Resist composition and patterning process

Abstract

An object of the invention is to provide a novel resist composition and a pattern forming process.SOLUTION: A resist material comprising a heteropolyacid salt having a modified deficient site or a mixture thereof, wherein an anion moiety of the heteropolyacid salt having a modified deficient site contains a plurality of polar groups each having an acid-labile group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resist material and a pattern forming method. [Background technology]

[0002] In recent years, advances in lithography technologies such as immersion lithography and EUV lithography have led to the advancement of finer circuit patterns. As lithography technology advances, new resist materials are needed to accommodate these advances.

[0003] In addition to conventional chemically amplified resists, new resist materials containing metal compounds, organometallic compounds, metal nanoparticles, metal clusters, etc. have been proposed.

[0004] For example, Patent Document 1 discloses a nanoparticle polymer resist containing nanoparticles containing ZrO2, HfO2, TiO2, or the like in the core, and a polymer. Patent Document 2 also discloses a nanoparticle polymer resist containing an alkyl tin cluster (t-BuSn) 12 O 14 Resists based on (OH)6(HCO2)2 are disclosed. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 9,696,624 [Patent Document 2] WO2019 / 195522 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel resist material and a pattern formation method. [Means for solving the problem]

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that resist materials containing heteropolyacid salts or mixtures thereof, in which the deficiency sites of a heteropolyacid anion having deficiency sites are modified to introduce multiple polar groups having acid-dissociable groups, exhibit drastic changes in physical properties, such as solubility in a developer, between exposed areas to actinic rays and unexposed areas, and have completed the present invention.

[0008] That is, the present invention relates to the following inventions. <1> (A) A resist material containing a heteropolyacid salt or a mixture thereof in which defect sites are modified, the anion moiety of the heteropolyacid salt whose defect sites have been modified contains a plurality of polar groups each having an acid-dissociable group; Resist material. <2> the resist material generates an acid upon exposure and changes its solubility in a developer by the action of the acid; <1> The resist material according to claim 1. <3> the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group; <1> The resist material according to claim 1. <4> the anion moiety of the heteropolyacid salt or mixture thereof (A) whose defective sites have been modified is a heteropolyacid anion having a defective site and wherein the defective site has been modified; <1> The resist material according to claim 1. <5> the modification is achieved by bonding a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded to the heteropoly acid anion having the defective site via some or all of the heteroatoms; the organic group has two or more polar groups each having an acid-dissociable group; <4> The resist material according to claim 1. <6> The organic group may have a substituent. 1-18 is a hydrocarbyl group, C which may have the above-mentioned substituent 1-18Any divalent carbon atom excluding that at the terminal end of the hydrocarbyl group may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), C which may have the above-mentioned substituent 1-18 Two or more hydrogen atoms in the hydrocarbyl group are replaced by a polar group having an acid-dissociable group. <5> The resist material according to claim 1. <7> The organic group is represented by general formula (VII): <5> The resist material according to claim 1. [ka] [In formula (VII), L 2 C may have a substituent 1-12 In the hydrocarbyl group, two hydrogen atoms on any carbon atom, including the terminal, are each R 2A and R 2B represents a group substituted with Said L 2 a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 2A and R 2B each independently represents a polar group having an acid-dissociable group, * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0009] <8> The polyatom of the heteropoly acid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <4> The resist material according to claim 1. <9> the heteropolyanion having a defect site is a defective Keggin heteropolyanion or a defective Dawson heteropolyanion; <4> The resist material according to claim 1. <10> The defective Keggin-type heteropolyacid anion is represented by general formula (II-1), (II-2) or (II-3): <9> The resist material according to claim 1. [XM 11 O 39 ] c11- (II-1) [XM 10 O 36 ] c12- (II-2) [XM9O 34 ] c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers. <11> The defective Dawson-type heteropolyacid anion is represented by general formula (III-1), (III-2) or (III-3): <9> The resist material according to claim 1. [X2M 17 O 61 ] c21- (III-1) [X2M 16 O 58 ] c22- (III-2) [X2M 15 O 56 ] c23- (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers. <12> The (A) heteropolyacid salt having a modified defect site or a mixture thereof is a heteropolyacid salt having a modified defect site represented by general formula (I) or a mixture thereof, <1> The resist material according to claim 1. (A m+ ) a (C (am)- ) (I) [In formula (I), A m+ are each independently H + , metal ions, NH4 + , an onium cation, or an onium dication; C (am)- represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer between 1 and 5, and a is a real number greater than 0. <13> The (A) heteropolyacid salt having a modified defect site or a mixture thereof is a heteropolyacid salt having a modified defect site represented by general formula (I') or a mixture thereof. <1> The resist material according to claim 1. (A' m’+ ) a’ (B n+ ) b (C' (a’m’+bn)- ) (I') [In formula (I'), A' m’+ are each independently H + , metal ions, or NH4 + represents; B n+ each independently represents an onium cation or an onium dication; C' (a’m’+bn)- represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0. <14> The onium cation is a sulfonium cation or an iodonium cation. <13> The resist material according to claim 1.

[0010] <15> Further containing (B) an acid diffusion controller, <1> The resist material according to claim 1. <16> the (B) acid diffusion controller is (B1) a photodegradable base; <15> The resist material according to claim 1. <17> Further containing an organic solvent, <1> The resist material according to claim 1. <18> A resist material that is sensitive to EUV, BEUV or electron beams. <1> ~ <17> 10. The resist material according to claim 9, wherein <19> <1> ~ <17> forming a resist film using the resist material according to any one of the preceding claims; exposing the resist film to light; developing the exposed resist film using a developer; A pattern forming method comprising: [Effects of the Invention]

[0011] According to the present invention, a novel resist material and a pattern formation method can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0012] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0013] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0014] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0015] In this specification, for example, "C 1-6 " and other terms refer to the number of carbon atoms in the core group.

[0016] As used herein, "C 1-18 The term "hydrocarbylene group" refers to a divalent hydrocarbon group generated by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbylene group may be linear or branched, or may be partially or entirely cyclic. Hydrocarbylene groups include alkylene groups and arylene groups. Also, "C 1-18 A divalent carbon atom at any position of the "hydrocarbylene group" may be replaced by -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time). "C 1-18 The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" groups such as methylene group, ethylene group, n-propylene group, i-propylene group, cyclopentadiyl group, cyclohexanediyl group, oxyethane-1,1-diyl group, oxyethane-1,2-diyl group, oxypropane-1,3-diyl group, oxypropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, and oxyethyleneoxyethane-1,1-diyl group. 1-18 alkylene groups such as 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 4,4'-biphenylene, anthracenediyl, phenanthrenediyl, naphthacenediyl, pyrenediyl, perylenediyl, and chrysenediyl groups; 6-18 arylene group" and the like.

[0017] As used herein, "C 1-18 The term "alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. Also, "C 1-18Any divalent carbon atom in the "alkyl group" at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2-, provided that adjacent divalent carbon atoms are not replaced at the same time. "C 1-18 The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 Examples of the alkyl group include 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. "C 1-18 Examples of alkyl groups in which a divalent carbon atom at any position excluding the terminal is replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- include, but are not limited to, a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0018] As used herein, "C 1-18 Haloalkyl group means "C 1-18 The term "alkyl group" refers to a group in which one or more hydrogen atoms of the "alkyl group" have been substituted with halogen atoms. "C 1-18The "haloalkyl group" is not particularly limited, and examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

[0019] As used herein, "C 2-18 An alkenyl group is a group with two or more carbon atoms. 1-18 The term "alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc. "C 2-18 The "alkenyl group" is not particularly limited, and examples thereof include a vinyl group (ethenyl group), an allyl group (2-propenyl group), a 1-propenyl group, an isopropenyl group (1-methylvinyl group), a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group.

[0020] As used herein, "C 2-18 An alkynyl group is a group with two or more carbon atoms. 1-18 The term "alkyl group" refers to an alkynyl group having one or more triple bonds in the alkyl group. "C 2-18 The "alkynyl group" is not particularly limited, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group.

[0021] As used herein, "C 3-18 The term "alicyclic group" refers to a hydrocarbon group having, in whole or in part, a monocyclic or polycyclic structure having 3 to 18 carbon atoms. Alicyclic groups also include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, and the like. Also, "C 3-18Any divalent carbon atom in the "alicyclic group" except for the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time). "C 3-18 The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

[0022] As used herein, the term "3- to 18-membered non-aromatic heterocyclic group" refers to a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms, and may be monocyclic, polycyclic, or fused rings, and may be saturated or partially unsaturated. The "3- to 18-membered non-aromatic heterocyclic group" is not particularly limited, and examples thereof include an aziridinyl group, an azetidyl group, a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a thiomorpholinyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydropyranyl group, an imidazolinyl group, an oxazolinyl group, a 2,5-diazabicyclo[2.2.1]heptyl group, a 2,5-diazabicyclo[2.2.2]octyl group, a 3,8-diazabicyclo[3.2.1]octyl group, a 1,4-diazabicyclo[4.3.0]nonyl group, a 1-azaadamantyl group, and a 2-azaadamantyl group.

[0023] As used herein, "C 2-18 The term "aryl group" refers to an aromatic hydrocarbon cyclic group having 6 to 18 carbon atoms or an aromatic heterocyclic group having 2 to 10 carbon atoms. In the case of an aromatic heterocyclic group, a ring is formed by a carbon atom having 2 to 10 carbon atoms and one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and each may be a monocyclic ring, a polycyclic ring, or a fused ring. "C 2-18 The "aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulenyl group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, and an anthracenyl group.

[0024] As used herein, "C 7-18 An aralkyl group is a group consisting of C 1-12 The substitutable part in "C alkyl group" is 2-12 The term "aryl group" refers to a group substituted with an "aryl group." "C 7-18 The "aralkyl group" is not particularly limited, and examples thereof include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, a 1-naphthylmethyl group, and a 2-naphthylmethyl group.

[0025] As used herein, "C 1-18The term "hydrocarbyl group" refers to a monovalent group generated by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbyl groups include alkyl groups, alkenyl groups, alkynyl groups, alicyclic groups, aryl groups, and aralkyl groups. Also, "C 1-18 Any divalent carbon atom in the "hydrocarbyl group" at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (however, adjacent divalent carbon atoms cannot be replaced at the same time). This point is explained in the following section "C 1-18 "C" used in the explanation of the definition of "hydrocarbyloxy group" 1-18 The same applies to "hydrocarbyl group" and the like. "C 1-18 The "hydrocarbyl group" is not particularly limited, and examples thereof include "C 1-18 alkyl group," "C 2-18 alkenyl group," "C 2-18 alkynyl group," "C 3-18 Alicyclic group”, “C 2-18 aryl group," "C 7-18 aralkyl groups, etc.

[0026] As used herein, "C 1-18 "Hydrocarbyloxy group" means "C 1-18 The term "hydrocarbyl group" refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group." "C 1-18The "hydrocarbyloxy group" is not particularly limited and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentoxy group, an i-pentoxy group, a sec-pentoxy group, an n-hexoxy group, an i-hexoxy group, a 1,1-dimethylpropyloxy group, a 1,2-dimethylpropyloxy group, a 2,2-dimethylpropyloxy group, a 1-methyl-2-ethylpropyloxy group, a 1-ethyl-2-methylpropyloxy group, a 1,1,2-trimethylpropyloxy group, a 1,2,2-trimethylpropyloxy group, a 1,1-dimethylbutyloxy group, a 1,2-dimethylbutyloxy group, a 2,2-dimethylbutyloxy group, a 2,3-dimethylbutyloxy group, a 1,3-dimethylbutyloxy group, a 2-ethylbutyloxy group, a 2-methylpentyloxy group, and a 3-methylpentyloxy group. 1-18 Alkoxy group"; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. 3-18 Alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentalenyloxy group, heptalenyloxy group, indacenyloxy group, acenaphthyloxy group, phenanthrenyloxy group, anthracenyloxy group, etc. 6-18 aryloxy group" and the like. "C 1-18 The "hydrocarbyloxy group" includes "C 1-18 It is preferred that a divalent carbon atom at any position except the terminal contained in the "hydrocarbyl group" is replaced with -O-, -C(=O)-, and / or -C(=O)O-. 1-18A "hydrocarbyloxycarbonylalkyloxy group" is more preferred, and from the viewpoint of solubility, it is even more preferred that the carbon bonded to the oxygen atom of the hydrocarbyloxy is a tertiary carbon. Specific examples of the hydrocarbyloxy include optionally substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, and the like.

[0027] As used herein, "C 1-18 "Hydrocarbyl carbonyl group" means "C 1-18 The term "hydrocarbyl group" refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbyl group." "C 1-18 The "hydrocarbyl carbonyl group" is not particularly limited, and examples thereof include "C" groups such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pentanoyl group, a 3-methylbutanoyl group, a pivaloyl group, a hexanoyl group, and a heptanoyl group. 1-18 alkylcarbonyl group; cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group, etc. 3-18 Alicyclic carbonyl group; C such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group 6-18 arylcarbonyl group" and the like.

[0028] As used herein, "C 1-18 "Hydrocarbylcarbonyloxy group" means "C 1-18 It means a group in which an oxygen atom (—O—) is bonded to a “hydrocarbyl carbonyl group.” "C 1-18The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, an isopentylcarbonyloxy group, and a hexylcarbonyloxy group. 1-18 alkylcarbonyloxy group; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. 3-18 Alicyclic carbonyloxy group; C such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenanthrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. 6-18 arylcarbonyloxy group" and the like.

[0029] As used herein, "C 1-18 "Hydrocarbyloxycarbonyl group" means "C 1-18 It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” "C 1-18 The "hydrocarbyloxycarbonyl group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, an n-pentoxycarbonyl group, and a neopentyloxycarbonyl group. 1-18 Alkoxycarbonyl group; cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclopentyloxycarbonyl group, 3-methylcyclopentyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 3-methylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, etc. 3-18Alicyclic oxycarbonyl group; phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. 6-18 aryloxycarbonyl group" and the like.

[0030] As used herein, "C 1-18 "Hydrocarbyloxycarbonyloxy group" means "C 1-18 It means a group in which an oxygen atom (—O—) is bonded to a “hydrocarbyloxycarbonyl group.” "C 1-18 The "hydrocarbyloxycarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propyloxycarbonyloxy group, an i-propyloxycarbonyloxy group, an n-butoxycarbonyloxy group, an i-butoxycarbonyloxy group, a sec-butoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-pentyloxycarbonyloxy group, an i-pentyloxycarbonyloxy group, and an n-hexyloxycarbonyloxy group. 1-18 alkoxycarbonyloxy group; cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. 3-18 Alicyclic oxycarbonyloxy group; phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenanthrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. 6-18 aryloxycarbonyloxy group" and the like.

[0031] As used herein, "C 1-18 A "hydrocarbyl amino group" is a group consisting of one "C 1-18 "Hydrocarbyl group" means a group attached to an amino group. "C 1-18The "hydrocarbylamino group" is not particularly limited, and examples thereof include a "C methylamino group, an ethylamino group, an n-propylamino group, an i-propylamino group, an n-butylamino group, an i-butylamino group, a sec-butylamino group, a t-butylamino group, an n-pentylamino group, an i-pentylamino group, a neopentylamino group, an n-hexylamino group, and the like. 1-18 alkylamino group"; cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, 2-methylcyclopentylamino group, 3-methylcyclopentylamino group, cyclohexylamino group, 2-methylcyclohexylamino group, 3-methylcyclohexylamino group, 4-methylcyclohexylamino group, etc. 3-18 Alicyclic amino group; phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. 6-18 arylamino group" and the like.

[0032] As used herein, "DiC 1-18 A "hydrocarbylamino group" is a group consisting of two identical or different "C 1-18 "Hydrocarbyl group" means a group attached to an amino group. "The C 1-18 The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-Nn-propylamino group, an N-isopropyl-N-methylamino group, an Nn-butyl-N-methylamino group, group, N-isobutyl-N-methylamino group, Nt-butyl-N-methylamino group, N-methyl-Nn-pentylamino group, Nn-hexyl-N-methylamino group, N-ethyl-Nn-propylamino group, N-ethyl-N-isopropylamino group, Nn-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, Nt-butyl-N-ethylamino group, N-ethyl-Nn-pentylamino group, N-ethyl-Nn-hexylamino group, and other "di-C" groups. 1-18alkylamino group; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. 3-18 Alicyclic amino group; diphenylamino group, phenylnaphthylamino group, etc. 6-18 Arylamino group; N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. 1-18 Alkyl-NC 3-18 Cycloalkylamino group; N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. 1-18 Alkyl-NC 6-18 arylamino group" and the like.

[0033] As used herein, "C 1-18 "Hydrocarbylaminocarbonyl group" means "C 1-18 It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” "C 1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, a t-butylaminocarbonyl group, an n-pentylaminocarbonyl group, a 2-pentylaminocarbonyl group, a neopentylaminocarbonyl group, a 4-methyl-2-pentylaminocarbonyl group, an n-hexylaminocarbonyl group, and a 3-methyl-n-pentylaminocarbonyl group. 1-18 alkylaminocarbonyl group; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. 3-18Alicyclic aminocarbonyl group; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc. 6-18 arylaminocarbonyl group.

