Heteropolyacid salt having modified deletion site or mixture thereof

Abstract

An object of the present invention is to provide a novel heteropolyacid salt having a modified deficient site.SOLUTION: The heteropolyacid salt has a modified defective site represented by general formula (I), wherein a plurality of polar groups having an acid-dissociable group are introduced into the anion moiety of the heteropolyacid salt. (Am+)a(C(am)-)(I) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a heteropolyacid salt or a mixture thereof in which the defect site is modified. [Background technology]

[0002] Polyacids have the general formula [M x O y ] n- (wherein x, y, and n are all natural numbers). The metal atom M constituting the polyacid is called a polyatom, and examples thereof include Mo (hexavalent or pentavalent), W (hexavalent or pentavalent), V (pentavalent), Nb (pentavalent), and Ta (pentavalent). Polyacids include isopolyacids composed of the polyatom M and an oxygen acid, and polyacids containing different types of heteroatoms X (for example, P as the heteroatom X) in addition to the polyatom M and oxygen. 5+ , Si 4+ , Ge 4+ , B 3+ , S 6+ Heteropolyacids ([X w M x O y ] n- (wherein w, x, y, and n are all natural numbers)

[0003] It is also known that polyacids exist in multiple defect species, where a portion of the basic skeleton is missing. The terminal oxygen atoms at the defect sites, where a portion of the basic skeleton of a polyacid is missing, have a certain degree of negative charge density on the oxygen atoms, making them highly reactive and nucleophilic. Therefore, by reacting these terminal oxygen atoms with electrophilic atoms or molecules, various functional polyacid complexes and organic / inorganic hybrid structures can be formed.

[0004] Patent Document 1 discloses a polyoxometalate compound having a metal-substituted polyoxometalate, which comprises a polyoxometalate having defect sites, a substituting metal atom (divalent platinum or palladium) introduced into the defect sites, and an organic ligand. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 1,142,0871 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a novel heteropolyacid salt or a mixture thereof in which the defect site is modified. [Means for solving the problem]

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that by modifying the defect sites of a heteropolyacid anion having defect sites and introducing multiple polar groups having acid-dissociable groups, it is possible to drastically change the physical properties, such as solubility in a developer, between the exposed portion to actinic rays and the unexposed portion, and have completed the present invention.

[0008] That is, the present invention relates to the following inventions. <1> A heteropolyacid salt having a modified defect site 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, 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. <2> 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> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1. <3> 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 contains two or more polar groups having an acid-dissociable group; <1> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1.

[0009] <4> The organic group may have a substituent. 1-18 is a hydrocarbyl group, C which may have the above-mentioned substituent 1-18 Any 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. <3> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1. <5> The organic group is represented by general formula (VII): <3> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 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 2Aand 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.]

[0010] <6> The polyatom of the heteropoly acid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <1> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1. <7> the heteropolyanion having a defect site is a defective Keggin heteropolyanion or a defective Dawson heteropolyanion; <1> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1. <8> The defective Keggin-type heteropolyacid anion is represented by general formula (II-1), (II-2) or (II-3): <7> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 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. <9> The defective Dawson-type heteropolyacid anion is represented by general formula (III-1), (III-2) or (III-3): <7> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 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. <10> The onium cation is a sulfonium cation or an iodonium cation. <1> 1. A heteropolyacid salt or a mixture thereof in which the defect site is modified as described in 1.

[0011] <11> A heteropolyacid salt having a modified defect site 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 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. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a novel heteropolyacid salt or a mixture thereof in which the defect site is modified. DETAILED DESCRIPTION OF THE INVENTION

[0013] Preferred embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0014] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0015] As used herein, the term "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0016] In this specification, for example, "C 1-6 " and other terms refer to the number of carbon atoms in the core group.

[0017] 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 1-18A 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.

[0018] 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 1-18 Any 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 1-18The "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.

[0019] 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 1-18 The "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.

[0020] As used herein, "C 2-18 An alkenyl group is a group with two or more carbon atoms. 1-18The 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.

[0021] 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.

[0022] 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 3-18 Any 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 3-18The "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.

