF2025134963000092.tif56140 (* and ** represent binding sites, * represents the binding site with Y.)

[0174] Examples of the group represented by formula (b1-8) include the following. TIFF2025134963000093.tif21132 (* and ** represent binding sites, * represents the binding site with Y.)

[0175] Examples of the group represented by formula (b1-2) include the following. TIFF2025134963000094.tif28140 (* and ** represent binding sites, * represents the binding site with Y.)

[0176] Examples of the group represented by formula (b1-9) include the following. TIFF2025134963000095.tif38125 (* and ** represent binding sites, * represents the binding site with Y.)

[0177] Examples of the group represented by formula (b1-10) include the following. TIFF2025134963000096.tif87155 (* and ** represent binding sites, * represents the binding site with Y.)

[0178] Examples of the group represented by formula (b1-11) include the following. TIFF2025134963000097.tif77150

[0179] 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.

[0180] The alicyclic hydrocarbon group represented by TIFF2025134963000098.tif85166Y is preferably a group represented by formula (Y1) to formula (Y20), 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 an oxygen atom spiro ring such as 40), the alkanediyl group between the two oxygen atoms is It is preferable that the alkanediamine contained in the ketal structure has one or more fluorine atoms. Among the methyl groups, the methylene group adjacent to the oxygen atom is not substituted with a fluorine atom. preferable.

[0181] 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 teeth, Alkyl groups having 1 to 16 carbon atoms, alicyclic hydrocarbon groups having 3 to 16 carbon atoms, aromatic hydrocarbon groups having 6 to 18 carbon atoms and the alkyl group and the alicyclic hydrocarbon group are each a cyclic group or a group in which the alkyl group and the alicyclic hydrocarbon group are combined. The —CH2— contained in the group may be replaced by —O—, —SO2— or —CO—. The hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group are each independently selected from the group consisting of aryl, ... may be substituted with a hydroxy group or a fluorine atom; ja is an integer of 0 to 4; ) and others. 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 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 8 or a group combining these, and the alkyl group and the alicyclic hydrocarbon The -CH2- in the hydrogen hydride group is replaced with -O-, -SO2- or -CO-. and the hydrogen atoms contained in the alkyl group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be may be substituted with a hydroxy group or a fluorine atom; ja is any one of 0 to 4; represents an integer.)

[0182] 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. The aromatic hydrocarbon group may be a chain hydrocarbon group or an alicyclic hydrocarbon group. It may have a hydrocarbon group, and may have an aromatic hydrocarbon group having a chain hydrocarbon group (tolyl group, Xylyl group, cumenyl group, mesityl group, p-ethylphenyl group, p-tert-butylphenyl group phenyl group, 2,6-diethylphenyl group, 2-methyl-6-ethylphenyl group, etc.) and fatty acids Aromatic hydrocarbon groups with cyclic hydrocarbon groups (p-cyclohexylphenyl group, p-adamantine group) phenyl group, etc.). 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.

[0183] Examples of Y include the following: TIFF2025134963000099.tif129150

[0184] 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: TIFF2025134963000100.tif58163

[0185] 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.

[0186] TIFF2025134963000101.tif79147

[0187] TIFF2025134963000102.tif133161

[0188] TIFF2025134963000103.tif102158

[0189] TIFF2025134963000104.tif67155

[0190] TIFF2025134963000105.tif110145

[0191] TIFF2025134963000106.tif125163

[0192] where R i2 ~R i7 are each independently, for example, an alkyl group having 1 to 4 carbon atoms, preferably is a methyl group or an ethyl group. i8 is, for example, a chain hydrocarbon group having 1 to 12 carbon atoms, preferably Preferably, the alkyl group has 1 to 4 carbon atoms, the alicyclic hydrocarbon group has 5 to 12 carbon atoms, or a combination thereof. A group formed by combining, more preferably a methyl group, an ethyl group, or a cyclohexyl group or an adamantyl group. A41 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 anion in the salt represented by formula (B1) include those described in JP-A-2010-20 Examples of anions include those described in JP-A-4646.