[0034] As used herein, "DiC 1-18 "Hydrocarbylaminocarbonyl group" means "diC 1-18 It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” "The C 1-18 The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-Nn-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an Nn-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl-N-methylaminocarbonyl group, an N-methyl-Nn-pentylaminocarbonyl group, an Nn-hexyl-N-methylaminocarbonyl group, "Di-C" groups such as N-ethyl-Nn-propylaminocarbonyl group, N-ethyl-N-isopropylaminocarbonyl group, Nn-butyl-N-ethylaminocarbonyl group, N-ethyl-N-isobutylaminocarbonyl group, Nt-butyl-N-ethylaminocarbonyl group, N-ethyl-Nn-pentylaminocarbonyl group, and N-ethyl-Nn-hexylaminocarbonyl group 1-18 alkylamino group; dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. 3-18 Alicyclic aminocarbonyl group; diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. 6-18 arylaminocarbonyl group" and the like.

[0035] As used herein, "C 1-18 "Hydrocarbyl carbonyl amino group" means "C 1-18 The term "hydrocarbyl carbonyl group" refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." "C 1-18 The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, and n-hexylcarbonylamino group. 1-18 alkylcarbonylamino group; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. 3-18 Alicyclic carbonylamino group; phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenanthrenylcarbonylamino group, anthracenylcarbonylamino group, etc. 6-18 arylcarbonylamino group" and the like.

[0036] As used herein, "C 1-18 The term "hydrocarbylaminocarbonyloxy group" refers to "C 1-18 It means a group in which an oxygen atom (—O—) is bonded to a “hydrocarbylaminocarbonyl group.” "C 1-18 The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group, etc. 1-18 alkylaminocarbonyloxy group; cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. 3-18Alicyclic aminocarbonyloxy group; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. 6-18 arylaminocarbonyloxy group" and the like.

[0037] As used herein, "DiC 1-18 The term "hydrocarbylaminocarbonyloxy group" refers to a "diC 1-18 It means a group in which an oxygen atom (—O—) is bonded to a “hydrocarbylaminocarbonyl group.” "The C 1-18 The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "di-C" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. 1-18 alkylaminocarbonyloxy group" and the like.

[0038] As used herein, "C 1-18 The term "hydrocarbylaminocarbonylamino group" refers to "C 1-18 A "hydrocarbylaminocarbonyl group" means a group attached to an amino group. "C 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc. 1-18 alkylaminocarbonylamino group; cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. 3-18 Alicyclic aminocarbonylamino group; phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. 6-18 arylaminocarbonylamino group" and the like.

[0039] As used herein, "DiC 1-18 "Hydrocarbylaminocarbonylamino group" means "diC 1-18 A "hydrocarbylaminocarbonyl group" means a group attached to an amino group. "The C 1-18The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. 1-18 alkylaminocarbonylamino group, etc.

[0040] As used herein, "C 1-18 "Hydrocarbyloxycarbonylamino group" means "C 1-18 "Hydrocarbyloxycarbonyl group" means a group bonded to an amino group. "C 1-18 The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. 1-18 alkoxycarbonylamino group; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. 3-18 Alicyclic oxycarbonylamino group; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. 6-18 aryloxycarbonylamino group" and the like.

[0041] As used herein, "C 1-18 "Hydrocarbylthio group" means "C 1-18 The term "hydrocarbyl group" refers to a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group." "C 1-18 The "hydrocarbylthio group" is not particularly limited, and examples thereof include a "C thio group" such as a methylthio group, an ethylthio group, an n-propylthio group, an i-propylthio group, an n-butylthio group, an i-butylthio group, a t-butylthio group, an n-pentylthio group, and an n-hexylthio group. 1-18alkylthio group; cyclopropylthio group, cyclobutylthio group, cyclopentylthio group, cyclohexylthio group, 2-methylcyclopentylthio group, 3-methylcyclopentylthio group, 2-methylcyclohexylthio group, 3-methylcyclohexylthio group, 4-methylcyclohexylthio group, etc. 3-18 Alicyclic thio group; phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenanthrenylthio group, anthracenylthio group, etc. 6-18 arylthio group" and the like.

[0042] As used herein, "C 1-18 The term "hydrocarbylsulfinyl group" means "C 1-18 The term "hydrocarbyl group" refers to a group in which a sulfinyl group (-S(=O)-) is bonded to a "hydrocarbyl group." "C 1-18 The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include "C methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, hexylsulfinyl group, etc. 1-18 alkylsulfinyl group"; cyclopropylsulfinyl group, cyclobutylsulfinyl group, cyclopentylsulfinyl group, cyclohexylsulfinyl group, 2-methylcyclopentylsulfinyl group, 3-methylcyclopentylsulfinyl group, 2-methylcyclohexylsulfinyl group, 3-methylcyclohexylsulfinyl group, 4-methylcyclohexylsulfinyl group, etc. 3-18 Alicyclic sulfinyl group; phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenanthrenylsulfinyl group, anthracenylsulfinyl group, etc. 6-18 arylsulfinyl group" and the like.

[0043] As used herein, "C 1-18 The term "hydrocarbylsulfonyl group" refers to a group consisting of "C 1-18 It means a group in which a sulfonyl group (—SO 2 —) is bonded to a “hydrocarbyl group.” "C 1-18 The "hydrocarbylsulfonyl group" is not particularly limited, and examples thereof include a "C methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, a pentylsulfonyl group, etc. 1-18 alkylsulfonyl group; cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, 4-methylcyclohexyl group, etc. 3-18 Alicyclic sulfonyl group; phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenanthrenylsulfonyl group, anthracenylsulfonyl group, etc. 6-18 arylsulfonyl group" and the like.

[0044] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom in a polar group such as a hydroxy group (including a phenolic hydroxy group), a carboxy group, an amino group, or a sulfo group, and that dissociates when acted upon by an acid. The compound having the acid-dissociable group can increase the polarity of the compound by dissociating the acid-dissociable group under the action of an acid, thereby generating the polar group. This can change the solubility of the compound in the developer. More specifically, when a developer with high polarity such as an alkaline aqueous solution is used as the developer, the solubility of the compound in the developer relatively increases, while when an organic developer with low polarity is used as the developer, the solubility of the compound in the developer relatively decreases. The polar group is preferably a hydroxy group (including a phenolic hydroxy group) or a carboxy group.

[0045] The acid-dissociable group is not particularly limited, and any known and commonly used acid-dissociable group that can be used in chemically amplified resists can be used. Examples of the acid-dissociable group include acid-dissociable groups G for polar groups having an acid-dissociable group represented by the following general formulas (G-1) to (G-4). [ka] [ka] [ka] [ka]

[0046] The acid-dissociable group G is not particularly limited as long as it dissociates under the action of an acid, and any known and commonly used group can be used. Examples of the acid-dissociable group G include "tertiary carbon-type acid-dissociable groups G" represented by the following general formula (g-1): A ", "allyl or benzyl acid-dissociable group G represented by the following general formula (g-2) B ", "acetal-type acid-dissociable group G represented by the following general formula (g-3) C Each of these will be explained in turn below. [ka] [ka] [ka]

[0047] <Tertiary carbon type acid dissociable group G A > The acid-dissociable group G includes a "tertiary carbon-type acid-dissociable group G" represented by the following general formula (g-1): A ", a carbon atom directly bonded to a polar group, and R A g1 ~R Ag3 An acid-labile group in which the carbon to which the group is bonded is a tertiary carbon atom can be used. [ka]

[0048] "R A g1 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0049] R A g1 As the C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12 An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-12 Alkyl group or C 3-12 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0050] Also, "R A g2 " and "R A g3 " are each independently optionally substituted C 1-12a hydrocarbyl group in which any divalent carbon atom except for the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), or R A g2 and R A g3 are combined to form C which may have a substituent. 3-18 It may form an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and a divalent carbon atom at any position except for the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0051] R A g2 and R A g3 As for R A g2 and R A g3 are combined to form C which may have a substituent. 3-18 It is preferable that the group forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and a divalent carbon atom at any position except for a terminal position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), C which may further have the above-mentioned substituent 3-18It is more preferable that the alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, in which a divalent carbon atom at any position except for a terminal may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0052] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1) A Examples of the aryl group include a t-butyl group, a t-amyl group, a 1,1-dimethylpropyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and a 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0053] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1) A Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0054] [ka]

[0055] <<Tertiary carbon type acid dissociable group G A1 and G A2 >> The "tertiary carbon-type acid-dissociable group G" represented by general formula (g-1) A " In R A g2and R A g3 are combined to form C which may have a substituent. 3-18 In the case where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) is A1 and a tertiary carbon-type oxygen-dissociating group G represented by (g-1-2): A2 etc.

[0056] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) A1 >> [ka] A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1) A1 In R A g11 may have a substituent C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12 In an aralkyl group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0057] Also Cy A g1 C which may have a substituent together with the tertiary carbon atom 3-18 It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0058] Cy A g1As the alkyl group, preferred are those which, together with the tertiary carbon atom, form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, which may have a substituent, and in which a divalent carbon atom at any position except for the terminal may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0059] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): A1 Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) A2 >> [ka] In the above general formula (g-1-2), RA g21 ~R A g23 each independently represents a hydro group or an optionally substituted C 1-12 In the hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), R A g21 and R A g22 , and / or R A g22 and R A g23 are directly or divalently linked to each other by a single bond, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring.

[0065] R A g21 and R A g22 , and / or R A g22 and R A g23 Examples of the case where R 1 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where R 1 forms a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, or the like, which may have a substituent.

[0066] Also Cy A g2 C which may have a substituent together with the tertiary carbon atom 3-18 It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (however, adjacent divalent carbon atoms are not replaced at the same time).

[0067] Cy A g2 As the alkyl group, preferred are those which, together with the tertiary carbon atom, form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, which may have a substituent, and in which a divalent carbon atom at any position except for the terminal may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0068] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): A2 Examples of such tertiary carbon-type acid-dissociable groups include the following:

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] Allyl or benzyl acid-dissociable group G B > The acid-dissociable group G is an allyl or benzyl acid-dissociable group G represented by the following general formula (g-2): B An acid-labile group in which the carbon atom directly bonded to the polar group is at an allylic or benzyl position, such as: [ka]

[0073] "R B g1 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0074] R B g1 As the C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12 An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-12 Alkyl group or C 3-12 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0075] Also, "R B g2 " ~ "R B g4 " each independently represents a hydro group or an optionally substituted C 1-12Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0076] R B g1 and R B g2 , R B g2 and R B g3 , and / or R B g3 and R B g4 are directly or divalently linked to each other by a single bond, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring.

[0077] An allyl or benzyl acid-dissociable group G represented by general formula (g-2): B In R B g1 and R B g2 , R B g2 and R B g3 , and / or R B g3 and R B g4 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond, examples of which include the formation of a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, a benzyl group, or a 2,3-dihydro-1H-indanyl group which may have a substituent.

[0078] An allyl or benzyl acid-dissociable group G represented by general formula (g-2): B Examples of the acid-dissociable group include the following allyl or benzyl acid-dissociable groups:

[0079] [ka]

[0080] <Acetal-type acid-dissociable group G C > The acid-dissociable group G is an acetal-type acid-dissociable group G represented by the following general formula (g-3): C An acid-dissociable group in which an oxygen atom is bonded to a carbon atom directly bonded to a polar group, such as [ka]

[0081] "R C g1 " and "R C g3 " each independently represents a hydro group or an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0082] R C g1 and R C g3 is a hydro group or an optionally substituted C 1-12 Alkyl group or C 3-12 An alicyclic group in which any divalent carbon atom excluding a terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Hydro group or optionally substituted C 1-6 Alkyl group or C 3-8Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0083] Also, "R C g2 " is an optionally substituted C 1-12 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0084] R C g2 As the C 1-12 Alkyl group or C 3-12 An alicyclic group in which any divalent carbon atom excluding a terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 1-6 Alkyl group or C 3-8 Alicyclic groups in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time) are more preferred.

[0085] An acetal-type acid-dissociable group G represented by general formula (g-3) CExamples of the alkoxy group include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, and a 1-cyclohexyloxyethoxy group.

[0086] As used herein, the term "hydroxy group or carboxy group having a protecting group" refers to a hydroxy group (including a phenolic hydroxy group) or a carboxy group that is protected with an ether-based protecting group, a silyl ether-based protecting group, an acyl-based protecting group, an aminocarbonyl-based protecting group, or the like.

[0087] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group. The silyl ether protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS). The acyl protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The aminocarbonyl protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0088] In this specification, the term "optionally having a substituent" is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the "substituent" include (1) a halogen atom, (2) a haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, (20) a polar group having an acid-dissociable group, or (21) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (20). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, C 1-18 Hydrocarbylthio group, C 1-18 Hydrocarbylsulfinyl group, C 1-18Examples of the hydrocarbylsulfonyl group include a hydrocarbylsulfonyl group in which a divalent carbon atom at any position excluding the terminal of the substituent may be replaced with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0089] [1. Resist materials] The resist material according to this embodiment is a resist material containing (A) a heteropolyacid salt or a mixture thereof in which defect sites have been modified, and is characterized in that a plurality of polar groups having an acid-dissociable group have been introduced into the anion moiety of the heteropolyacid salt or the mixture thereof in which defect sites have been modified. The resist material according to this embodiment may also contain optional components such as (B) an acid diffusion controller and an organic solvent.

[0090] [1-1. (A) Heteropolyacid salts or mixtures thereof with modified defect sites] (A) When the heteropolyacid salt or the mixture thereof in which the defective site is modified contains an onium cation or an onium dication in the cation moiety, the heteropolyacid salt or the mixture thereof may function as a photoacid generator that generates an acid upon exposure to actinic rays (including visible light, ultraviolet light, DUV, XUV, EUV, BEUV, X-rays, electron beams, α-rays, β-rays, γ-rays, etc.). When the cation moiety does not contain an onium cation or an onium dication, a known, commonly used photoacid generator may be added to the resist material.

[0091] Furthermore, the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment contains a plurality of polar groups having an acid-dissociable group in its anion moiety, i.e., at least two polar groups having an acid-dissociable group, and therefore can dramatically change its solubility in a developer by the action of an acid. The number of polar groups having an acid-dissociable group contained in the anion moiety is not particularly limited, and is preferably, for example, 2 to 12, more preferably 4 to 10, and even more preferably 4 to 8. From the viewpoint of ease of synthesis, the number of polar groups having an acid-dissociable group contained in the anion moiety is preferably 2, 4, 6, 8, 10, or 12, more preferably 4, 6, 8, or 10, and even more preferably 4, 6, or 8. Furthermore, by adjusting the bulkiness, hydrophobicity, liposolubility, etc. of the acid-labile group, it is possible to adjust the range of change in physical properties, such as solubility in a developer, between the exposed and unexposed areas to actinic rays, etc.

[0092] Therefore, the resist material according to this embodiment can be suitably used as a resist material that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid.

[0093] The resist material containing the heteropolyacid salt or mixture thereof in which the defect sites have been modified according to this embodiment can drastically change the solubility in a developer between the exposed portion to actinic radiation or the like and the unexposed portion, and therefore can provide an excellent resist material that has good dimensional controllability and a good LWR (Line Width Roughness) evaluation, i.e., can suppress the 3σ (σ: standard deviation) of the line width variation. Furthermore, by adding an optional component (B) an acid diffusion controller to the resist material according to this embodiment in addition to the component (A), it is possible to further improve the evaluation of the dimension controllability and LWR.

[0094] The anion moiety and the cation moiety of the heteropolyacid salt (A) or mixture having defective sites according to this embodiment will be described below.

[0095] [1-1-1. Anion portion of heteropolyacid salt or mixture thereof with modified defect sites] The anion moiety of the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment can be obtained by reacting a terminal oxygen atom at the defect site of a heteropolyacid anion having defect sites with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups.

[0096] [1-1-1-1. Heteropolyanion with defective sites] The heteropolyacid anion having a defect site according to this embodiment is not particularly limited, and may be a defect species in which a part of the basic skeleton of the heteropolyacid anion is defective, and any of a one-defect species, a two-defect species, a three-defect species, etc. Examples of the heteropolyacid anion having a defect site include a defective Keggin-type heteropolyacid anion and a defective Dawson-type heteropolyacid anion.

[0097] [1-1-1-1-1. Defective Keggin-type heteropolyanion] Examples of the defective Keggin type heteropolyacid anion include a one-deficient Keggin type heteropolyacid anion represented by the following general formula (II-1), a two-deficient Keggin type heteropolyacid anion represented by the following general formula (II-2), and a three-deficient Keggin type heteropolyacid anion represented by the following general formula (II-3). [XM 11 O 39 ] c11- (II-1) [XM 10 O 36 ] c12- (II-2) [XM9O 34 ] c13- (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.