[0023] 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.

[0024] As used herein, "C 2-18The 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.

[0025] 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.

[0026] As used herein, "C 1-18 The 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.

[0027] 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 1-18 The "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. 3-18Alicyclic 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-. 1-18 A "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.

[0028] 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. 3-18Alicyclic carbonyl group; C such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group 6-18 arylcarbonyl group" and the like.

[0029] 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 1-18 The "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.

[0030] 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. 3-18 Alicyclic oxycarbonyl group; phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenanthrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. 6-18 aryloxycarbonyl group" and the like.

[0031] 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. 6-18aryloxycarbonyloxy group" and the like.

[0032] 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 1-18 The "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.

[0033] 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 1-18The "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. 1-18 alkylamino 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.

[0034] 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 1-18The "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. 3-18 Alicyclic aminocarbonyl group; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc. 6-18 arylaminocarbonyl group.

[0035] 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 1-18The "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.

[0036] 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 1-18The "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.

[0037] 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. 3-18 Alicyclic aminocarbonyloxy group; phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group, etc. 6-18 arylaminocarbonyloxy group" and the like.

[0038] As used herein, "DiC 1-18 "Hydrocarbylaminocarbonyloxy group" means "diC 1-18It 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, etc.

[0039] 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.

[0040] As used herein, "DiC 1-18 The term "hydrocarbylaminocarbonylamino group" refers to a "diC 1-18 A "hydrocarbylaminocarbonyl group" means a group attached to an amino group. "The C 1-18 The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "di-C" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. 1-18 alkylaminocarbonylamino group, etc.

[0041] 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.

[0042] 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. 1-18 alkylthio 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.

[0043] As used herein, "C 1-18The 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.

[0044] 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.

[0045] 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.

[0046] 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]

[0047] 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]

[0048] <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 A g3 An acid-labile group in which the carbon to which the group is bonded is a tertiary carbon atom can be used. [ka]

[0049] "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).

[0050] RA 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.

[0051] Also, "R A g2 " and "R A g3 " are each independently optionally substituted C 1-12 a 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).

[0052] 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 3-18 It 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).

[0053] 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.

[0054] 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:

[0055] [ka]

[0056] <<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 g2 and 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.

[0057] <<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 7-12In 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).

[0058] 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).

[0059] Cy A g1 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).

[0060] 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:

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) A2 >> [ka] In the above general formula (g-1-2), R A 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.

[0066] 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.

[0067] 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).

[0068] 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).

[0069] 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:

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] 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]

[0074] "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).

[0075] R B g1 As the C 1-12 Alkyl group, C 3-12 Alicyclic group, C 6-12 an aryl group, or C 7-12An 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.

[0076] Also, "R B g2 " ~ "R B g4 " 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).

[0077] 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.

[0078] 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 an optionally substituted cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexylideneethenyl group, benzyl group, and 2,3-dihydro-1H-indanyl group.

[0079] 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:

[0080] [ka]

[0081] <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]

[0082] "R C g1 " and "R C g3 " 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).

[0083] 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 3-8 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.

[0084] 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).

[0085] R C g2 As the C 1-12 Alkyl group or C 3-12An 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.

[0086] An acetal-type acid-dissociable group G represented by general formula (g-3) C Examples 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.

[0087] 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.

[0088] 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.

[0089] 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, C1-18 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 1-18 Examples 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).

[0090] [1. Heteropolyacid salt or mixture thereof having modified defect sites (general formula (I)] The heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment is represented by 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.

[0091] 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.

[0092] The heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment has a cation moiety (A m+ When the cation moiety contains an onium cation or an onium dication, it may function as a photoacid generator that generates an acid upon exposure to actinic rays (including visible light, ultraviolet light, DUV, XUV, EUV, 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 or commonly used photoacid generator may be added.

[0093] In addition, the heteropolyacid salt or mixture thereof in which the defect site is modified according to this embodiment has an anion portion (C (am)- ) contains a plurality of polar groups having an acid-dissociable group, i.e., at least two or more polar groups having an acid-dissociable group, and therefore the solubility in a developer can be drastically changed 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, for example, preferably 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.