[0193] 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). TIFF2025134963000107.tif175143

[0194] TIFF2025134963000108.tif34140

[0195] TIFF2025134963000109.tif153163

[0196] 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.

[0197] 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) + represents the organic cation Z in the structural unit represented by formula (I). + Same as Examples include:

[0198] 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).

[0199] 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. TIFF2025134963000110.tif62150

[0200] TIFF2025134963000111.tif72164

[0201] TIFF2025134963000112.tif79152

[0202] TIFF2025134963000113.tif63150

[0203] TIFF2025134963000114.tif163153

[0204] TIFF2025134963000115.tif159148

[0205] 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 100% by weight of the resin (A) described below. 00 parts by mass, preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less.

[0206] <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.

[0207] <Quencher (C)> The quencher (C) is a compound selected from a basic nitrogen-containing organic compound and an acid generator (B). Examples of the acid generating salt include a salt that generates an acid weaker in acidity than the acid generated. When the resist composition contains a quencher (C), the content of the quencher (C) is determined based on the solid content of the resist composition. Based on this, the content is preferably about 0.01 to 15% by mass, and more preferably about 0.1 to 10% by mass. It is more preferable to have one. 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 amine, 2,2'-dipyridylamine, 2,2'-dipicolylamine, bipyridine, etc. Among them, diisopropylaniline is preferred, and 2,6-diisopropylaniline is more preferred. Propylaniline is an example. Ammonium salts include tetramethylammonium hydroxide, tetraisopropyl Lithium hydroxide, tetrabutylammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethyl ammonium hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylammonium salicylate, choline, and the like can be mentioned. etc.

[0208] The acidity of the salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is indicated by the acid dissociation constant (pKa). The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is a salt with an acid dissociation constant of the acid generated from the salt usually being -3 < pKa, preferably a salt with -1 < pKa < 7, and more preferably a salt with 0 < pKa < 5. Examples of the salt that generates an acid weaker in 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 intramolecular salt (D)"), and salts described in JP-A-2012-229206, JP-A-2012-6908, JP-A-2012-72109, JP-A-2011-3 9502, and JP-A-2011-191745. The salt that generates an acid weaker in acidity than the acid generated from the acid generator (B) is preferably a salt that generates a carboxylic acid weaker in acidity than the acid generated from the acid generator (B) (a salt having a carboxylic acid anion), and more preferably a weak acid intramolecular salt (D). Examples of the weak acid intramolecular salt (D) include the following salts. etc. TIFF2025134963000116.tif891,65

[0209] Examples of the weak acid intramolecular salt (D) include the following salts. TIFF2025134963000117.tif72165

[0210] <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.

[0211] <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

[0212] <Method for Producing Resist Pattern> The method for producing a resist pattern of the present invention comprises the steps of: (1) applying the resist composition of the present invention onto a substrate; (2) 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.

[0213] <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]

[0214] 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."

[0215] Synthesis Example 1: Synthesis of a salt represented by formula (I-1) TIFF2025134963000118.tif36120 10 parts of a compound represented by formula (I-1-a), 50 parts of chloroform and a compound represented by formula (I-1-b) To the resulting mixture was added 9.09 parts of a compound represented by the formula 6.33 parts of the compound represented by (I-1-c) was added dropwise over 10 minutes, and the mixture was stirred at 23°C for 12 hours. To the resulting mixture, 20 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes, followed by separation. This water washing procedure was repeated three times to obtain an organic layer. The obtained organic layer was concentrated. The concentrated mixture was then passed through a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm The compound of formula (I- 8.61 parts of the compound represented by 1-d) were obtained. TIFF2025134963000119.tif38168 2.99 parts of a salt represented by formula (I-1-e), 15 parts of acetonitrile and 1.0 parts of a salt represented by formula (I-1-b ) was added, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 1.47 parts of the compound was added, and the mixture was stirred at 23°C for 12 hours. To the concentrated residue, 45 parts of chloroform and 15 parts of ion-exchanged water were added, and the mixture was stirred at 23°C for 30 minutes. The mixture was stirred and separated to obtain an organic layer. 15 parts of ion-exchanged water was added to the obtained organic layer. The mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. This water washing procedure was repeated five times. The obtained organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue. The resulting residue was dissolved in acetonitrile and concentrated. This gave 2.70 parts of the salt represented by formula (I-1). MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 397.1