[0098] In the general formulae (II-1) to (II-3), the values ​​of c11 to c13 vary depending on the types of X and M. For example, in the general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo 11 O 39 ] 7- , [PW 11 O 39 ] 7- ) and when X is Si and M is Mo or W, c11 is 8([SiMo 11 O 39 ] 8- , [SiW 11 O 39 ] 8- ) and when X is S and M is Mo or W, c11 is 6([SMo 11 O 39 ] 6- , [SW 11 O 39 ] 6- ) and when X is B and M is Mo or W, c11 is 9([BMo 11 O 39 ] 9- , [BW 11 O 39 ] 9- ) and when X is Ge and M is Mo or W, c11 is 8([GeMo 11 O 39 ] 8- , [GeW 11 O 39 ] 8- ) In addition, in the general formula (II-2), when X is P and M is Mo or W, c12 is 7([PMo 10 O 36 ] 7- , [PW 10 O 36 ] 7- ) and when X is Si and M is Mo or W, c12 is 8([SiMo 10 O 36 ] 8- , [SiW 10 O 36 ] 8-) and when X is B and M is Mo or W, c12 is 9([BMo 10 O 36 ] 9- , [BW 10 O 36 ] 9- ) and when X is Ge and M is Mo or W, c12 is 8([GeMo 10 O 36 ] 8- , [GeW 10 O 36 ] 8- ) Furthermore, in the general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9([PMo9O 34 ] 9- , [PW9O 34 ] 9- ) and when X is Si and M is Mo or W, c13 is 10([SiMo9O 34 ] 10- , [SiWO 34 ] 10- ) and when X is S and M is Mo or W, c13 is 8([SMo9O 34 ] 8- , [SW9O 34 ] 8- ) and when X is Ge and M is Mo or W, c13 is 10([GeMo9O 34 ] 10- , [GeW9O 34 ] 10- )

[0099] The defective Keggin type heteropoly acid anion preferably has an isomeric structure of α, β or γ. The isomeric structure of the one-deficient Keggin-type heteropolyanion represented by general formula (II-1) is [α-PW 11 O 39 ] 7- , [β-PW 11 O 39 ] 7- , [γ-PW 11 O 39 ] 7- , [α-PMo 11 O 39 ] 7- , [β-PMo 11O 39 ] 7- , [γ-PW 11 O 39 ] 7- , [α-SiW 11 O 39 ] 8- , [β-SiW 11 O 39 ] 8- , [γ-SiW 11 O 39 ] 8- , [α-SiMo 11 O 39 ] 8- , [β-SiMo 11 O 39 ] 8- , [γ-SiW 11 O 39 ] 8- is preferred, and [α-PW 11 O 39 ] 7- , [α-PMo 11 O 39 ] 7- , [α-SiW 11 O 39 ] 8- , [α-SiMo 11 O 39 ] 8- is more preferred. The isomeric structure of the two-deficient Keggin heteropolyanion represented by general formula (II-1) is [α-PW 10 O 36 ] 7- , [β-PW 10 O 36 ] 7- , [γ-PW 10 O 36 ] 7- , [α-PMo 10 O 36 ] 7- , [β-PMo 10 O 36 ] 7- , [γ-PW 10 O 36 ] 7- , [α-SiW 10 O 36 ] 8- , [β-SiW 10 O 36 ]8- , [γ-SiW 10 O 36 ] 8- , [α-SiMo 10 O 36 ] 8- , [β-SiMo 10 O 36 ] 8- , [γ-SiW 10 O 36 ] 8- is preferred, and [γ-PW 10 O 36 ] 7- , [γ-PMo 10 O 36 ] 7- , [γ-SiW 10 O 36 ] 8- , [γ-SiMo 10 O 36 ] 8- is more preferred. Furthermore, the isomeric structure of the 3-deficient Keggin heteropolyanion represented by general formula (III-1) is [α-PW9O 34 ] 9- , [β-PW9O 34 ] 9- , [γ-PW9O 34 ] 9- , [α-PMo9O 34 ] 9- , [β-PMo9O 34 ] 9- , [γ-PW9O 34 ] 9- , [α-SiWO 34 ] 10- , [β-SiWO 34 ] 10- , [γ-SiWO 34 ] 10- , [α-SiMo9O 34 ] 10- , [β-SiMo9O 34 ] 10- , [γ-SiWO 34 ] 10- is preferred.

[0100] [1-1-1-1-2. Lack of Dawson-type heteropolyanions] Examples of the defective Dawson type heteropolyacid anion include a mono-defective Dawson type heteropolyacid anion represented by the following general formula (III-1), a di-defective Dawson type heteropolyacid anion represented by the following general formula (III-2), and a tri-defective Dawson type heteropolyacid anion represented by the following general formula (III-3). [X2M 17 O 61 ] c21- (III-1) [X2M 16 O 58 ] c22- (III-2) [X2M 15 O 56 ] c23- (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.

[0101] In the general formulae (III-1) to (III-3), the values ​​of c21 to c23 change depending on the types of X and M. For example, in the general formula (III-1), when X is P and M is Mo or W, c21 is 10([P2Mo 17 O 61 ] 10- , [P2W 17 O 61 ] 10- ), and if X is S and M is W, c21 is 8([S2W 17 O 61 ] 8- ) In addition, in the general formula (III-2), when X is Ge and M is Mo, c22 is 12([Ge2Mo 16 O 58 ] 12- ) Furthermore, in the general formula (III-3), when X is P and M is Mo or W, c23 is 12([P2Mo 15 O 56 ] 12- , [P2W 15O 56 ] 12- )

[0102] The defective Dawson type heteropolyacid anion preferably has an isomeric structure of α, β, or γ. The isomeric structures of the defective Dawson-type heteropolyanions represented by the general formulae (III-1) to (III-3) include [α-P2W 17 O 61 ] 10- , [α-P2W 15 O 56 ] 12- , [α-S2W 17 O 61 ] 8- etc. can be suitably used.

[0103] [1-1-1-2. Modification of the defect site] The modification of the defect sites of the heteropolyanion having defect sites according to this embodiment can be achieved by reacting a terminal oxygen atom at the defect site of the heteropolyanion having defect sites with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups to modify the defect site. By the above reaction, the terminal oxygen atoms at the defective sites of the heteropolyacid anion are bonded to a group having a heteroatom of P, Si, Ge, or Sn to which one or more organic groups are bonded, via some or all of the heteroatoms, thereby modifying the defective sites.

[0104] [1-1-1-2-1. Bonding type and notation of the missing part] In the heteropolyacid anion having a modified defect site according to this embodiment, the terminal oxygen atom of the defect site of the heteropolyacid anion having a defect site is modified with a group having a heteroatom of P, Si, Ge, or Sn bonded to one or more organic groups.

[0105] The bonding form between the terminal oxygen atom at the vacant site of the heteropoly acid anion and the group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded is not particularly limited, and can be represented, for example, by the following general formulas (IV-1) to (IV-5). [ka] [ka] [ka] [ka] [ka] [In formulas (IV-1) to (IV-5), X' represents Si or Ge; X″ represents a heteroatom of Si, Ge or Sn; R 1A1 ~R 1E1 each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 1A1 ~R 1E1 a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), Above R 1A1 ~R 1E1a hydrogen atom contained in the group may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; Above R 1A1 ~R 1E1 Two or more hydrogen atoms in (t) are replaced by polar groups having an acid-dissociable group; * represents the bond between the terminal oxygen atom of the vacant site of the heteropoly acid anion.]

[0106] In this specification, for convenience, a heteropoly acid anion in which the defective site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-1) may be represented as in the following general formula (V-1). [X w M x O y (R 1A1 X')(R 1A2 X')O] c- (V-1) (In the formula, w, x, y, and c are all natural numbers, and X, M, X', and R 1A1 and R 1A2 is the same as above.) Also R 1A1 and R 1A2 If these are the same, call this R 1A and can be expressed as the following general formula (V-1'). [X w M x O y (R 1A X')2O] c- (V-1')

[0107] The heteropolyacid anion having a modified defect site represented by general formula (V-1) or (V-1′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R 1A )X'Y3 (Y represents a leaving group, such as a halogen atom, a hydroxy group, an alkoxy group (C 1-4 An alkoxy group is preferred, and C 1-2 An alkoxy group is more preferred.) and an alkylcarbonyloxy group (C 1-4 alkylcarbonyloxy group, hydrocarbylsulfonyloxy group (C 1-6 Alkyl or C 7-10 An aralkylsulfonyloxy group is preferred. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group.

[0108] Similarly, in this specification, a heteropolyacid anion in which the defective site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-2) may be represented, for convenience, as in the following general formula (V-2). [X w M x O y (R 1B1 R 1B2 X')(R 1B3 R 1B4 X')] c- (V-2) (In the formula, w, x, y, and c are all natural numbers, and X, M, X', and R 1B1 , R 1B2 , R 1B3 and R 1B4 is the same as above.) Also R 1B1 R 1B2 and R 1B3 R 1B4 are the same, it can be expressed as the following general formula (V-2'). [X w M x O y (R 1B1 R 1B2 X')2]c- (V-2')

[0109] The heteropolyacid anion having a modified defect site represented by general formula (V-2) or (V-2′) is not particularly limited, and may be, for example, a heteropolyacid anion having a defect site and (R 1B1 )(R 1B2 )X'Y2 (Y represents a leaving group as above), it can be obtained by reacting.

[0110] In this specification, for convenience, a heteropoly acid anion in which the defective site is modified with a group having a heteroatom Si or Ge bonded to one or more organic groups represented by general formula (IV-3) may be represented as in the following general formula (V-3). [X w M x O y (R 1C1 X'O)(R 1C2 X'O)(R 1C3 X'O)(R 1C4 X'O)] c- (V-3) (In the formula, w, x, y, and c are all natural numbers, and X, M, X', and R 1C1 , R 1C2 , R 1C3 and R 1C4 is the same as above.) Also R 1C1 , R 1C2 , R 1C3 and R 1C4 If these are the same, call this R 1C and can be expressed as the following general formula (V-3'). [X w M x O y (R 1C X'O)4] c- (V-3')

[0111] The heteropoly acid anion having modified vacancy sites represented by general formula (V-3) or (V-3′) is not particularly limited, and examples thereof include a heteropoly acid anion of two vacancy sites, a Keggin type or a Dawson type, and a compound represented by general formula (V-4) or (V-5). 1CIt can be obtained by reacting with X'Y3 (Y represents a leaving group as above).

[0112] In this specification, for convenience, a heteropolyacid anion in which the defective site is modified with a group having a heteroatom P bonded to one or more organic groups represented by general formula (IV-4) may be represented as in the following general formula (V-4). [X w M x O y (R 1D1 P=O)(R 1D2 P=O)] c- (V-4) (In the formula, w, x, y, and c are all natural numbers, and X, M, and R 1D1 and R 1D2 is the same as above.) Also R 1D1 and R 1D2 If these are the same, call this R 1D and can be expressed as the following general formula (V-4'). [X w M x O y (R 1D P=O)2)] c- (V-4')

[0113] The heteropolyacid anion having a modified defect site represented by general formula (V-4) or (V-4′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R 1D It can be obtained by reacting with P(=O)Y2 (Y represents a leaving group as above).

[0114] In this specification, for convenience, a heteropoly acid anion in which the defective site is modified with a group having a heteroatom Si, Ge, or Sn bonded to one or more organic groups represented by general formula (IV-5) may be represented as general formula (V-5) below. [X w M x O y (R 1E1 X')]c- (V-5) (In the formula, w, x, y, and c are all natural numbers, and X, M, X″, and R 1E1 is the same as above.) In addition, the above (V-5) may be expressed as the following general formula (V-5') in some cases. 1E is R 1E1 The same definition is used. [X w M x O y (R 1E X')] c- (V-5')

[0115] The heteropolyacid anion having a modified defect site represented by general formula (V-5) or (V-5′) is not particularly limited, and for example, a heteropolyacid anion having a defect site and R 1E It can be obtained by reacting with X″Y3 (Y represents a leaving group as above).

[0116] Among the heteropolyacid anions having modified defect sites represented by general formulas (V-1) to (V-5) and (V-1') to (V-5'), heteropolyacid anions having modified defect sites represented by the following general formulas (VI-1) to (VI-12) are preferred, from the viewpoint of being relatively stable and allowing control of reactivity. [XM 11 O 39 (R 1A X')2O] c31- (VI-1) [XM 11 O 39 (R 1B1 R 1B2 X')2] c31- (VI-2) [XM 11 O 39 (R 1D P=O)2] c31- (VI-3) [XM 11 O 39 (R 1E X')] c31- (VI-4) [XM 10O 36 (R 1A X')2O] c32- (VI-5) [XM 10 O 36 (R 1B1 R 1B2 X')2] c32- (VI-6) [XM 10 O 36 (R 1C X'O)4] c32- (VI-7) [XM 10 O 36 (R 1D P=O)2] c32- (VI-8) [X2M 17 O 61 (R 1A X')2O] c33- (VI-9) [X2M 17 O 61 (R 1B1 R 1B2 X')2] c33- (VI-10) [X2M 17 O 61 (R 1D P=O)2] c33- (VI-11) [X2M 17 O 61 (R 1E X')] c33- (VI-12) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; X' represents a heteroatom of Si or Ge; X″ represents a heteroatom of Si, Ge or Sn; R 1A ~R 1E each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 1A ~R 1Ea divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), Above R 1A ~R 1E a hydrogen atom contained in the group may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; Above R 1A ~R 1E Two or more hydrogen atoms in (t) are replaced by polar groups having an acid-dissociable group; c31, c32 and c33 are natural numbers.)

[0117] In a heteropolyacid anion in which the vacant sites are modified, four terminal oxygen atoms of the vacant sites are modified, so the value of c31 above is usually c11-4 (c11 represents the absolute value of the number of negative charges in a mono-vacant Keggin type heteropolyacid anion represented by general formula (II-1)), the value of c32 above is c12-4 (c12 represents the absolute value of the number of negative charges in a doubly vacant Keggin type heteropolyacid anion represented by general formula (II-2)), and the value of c33 above is c21-4 (c21 represents the absolute value of the number of negative charges in a mono-vacant Dawson type heteropolyacid anion represented by general formula (III-1)). On the other hand, for example, when the organic group contains an amino group that is protonated to form an ammonium cation, or when the organic group contains a carboxy group that is a carboxy anion, the values ​​of c31 to c33 will differ from the above values.

[0118] [1-1-1-2-2.Organic group] Above R 1A , R 1B1 and R 1B2 , R 1C , R 1D , and R 1E The organic group represented by the formula (I) is not particularly limited, and any known and commonly used organic group can be used. From the viewpoint of providing a functional building block having different physical properties, such as solubility in a developer, between the exposed and unexposed portions to actinic rays, the organic group is preferably an organic group having two or more polar groups each having an acid-dissociable group. The number of polar groups having an acid-dissociable group contained in the organic group is not particularly limited, and preferably includes 1 to 6, more preferably includes 2 to 5, and further preferably includes 2 to 4.

[0119] an organic group R having two or more polar groups having the above acid-dissociable group; 1A , R 1B1 and R 1B2 , R 1C , R 1D , and R 1E As for R 1A ~R 1E C which may have a substituent 1-18 is a hydrocarbyl group; 1A ~R 1E Any divalent carbon atom except for the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 1A ~R 1Eone or more hydrogen atoms contained in the R may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; 1A ~R 1E at least two hydrogen atoms of which are replaced by (t) a polar group having an acid-dissociable group, R 1A ~R 1E C which may have a substituent 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 1A ~R 1E a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 1A ~R 1E a hydrogen atom contained in the above R may be replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or a carboxy group having a protecting group, or (t) a polar group having an acid-dissociable group; 1A ~R 1Emore preferably, at least two hydrogen atoms of the formula (1) are replaced by (t) a polar group having an acid-dissociable group, R 1A ~R 1E C which may have a substituent 1-18 Alkyl group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 1A ~R 1E a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); 1A ~R 1E More preferably, at least two hydrogen atoms of (t) are replaced by a polar group having an acid-dissociable group.

[0120] Above R 1A , R 1B1 and R 1B2 , R 1C , R 1D , and R 1E is characterized by having two or more polar groups having an acid-dissociable group, for example, two or more polar groups such as a hydroxy group, a carboxy group, an amino group, or a sulfo group having an acid-dissociable group are introduced. In addition, as the acid-dissociable group, for example, a tertiary carbon-type acid-dissociable group G A , an allylic or benzyl acid-dissociable group G B , acetal-type acid-dissociable group G C Examples of the acid-dissociable group G include the following. R having two or more polar groups having the above acid-dissociable group 1A , R 1B1 and R 1B2 , R 1C , R 1D , and R 1E For example, the following can be exemplified:

[0121] [ka] [G represents an acid-dissociable group G, and * represents a bond between the organic group and a heteroatom P, Si, Ge, or Sn.]