[0094] For this reason, the heteropolyacid salt or mixture thereof in which the defect sites have been modified according to this embodiment can be suitably used as a functional building block in which the physical properties, such as solubility in a developer, are significantly different between the exposed portion to actinic rays or the like and the unexposed portion.

[0095] The anion moiety and the cation moiety of the heteropolyacid salt having defective portions or the mixture thereof according to this embodiment will be described below.

[0096] [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.

[0097] [1-1-1. Heteropolyacid anions 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.

[0098] [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.

[0099] 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- )

[0100] 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 11 O 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-PMo10 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.

[0101] [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.

[0102] 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([Ge2Mo16 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 15 O 56 ] 12- )

[0103] 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.

[0104] [1-1-2. Modification of the defective 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 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.

[0105] [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.

[0106] 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.]

[0107] 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')

[0108] 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.

[0109] 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')

[0110] 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.

[0111] 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')

[0112] 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).

[0113] 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')

[0114] 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).

[0115] 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')

[0116] 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).

[0117] 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.)

[0118] 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.

[0119] [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.

[0120] an organic group R having two or more polar groups each having the 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.

[0121] 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:

[0122] [ka] [G represents an acid-dissociable group G, and * represents a bond between the organic group and a heteroatom P, Si, Ge, or Sn.]

[0123] [ka] [* denotes the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0124] <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.]

[0125] 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).

[0126] 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 , more preferably 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:

[0127] [1-2. Cation Moiety of Heteropolyacid Salt or Mixtures of Heteropolyacid Salts 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.

[0128] [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.

[0129] [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.

[0130] 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, an electron beam, or the like.

[0131] [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 ) + ) can be mentioned. 3A ~R 3D shall represent the same as defined below.

[0132] 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]

[0133] In general formula (VIII-1), R 3A ~R 3D 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 3A ~R 3Da 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 1-18 Hydrocarbylaminocarbonylamino group, diC 1-18 Hydrocarbylaminocarbonylamino group, C 1-18 Hydrocarbyloxycarbonylamino group, or C 1-18may 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).

[0134] 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.

[0135] [1-2-2-2. Ammonium dication] The ammonium dication is not particularly limited, and any known and 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]

[0136] 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, C 1-18Hydrocarbyl 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).

[0137] 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.

[0138] [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]

[0139] 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).

[0140] 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.

[0141] [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]

[0142] 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).

[0143] 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.

[0144] [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]

[0145] 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).

[0146] 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).

[0147] 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.

[0148] [ka]

[0149] 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.

[0150] [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]

[0151] 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).

[0152] [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]

[0153] 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).

[0154] 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).

[0155] 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.

[0156] [2. Heteropolyacid salt or mixture thereof having modified defect sites (general formula (I'))] Another heteropolyacid salt or mixture thereof in which the defect sites have been modified according to this embodiment can be a heteropolyacid salt or mixture thereof in which the defect sites have been modified, 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.

[0157] 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.

[0158] The heteropolyacid salt or mixture thereof having modified vacant 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, an electron beam, or the like.

[0159] 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.

[0160] 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. [Example]

[0161] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0162] [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).

[0163] <Production Example 2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B)> [ka]

[0164] 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.

[0165] 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).

[0166] <Production Example 3: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D)> [ka]

[0167] 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).

[0168] 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).

[0169] <Production Example 4: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F)> [ka]

[0170] 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).

[0171] 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).

[0172] <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]

[0173] 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(center value)([C 38 H 62 O 48 S2Si3W 11 ] 4- )

[0174] <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

[0175] 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- )

[0176] <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

[0177] 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- )

[0178] <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]

[0179] 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- )

[0180] <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]

[0181] 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- )

[0182] <Synthesis Example 6: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)silicate (polyacid salt (A-6))> [ka]

[0183] 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- )

[0184] <Production Example 5: Production of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane (Compound G)> [ka]

[0185] 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).