[0216] Synthesis Example 2: Synthesis of a salt represented by formula (I-3) TIFF2025134963000120.tif38137 8 parts of a compound represented by formula (I-1-a), 32 parts of chloroform and 1 part of a compound represented by formula (I-1-b) To the resulting mixture was added 6.61 parts of a compound represented by the formula ( 7.35 parts of the compound represented by I-3-c) was added dropwise over 10 minutes, and the mixture was stirred at 23°C for 12 hours. To the resulting mixture, 16 parts of a 5% aqueous oxalic acid solution was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was separated to obtain an organic layer. 16 parts of ion-exchanged water was added to the obtained organic layer, and The mixture was stirred at 3° C. for 30 minutes and then separated to obtain an organic layer. This water washing procedure was repeated three times. The resulting organic layer was concentrated, and the concentrated mixture was then passed through a column (Kanto Chemical Silica Gel 60N (spherical, medium Separation using 100-210 μm developing solvent: n-heptane / ethyl acetate = 2 / 1 This gave 7.12 parts of a compound represented by formula (I-3-d). TIFF2025134963000121.tif36168 11.64 parts of a salt represented by formula (I-1-e), 60 parts of chloroform and 1.64 parts of a salt represented by formula (I-1-b ) was added, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 3 hours. 7.12 parts of the compound (I) were added thereto, and the mixture was stirred at 23°C for 12 hours. To the concentrated residue, 170 parts of chloroform and 60 parts of a 5% aqueous oxalic acid solution were added, and the mixture was stirred at 23°C. The mixture was stirred for 30 minutes and separated to obtain an organic layer. The mixture was stirred at 23°C for 30 minutes and then separated to obtain an organic layer. The obtained organic layer was concentrated, and then tert-butyl methyl ether was added to the concentrated residue. After adding 50 parts of ethyl acetate to the resulting residue, the supernatant was removed. After stirring, the supernatant was removed. The resulting residue was dissolved in acetonitrile and concentrated. As a result, 9.41 parts of the salt represented by formula (I-3) was obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 425.1

[0217] Synthesis Example 3: Synthesis of a salt represented by formula (I-4) TIFF2025134963000122.tif32168 5 parts of the compound represented by formula (I-1-a), 25 parts of dimethylformamide and potassium carbonate 1.76 parts of methylcellulose was added, and the mixture was stirred at 50° C. for 2 hours. The resulting mixture was stirred at 50° C. for 30 hours. After cooling to 3°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 3 hours at 23°C. The mixture was stirred for 10 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. The mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60 N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1 By separating the mixture using a solvent, 7.08 parts of the compound represented by formula (I-4-d) was obtained. TIFF2025134963000123.tif33168 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then stirred. 3.38 parts of chloroform was added to the resulting mixture, and the mixture was stirred at 23° C. for 12 hours. 25 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. This water washing procedure was repeated five times. After condensation, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred, and the supernatant was The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I- 5.92 parts of the salt represented by 4) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 453.1

[0218] Synthesis Example 4: Synthesis of a salt represented by formula (I-5) TIFF2025134963000124.tif31163 5 parts of the compound represented by formula (I-1-a), 25 parts of dimethylformamide and potassium carbonate 1.76 parts of methylcellulose was added, and the mixture was stirred at 50° C. for 2 hours. The resulting mixture was stirred at 50° C. for 30 hours. After cooling to 3°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 3 hours at 23°C. The mixture was stirred for 10 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. The mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60 N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1 By separating the mixture using a solvent, 7.11 parts of the compound represented by the formula (I-5-d) was obtained. TIFF2025134963000125.tif33167 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then stirred. 3.70 parts of chloroform was added to the resulting mixture, and the mixture was stirred at 23° C. for 12 hours. 25 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. This water washing procedure was repeated five times. After condensation, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred, and the supernatant was The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I- 5.66 parts of the salt represented by formula 5) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 481.2