[0122] [ka] [* denotes the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0123] <Organic group having two or more polar groups having an acid-dissociable group> The organic group having two or more polar groups having an acid-dissociable group according to another embodiment is not particularly limited, and examples thereof include an organic group represented by general formula (VII). [ka] [In formula (VII), L 2 C may have a substituent 1-12 In the hydrocarbyl group, the hydrogen atoms on any carbon atom, including the terminals, are each R 2A and R 2B represents a group substituted with Said L 2 a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 2A and R 2B each independently represents a polar group having an acid-dissociable group, * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0124] L in the organic group represented by general formula (VII) 2 As for L 2 C which may have a substituent 2-10 In the hydrocarbyl group, the hydrogen atoms on any carbon atom, including the terminals, are each R2A and R 2B is a group substituted with: 2 and R 2A or R 2B is preferably a group in which a divalent carbon atom at any position except for the carbon atom to which is bonded may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), L 2 C which may have a substituent 2-10 Alkyl group, C 3-10 Alicyclic group, C 6-10 an aryl group, or C 6-10 In an aralkyl group, the hydrogen atoms on any carbon atom, including the terminal, are each R 2A and R 2B is a group substituted with: 2 and R 2A or R 2B is more preferably a group in which a divalent carbon atom at any position except for the carbon atom to which is bonded may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), L 2 C which may have a substituent 2-8 Alkyl group, C 3-8 Alicyclic group, C 6-8 an aryl group, or C 6-8 In an aralkyl group, the hydrogen atoms on any carbon atom, including the terminal, are each R 2A and R 2B is a group substituted with: 2 and R 2A or R 2B is more preferably a divalent carbon atom at any position except for the carbon atom to which it is bonded, which may be replaced by -O- or -S- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0125] R in the organic group represented by general formula (VII) 2A and R 2B As for R 2A and R 2B are preferably each independently a hydroxy group (including a phenolic hydroxy group) having an acid-dissociable group or a carboxy group, R 2A and R 2B are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; and the acid-dissociable group is a tertiary carbon-type acid-dissociable group G A , an allylic or benzyl acid-dissociable group G B or an acetal-type acid-dissociable group G C It is more preferable that R 2A and R 2B are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group; A It is more preferable that:

[0126] [1-1-2. Cation moiety of heteropolyacid salt or mixture thereof with modified defect sites] The cation moiety of the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment is H + , metal ions, onium cations or onium dications can be used.

[0127] [1-1-2-1. Metal ions] The metal ions that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect sites are modified are not particularly limited, and examples thereof include Li + , Na + , K. + , Rb + , Cs + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al3+ , Co 3+ , Bi 3+ , Zr 4+ , Hf 4+ , Bi 5+ etc. Metal ions include Li + , Na + , K. + , Rb + , Cs + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Al 3+ , Co 3+ is preferred, Na + , K. + , Rb + , Cs + , Ca 2+ , Al 3+ , Co 3+ is more preferred. These metal ions may be used alone or in combination of two or more.

[0128] [1-1-2-2. Onium cation or onium dication] The onium cation or onium dication that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect sites have been modified is not particularly limited, and any known or commonly used one can be used. Examples of the onium cation or onium dication include ammonium cation, ammonium dication, phosphonium cation, phosphonium dication, sulfonium cation, sulfonium dication, and iodonium cation. These onium cations or onium dications may be used alone or in combination of two or more.

[0129] The onium cation or onium dication is preferably a sulfonium cation, sulfonium dication, or iodonium cation, from the viewpoint of providing a building block that generates an acid when exposed to DUV, XUV, EUV, BEUV, an electron beam, or the like.

[0130] [1-1-2-2-1. Ammonium cation] The ammonium cation is not particularly limited, and known and commonly used ammonium cations can be used. The ammonium cation is not particularly limited, and examples thereof include ammonium ions (NH + ), primary ammonium cation (NH3(R 3A ) + )), secondary ammonium cation (NH2(R 3A )(R 3B )) + ), tertiary ammonium cation (NH(R 3A )(R 3B )(R 3C ) + ), quaternary ammonium cation (N(R 3A )(R 3B )(R 3C )(R 3D ) + ) are listed. 3A ~R 3D shall represent the same as defined below.

[0131] The ammonium cation is ammonium ion (NH4 + ), and quaternary ammonium cations are preferred, and in particular, ammonium ions (NH + ), and organic quaternary ammonium cations represented by the following general formula (VIII-1) are more preferred. [ka]

[0132] In general formula (VIII-1), R 3A ~R 3Deach independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 3A ~R 3D a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), Above R 3A ~R 3D The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 3A ~R 3D Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (VIII-1).

[0133] Specific examples of the organic quaternary ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, tetraheptylammonium cation, trimethylethylammonium cation, dimethyldiethylammonium cation, dimethylethylpropylammonium cation, methylethylpropylbutylammonium cation, trimethylphenylammonium cation, triethylhexylammonium cation, triethylcyclohexylammonium cation, dodecyltrimethylammonium cation, diallyldimethylammonium cation, (3-acrylamidopropyl)trimethylammonium cation, trimethyl-2-methacryloyloxyethylammonium cation, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, Examples include ammonium cation, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamido)ethyldimethylammonium cation, allyltrimethylammonium cation, butyl(2-methacryloyloxyethyl)dimethylammonium cation, ethoxycarbonylmethyltriethylammonium cation, 2-hydroxyethyltrimethylammonium cation, 2-acetylethyltrimethylammonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)trimethylammonium cation, (4-(methacryloyloxy)phenyl)trimethylammonium cation, trimethyl(4-(nonanoyloxy)phenyl)ammonium cation, and the like.

[0134] [1-1-2-2-2. Ammonium dication] The ammonium dication is not particularly limited, and any known or commonly used ammonium dication can be used. Examples of the ammonium dication include organic quaternary ammonium dications represented by the following general formula (VIII-2): [ka]

[0135] In general formula (VIII-2), R 4A ~R 4F each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 4A ~R 4F a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); L 4 C may have a substituent 1-18 represents a hydrocarbylene group, The above L 4 any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 4A ~R 4F and L 4 The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 4A ~R 4F Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (VIII-2).

[0136] The organic quaternary ammonium dication represented by the general formula (VIII-2) is not particularly limited, and examples thereof include 1,4-diallyl-1,4-diazabicyclo[2.2.2]octane-1,4-diium, 1,4-di(2-(meth)acryloyloxyethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium, and 1,4-bis(2-(meth)acrylamidoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0137] [1-1-2-2-3. Phosphonium cation] The phosphonium cation is not particularly limited, and known and commonly used phosphonium cations can be used. Examples of the phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VIII-3). [ka]

[0138] In general formula (VIII-3), R 5A ~R 5D each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; Above R 5A ~R 5D a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 5A ~R 5DThe hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 5A ~R 5DAny two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VIII-3).

[0139] The organic quaternary phosphonium cation represented by the general formula (VIII-3) is not particularly limited, and examples thereof include tributylcyanomethylphosphonium cation, methyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, cyanomethyltriphenylphosphonium cation, formylmethyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, chloromethyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, tributyl-1,3-dioxan-2-ylmethylphosphonium cation, triphenylpropargylphosphonium cation, allyltriphenylphosphonium cation, and the like. arylphosphonium cation, cyclopropyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis(hydroxymethyl)phosphonium cation, 2-carboxyethyltriphenylphosphonium cation, methoxycarbonylmethyltriphenylphosphonium cation, t-butoxycarbonylmethyltriphenylphosphonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cation, (4-(methacryloyloxy)phenyl)triphenylphosphonium cation, triphenyl(4-(nonanoyloxy)phenyl)phosphonium cation, and the like.

[0140] [1-1-2-2-4. Phosphonium dication] The phosphonium dication is not particularly limited, and known and commonly used phosphonium dications can be used. Examples of the phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VIII-4): [ka]

[0141] In general formula (VIII-4), R 6A ~R 6F each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 6A ~R 6F a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time), L 6 C may have a substituent 1-18 represents a hydrocarbylene group, The above L 6 any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 6A ~R 6F and L 6 The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 6A ~R 6F Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VIII-4).

[0142] The organic quaternary phosphonium dication represented by the general formula (VIII-4) is not particularly limited, and examples thereof include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, and pentamethylenebis(triphenylphosphonium) dication.

[0143] [1-1-2-2-5. Sulfonium cation] The sulfonium cation is not particularly limited, and any known and commonly used sulfonium cation can be used. Examples of the sulfonium cation include organic sulfonium cations represented by the following general formula (VIII-5): [ka]

[0144] In general formula (VIII-5), R 7A , R 7B and R 7C each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 7A , R 7B and R 7C a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 7A , R 7B and R 7C The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 7A , R 7B and R 7C Any two of these are directly connected to each other by a single bond, or are a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (VIII-5).

[0145] In the organic sulfonium cation represented by the general formula (VIII-5), the R 7A , R 7B and R 7C As for R 7A , R 7B and R 7C each independently represents C which may have a substituent 1-18is a hydrocarbyl group; 7A , R 7B and R 7C wherein a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), R 7A , R 7B and R 7C each independently represents C which may have a substituent 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 7A , R 7B and R 7C wherein a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), R 7A , R 7B and R 7C each independently represents C which may have a substituent 6-18 is an aryl group; 7A , R 7B and R 7C The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is more preferable that the divalent carbon atom at any position of these substituents except for the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0146] Also R 7A , R 7B and R 7C Any two of these are directly connected to each other by a single bond, or are a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 Examples of compounds that are linked via an alkylene group to form a ring together with the sulfur atom in formula (VIII-5) include compounds having a thian-1-ium skeleton, a thiophen-1-ium skeleton, a 1,4-oxathiane-4-ium skeleton, a 1,4-dithian-1-ium skeleton, a 1H-thiophen-1-ium skeleton, a benzo[b]thiophen-1-ium skeleton, a dibenzothiophenium skeleton, a 9,10-dihydrothioxanthylium skeleton, a 10H-phenoxathiane-10-ium skeleton, and a 5H-thianthren-5-ium skeleton, and the following can also be mentioned. Note that * indicates that the compound is not involved in the formation of a ring. R 7A , R 7B or R 7C It means the junction with.

[0147] [ka]

[0148] Examples of the organic sulfonium cation include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, di(naphthalen-1-yl)(phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthren-5-ium cation, 5-(2,5-dimethylphenyl)thianthren-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophen-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,d]thiophen-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolyl sulfonium cation, and the like.

[0149] [1-1-2-2-6. Sulfonium dication] The sulfonium dication is not particularly limited, and any known and commonly used sulfonium dication can be used. Examples of the sulfonium dication include organic sulfonium dications represented by the following general formula (VIII-6): [ka]

[0150] In general formula (VIII-6), R 8A , R 8B , R 8C and R 8D each independently represents a C group which may have a substituent; 1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 8A , R 8B , R 8C and R 8Da divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); L 8 C may have a substituent 1-18 represents a hydrocarbylene group, The above L 8 any divalent carbon atom at any position may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S- or SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 8A , R 8B , R 8C , R 8D , and L 8 The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 a hydrocarbylthio group, and any divalent carbon atom at any position of these substituents except the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); R 8A , R 8B and L 8 Any two of and / or R 8C , R 8D and L 8 Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (VIII-6).

[0151] [1-1-2-2-7. Iodonium cation] The iodonium cation is not particularly limited, and any known and commonly used iodonium cation can be used. Examples of the iodonium cation include organic iodonium cations represented by the following general formula (VIII-7): [ka]

[0152] In general formula (VIII-7), R 9A and R 9B each independently represents a C group which may have a substituent;1-18 represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, Above R 9A and R 9B a divalent carbon atom at any position except the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Above R 9A and R 9B The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, C 1-18 Hydrocarbylamino group, diC 1-18 Hydrocarbylamino group, C 1-18 Hydrocarbyl aminocarbonyl group, diC 1-18 Hydrocarbylaminocarbonyl group, C 1-18 Hydrocarbyl carbonyl amino group, C 1-18 Hydrocarbylaminocarbonyloxy group, diC 1-18 Hydrocarbylaminocarbonyloxy group, C 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18 may be substituted with a hydrocarbylthio group, and any divalent carbon atom of these substituents, excluding the terminals, may be substituted with -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time); Further R 9A and R 9B are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -C(=O)O-, or C 1-3 They may be linked via an alkylene group to form a ring together with the iodine atom in formula (VIII-7).

[0153] In the organic iodonium cation represented by general formula (VIII-7), R 9A and R 9B As for R 9A and R 9B each independently represents C which may have a substituent 1-18 is a hydrocarbyl group; 9A and R 9B wherein a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), R 9A and R 9B each independently represents C which may have a substituent 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 is an aralkyl group; 9A and R 9Bwherein a divalent carbon atom at any position excluding the terminal may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), R 9A and R 9B each independently represents C which may have a substituent 6-18 is an aryl group; 9A and R 9B The hydrogen atoms contained in the formula (I) are selected from the group consisting of (a) halogen atoms, (b) haloalkyl groups, (c) hydroxy groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxy groups, (h) amino groups, (i) sulfo groups, (j) vinyl groups, (k) allyl groups, (l) (meth)acryloyl groups, (m) (meth)acryloyloxy groups, (n) (meth)acrylamide groups, (o) styryl groups, (p) epoxy groups, (q) glycidyl groups, (r) amide groups, (s) hydroxy groups or carboxy groups having a protecting group, (t) polar groups having an acid-dissociable group, and (u) C in which at least a part of the hydrogen atoms may be substituted with any of the above (a) to (t). 1-18 Hydrocarbyl group, C 1-18 Hydrocarbyloxy group, C 1-18 Hydrocarbyl carbonyl group, C 1-18 Hydrocarbylcarbonyloxy group, C 1-18 Hydrocarbyloxycarbonyl group, C 1-18 Hydrocarbyloxycarbonyloxy group, or C 1-18 It is more preferable that the divalent carbon atom at any position of these substituents except for the terminals may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0154] Examples of the organic iodonium cation include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, )iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 -trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-me (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation, and the like.

[0155] [1-1-3. Heteropolyacid salts or mixtures thereof with modified defect sites (general formulas (I) and (I'))] <Heteropolyacid salts having modified defect sites represented by general formula (I) or mixtures thereof> According to another embodiment, the heteropolyacid salt or a mixture thereof in which the defect site is modified is represented by the following general formula (I). (A m+ ) a (C (am)- ) (I) [In formula (I), A m+ are each independently H + , metal ions, NH4 + , an onium cation, or an onium dication; C (am)- represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer between 1 and 5, and a is a real number greater than 0.

[0156] In the heteropolyacid salt having modified defect sites represented by the above general formula (I) or a mixture thereof, the "metal ion," the "onium cation," the "onium dication," and the "heteropolyacid anion having defect sites and having the defect sites modified" can be any of those described above.

[0157] The mixture of heteropolyacid salts having modified defect sites represented by the general formula (I) contains a plurality of types of A m+ In the above case, multiple types of A may be included. m+ The content ratio can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0158] <Heteropolyacid salts having modified defect sites represented by general formula (I') or mixtures thereof> Yet another heteropolyacid salt or a mixture thereof in which defect sites have been modified according to this embodiment is represented by the following general formula (I'). (A' m’+ ) a’ (B n+ ) b (C' (a’m’+bn)- ) (I') [In formula (I'), A' m’+ are each independently H + , metal ions, or NH4 + represents; B n+ each independently represents an onium cation or an onium dication; C' (a’m’+bn)- represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m' is an integer of 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.

[0159] In the heteropolyacid salt having modified defect sites represented by the above general formula (I') or a mixture thereof, the "metal ion," the "onium cation," the "onium dication," and the "heteropolyacid anion having defect sites and having the defect sites modified" can be appropriately selected from those described above.

[0160] The heteropolyacid salt or mixture thereof having modified vacancy sites represented by the above general formula (I') has a sulfonium cation, a sulfonium dication, or an iodonium cation in the cation moiety, and therefore can be endowed with the function of generating an acid by exposure to DUV, XUV, EUV, BEUV, electron beam, or the like.

[0161] The mixture of heteropolyacid salts having modified defect sites represented by general formula (I') contains A' m’+ and B n+The heteropolyacid salt may include a heteropolyacid salt modified with a plurality of defect sites having different ratios of a' and b. In this case, the values ​​of a' and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0162] The ratio of a' to b is the heteropoly acid anion with the defect site modified, A' m’+ , B n+ Although it depends on the type of the compound, a':b is preferably 0-8:1-12, more preferably 0-4:2-8, and even more preferably 0-2:1-4. In particular, when the value of a'm'+bn is an integer of 2 to 8 and m' and n are 1, it is preferable that a' is a real number of 0 to 7 and b is a real number of 1 to 8, and it is more preferable that a' is a real number of 0 to 4 and b is a real number of 2 to 8.

[0163] [1-1-4. (A) Component Content] There are no particular limitations on the amount of component (A) in the resist material, and this can be set as appropriate depending on the method for applying the resist material to a substrate, the thickness of the applied film, etc. The amount of component (A) in the resist material is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.2 to 10 mass%, based on 100 mass% of the resist material.

[0164] [1-2. (B) Acid diffusion controller] The resist material according to this embodiment may contain (B) an acid diffusion controller that traps acid generated by exposure.

[0165] The acid diffusion controller is not particularly limited, and any known or commonly used one can be used. Examples of the acid diffusion controller include (B1) a photodecomposable base that decomposes upon exposure to light and loses its acid diffusion control ability, and (B2) a nitrogen-containing organic compound that does not fall under the category of component (B1). These may be used alone or in combination of two or more.

[0166] [1-2-1. (B1) Photodegradable bases] The photodegradable base (B1) loses its ability to control acid diffusion when decomposed by exposure, but acts as a quencher in unexposed areas, thereby controlling acid diffusion. Therefore, by incorporating the photodegradable base (B1) into a resist material, it is possible to improve properties such as increased sensitivity, reduced roughness, and suppression of coating defects.