[0186] <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))>

Chemical Structure

[0187] [[ID=I0]]In Synthesis Example 1, Compound B was changed to Compound G to obtain Polyacid Salt (A-7). 1 H-NMR (400 MHz, 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 (119.22 MHz, 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- )

[0188] <Synthesis Example 8: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-]]

Chemical Structure

[0189] <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).

[0190] <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- )

[0191] <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- )

[0192] <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- )

[0193] <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- )

[0194] <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).

[0195] <Production Example 8: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I)> [ka]

[0196] Production Example 8-1: Production of di(1-phenylcyclohexyl)(2E)-but-2-enedioate (Compound H) Compound H was obtained in Production Example 2-1, except that 1-methylcyclopentanol was replaced with 1-phenylcyclohexanol. 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).

[0197] 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).

[0198] <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- )

[0199] <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).

[0200] <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- )

[0201] <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).

[0202] <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- )

[0203] <Production Example 11: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K)> [ka]

[0204] 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).

[0205] 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).

[0206] <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- )

[0207] <Production Example 12: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M)> [ka]

[0208] Production Example 12-1: Production 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).

[0209] 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).

[0210] <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-)

[0211] <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).

[0212] <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- )

[0213] <Production Example 14: Production of di(1-methylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound N)> [ka]

[0214] 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).

[0215] <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, thereby obtaining 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- )

[0216] <Production Example 15: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P)> [ka]

[0217] 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).

[0218] 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).

[0219] <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- )

[0220] <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).

[0221] <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- )

[0222] <Production Example 17: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S)> [ka]

[0223] 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).

[0224] 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).

[0225] <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- )

[0226] <Production Example 18: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U)> [ka]

[0227] 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).

[0228] 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).

[0229] <Synthesis Example 23: Synthesis of Tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)propane-1-yl)disiloxane-1,1,3,3-tetrayl)undecatangustosilicate (Polyacid Salt (A-23))>

Chemical Structure

[0231] <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- )

[0232] <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]

[0233] 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).

[0234] 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).

[0235] 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).

[0236] <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- )

[0237] <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]

[0238] Production Example 21-1: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-hydroxypropylthio)butanedioate (Compound AA) Compound Z was obtained by changing Compound A to Compound O and 3-mercaptopropyltrimethoxysilane to 2,3-mercapto-1-propanol in Production Example 2-2. 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).

[0239] 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).

[0240] <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- )

[0241] 2. Preparation of test film-forming materials Test film-forming materials (R-1) to (R-26) were prepared by blending the polyacid salts (A-1) to (A-26) synthesized above and an organic solvent (cyclopentanone) in the amounts (unit: parts by mass) shown in Tables 1 to 3 below.

[0242] [Table 1]

[0243] [Table 2]

[0244] [Table 3]

[0245] [3. Formation of test film and its evaluation] Each test film-forming material (R-1) to (R-26) 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 form a 50 nm thick resist film. The thickness of the test films (M-1) to (M-26) formed was measured using a film thickness measuring device (JA Woollam's "M-2000D").

[0246] <Evaluation of remaining film rate before exposure and after development> The test films (M-1) to (M-26) were subjected to alkaline development for 60 seconds using a 2.38% by mass TMAH aqueous solution (trade name "NMD-3", manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., followed by rinsing with pure water for 15 seconds. The film thickness (average thickness) of each test film after development was measured using the film thickness measuring device described above, and the reduction rate of film thickness before and after development was calculated according to the following formula. The pre-exposure film remaining rate of each test film was also evaluated according to the following criteria. The results are shown in Tables 4 to 6. Film thickness reduction rate = ((film thickness before development - film thickness after development) / film thickness before development) x 100 (%) A: The film thickness reduction rate is 0% or more but less than 10% B: The film thickness reduction rate is 10% or more but less than 20% C: Film thickness reduction rate is 20% or more

[0247] <Evaluation of film remaining rate after exposure and development> The test films (M-1) to (M-26) were exposed to light by open frame exposure using a KrF exposure device (NIKON Corporation's "NSR-S203B", NA (numerical aperture) = 0.68, σ = 0.75) at an exposure dose of 100 mJ / cm 2 The exposure was carried out under the following exposure conditions. After the exposure, a post-exposure bake (PEB) treatment was carried out at 100° C. for 60 seconds.