[0219] Synthesis Example 5: Synthesis of a salt represented by formula (I-7) TIFF2025134963000126.tif32157 5 parts of the compound represented by formula (I-1-a), 25 parts of dimethylformamide and potassium carbonate 1.76 parts of methylcellulose was added, and the mixture was stirred at 50° C. for 2 hours. The resulting mixture was stirred at 50° C. for 30 hours. After cooling to 3°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 3 hours at 23°C. The mixture was stirred for 10 minutes and separated to obtain an organic layer. 25 parts of ion-exchanged water was added to the obtained organic layer. The mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60 N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1 By separating the mixture using a solvent, 6.25 parts of a compound represented by formula (I-7-d) was obtained. TIFF2025134963000127.tif75158 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then stirred. 4.34 parts of chloroform was added and the mixture was stirred at 23° C. for 12 hours. 25 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. This water washing procedure was repeated five times. After condensation, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred, and the supernatant was The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I- 7.42 parts of the salt represented by formula 7) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 537.2

[0220] Synthesis Example 6: Synthesis of salt represented by formula (I-9) TIFF2025134963000128.tif29160 4.95 parts of the compound represented by formula (I-9-a), 25 parts of dimethylformamide and carbonate 1.76 parts of potassium was added, and the mixture was stirred at 50° C. for 2 hours. 5.32 parts of the compound represented by formula (c) was added thereto, and the mixture was stirred at 50° C. for 30 hours. After cooling the mixture to 23°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 23 The mixture was stirred at ℃ for 30 minutes and separated to obtain an organic layer. 25 parts of the water was added, and the mixture was stirred at 23°C for 30 minutes, followed by separation to obtain an organic layer. The procedure was repeated five times. The resulting organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel). 60N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 6.23 parts of the compound represented by formula (I-9-d). Ta. TIFF2025134963000129.tif76154 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then stirred. 3.68 parts of chloroform was added and the mixture was stirred at 23° C. for 12 hours. 25 parts of 5% oxalic acid aqueous solution were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. This water washing procedure was repeated five times. After condensation, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred, and the supernatant was The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I- 5.82 parts of the salt represented by formula 9) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 479.2

[0221] Synthesis Example 7: Synthesis of salt represented by formula (I-10) TIFF2025134963000130.tif40163 8.62 parts of the compound represented by formula (I-10-a), 25 parts of dimethylformamide and charcoal 1.76 parts of potassium carbonate was added, and the mixture was stirred at 50° C. for 2 hours. 5.32 parts of the compound represented by 5-c) was added, and the mixture was stirred at 50°C for 30 hours. After the mixture was cooled to 23°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 2 The mixture was stirred at 3°C ​​for 30 minutes and separated to obtain an organic layer. 25 parts of water was added, and the mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The above procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1) to obtain 7.19 parts of the compound represented by formula (I-10-d). obtained. TIFF2025134963000131.tif31166 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then the compound represented by formula (I-10-d) was added. 5.32 parts of the product was added, and the mixture was stirred at 23°C for 12 hours. 5 parts of a 5% aqueous solution of oxalic acid and 25 parts of a 5% aqueous solution of oxalic acid were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was obtained by stirring and separating the solution. This water washing procedure was repeated five times. After concentration, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The clear liquid was removed. The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I) 8.89 parts of the salt represented by formula (10) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 623.2