[0167] The photodegradable base is not particularly limited, and known and commonly used ones can be used. Examples of the photodegradable base include "carboxylate compound B" represented by the following general formula (IX-1): A ", "sulfonate compound B" represented by the following general formula (IX-2) B ", "sulfonylamide salt compound B" represented by the following general formula (IX-3) C ", etc. In the following, carboxylate anions, sulfonate anions, sulfonylamide anions, onium cations or onium dications (D p+ ) will be explained in this order. [ka] [ka] [ka]

[0168] [1-2-1-1. Carboxylate Compound B A ] The photodecomposable base (B1) is a carboxylate compound B represented by the following general formula (IX-1): A ", a carboxylate anion and an onium cation or an onium dication (D p+ ) can be used as a salt. [ka]

[0169] "R Ab1 " is an optionally substituted C 1-18 In the hydrocarbyl group, the 3- to 18-membered non-aromatic heterocyclic group, or the 5- to 18-membered aromatic heterocyclic group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0170] R A b1 As the C 1-18 A hydrocarbyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred. Optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0171] <Carboxylate Compound B A1 > Carboxylate compound B represented by the above general formula (IX-1) A is a carboxylate compound B represented by the following general formula (IX-1-1): A1 may be. [ka]

[0172] "X A " is an optionally substituted C 1-18Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 In an aralkyl group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0173] X A As the C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 3-18 an alicyclic group, or C 6-18 An aryl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0174] "L A " is X A and -COO - and a group having the following general formula (L A -1)~(L A A linking group represented by the formula (I)-7) can be used. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, L A b1 and L A b2 represents a single bond or an optionally substituted C 1-8 represents a hydrocarbylene group, and *1 represents X A The connection part is *2 -COO - ]

[0175] L A b1 and L A b2 is a single bond or an optionally substituted C 1-8 Alkylene group or C 6-8 An arylene group is preferred, and C 1-8 An alkylene group is more preferred.

[0176] <Examples of carboxylate anions> The above carboxylate compound B A or B A1The carboxylate anion is not particularly limited, and examples thereof include trifluoroacetate anion, pentafluoropropionate anion, 2-methoxyacetate anion, 2-methoxy-2-methylpropionate anion, 2-hydroxyacetate anion, 2-hydroxy-2-methylpropionate anion, 2-acetoxyacetate anion, adamantane-1-carboxylate anion, 9,10-dihydro-9,10-ethanoanthracene-11-carboxylate anion, 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-carboxylate anion, benzoate anion, salicylate anion, 3-hydroxybenzoate anion, and 3-trifluoromethylbenzoate anion.

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] [1-2-1-2. Sulfonate Compound B B ] The photodegradable base (B1) is a sulfonate compound B represented by the following general formula (IX-2): B ", a sulfonate anion and an onium cation or an onium dication (D p+ ) can be used as a salt. [ka]

[0181] "R B b1 " is an optionally substituted C 1-18In the hydrocarbyl group, the 3- to 18-membered non-aromatic heterocyclic group, or the 5- to 18-membered aromatic heterocyclic group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0182] R B b1 As the C 1-18 A hydrocarbyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred. Optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0183] <Sulfonate Compound B B1 > Sulfonate compound B represented by the above general formula (IX-2) B is a sulfonate compound B represented by the following general formula (IX-2-1): B1 may be. [ka]

[0184] "X B " is an optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18an aryl group, or C 7-18 In an aralkyl group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0185] X B As the C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 3-18 an alicyclic group, or C 6-18 An aryl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0186] "L B " is X B and -SO2-O - and a group having the following general formula (L B -1)~(L B A linking group represented by the formula (I)-7) can be used. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, L B b1 and L B b2 represents a single bond or an optionally substituted C 1-8 represents a hydrocarbylene group, and *1 represents X B The connection part is *2 -SO2-O - ]

[0187] L B b1 and L B b2 is a single bond or an optionally substituted C 1-8 Alkylene group or C 6-8 An arylene group is preferred, and C 1-8 An alkylene group is more preferred.

[0188] <Examples of sulfonate anions> The above sulfonate compound B B or B B1 The sulfonate anion is not particularly limited, and examples thereof include camphorsulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantane-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, and 4-methylbenzenesulfonate anion.

[0189] [ka]

[0190] [1-2-1-3. Sulfonylamide salt compound B C ] The photodecomposable base (B1) is a sulfonylamide salt compound B represented by the following general formula (IX-3): C ", a sulfonyl amide anion and an onium cation or an onium dication (D p+ ) can be used as a salt. [ka]

[0191] "R C b1 " is an optionally substituted C 1-18 In the hydrocarbyl group, the 3- to 18-membered non-aromatic heterocyclic group, or the 5- to 18-membered aromatic heterocyclic group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time). "R C b2 " is an optionally substituted C 1-18 Any divalent carbon atom in the hydrocarbyl group, excluding the terminal one, may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0192] R C b1 As the C 1-18 A hydrocarbyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred. Optionally substituted C1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0193] R C b2 As the C 1-18 Alkyl group, C 3-18 An alicyclic group in which any divalent carbon atom excluding a terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; C 1-12 More preferably, it is a haloalkyl group, and C 1-5 A fluorinated alkyl group is more preferred.

[0194] <Sulfonylamide salt compound B C1 > Sulfonylamide salt compound B represented by the above general formula (IX-3) C is a sulfonylamide salt compound B represented by the following general formula (IX-3-1): C1 may be. [ka]

[0195] "X C " is an optionally substituted C 1-18 Alkyl group, C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18In an aralkyl group, any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0196] X C As the C 3-18 Alicyclic group, C 6-18 an aryl group, or C 7-18 An aralkyl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO- (provided that adjacent divalent carbon atoms are not replaced at the same time), is preferred; Optionally substituted C 3-18 an alicyclic group, or C 6-18 An aryl group in which any divalent carbon atom excluding the terminal one may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO2- (provided that adjacent divalent carbon atoms are not replaced at the same time) is more preferred.

[0197] "L C " is X C and -N - -SO2-R C b2 and a group having the following general formula (L C -1)~(L C A linking group represented by the formula (I)-7) can be used. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [In the formula, L C b1 and L C b2 represents a single bond or an optionally substituted C 1-12 represents a hydrocarbylene group, and *1 represents X C The connection part with *2 is -N - -SO2-R C b2 ]

[0198] L C b1 and L C b2 is a single bond or an optionally substituted C 1-12 Alkylene group, C 1-12 Cycloalkylene group or C 6-12 An arylene group is preferred, and C 1-8 Alkylene group or C 1-8 A cycloalkylene group is more preferred.

[0199] <Examples of sulfonylamide anions> The sulfonylamide salt compound B C or B C1The sulfonylamide anion is not particularly limited, and examples thereof include methyl((trifluoromethyl)sulfonyl)amide anion, i-propyl((trifluoromethyl)sulfonyl)amide anion, methacryloyloxy((trifluoromethyl)sulfonyl)amide anion, 2-(methacryloyloxy)ethyl((trifluoromethyl)sulfonyl)amide anion, cyclohexyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclopentanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclohexanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1 ]heptan-2-ylmethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptan-7-ylmethyl((trifluoromethyl)sulfonyl)amide anion, 2-((adamantane-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(adamantane-1-carboxamido)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantane-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anion, 4-((adamantane-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anion, and the like.

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] [1-2-1-4. Onium cation or onium dication (D p+ )] The cation moiety of the photodegradable base (B1) is an onium cation or an onium dication (D p+ ) can be used. Here, "(D p+ ) 1 / p In the formula, D represents an onium cation or an onium dication, and p represents an integer of 1 or 2. The onium cation or onium dication is not particularly limited, and the above-mentioned "sulfonium cation," "sulfonium dication," "iodonium cation," "ammonium cation," "ammonium dication," "phosphonium cation," "phosphonium dication," etc. can be used.

[0204] [1-2-2.(B2) Nitrogen-containing organic compound] Other (B) acid diffusion controllers may include (B2) and (B1) nitrogen-containing organic compounds that do not fall under the category of (B1). The nitrogen-containing organic compounds are not particularly limited, and examples thereof include aliphatic amines, aromatic amines, and heterocyclic amines.

[0205] Examples of the nitrogen-containing organic compound include aliphatic amines such as n-hexylamine, n-heptylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-octylamine; aromatic amines such as aniline, N-methylaniline, N-ethylamine, N,N-dimethylaniline, 4-methylaniline, and pyrrole; and heterocyclic amines such as pyridine, imidazole, benzimidazole, piperidine, piperazine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane. These nitrogen-containing organic compounds may be used alone or in combination of two or more.

[0206] [1-2-3. Amount] The amount of (B) acid diffusion controller contained in the resist material according to this embodiment is not particularly limited and can be set appropriately depending on the amount and type of component (A), etc. The amount of component (B) in the resist material is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A).

[0207] [1-3. Organic solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and any known or commonly used organic solvent can be used. The organic solvent is preferably an organic solvent that can uniformly dissolve or disperse (A) the heteropolyacid salt having modified defect sites or a mixture thereof when prepared.

[0208] Examples of organic solvents include polar solvents such as alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, nitrile solvents, and aprotic polar solvents, and nonpolar solvents such as hydrocarbon solvents. These organic solvents may be used alone or in combination of two or more.

[0209] Specific examples of the polar solvent include: Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Nitrile solvents such as acetonitrile, propionitrile, and benzonitrile: Examples of the solvent include aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Examples of non-polar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The organic solvents may be used alone or in combination of two or more.

[0210] The organic solvent contained in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, an ester solvent, an alcohol solvent, or a ketone solvent in terms of solubility. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. Furthermore, the ester solvent or alcohol solvent preferably has an ester bond and / or a hydroxyl group in terms of solubility, and among the above, at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate is preferred.

[0211] The amount of organic solvent in the resist material is not particularly limited and can be set appropriately depending on the method for applying the resist material to a substrate, the thickness of the applied film, etc. The amount of organic solvent in the resist material is preferably such that the solids concentration of the resist material is 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.2 to 10 mass%.

[0212] [1-4.Other] The resist material according to this embodiment may further contain, as desired, miscible additives, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and dyes. The resist material according to this embodiment preferably does not contain an epoxy resin, and also preferably does not contain hydrogen peroxide.

[0213] [2. Pattern formation method] The pattern forming method according to this embodiment includes the steps of applying a resist material to a substrate, exposing the resist film formed by the application step, and developing the exposed resist film.

[0214] [2-1. Coating process] The pattern formation method according to this embodiment includes a step of applying a resist material to a substrate.

[0215] <Substrate> The substrate used in this embodiment is not particularly limited, and any known and commonly used substrate can be used. For example, a substrate for electronic components or a substrate on which a predetermined wiring pattern is formed may be used. The material of the substrate is not particularly limited, and examples thereof include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and substrates made of inorganic materials such as glass, titanium oxide, and silicon dioxide. The size, shape, etc. of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or may be a thin plate-shaped substrate.

[0216] The surface of the substrate may be subjected to a surface treatment as necessary. In the case of a substrate having hydroxyl groups on its surface layer, the surface of the substrate can be treated with a silane coupling agent capable of reacting with the hydroxyl groups, thereby changing the surface layer of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane coupling agent include hexamethyldisilazane (HMDS).

[0217] <Application method> The method for applying the resist material to the substrate is not particularly limited, and any known or commonly used method can be used. Examples of dry application methods include CVD (chemical vapor deposition) methods such as thermal CVD, plasma CVD, and photo-CVD; and PVD (physical vapor deposition) methods such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Examples of wet application methods include spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0218] As a method for applying the resist material according to this embodiment to a substrate, a wet method such as spin coating or screen printing is preferably used, and spin coating is more preferable, from the viewpoint of forming a uniform film thickness, etc. After forming the coating film, a backside rinse, an edge bead removal step, etc. may be performed to remove the edge bead.

[0219] The method for drying the resist film formed by applying the resist material to the substrate is not particularly limited, and can be carried out using, for example, a heating device such as a hot plate (post-apply bake (PAB)), a pressure reducing device, or the like. The baking conditions are not particularly limited and can be set appropriately depending on the type of resist film, the application, etc. The baking temperature is preferably 80 to 300° C., more preferably 80 to 200° C., and even more preferably 80 to 130° C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0220] The thickness of the resist film after drying is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 75 nm, and even more preferably 1 to 60 nm.

[0221] [2-2. Exposure process] The pattern forming method according to this embodiment includes a step of exposing the resist film formed in the above coating step.

[0222] The exposure device used in the exposure step of the resist film may be, for example, an ArF exposure device, an electron beam lithography device, an EUV exposure device, a BEUV exposure device, etc. In the exposure step, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by lithography using direct irradiation with an electron beam without using a mask pattern.

[0223] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser (wavelength 193 nm), KrF excimer laser (wavelength 248 nm), F2 excimer laser (wavelength 157 nm), EUV (extreme ultraviolet (wavelength 13.5 nm)), BEUV (Beyond EUV (wavelength 6.X nm)), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may be used.

[0224] The exposure dose on the resist film is 1 to 200 mJ / cm in the case of an ArF excimer laser or a KrF excimer laser. 2 is preferably 20 to 60 mJ / cm 2 In the case of extreme ultraviolet rays, the exposure dose is, for example, 500 mJ / cm 2 2 or less, 0.1 to 200 mJ / cm 2 is preferably 3 to 100 mJ / cm 2 More preferably, it is 5 to 50 mJ / cm 2 Furthermore, in the case of BEUV, the exposure dose is, for example, 1000 mJ / cm 2 2 or less, 0.1 to 400 mJ / cm 2 is preferably 1 to 200 mJ / cm 2 More preferably, it is 5 to 150 mJ / cm 2 It is more preferable that: For electron beams, 3 μC / cm at 50 kV 2 ~2mC / cm 2 It is preferable to expose at a dose of 10 μC / cm 2 ~1.5mC / cm 2 It is more preferable to expose at a dose of 1000 ppm.

[0225] After exposing the resist film, baking (post-exposure bake (PEB)) may or may not be performed. The baking conditions are not particularly limited and can be set appropriately depending on the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C, using a heating device such as a hot plate. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0226] [2-3. Development process] The pattern forming method according to this embodiment includes a step of developing the exposed resist film. In the development step, a pattern can be formed by developing the exposed resist film with a developer. A negative pattern formation process is one in which the exposed region remains as a pattern after development, while a positive pattern formation process is one in which the exposed region is removed after development. Whether a positive or negative pattern is formed can be appropriately selected depending on the resist material or the developer. After the development, the resist film may be washed with a rinse solution and then dried, and in some cases, a baking treatment may be further performed.

[0227] The developer used in this embodiment may be an alkaline developer for an alkaline development process, or a developer containing an organic solvent (organic developer) for an organic solvent development process.

[0228] <Alkaline development process> With conventional metal oxide resist materials, it has been difficult to form positive patterns with good resolution using an alkaline development process. In contrast, the resist material according to this embodiment can be used to form a pattern with good resolution using a developer containing water.

[0229] The alkaline developer used in the alkaline development process is not particularly limited, and any known or commonly used one can be used. Examples of the alkaline developer include aqueous solutions containing one or more of quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide, inorganic alkalis such as sodium hydroxide and potassium hydroxide, and alkanolamines such as dimethylethanolamine and triethanolamine.

[0230] The method for developing the exposed resist film using the alkaline developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0231] Furthermore, pure water can be used as a rinse liquid in the alkaline development process.

[0232] <Organic solvent development process> Examples of developers used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents, such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, and hydrocarbon-based solvents.

[0233] Specific examples of organic solvents include: ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); Alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); Nitrile solvents such as acetonitrile, propionitrile, and benzonitrile: Amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; Hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene; These may be used alone or in combination of two or more.

[0234] Among these, the organic solvent used in the developer is preferably a polar solvent, and preferably contains an amide solvent, an alcohol solvent, or an ester solvent, and more preferably contains an amide solvent or an ester solvent and an alcohol solvent. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent is preferably at least one selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol-based solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol.

[0235] When the developer contains both an amide solvent or an ester solvent and an alcohol solvent, the blending ratio (weight ratio) of the amide solvent or the ester solvent to the alcohol solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0236] The method for developing the exposed resist film using the developer is not particularly limited, and any known or commonly used method can be used. Examples of the method for developing using the developer include a method of immersing a substrate having an exposed resist film in the developer for a certain period of time (dip method), a method of spraying the developer onto the surface of the exposed resist film (spray method), and a method of discharging the developer at a constant speed from a discharge nozzle toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispense method).

[0237] After development with the developer, a step of washing with a rinse liquid may be included. The rinse liquid is not particularly limited, and any known or commonly used liquid may be used. As the rinse liquid, water or an organic solvent contained in the developer that does not easily dissolve the resist pattern may be appropriately selected and used.

[0238] The rinse liquid is not particularly limited, and may be, for example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Among these, it is preferable to use at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents as the rinse liquid, it is more preferable to use at least one solvent selected from the group consisting of alcohol solvents and ester solvents, and it is even more preferable to use at least one alcohol solvent.

[0239] The alcohol-based solvent used in the rinse liquid is preferably a monohydric alcohol having 2 to 8 carbon atoms, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the monohydric alcohol include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. These organic solvents may be used alone or in combination of two or more.

[0240] The method for cleaning the resist pattern with the rinse liquid is not particularly limited, and any known or commonly used method can be used. Examples of the cleaning method using the rinse liquid include a method of immersing the resist pattern in the rinse liquid for a certain period of time (dip method), a method of spraying the rinse liquid onto the surface of the resist pattern (spray method), and a method of discharging the rinse liquid at a constant speed from a discharge nozzle toward the surface of the resist pattern rotating at a constant speed (dynamic dispense method).

[0241] [3. Patterned Structure] The patterned structure according to this embodiment can be obtained by forming a pattern of the resist material on a substrate using the pattern formation method.

[0242] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be appropriately set depending on the intended use, etc. The patterned structure preferably has portions with an average thickness of 1 to 100 nm, more preferably 5 to 75 nm, and even more preferably 10 to 60 nm.

[0243] Furthermore, the pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set appropriately depending on the intended use, etc. The patterned structure preferably has a portion with a pitch of 100 nm or less, more preferably has a portion with a pitch of 50 nm or less, and even more preferably has a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the patterning method described above, it is possible to create portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0244] [4. Resist materials for EUV, BEUV or electron beams] The resist material according to this embodiment contains a heteropolyacid salt or a mixture thereof in which vacancy sites have been modified. By introducing an onium cation or an onium dication into the cation moiety of the heteropolyacid salt or the mixture thereof, the resist material can generate an acid upon exposure to extreme ultraviolet (EUV), very extreme ultraviolet (BEUV), electron beams, or the like.

[0245] Furthermore, the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment has a plurality of polar groups having an acid-dissociable group introduced into the anion moiety, and therefore the resist material has the function of significantly changing its solubility in a developer by the action of an acid or the like.

[0246] That is, the resist material according to this embodiment contains a heteropolyacid salt or a mixture thereof in which the defect sites have been modified, and can significantly change the solubility in a developer between the exposed portion and the unexposed portion by EUV, BEUV, electron beam, or the like.

[0247] Additionally, in the heteropolyacid anion used in the anion portion of the heteropolyacid salt or mixture thereof whose defect sites have been modified according to this embodiment, the polyatom is Mo, W, V, Nb, or Ta, thereby enabling efficient absorption of actinic rays such as EUV, BEUV, and electron beams. In particular, when the polyatom is W, W has a high absorption cross section in BEUV, and therefore is particularly suitable for use in microfabrication processes using BEUV exposure.

[0248] Therefore, the resist material according to this embodiment is a resist material that is sensitive to EUV, BEUV, or electron beams, and can be suitably used as a resist material for EUV, BEUV, or electron beams. [Example]

[0249] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0250] [1. Synthesis of Polyacid Salts] <Production Example 1: Potassium undecatungstosilicate (α-K8[SiW 11 O 39 ]) Manufacturing> Silicotungstic acid hydrate (Nippon Inorganic Chemical Industry Co., Ltd.: H4[SiW 12 O 40 380 g of 1 M acetic acid was added to 63 g of HCl (HCl·xH2O), and the reaction mixture was heated to 45 °C. Potassium bicarbonate (52 g) was added to adjust the pH to 6.0. The reaction mixture was then cooled to room temperature and filtered off by suction, yielding 56 g of crude product. 216 g of purified water was added to the crude product, which was then redissolved by heating to 73 °C. The solution was cooled at 4 °C for 16 hours to allow recrystallization, which was then filtered off by suction and dried in vacuo to yield 34 g of the target compound. 29 Si-NMR(119.22MHz,D2O):δ(ppm)=-84.6(s,1Si). 183 W-NMR (20.84MHz, D2O): δ(ppm)=-101.85(s,2W),-116.26(s,2W),-119.29(s,1W),-125.62(s,2W),-140.85(s,2W),-174.53(s,2W).

[0251] <Production Example 2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B)> [ka]

[0252] Production Example 2-1: Production of di(1-methylcyclopentyl) (2E)-but-2-enedioate (Compound A) 1-Methylcyclopentanol (14.1 g), dichloromethane (60 g), and triethylamine (21.3 g) were charged and cooled on ice while stirring. Fumaryl chloride (10.3 g) was added and stirred for 1 hour. Then, 5% aqueous potassium carbonate solution (60 g) was charged and stirred. After stopping the stirring, the aqueous layer was removed and washed with ultrapure water (60 g). The organic layer was concentrated under reduced pressure to obtain 14.5 g of compound A.

[0253] Production Example 2-2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B) Compound A (7.7 g), 3-mercaptopropyltrimethoxysilane (9.8 g), methyl ethyl ketone (20 ml), and 1,1'-azobis(cyclohexane-1-carbonitrile) (0.3 g) were added in this order and stirred. The mixture was then heated from room temperature to 90°C and stirred for 7 hours. The reaction solution was evaporated and further dried in vacuo to obtain 16.6 g of compound B. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,2H),1.38-1.82(m,20H),1.90-2.10(m,4H),2.50-2.80(m,4H),3.45-3.50(m,10H).

[0254] <Production Example 3: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D)> [ka]

[0255] Production Example 3-1: Production of di(1-t-butylcyclopentyl) (2E)-but-2-enedioate (Compound C) Compound C was obtained in Production Example 2-1, except that 1-methylcyclopentanol was changed to 1-t-butylcyclopentanol. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=0.95(s,18H), 1.78-1.98(m,8H), 2.12-2.21(m,4H), 2.47-2.53(m,4H), 6.80(s,2H).

[0256] Production Example 3-2: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D) In Production Example 2-2, Compound A was changed to Compound C to obtain Compound D. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,2H),0.95(s,18H),1.62-1.82(m, 10H),1.90-2.10(m,4H),2.20-2.32(m,4H),2.50-2.80(m,4H),3.45-3.50(m,10H).

[0257] <Production Example 4: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F)> [ka]

[0258] Production Example 4-1: Production of di(1-phenylcyclopentyl)(2E)-but-2-enedioate (Compound E) Compound E was obtained by changing 1-methylcyclopentanol to 1-phenylcyclopentanol in Production Example 2-1. 1H-NMR (400MHz, DMSO-d6): δ(ppm)=1.78-1.98(m,8H), 2.02-2.21(m,4H), 2.37-2.53(m,4H), 6.80(s,2H), 7.20-7.49(m,10H).

[0259] Production Example 4-2: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F) In Production Example 2-2, Compound A was changed to Compound E to obtain Compound F. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,2H),1.62-1.82(m,10H),1.90-2.10( m,4H),2.20-2.32(m,4H),2.50-2.80(m,4H),3.45-3.50(m,10H),7.10-7.39(m,10H).

[0260] <Synthesis Example 1: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-1))> [ka]

[0261] 5.6 g of compound B was added to a mixed solvent of 402 g of acetonitrile and 184 g of pure water to form the mono-defective Keggin-type potassium undecatungstosilicate (α-K8[SiW 11 O 39 10.9 g of bis(2-trifluoromethylphenylphenylsulfonium chloride) was added. The pH was adjusted to 1.8 with 1 M hydrochloric acid, and after stirring for 2 hours, the filtrate was concentrated to approximately 200 g. 9.9 g (18.2 mol) of bis(2-trifluoromethylphenylphenylsulfonium chloride) and 40 g of pure water were added to this concentrated solution to precipitate a powder. The precipitated powder was filtered off, washed three times with 180 mL of pure water, and then filtered off again. Further thorough vacuum drying yielded 15.8 g of polyacid salt (A-1). 1H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.38-1.82 (m, 40H), 1 .90-2.10(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS:POSITIVE m / z 399.1([C 20 H 13 F6S] + ) NEGATIVE m / z 864.1(central value)([C 38 H 62 O 48 S2Si3W 11 ] 4- )

[0262] <Synthetic example 2: テトラキス(ビス(2-トリフルオロメチルフェニル)フェニルスルホニウム)(1,3-ビス(3-(1,2-ビス(1-t-ブチルシクロペンチルオキシカボニル)エチルチオ)プロパン-1-イル)ジシロキサン-1,1,3 ,Synthesis of 3-テトライル)ウンデカタングストシリケート (ポリ acid acid (A-2))>

change

[0263] Synthesis Example 1: Compound B, Compound D, Compound D, and Polymer acid (A-2) were obtained. 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 0.95 (s, 36H), 1.62-1.82 (m, 20H), 1.9 0-2.10(m,8H),2.20-2.32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.65-8.35(m,52H). 29Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.03 (s, 1Si). ESI-MS:POSITIVE m / z 399.1([C 20 H 13 F6S] + ) NEGATIVE m / z 906.2(center value)([C 50 H 86 O 48 S2Si3W 11 ] 4- )

[0264] <Synthetic example 3: テトラキス(ビス(2-トリフルオロメチルフェニル)フェニルスルホニウム)(1,3-ビス(3-(1,2-ビス(1-フェニルシクロペンチルオキシカルボニル)エチルチオ)プロパン-1-イル)ジシロキサン-1,1,3, 3-Synthesis of テトライル)ウンデカタングストシリケート (ポリ acid acid (A-3))>

change

[0265] Synthesis Example 1: Compound B, Compound F, Compound F, and Polymer acid (A-3) were obtained. 1 H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2. 20-2.32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.10-7.39(m,20H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS:POSITIVE m / z 399.1([C 20 H 13 F6S] + ) NEGATIVE m / z 926.2(center value)([C 58H 70 O 48 S2Si3W 11 ] 4- )

[0266] <Synthesis Example 4: Synthesis of tetrakis((4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium)(1,3-bis(3-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-4))> [ka]

[0267] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide, to obtain polyacid salt (A-4). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),0.77-0.81(t,12H),1.38-1.82(m,64H),1.90-2.10(m,2) 4H),2.20-2.32(m,24H),2.50-2.80(m,8H),3.45-3.50(m,2H),4.55(s,8H),7.59(s,8H),7.76-7.82(m,40H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.05(s,2Si),-85.04(s,1Si). ESI-MS: POSITIVE m / z 461.2 ([C 29 H 33 O3S] + ) NEGATIVE m / z 864.1 (median) ([C 38 H 62 O 48 S2Si3W 11 ] 4- )

[0268] <Synthesis Example 5: Synthesis of tetrakis(triphenylsulfonium)(1,3-bis(3-(1,2-di(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-5))> [ka]

[0269] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to triphenylsulfonium chloride to obtain polyacid salt (A-5). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.38-1.82(m,40H),1 .90-2.10(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.78-7.87(m,60H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.05(s,2Si),-85.04(s,1Si). ESI-MS: POSITIVE m / z 263.1 ([C 18 H 15 S] + ) NEGATIVE m / z 864.1 (median) ([C 38 H 62 O 48 S2Si3W 11 ] 4- )

[0270] <Synthesis Example 6: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)silicate (polyacid salt (A-6))> [ka]

[0271] 37.26 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was dissolved in 50 g of cyclohexanone, and silicotungstic acid (H4[SiW 12 O 40 41.06 g of HCl (26H2O) was added, and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was filtered, and the resulting powder was dried under reduced pressure at room temperature for 18 hours. The dried powder was crystallized at room temperature using dichloromethane and acetonitrile to obtain polyacid salt (A-6). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=7.63-8.34(m,52H). 183 W-NMR(20.84MHz,DMSO-d6):δ(ppm)=-92.7(s12W). ESI-MS:NEGATIVE m / z 718.5 (median) ([SiW 12 O 40 ] 4- )

[0272] <Production Example 5: Production of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane (Compound G)> [ka]

[0273] Compound G was obtained by changing Compound A in Production Example 2-2 to 1-methylcyclopentyl acrylate. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.67(t,2H),1.49(s,3H),1.54-1.71(m, 8H),1.99-2.08(m,2H),2.49(t,2H),2.58(t,2H),2.67(t,2H),3.50(s,9H).

[0274] <Synthesis Example 7: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-7))> [ka]

[0275] In Synthesis Example 1, compound B was changed to 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane to obtain polyacid salt (A-7). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.67(t,4H),1.49(s,6H),1.54-1.71(m,16H) ,1.99-2.08(m,4H),2.49(t,4H),2.58(t,4H),2.67(t,4H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.02(s,2Si),-85.04(s,1Si). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 801.1 (median) ([C 24 H 42 O 44 S2Si3W 11 ] 4- )

[0276] <Synthesis Example 8: Synthesis of tetrakis(bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-8))> [ka] In Synthesis Example 1, Compound B was changed to Compound F, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium triflate to obtain polyacid salt (A-8). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62-1.82(m,20H),1.90-2.10(m,8H),2.20-2. 32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),6.75-6.81(m,24H),7.10-7.39(m,28H),7.77(d,8H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 460.9 ([C 18 H 10 F4IS] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0277] <Production Example 6: Production of bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium triflate> [ka] 5.8 g of bis(3,5-difluorophenyl) sulfoxide and 8.3 g of 1,2-diiodobenzene were dissolved in 30 g of chloroform, stirred at room temperature for 30 minutes, and then cooled to 5°C. 7.1 g of trifluoromethanesulfonic anhydride was added to the resulting mixed solution and stirred at room temperature for 1 hour. 10 g of purified water was added and stirred at room temperature for 30 minutes, after which the organic layer was separated and separated. This organic layer was washed three times with purified water and then concentrated using a rotary evaporator. 30 g of t-butyl methyl ether was added to the resulting crude product, and 4.3 g of the precipitated powder was obtained as the target compound. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=6.75-6.81(m,6H),7.09(d,1H),7.48(s,1H),7.54(d,1H).

[0278] <Synthesis Example 9: Synthesis of tetrakis(bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-9))> [ka] In Synthesis Example 1, Compound B was changed to Compound F, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium triflate to obtain polyacid salt (A-9). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62-1.82(m,20H),1.90-2.10(m,8H),2.20-2.32(m,8 H),2.50-2.80(m,8H),3.45-3.50(m,2H),6.75-6.81(m,24H),7.09-7.39(m,24H),7.48(s,4H),7.54(d,4H). 29Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 586.8 ([C 18 H9F4I2S] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0279] <Synthesis Example 10: Synthesis of tetrakis(bis(4-fluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-10))> [ka] In Synthesis Example 1, Compound B was changed to Compound F, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(4-fluorophenyl)(4-iodophenyl)sulfonium chloride to obtain polyacid salt (A-10). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62-1.82(m,20H),1.90-2.10(m,8H) ,2.20-2.32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.10-7.39(m,60H),7.77(d,8H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 425.0 ([C 18 H 12 F2IS] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0280] <Synthesis Example 11: Synthesis of tetrakis((3,4-diiodophenyl)di(4-fluorophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-11))> [ka] In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (3,4-diiodophenyl)di(4-fluorophenyl)sulfonium chloride to obtain polyacid salt (A-11). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62-1.82(m,20H),1.90-2.10(m,8H),2.20 -2.32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.09-7.39(m,56H),7.48(d,4H),7.54(d,4H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 550.9 ([C 18 H 11 F2I2S] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0281] <Synthesis Example 12: Synthesis of tetrakis((4-iodophenyl)di(4-(trifluoromethyl)phenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-12))> [ka] In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-iodophenyl)di(4-(trifluoromethyl)phenyl)sulfonium chloride to obtain polyacid salt (A-12). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62-1.82(m,20H),1.90-2.10(m,8H),2.20- 2.32(m,8H),2.50-2.80(m,8H),3.45-3.50(m,2H),7.10-7.39(m,44H),7.47(d,16H),7.77(d,8H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 525.0 ([C 20 H 12 F6IS] + ) NEGATIVE m / z 926.2 (median) ([C 58 H 70 O 48 S2Si3W 11 ] 4- )

[0282] <Production Example 7: Production of (3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium bromide> [ka] 6.04 g (15.6 mmol) of (4-hydroxy-3,5-dimethylphenyl)diphenylsulfonium bromide and 10.15 g (31.1 mmol) of cesium carbonate were dissolved in 150 mL of dimethylformamide, and 3.99 g (17.1 mmol) of 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was added dropwise at 0°C under a nitrogen atmosphere. The solution was gradually warmed to room temperature and stirred for 16 hours, after which 400 mL of water and 400 mL of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers were extracted with water, dried over sodium sulfate, and concentrated to a volume of 100 mL. 700 mL of methyl t-butyl ether was added to this solution, resulting in the deposition of a precipitate. The precipitate was filtered, washed with methyl t-butyl ether, and thoroughly dried under vacuum to obtain 8.07 g of the target compound as a white solid. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=1.60-2.01(m,9H),2.15(s,6H),4.90(s,2H),5.13(q,1H),5.37(d,1H),7.11(s,2H),7.33-7.36(m,10H).

[0283] <Production Example 8: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I)> [ka]

[0284] Production Example 8-1: Production of di(1-phenylcyclohexyl)(2E)-but-2-enedioate (Compound H) Compound H was obtained by changing 1-methylcyclopentanol to 1-phenylcyclohexanol in Production Example 2-1. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=1.43-1.53(12H),1.86(m,4H),2.12(m,4H),6.31(s,2H),7.17(m,2H),7.30(t,4H),7.54(dd,4H).

[0285] Production Example 8-2: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I) Compound I was obtained in Production Example 2-2 by changing Compound A to Compound H and changing 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.95(t,2H),1.43-1.53(m,12H),1.86(m,4H),2.12(m,4H),2.40(t, 2H),2.81-2.85(m,5H),3.10(m,1H),3.55(s,9H),4.00(t,1H),7.17(m,2H),7.30(t,4H),7.54(dd,4H).