[0222] Synthesis Example 8: Synthesis of a salt represented by formula (I-18) TIFF2025134963000132.tif27165 3.57 parts of the compound represented by formula (I-18-a), 25 parts of dimethylformamide and charcoal 1.76 parts of potassium carbonate was added, and the mixture was stirred at 50° C. for 2 hours. 5.32 parts of the compound represented by 5-c) was added, and the mixture was stirred at 50°C for 30 hours. After the mixture was cooled to 23°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 2 The mixture was stirred at 3°C ​​for 30 minutes and separated to obtain an organic layer. 25 parts of water was added, and the mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The above procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1), 4.88 parts of the compound represented by formula (I-18-d) obtained. TIFF2025134963000133.tif32165 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then the compound represented by formula (I-18-d) was added. 3.06 parts of the compound was added, and the mixture was stirred at 23°C for 12 hours. 5 parts of a 5% aqueous solution of oxalic acid and 25 parts of a 5% aqueous solution of oxalic acid were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was obtained by stirring and separating the solution. This water washing procedure was repeated five times. After concentration, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The clear liquid was removed. The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I) 6.22 parts of the salt represented by formula (18) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 425.1

[0223] Synthesis Example 9: Synthesis of a salt represented by formula (I-19) TIFF2025134963000134.tif27167 6.32 parts of the compound represented by formula (I-19-a), 25 parts of dimethylformamide and charcoal 1.76 parts of potassium carbonate was added, and the mixture was stirred at 50° C. for 2 hours. 5.32 parts of the compound represented by 5-c) was added, and the mixture was stirred at 50°C for 30 hours. After the mixture was cooled to 23°C, 50 parts of chloroform and 25 parts of ion-exchanged water were added, and the mixture was stirred for 2 The mixture was stirred at 3°C ​​for 30 minutes and separated to obtain an organic layer. 25 parts of water was added, and the mixture was stirred at 23°C for 30 minutes and separated to obtain an organic layer. The above procedure was repeated five times. The obtained organic layer was concentrated, and the concentrated mixture was passed through a column (Kanto Chemical Silica Gel 60N (spherical, neutral) 100-210 μm Developing solvent: n-heptane / ethyl acetate = 2 / 1), 4.51 parts of the compound represented by formula (I-19-d) obtained. TIFF2025134963000135.tif32166 5 parts of a salt represented by formula (I-1-e), 25 parts of chloroform and 1 part of a salt represented by formula (I-1-b) 2.03 parts of the compound to be mixed was added, and the mixture was stirred at 23°C for 30 minutes, and then further stirred at 50°C for 2 hours. The resulting mixture was cooled to 23°C and then the compound represented by formula (I-19-d) was added. 4.29 parts of the compound was added, and the mixture was stirred at 23° C. for 12 hours. 5 parts of a 5% aqueous solution of oxalic acid and 25 parts of a 5% aqueous solution of oxalic acid were added, and the mixture was stirred at 23°C for 30 minutes and separated. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 30 minutes. The organic layer was obtained by stirring and separating the solution. This water washing procedure was repeated five times. After concentration, 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The clear liquid was removed. The resulting residue was dissolved in acetonitrile and concentrated to give a compound of formula (I) 7.19 parts of the salt represented by formula (-19) were obtained. MS(ESI(+)Spectrum):M + 263.1 MS(ESI(-)Spectrum):M - 533.0

[0224] Synthesis Example 10: Synthesis of a salt represented by formula (I-77) TIFF2025134963000136.tif36167 5.62 parts of a salt represented by formula (I-77-e), 25 parts of chloroform and 1.62 parts of a compound represented by formula (I-1-b 2.03 parts of a compound represented by the formula (I) was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 3.70 parts of the compound was added and stirred at 23°C for 12 hours. Add 75 parts of aluminum and 25 parts of a 5% aqueous oxalic acid solution, stir at 23°C for 30 minutes, and separate the layers. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was obtained by stirring for 1 minute and separating the layers. This water washing procedure was repeated 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The supernatant was then removed, and the resulting residue was dissolved in acetonitrile and concentrated to give 5.91 parts of the salt of formula (I-77) were obtained. MS(ESI(+)Spectrum):M + 317.1 MS(ESI(-)Spectrum):M - 481.2

[0225] Synthesis Example 11: Synthesis of a salt represented by formula (I-81) TIFF2025134963000137.tif34169 5.62 parts of a salt represented by formula (I-77-e), 25 parts of chloroform and 1.62 parts of a compound represented by formula (I-1-b 2.03 parts of a compound represented by the formula (I) was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 3.68 parts of the compound was added and stirred at 23°C for 12 hours. Add 75 parts of aluminum and 25 parts of a 5% aqueous oxalic acid solution, stir at 23°C for 30 minutes, and separate the layers. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23° C. for 30 minutes. The organic layer was obtained by stirring for 1 minute and separating the layers. This water washing procedure was repeated 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The supernatant was then removed, and the resulting residue was dissolved in acetonitrile and concentrated to give 6.12 parts of the salt of formula (I-81) were obtained. MS(ESI(+)Spectrum):M + 317.1 MS(ESI(-)Spectrum):M - 479.2

[0226] Synthesis Example 12: Synthesis of a salt represented by formula (I-82) TIFF2025134963000138.tif71159 5.62 parts of a salt represented by formula (I-77-e), 25 parts of chloroform and 1.62 parts of a compound represented by formula (I-1-b 2.03 parts of a compound represented by the formula (I) was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 5.32 parts of the compound to be added and stirred at 23°C for 12 hours. Add 75 parts of formaldehyde and 25 parts of a 5% aqueous oxalic acid solution, stir at 23°C for 30 minutes, and separate the liquids. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 3 The mixture was stirred for 10 minutes, and then separated to obtain an organic layer. This water washing procedure was repeated 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The resulting residue was dissolved in acetonitrile and concentrated to give a 1,000 ml solution of acetonitrile. As a result, 8.94 parts of the salt represented by formula (I-82) was obtained. MS(ESI(+)Spectrum):M + 317.1 MS(ESI(-)Spectrum):M - 623.2

[0227] Synthesis Example 13: Synthesis of a salt represented by formula (I-90) TIFF2025134963000139.tif68153 5.62 parts of a salt represented by formula (I-77-e), 25 parts of chloroform, and a compound represented by formula (I-1-b 2.03 parts of a compound represented by the formula (I) was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 3.06 parts of the compound (II) was added to the resulting mixture, and the mixture was stirred at 23°C for 12 hours. Add 75 parts of formaldehyde and 25 parts of a 5% aqueous oxalic acid solution, stir at 23°C for 30 minutes, and separate the liquids. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 3 The mixture was stirred for 10 minutes, and then separated to obtain an organic layer. This water washing procedure was repeated 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The resulting residue was dissolved in acetonitrile and concentrated to give a 1,000 ml solution of acetonitrile. As a result, 7.19 parts of the salt represented by the formula (I-90) was obtained. MS(ESI(+)Spectrum):M + 317.1 MS(ESI(-)Spectrum):M - 425.1

[0228] Synthesis Example 14: Synthesis of salt represented by formula (I-91) TIFF2025134963000140.tif33164 5.62 parts of a salt represented by formula (I-77-e), 25 parts of chloroform and 1.62 parts of a compound represented by formula (I-1-b 2.03 parts of a compound represented by the formula (I) was added to the mixture, and the mixture was stirred at 23°C for 30 minutes. The resulting mixture was cooled to 23°C and stirred at 4°C for 2 hours. 4.29 parts of the compound to be added, and the mixture was stirred at 23°C for 12 hours. Add 75 parts of formaldehyde and 25 parts of a 5% aqueous oxalic acid solution, stir at 23°C for 30 minutes, and separate the liquids. To the obtained organic layer, 25 parts of ion-exchanged water was added, and the mixture was stirred at 23°C for 3 The mixture was stirred for 10 minutes, and then separated to obtain an organic layer. This water washing procedure was repeated 5 times. The organic layer was concentrated, and then 30 parts of tert-butyl methyl ether was added to the concentrated residue and stirred. The resulting residue was dissolved in acetonitrile and concentrated to give a 1,000 ml solution of acetonitrile. As a result, 7.31 parts of the salt represented by the formula (I-91) was obtained. MS(ESI(+)Spectrum):M + 317.1 MS(ESI(-)Spectrum):M - 533.0