[0286] <Synthesis Example 13: Synthesis of tetrakis((3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-13))> [ka] In Synthesis Example 1, Compound B was changed to Compound I, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium bromide, to obtain polyacid salt (A-13). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.79(m,4H),1.43-2.15(m,100H),2.40(t,4H),2.81-2.85(m,10H),3.10(m, 2H),4.00(t,2H),4.90(s,8H),5.13(q,4H),5.37(d,4H),7.11-7.17(m,12H),7.30-7.36(m,48H),7.54(dd,8H). 29Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-57.02(s,2Si),-85.03(s,1Si). ESI-MS: POSITIVE m / z 459.2 ([C 29 H 31 O3S] + ) NEGATIVE m / z 963.4 (median) ([C 64 H 82 O 48 S4Si3W 11 ] 4- )

[0287] <Production Example 9: Production of (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> [ka] The target compound was obtained in Production Example 7, except that 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was replaced with 2-cyclopenten-1-yl 2-bromoacetate. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=2.02(m,1H),2.15(s,6H),2.23-2.33(m,3H) ,4.90(s,2H),5.45(m,1H),5.60-5.61(m,2H),7.11(s,2H),7.33-7.36(m,10H).

[0288] <Synthesis Example 14: Synthesis of tetrakis((4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-14))> [ka] In Synthesis Example 1, Compound B was changed to Compound I, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide, to obtain polyacid salt (A-14). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.79(m,4H),1.43-1.53(m,24H),1.86(m,8H),2.02-2.40(m,52H),2.81-2.85(m,10H),3. 10(m,2H),4.00(t,2H),4.90(s,8H),5.45(m,4H),5.60-5.61(m,8H),7.11-7.17(m,12H),7.30-7.36(m,48H),7.54(dd,8H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-57.02(s,2Si),-85.03(s,1Si). ESI-MS: POSITIVE m / z 431.2 ([C 27 H 27 O3S] + ) NEGATIVE m / z 963.4 (median) ([C 64 H 82 O 48 S4Si3W 11 ] 4- )

[0289] <Production Example 10: Production of (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> [ka] The target compound was obtained in Production Example 7, except that 3-methyl-2-cyclohexen-1-yl 2-bromoacetate was replaced with 1-indanyl 2-bromoacetate. 1H-NMR (400MHz, DMSO-d6): δ(ppm)=2.15(m,7H),2.40(m,1H),3.11-3.21(m,2H),4. 90(s,2H),6.08(t,1H),7.06-7.13(m,4H),7.22-7.26(m,2H),7.33-7.36(m,10H).

[0290] <Synthesis Example 15: Synthesis of tetrakis((4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-15))> [ka] In Synthesis Example 1, Compound B was changed to Compound I, and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide, to obtain polyacid salt (A-15). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.79(m,4H),1.43-1.53(m,24H),1.86(m,8H),2.12-2.40(m,44H),2.81- 2.85(m,10H),3.10-3.21(m,10H),4.00(t,2H),4.90(s,8H),6.08(t,4H),7.06-7.36(m,76H),7.54(dd,8H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)δ(ppm)=-57.02(s,2Si),-85.03(s,1Si). ESI-MS: POSITIVE m / z 481.2 ([C 31 H 29 O3S] + ) NEGATIVE m / z 963.4 (median) ([C 64H 82 O 48 S4Si3W 11 ] 4- )

[0291] <Production Example 11: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K)> [ka]

[0292] Production Example 11-1: Production of di(2-cyclopenten-1-yl)(2E)-but-2-enedioate (Compound J) Compound J was obtained by changing 1-methylcyclopentanol to 2-cyclopenten-1-ol in Production Example 2-1. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=2.02-2.33(m,8H),5.45(m,2H),5.60-5.61(m,4H),6.31(s,2H).

[0293] Production Example 11-2: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K) In Production Example 2-2, Compound A was changed to Compound J to obtain Compound K. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.56(t,2H),1.62(quint,2H),2.02-2.33(m,8H),2.60( t,2H),2.85(m,1H),3.10(m,1H),3.55(s,9H),4.00(t,1H),5.45(m,2H),5.60-5.61(m,4H).

[0294] <Synthesis Example 16: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(2-cyclopenten-1-yloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-16))> [ka] In Synthesis Example 1, compound B was changed to compound K to obtain polyacid salt (A-16). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62(quint,4H),2.02-2.33(m,16H),2.60( t,4H),2.85(m,2H),3.10(m,2H),4.00(t,2H),5.45(m,4H),5.60-5.61(m,8H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.02(s,2Si),-85.01(s,1Si). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 847.9 (median) ([C 34 H 46 O 48 S2Si3W 11 ] 4- )

[0295] <Production Example 12: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M)> [ka]

[0296] Preparation Example 12-1: Preparation of di(1-indanyl)(2E)-but-2-enedioate (Compound L) Compound L was obtained by changing 1-methylcyclopentanol to 1-indanol in Production Example 2-1. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=2.15(m,2H),2.40(m,2H),3.11-3.21(m,4H),6.08(t,2H),6.31(s,2H),7.06-7.26(m,8H).

[0297] Production Example 12-2: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M) In Production Example 2-2, Compound A was changed to Compound L to obtain Compound M. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.56(t,2H),1.62(quint,2H),2.15(m,2H),2.40(m,2H),2.60( t,2H),2.85(m,1H),3.10-3.21(m,5H),3.55(s,9H),4.00(t,1H),6.08(t,2H),7.06-7.26(m,8H).

[0298] <Synthesis Example 17: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-indanyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-17))> [ka] In Synthesis Example 1, compound B was changed to compound M to obtain polyacid salt (A-17). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.62(quint,4H),2.15(m,4H),2.40(m,4H),2.60(t ,4H),2.85(m,2H),3.10-3.21(m,10H),4.00(t,2H),6.08(t,4H),7.06-7.26(m,16H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.04(s,2Si),-85.03(s,1Si). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 898.4 (median) ([C 50 H 54 O 48 S2Si3W 11 ] 4-)

[0299] <Production Example 13: Potassium undecatungstophosphate (α-K7[PW 11 O 39 ]) Manufacturing> Phosphotungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H3[PW 12 O 40 380 g of 1 M acetic acid was added to 63 g of HCl (HCl·xH2O), and the reaction mixture was heated to 45 °C. Sodium bicarbonate (43 g) was added to adjust the pH to 4.8. The reaction mixture was then cooled to room temperature. 41 g of potassium chloride was added to the resulting solution, and the mixture was redissolved by heating to 73 °C. The solution was cooled at 4 °C for 16 hours to allow recrystallization. The recrystallized product was filtered off by suction filtration and dried in vacuo to obtain 38 g of the target compound. 31 P-NMR(242.92MHz,D2O):δ(ppm)=10.08(s,1P).

[0300] <Synthesis Example 18: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-18))> [ka] In Synthesis Example 1, Compound B was changed to Compound I, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-18). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.04(m,4H),1.43-1.53(m,24H),1.86(m,8H),2.12(m,8H),2.40(t,4H), 2.81-2.85(m,10H),3.10(m,2H),4.00(t,2H),7.17(m,4H),7.30(t,8H),7.54(dd,8H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.04(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.73(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1285.6 (median) ([C 64 H 82 O 48 PS4Si2W 11 ] 3- )

[0301] <Production Example 14: Production of di(1-methylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound N)> [ka]

[0302] Compound N was obtained in Production Example 2-2, except that 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.95(t,2H),1.39(s,6H),1.56-1.81(m,1 6H),2.40(t,2H),2.81-2.85(m,5H),3.10(m,1H),3.55(s,9H),4.00(t,1H).

[0303] <Synthesis Example 19: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-methylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-19))> [ka] In Synthesis Example 1, compound B was changed to compound N, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-19). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.04(m,4H),1.39(s,12H),1.56-1.81(m,32H) ,2.40(t,4H),2.81-2.85(m,10H),3.10(m,2H),4.00(t,2H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.02(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.75(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1184.2 (median) ([C 40 H 66 O 48 PS4Si2W 11 ] 3- )

[0304] <Production Example 15: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P)> [ka]

[0305] Production Example 15-1: Production of di(1-ethylcyclopentyl) (2E)-but-2-enedioate (Compound O) Compound O was obtained in Production Example 2-1, except that 1-methylcyclopentanol was replaced with 1-ethylcyclopentanol. 1H-NMR (400MHz, DMSO-d6): δ(ppm)=0.90(t,6H),1.49-1.81(m,20H),6.31(s,2H).

[0306] Production Example 15-2: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P) Compound P was obtained in Production Example 2-2 by changing Compound A to Compound O and changing 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=0.90-0.95(m,8H),1.49-1.81(m,20H),2.40(t,2H),2.81-2.85(m,5H),3.10(m,1H),3.55(s,9H),4.00(t,1H).

[0307] <Synthesis Example 20: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-20))> [ka] In Synthesis Example 1, compound B was changed to compound P, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-20). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.90-1.04(m,16H),1.49-1.81(m,40H),2. 40(t,4H),2.81-2.85(m,10H),3.10(m,2H),4.00(t,2H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.05(s,2Si). 31P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.74(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1202.2 (median) ([C 44 H 74 O 48 PS4Si2W 11 ] 3- )

[0308] <Production Example 16: Production of di(1-phenylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound Q)> [ka] Compound Q was obtained in Production Example 2-2, except that 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=0.95(t,2H),1.63-1.92(m,12H),2.17(m,4H),2.40(t,2H),2. 81-2.85(m,5H),3.10(m,1H),3.55(s,9H),4.00(t,1H),7.17(m,2H),7.30(t,4H),7.54(dd,4H).

[0309] <Synthesis Example 21: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-21))> [ka] In Synthesis Example 1, compound B was changed to compound Q, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-21). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.04(m,4H),1.63-1.92(m,24H),2.17(m,8H),2.40(t,4H),2.81- 2.85(m,10H),3.10(m,2H),4.00(t,2H),7.17(m,4H),7.30(t,8H),7.54(dd,8H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.03(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.73(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1266.2 (median) ([C 60 H 74 O 48 PS4Si2W 11 ] 3- )

[0310] <Production Example 17: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S)> [ka]

[0311] Production Example 17-1: Production of di(3-methyl-2-cyclohexen-1-yl)(2E)-but-2-enedioate (Compound R) Compound R was obtained by changing 1-methylcyclopentanol to 3-methyl-2-cyclohexen-1-ol in Production Example 2-1. 1H-NMR (400MHz, DMSO-d6): δ(ppm)=1.60-2.01(m,18H),5.13(q,2H),5.37(d,2H),6.31(s,2H).

[0312] Production Example 17-2: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S) In Production Example 2-2, 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane, and Compound A was changed to Compound R, thereby obtaining Compound S. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.95(t,2H),1.60-2.01(m,18H),2.40(t,2H),2 .81-2.85(m,5H),3.10(m,1H),3.55(s,9H),4.00(t,1H),5.13(q,2H),5.37(t,2H).

[0313] <Synthesis Example 22: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2-bis(3-methyl-2-cyclohexen-1-yloxycarbonyl)ethylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-22))> [ka] In Synthesis Example 1, compound B was changed to compound S, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-22). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.04(m,4H),1.60-2.01(m,36H),2.40(t,4H),2.81- 2.85(m,10H),3.10(m,2H),4.00(t,2H),5.13(q,4H),5.37(t,4H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.04(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.72(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1200.2 (median) ([C 44 H 66 O 48 PS4Si2W 11 ] 3- )

[0314] <Production Example 18: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U)> [ka]

[0315] Production Example 18-1: Production of tri(1-methylcyclopentyl) (E)-1-propene-1,2,3-tricarboxylate (Compound T) 2.54 g (20.0 mmol) of trans-aconitic acid was dissolved in 20 g of DCM, and a solution of 5.58 g (44.0 mmol) of oxalyl chloride and 0.15 g (2.0 mmol) of DMF was added dropwise at 0°C. The reaction mixture was stirred at room temperature for 12 hours, and the solvent was removed from the resulting reaction mixture under vacuum to obtain a mixture containing trans-aconitic acid chloride. Thereafter, 4.46 g of Compound T was obtained by the same method as in Production Example 2-1, except that fumaryl chloride was replaced with trans-aconitic acid chloride. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=1.39(s,9H),1.63-1.81(m,24H),3.58(s,2H),6.79(s,1H).

[0316] Production Example 18-2: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U) In Production Example 2-2, Compound A was changed to Compound T to obtain Compound U. 1H-NMR(400MHz, DMSO-d6): δ(ppm) = 0.56 (t, 2H), 1.39 (s, 9H), 1.56 - 1.81 (m, 26H), 2.60 - 2.69 (m, 3H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86 - 3.90 (m, 2H).

[0317] <Synthesis Example 23: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatangustosilicate (Polyacid Salt (A-23))>

Chemical Structure

[0318] <Production Example 19: Production of Tri(trimethylcyclopentyl) 1-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)-1,2,3-propanetricarboxylate (Compound V)> [ka] In Production Example 2-2, Compound A was changed to Compound T and 3-mercaptopropyltrimethoxysilane was changed to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane, thereby obtaining Compound V. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.95(t,2H),1.39(s,9H),1.56-1.81(m,24H),2 .40(t,2H),2.69(m,1H),2.81(s,4H),2.94(m,1H),3.55(s,9H),3.86-3.90(m,2H).

[0319] <Synthesis Example 24: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(2-(2-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)ethylthio)ethan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-24))> [ka] In Synthesis Example 1, compound B was changed to compound V, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain polyacid salt (A-24). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.04(m,4H),1.39(s,18H),1.56-1.81(m,48H),2.40 (t,4H),2.69(m,2H),2.81(s,8H),2.94(m,2H),3.86-3.90(m,4H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-54.02(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.74(s,1P). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1277.6 (median) ([C 56 H 90 O 52 PS4Si2W 11 ] 3- )

[0320] <Production Example 20: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanedioate (Compound Y)> [ka]

[0321] Production Example 20-1: Production of di(1,2-bis(methyloxycarbonyl)ethyl) (2E)-but-2-enedioate (Compound W) Compound W was obtained in Production Example 2-1, except that 1-methylcyclopentanol was replaced with DL-dimethyl malate. 1 H-NMR (400MHz, DMSO-d6): δ(ppm)=2.75(m,2H),3.00(m,2H),3.60(s,6H),3.70(s,6H),6.13(t,2H),6.31(s,2H).

[0322] Production Example 20-2: Production of di(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyl)(2E)-but-2-enedioate (Compound X) 8.09 g (20.0 mmol) of compound W was dissolved in pure water / 1,4-dioxane (480 mL / 320 mL), and 17.24 g (431.0 mmol) of sodium hydroxide was added. The reaction solution was stirred at room temperature for 20 hours and washed twice with 200 mL of t-butyl methyl ether. The pH of the aqueous layer was then adjusted to 1 with 6 M hydrochloric acid, and the target product was extracted into the organic layer with 400 mL of t-butyl methyl ether. This procedure was repeated five times, and the resulting organic layer was concentrated using a rotary evaporator and dried in vacuo to obtain a carboxylic acid. Subsequently, in Production Example 18-1, trans-aconitic acid was replaced with the carboxylic acid obtained above, and this was converted into a carboxylic acid chloride. Then, in Production Example 2-1, fumaryl chloride was replaced with this carboxylic acid chloride and 1-methylcyclopentanol was replaced with 1-phenylcyclohexanol, and 11.77 g of compound X was obtained by the same method. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=1.43-1.53(m,24H),1.86(m,8H),2.12(m,8H),2.75( m,2H),3.00(m,2H),6.13(t,2H),6.31(s,2H),7.17(m,4H),7.30(t,8H),7.54(dd,8H).

[0323] Production Example 20-3: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanedioate (Compound Y) In Production Example 2-2, Compound A was changed to Compound X to obtain Compound Y. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.56(t,2H),1.43-1.62(m,26H),1.86(m,8H),2.12(m,8H),2.60(t,2H),2.75 -2.85(m,3H),3.00-3.10(m,3H),3.55(s,9H),4.00(t,1H),6.13(t,2H),7.17(m,4H),7.30(t,8H),7.54(dd,8H).

[0324] <Synthesis Example 25: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-25))> [ka] In Synthesis Example 1, compound B was changed to compound Y to obtain polyacid salt (A-25). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.52-0.68(m,4H),1.43-1.62(m,52H),1.86(m,16H),2.12(m,16H),2.60(t,4H),2.75- 2.85(m,6H),3.00-3.10(m,6H),4.00(t,2H),6.13(t,4H),7.17(m,8H),7.30(t,16H),7.54(dd,16H),7.65-8.35(m,52H). 29 Si-NMR (119.22MHz, DMSO-d6): δ(ppm)=-53.03(s,2Si),-85.04(s,1Si). ESI-MS: POSITIVE m / z 399.1 ([C 20 H 13 F6S] + ) NEGATIVE m / z 1214.8 (median) ([C 126 H 150 O 64 S2Si3W 11 ] 4- )

[0325] <Production Example 21: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanedioate (Compound AA)> [ka]

[0326] Production Example 21-1: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-hydroxypropylthio)butanedioate (Compound AA) In Production Example 2-2, Compound A was changed to Compound O, and 3-mercaptopropyltrimethoxysilane was changed to 2,3-mercapto-1-propanol, thereby obtaining Compound Z. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.90(t,12H),1.49-1.81(m,40H),2.62(m,1H) ),2.81-2.88(m,4H),3.10(m,2H),3.71(m,1H),3.96-4.00(m,3H),6.24(s,1H).