[0229] 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. TIFF2025134963000141.tif41164

[0230] Synthesis Example 15 [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. TIFF2025134963000142.tif29126

[0231] Synthesis Example 16 [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: TIFF2025134963000143.tif2887

[0232] Synthesis Example 17 [Synthesis of Resin A3] As the monomers, monomer (a1-4-2), monomer (a1-1-3), monomer ( a1-2-2), monomer (a2-1-1), monomer (a3-1-1) and monomer ( a3-2-2) was used, and the molar ratio [monomer (a1-4-2):monomer (a1-1- 3): Monomer (a1-2-2): Monomer (a2-1-1): Monomer (a3-1-1) ):monomer (a3-2-2) in a ratio of 35:28:14:2:11:10 and then adding 1.5 mass % of methyl methyl acrylate to the monomer mixture based on the total mass of all the monomers. The resulting mixture was mixed with 2 times the amount of methyl isobutyl ketone. Butyronitrile was added in an amount of 7 mol % based on the total mole number of all monomers. The mixture was heated at 85°C for about 5 hours to carry out polymerization. An aqueous solution of benzophenone sulfonic acid was added, and the mixture was stirred for 6 hours, followed by separation of the layers. -By pouring into heptane to precipitate the resin and then filtering and recovering it, a weight average molecular weight of approximately 5. 4×10 3 Resin A3 (copolymer) having the following structure was obtained in a yield of 60%. It has a structural unit. TIFF2025134963000144.tif37161

[0233] Synthesis Example 18: Synthesis of Resin AY1 As the monomers, monomer (a1-1-3), monomer (a1-2-2), and monomer ( a2-1-1), monomer (a3-1-1) and monomer (a3-2-2), Molar ratio [monomer (a1-1-3):monomer (a1-2-2):monomer (a2-1- 1): Monomer (a3-1-1): Monomer (a3-2-2) 28:14:6:31 :21, and propylene glycol monomer in an amount 1.5 times the total amount of monomers was added. To this solution, azobisisobutyric acid was added as an initiator. Tyronitrile and azobis(2,4-dimethylvaleronitrile) based on the total amount of monomers The mixture was heated at 73°C for about 5 hours. The reaction mixture was poured into a large amount of methanol / water mixed solvent to precipitate the resin, which was then filtered. The obtained resin was dissolved again in propylene glycol monomethyl ether acetate. The resulting solution is poured into a methanol / water mixed solvent to precipitate the resin, and the resin is filtered. The weight-average molecular weight was 7.9 × 10 3 Yield of resin AY1 The resin AY1 was obtained at 63%. The resin AY1 has the following structural units: TIFF2025134963000145.tif39166

[0234] <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.

[0235] [Table 2]

[0236] <Resin> A1 to A3, AY1: Resin A1 to Resin A3, Resin AY1 <Salt (I)> I-1: A salt represented by formula (I-1) I-3: A salt represented by formula (I-3) I-4: Salt represented by formula (I-4) I-5: Salt represented by formula (I-5) I-7: Salt represented by formula (I-7) I-9: Salt represented by formula (I-9) I-10: Salt represented by formula (I-10) I-18: A salt represented by formula (I-18) I-19: A salt represented by formula (I-19) I-77: A salt represented by formula (I-77) I-81: A salt represented by formula (I-81) I-82: A salt represented by formula (I-82) I-90: A salt represented by formula (I-90) I-91: A salt represented by formula (I-91) <Quencher (C)> C1: Synthesized by the method described in JP 2011-39502 A TIFF2025134963000147.tif3646 <Solvent> 400 parts of propylene glycol monomethyl ether acetate 100 parts of propylene glycol monomethyl ether 5 parts of γ-butyrolactone