[0327] Production Example 21-2: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanedioate (Compound AA) Tosyl chloride was added dropwise to a DCM solution of compound Z and pyridine at 0°C. The mixture was then stirred at room temperature for 18 hours, and the resulting crude product was purified by column chromatography. The resulting tosylate ester was then reacted with 3-mercaptopropyltrimethoxysilane in a DCM solution in the presence of triethylamine to obtain compound AA. 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.56(t,2H),0.90(t,12H),1.49-1.81(m,42H), 2.60-2.62(m,4H),2.85-2.88(m,4H),3.08-3.10(m,3H),3.55(s,9H),4.00(t,2H).

[0328] <Synthesis Example 26: Synthesis of tris(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(2,3-bis(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstophosphate (polyacid salt (A-26))> [ka] In Synthesis Example 1, compound B was changed to compound AA, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, thereby obtaining polyacid salt (A-26). 1 H-NMR(400MHz,DMSO-d6):δ(ppm)=0.77-0.93(m,28H),1.49-1.81(m,84H),2.60-2 .62(m,8H),2.85-2.88(m,8H),3.08-3.10(m,6H),4.00(t,4H),7.65-8.35(m,39H). 29 Si-NMR(119.22MHz,DMSO-d6):δ(ppm)=-58.08(s,2Si). 31 P-NMR(242.92MHz,DMSO-d6):δ(ppm)=-13.73(s,1P). ESI-MS: POSITIVE m / z 399.1 ([[C 20 H 13 F6S] + ) NEGATIVE m / z 1448.7 (median) ([C 84 H 138 O 56 PS6Si2W 11 ] 3- )

[0329] 2. Preparation of Test Resist Materials Test resist materials (R-1) to (R-30) were prepared by blending the polyacid salts (A-1) to (A-26) synthesized above, an acid diffusion controller, and an organic solvent in the amounts (unit: parts by mass) shown in Tables 1 to 3 below.

[0330] As the acid diffusion controller (B) shown in Table 1, the acid diffusion controllers (B-1) to (B-3) shown below were used. Acid diffusion controller (B-1): an acid diffusion controller which is a salt of a triphenylsulfonium cation represented by the following formula (B-1) and a salicylic acid anion [ka] Acid diffusion controller (B-2): an acid diffusion controller which is a salt of (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium cation represented by the following formula (B-2) and salicylic acid anion [ka] Acid diffusion controller (B-3): an acid diffusion controller which is a salt of a triphenylsulfonium cation represented by the following formula (B-3) and a heptafluorobutyrate anion [ka]

[0331] [Table 1]

[0332] [Table 2]

[0333] [Table 3]

[0334] [3. Formation of test LS pattern] Each test resist material (R-1) to (R-30) was applied using a spinner to an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then post-applied bake (PAB) was performed on a hot plate at 120°C for 60 seconds, followed by drying to produce a 50 nm thick resist film. The thickness of the formed resist film was measured using a film thickness measurement device (JA Woollam's "M-2000D"). Using an electron beam lithography apparatus F7000S-VD2 (manufactured by Advantest Corporation), the resist film was exposed at an acceleration voltage of 50 kV with a target size of a 1:1 line and space pattern with a line width of 50 nm (hereinafter also referred to as "LS pattern"). Thereafter, post-exposure baking (PEB) treatment was performed at 90 °C for 60 seconds. Next, at 23 °C, development was carried out for 60 seconds using a developer (NMD-W, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and rinsing was carried out for 60 seconds using pure water. As described above, a 1:1 LS pattern with a line width of 50 nm was formed, and test LS patterns (LS-1) to (LS-30) corresponding to each test resist material (R-1) to (R-30) were obtained. Note that all of the test LS patterns (LS-1) to (LS-30) are positive patterns.

[0335] [4. Evaluation of the Shape of the Test LS Pattern] The shapes of the test LS patterns (LS-1) to (LS-30) were observed with a length measuring SEM (scanning electron microscope, acceleration voltage 10 kV, trade name: SU-5000, manufactured by Hitachi High-Technologies Corporation), and the shapes were evaluated according to the following criteria.

[0336] <Evaluation of Dimension Control> In the test LS pattern, the interface between the substrate and the resist pattern was observed with a scanning electron microscope. When no footing was observed or when footing was observed but the length of the footing was less than 13 nm, it was evaluated as "A". When the length of the footing was 13 nm or more and less than 14 nm, it was evaluated as "B". When the length of the footing was 14 nm or more and less than 15 nm, it was evaluated as "C". When the length of the footing was 15 nm or more, it was evaluated as "D". The above evaluation results of each test LS pattern are shown in Tables 4 to 6.

[0337] <Evaluation of LWR (Line Width Roughness)> In each test LS pattern, 3σ, which is a measure indicating LWR, was obtained. [[ID=?]] "3σ" indicates three times the standard deviation (σ) (unit: nm) obtained from the measurement results of measuring 400 line positions in the longitudinal direction of the line using a scanning electron microscope. The smaller the value of 3σ, the less rough the line sidewalls are, meaning that an LS pattern with a more uniform width is obtained. The 3σ values ​​for each test LS pattern are shown in Tables 4 to 6.

[0338] [Table 4]

[0339] [Table 5]

[0340] [Table 6]

[0341] Comparing the results of LS-8 and LS-9 in Table 4, it can be seen that LS-8 prepared using test resist material R-8 containing polyacid salt (A-1), which is a heteropolyacid salt in which defect sites have been modified by the introduction of multiple polar groups having an acid-dissociable group, gave better results in both the dimension controllability and LWR evaluations than LS-9 prepared using test resist material R-9 containing polyacid salt (A-6), which is a heteropolyacid salt that does not have a polar group having an acid-dissociable group.

[0342] Furthermore, comparing the results of LS-8 and LS-11 in Table 4, it can be seen that LS-8 prepared using test resist material R-8 containing polyacid salt (A-1), which is a heteropolyacid salt modified at defect sites having four polar groups each having an acid-dissociable group, gave better results in the LWR evaluation than LS-11 prepared using test resist material R-11 containing polyacid salt (A-7), which is a heteropolyacid salt modified at defect sites having two polar groups each having an acid-dissociable group.

[0343] Comparing the results of LS-1 to LS-7 and LS-10 in Table 4, LS-1 to LS-7, which were prepared using test resist materials R-1 to R-7 containing any of polyacid salts (A-1) to (A-5), which are heteropolyacid salts modified at defect sites by the introduction of multiple polar groups having acid-dissociable groups, provided better results in the evaluation of dimensional controllability and also in the evaluation of LWR, compared to LS-10, which was prepared using resist material R-10 containing polyacid salt (A-6), which is a heteropolyacid salt that does not have a polar group having an acid-dissociable group.

[0344] Furthermore, comparing the results of LS-1 to LS-7 and LS-8 in Table 4, it can be seen that LS-1 to LS-7, which were prepared using test resist materials R-1 to R-7 containing acid diffusion controllers (B-1) to (B-3) in the test resist material, gave better results in both dimension controllability and LWR evaluation than LS-8, which was prepared using test resist material R-8 which did not contain an acid diffusion controller.

[0345] Table 5 shows that when resist materials R-12 to R-16, which contain polyacid salts (A-8) to (A-12) having sulfonium cations into which iodine atoms and / or fluorine atoms have been introduced, are used, as in LS-12 to LS-16, good results are obtained in both the evaluation of LS pattern size controllability and LWR.

[0346] Furthermore, Table 5 shows that when resist materials R-17 to R-21, which contain polyacid salts (A-13) to (A-17) in which a polar group having an allyl or benzyl acid-dissociable group as the acid-dissociable group is introduced into the cation or anion moiety, are used, as in LS-17 to LS-21, good results are obtained in both the evaluation of LS pattern size controllability and LWR. In particular, it has been found that LS-20 and LS-21, which use resist materials R-20 and R-21 containing polyacid salts (A-16) and (A-17), in which multiple polar groups having allyl or benzyl acid-labile groups have been introduced into the anion moiety, provide excellent results in the evaluation of LS pattern size controllability and LWR.

[0347] Table 6 shows that when resist materials R-22 to R26, R-28, and R-30, which contain polyacid salts (A-18) to (A-22), (A-24), or (A-26) having a heteropolyacid anion in the anion portion, in which the defect site is modified with one defect Keggin-type undecatungstophosphate, are used, as in LS-22 to LS-26, LS-28, and LS-30, excellent results are obtained in both the evaluation of LS pattern size controllability and LWR. Furthermore, Table 6 shows that when resist materials R-27 and R-28, which contain polyacid salts (R-23) and (R-24) in which six polar groups having an acid-dissociable group have been introduced into the anion moiety, as in LS-27 and LS-28, are used, and when resist materials R-29 and R-30, which contain polyacid salts (R-25) and (R-26) in which eight polar groups having an acid-dissociable group have been introduced into the anion moiety, as in LS-29 and LS-30, are used, significantly better results are obtained in the evaluation of LS pattern size controllability and LWR.

[0348] [5. Microfabrication by BEUV exposure] <Preparation of test resist material> Test resist materials (R'-1) and (R'-2) shown in Table 7 below were prepared as test resist materials. The test resist material (R'-1) is a metal oxide resist, whereas the test resist material (R'-2) is a polymer-type chemically amplified resist (CAR).

[0349] The following polymers (P-1), photoacid generators (PAG), acid diffusion controllers (B'-1) and (B'-2), and quenchers were used as listed in Table 7. In Table 7, CP represents cyclopentanone, PGMEA represents propylene glycol methyl ether acetate, and PGME represents propylene glycol monomethyl ether.

[0350] Polymer (P-1): A copolymer of 4-vinylphenol and 1-phenylcyclopentyl methacrylate, as shown in the following formula (P-1) (molar ratio: 40:60; weight average molecular weight (Mw) of 7000 in terms of standard polystyrene obtained by GPC measurement) [ka]

[0351] Photoacid generator (PAG): a photoacid generator which is a salt of bis(3,5-difluorophenyl)(phenyl)sulfonium cation represented by the following formula (PAG) and a specific sulfonate anion. [ka]

[0352] Acid diffusion controller (B'-1): an acid diffusion controller which is a salt of a (phenyl)bis(2-(trifluoromethyl)phenyl)sulfonium cation represented by the following formula (B'-1) and a salicylic acid anion [ka]

[0353] Acid diffusion controller (B'-2): an acid diffusion controller which is a salt of bis(3,5-difluorophenyl)(phenyl)sulfonium cation represented by the following formula (B'-2) and salicylic acid anion [ka]

[0354] Quencher: A quencher which is salicylic acid represented by the following formula: [ka]

[0355] [Table 7]

[0356] <Formation of test LS' pattern> Each test resist material (R'-1) and (R'-2) was applied using a spinner to a 4-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and then prebaked (PAB) on a hot plate at 110°C for 60 seconds, followed by drying to form a resist film with a thickness of 28 nm. The thickness of the formed resist film was measured using a film thickness measuring device (JA Woolam's "M-2000D"). The resist film was subjected to two-beam interference exposure using 6.7 nm light irradiated through a diffraction grating to produce a 1:1 run-and-space pattern (hereinafter referred to as "LS' pattern") with a 50 nm pitch. The LS' pattern produced from the test resist material (R'-1) was then subjected to post-exposure bake (PEB) at 85°C for 60 seconds. The LS' pattern produced from the test resist material (R'-2) was also subjected to PEB at 90°C for 60 seconds. Next, the LS' patterns were each subjected to alkaline development for 30 seconds at 23°C using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), and then rinsed with pure water for 15 seconds. As a result of the above, test LS' patterns (LS'-1) and (LS'-2) corresponding to the test resist materials (R'-1) and (R'-2) were obtained.

[0357] <Evaluation of test LS' patterns> The shapes of the LS' patterns (LS'-1) and (LS'-2) were observed using a scanning electron microscope (SU8200, manufactured by Hitachi High-Technologies Corporation). As a result, the resist film made from the test resist material (R'-1) formed a 50 nm pitch LS' pattern even at 50% of the exposure dose of the resist film made from the test resist material (R'-2), which was 100%, and produced a good LS' pattern without residue or breaks.Furthermore, under the above conditions, the LWR(3σ) of the LS' pattern made from the test resist material (R'-2) was 5.9 nm, while the LWR(3σ) of the LS' pattern made from the test resist material (R'-1) was 5.7 nm, showing good LWR(3σ) values.

[0358] The above results show that by incorporating W, which has a high absorption cross section beyond EUV, as in the test resist material (R'-1), good results can be obtained in the microfabrication process using beyond EUV exposure.

Claims

1. (A) A resist material containing a heteropolyacid salt or a mixture thereof in which defect sites are modified, the anion moiety of the heteropolyacid salt whose defect sites have been modified contains a plurality of polar groups each having an acid-dissociable group; Resist material.

2. 2. The resist material according to claim 1, wherein the resist material generates an acid upon exposure and changes its solubility in a developer by the action of the acid.

3. 2. The resist material according to claim 1, wherein the acid-dissociable group is a tertiary carbon-type acid-dissociable group, an allyl-type or benzyl-type acid-dissociable group, or an acetal-type acid-dissociable group.

4. 2. The resist material according to claim 1, wherein the anion moiety of the heteropolyacid salt or mixture thereof (A) having modified deficiency sites is a heteropolyacid anion having deficiency sites and wherein the deficiency sites are modified.

5. the modification is achieved by bonding a group having one or more heteroatoms P, Si, Ge, or Sn to which one or more organic groups are bonded to the heteropoly acid anion having the defective site via some or all of the heteroatoms; the organic group has two or more polar groups each having an acid-dissociable group; The resist material according to claim 4.

6. The organic group may be C １－１８ is a hydrocarbyl group, C which may have the above-mentioned substituent １－１８ Any divalent carbon atom excluding the terminal carbon atom of the hydrocarbyl group may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time), C which may have the above-mentioned substituent １－１８ two or more hydrogen atoms contained in the hydrocarbyl group are replaced by polar groups having an acid-dissociable group; The resist material according to claim 5 .

7. The resist material according to claim 5 , wherein the organic group is represented by general formula (VII): 【Chemistry 1】 [In formula (VII), L ２ is an optionally substituted C １－１２ In the hydrocarbyl group, two hydrogen atoms on any carbon atom, including the terminal, are each R ２Ａ and R ２Ｂ represents a group substituted with Said L ２ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time); R ２Ａ and R ２Ｂ each independently represents a polar group having an acid-dissociable group, * represents a bond between the organic group and a heteroatom P, Si, Ge, or Sn.]

8. 5. The resist material according to claim 4, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge.

9. 5. The resist material according to claim 4, wherein the heteropoly acid anion having a defect site is a defective Keggin type heteropoly acid anion or a defective Dawson type heteropoly acid anion.

10. 10. The resist material according to claim 9, wherein the defective Keggin-type heteropolyacid anion is represented by general formula (II-1), (II-2), or (II-3). [XM １１ O ３９ ] ｃ１１－ (II-1) [XM １０ O ３６ ] ｃ１２－ (II-2) [XM ９ O ３４ ] ｃ１３－ (II-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the number of negative charges, and c11 to c13 are natural numbers.

11. 10. The resist material according to claim 9, wherein the deficient Dawson type heteropoly acid anion is represented by general formula (III-1), (III-2), or (III-3). [X ２ M １７ O ６１ ] ｃ２１－ (III-1) [X ２ M １６ O ５８ ] ｃ２２－ (III-2) [X ２ M １５ O ５６ ] ｃ２３－ (III-3) (In the formula, X represents a heteroatom of P, Si, B, S or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.

12. 2. The resist material according to claim 1, wherein the (A) heteropolyacid salt having modified defect sites or a mixture thereof is a heteropolyacid salt having modified defect sites represented by general formula (I) or a mixture thereof: (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; C （ａｍ）－ represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer from 1 to 5, and a is a real number greater than 0.

13. 2. The resist material according to claim 1, wherein the (A) heteropolyacid salt having modified defect sites or a mixture thereof is a heteropolyacid salt having modified defect sites represented by general formula (I') or a mixture thereof: (A’ ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C’ （ａ’ｍ’＋ｂｎ）－ ) (I’) [In formula (I'), A' ｍ’＋ are each independently H ＋ , metal ions, or NH ４ ＋ represents; B ｎ＋ each independently represents an onium cation or an onium dication; C' （ａ’ｍ’＋ｂｎ）－ represents a heteropolyanion having a defect site, the defect site of which has been modified, the heteropolyacid anion having a defect site and modified at the defect site contains a plurality of polar groups having an acid-dissociable group, m' is an integer from 1 to 5, n is an integer of 1 or 2, a' is a real number, and b is a real number greater than 0.

14. The resist material of claim 13 , wherein the onium cation is a sulfonium cation or an iodonium cation.

15. The resist material according to claim 1 , further comprising (B) an acid diffusion controller.

16. The resist material according to claim 15 , wherein the (B) acid diffusion controller is (B1) a photodegradable base.

17. The resist material according to claim 1 , further comprising an organic solvent.

18. The resist material according to any one of claims 1 to 17, which is a resist material that is sensitive to EUV, BEUV, or an electron beam.

19. A step of forming a resist film using the resist material according to any one of claims 1 to 17; exposing the resist film to light; developing the exposed resist film using a developer; A pattern forming method comprising:

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