[0237] (Electron beam exposure evaluation of resist composition) A 6-inch silicon wafer was treated on a direct hot plate with hexamethyldisilazane at 90 °C for 60 seconds. The resist composition was spin-coated onto this silicon wafer so that the film thickness of the composition layer was 0.04 μm. Then, it was pre-baked for 60 seconds at the temperature shown in the "PB" column of Table 2 on a direct hot plate to form the composition layer. A contact hole pattern (hole pitch 40 nm / hole diameter 17 nm) was directly drawn on the composition layer formed on the wafer using an electron beam lithography machine [(ELS-F1 25 125 keV" manufactured by Elionix Co., Ltd.] while changing the exposure dose step by step . After exposure, post-exposure baking was performed for 60 seconds at the temperature shown in the "PEB" column of Table 2 on a hot plate, and further, paddle development was performed for 60 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern .

[0238] 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 .

[0239] <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. Within the same wafer The average hole diameter of a pattern formed with a hole diameter of 17 nm was measured at 400 locations. The standard deviation was calculated as a group. The results are shown in Table 3. The values ​​in the table indicate the standard deviation (nm).

[0240] [Table 3] Compared with Comparative Composition 1, Compositions 1 to 17 have smaller standard deviations, and CD uniformity (CDU )The evaluation was favorable. [Industrial Applicability]

[0241] The resist composition of the present invention can produce a resist pattern with good CD uniformity (CDU). Therefore, it is suitable for semiconductor microfabrication and is extremely useful industrially.

Claims

1. A resist composition comprising a resin containing a structural unit represented by formula (a2-A) and a structural unit having an acid labile group, and a salt represented by formula (I). [In formula (a2-A), R a50 represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom. R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group, or a methacryloyloxy group. A a50 is a single bond or *-X a51 - (A a52 -X a52 ) nｂ -, * represents -R a50 represents the bond to the carbon atom to which it is bonded. A a52 represents an alkanediyl group having 1 to 6 carbon atoms. X a51 and X a52 each independently represents —O—, —CO—O—, or —O—CO—. nb represents 0 or 1. mb represents an integer of 0 to 4; When mb is an integer of 2 or more, a plurality of R a51 may be the same or different.] [In formula (I), Q １ and Q ２ each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms. R １ and R ２ each independently represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group having 1 to 6 carbon atoms. z represents an integer of 0 to 6, and when z is 2 or more, a plurality of R １ and R ２ may be the same or different from each other. X 1 represents *-CO-O-, *-O-CO-, *-O-CO-O- or *-O-, and * represents C(R １ ) (R ２ ) or C(Q １ ) (Q ２ ) binding site. X ２ represents **-CO-O-, **-O-CO-, **-O-CO-O- or **-O-, and ** represents L １ represents the binding site with L 1 represents a linear alkanediyl group having 2 to 12 carbon atoms. R 3’ represents an alicyclic hydrocarbon group having 3 to 18 carbon atoms which may have a substituent, and —CH 2 - is -O-, -S-, -SO ２ However, the alicyclic hydrocarbon group does not have an alkyl group, and the substituent is selected from the group consisting of a halogen atom, a hydroxy group, a cyano group, a carboxy group, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, and a group formed by combining two or more of these groups, and the alicyclic hydrocarbon group has at least one substituent, or at least one —CH contained in the alicyclic hydrocarbon group 2 - is -O-, -S-, -SO ２ - or -CO- is replaced. Z ＋ represents an organic cation.

2. 2. The resist composition according to claim 1, wherein the structural unit having an acid labile group is at least one selected from the group consisting of structural units represented by formula (a1-1) and structural units represented by formula (a1-2): [In formula (a1-1) and formula (a1-2), L a1 and L a2 are each independently —O— or *—O—(CH ２ ) k1 represents —CO—O—, k1 represents an integer of 1 to 7, and * represents a bond to —CO—. R a4 and R a5 each independently represents a hydrogen atom or a methyl group. R a6 and R a7 each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a 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.

3. 3. The resist composition according to claim 1, further comprising a salt that generates an acid weaker in acidity than the acid generated from the salt represented by formula (I).

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

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