[0248] After the PEB treatment, each test film was subjected to alkaline development for 60 seconds using a 2.38% by mass TMAH aqueous solution (trade name "NMD-3", manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23° C., followed by rinsing with pure water for 15 seconds. The film thickness (average thickness) of each test film after development was measured using the film thickness measuring device, and the remaining film ratio of the test film after development was calculated according to the following formula. The remaining film ratio of each test film after exposure and development was also evaluated according to the following criteria. The results are shown in Tables 4 to 6. Residual film rate after development = (film thickness after development / film thickness before development) x 100 (%) A: Residual film rate after development is 0% or more and less than 10% B: Residual film rate after development is 10% or more but less than 20% C: Residual film rate after development is 20% or more

[0249] [Table 4]

[0250] [Table 5]

[0251] [Table 6]

[0252] The results in Tables 4 to 6 show that the solubility in the developer before and after exposure changes dramatically in all cases: test films (M-1) to (M-5) and (M-8) to (M-22) containing polyacid salts (A-1) to (A-5) or (A-8) to (A-22) having heteropolyacid anions modified with defect sites in which four polar groups having an acid-dissociable group have been introduced; test films (M-23) and (M-24) containing polyacid salts (A-23) or (A-24) having heteropolyacid anions modified with defect sites in which six polar groups having an acid-dissociable group have been introduced; and test films (M-25) and (M-26) containing polyacid salts (A-25) or (A-26) having heteropolyacid anions modified with defect sites in which eight polar groups having an acid-dissociable group have been introduced. On the other hand, when the test film (M-6) contains a polyacid salt (A-6) having a heteropolyacid anion without a polar group having an acid-dissociable group introduced therein, the evaluation of the residual film rate after exposure and development was not good, and it was found that the residual film rate after development was 20% or more.

[0253] Furthermore, the results in Tables 4 to 6 show that when the test film (M-7) contained a polyacid salt (A-7) having a heteropolyacid anion modified with defect sites in which two polar groups having an acid-dissociable group had been introduced, the remaining film rate before exposure and after development was evaluated as B. This is thought to be due to the fact that the polyacid salts (A-1) to (A-5) and (A-8) to (A-26) contain four or more bulky, fat-soluble acid-dissociable groups, whereas the polyacid salt (A-7) contains only two such acid-dissociable groups.

[0254] Furthermore, the above results show that in heteropolyacid salts in which the defect sites are modified, such as the polyacid salts (A-1) to (A-5) and (A-7) to (A-26), when an onium cation is contained in the cation moiety, the polyacid salt also functions as a photoacid generator that generates acid upon exposure to light.

[0255] Furthermore, it was found that the sensitivity to actinic rays and the like can be adjusted by incorporating an onium cation into which an electron-withdrawing group such as a fluorine atom, an iodine atom, or a trifluoromethyl group has been introduced, into the cation moiety of a heteropolyacid salt whose defect sites have been modified, as in the polyacid salts (A-8) to (A-12).

[0256] Furthermore, it was found that by incorporating an onium cation into which a polar group having an acid-dissociable group has been introduced into the cation moiety of a heteropolyacid salt in which the defect sites have been modified, as in the polyacid salts (A-13) to (A-15), it is possible to further adjust the physical properties, such as the solubility in a developer, between the exposed and unexposed areas to actinic rays or the like.

[0257] In addition, it was found that organic / inorganic hybrid polyacid structures having similar functionality can be provided not only when one defective Keggin type undecatungstosilicate is used as in the polyacid salts (A-1) to (A-5), (A-8) to (A-17), (A-23), and (A-25), but also when one defective Keggin type undecatungstophosphate is used as in the polyacid salts (A-18) to (A-22), (A-24), and (A-26).

[0258] From the above, it can be seen that heteropolyacid salts in which defect sites have been modified by introducing four or more polar groups having an acid-labile group can drastically change physical properties, such as solubility in a developer, between the exposed and unexposed areas to actinic rays, etc., and are therefore useful as functional building blocks with the above-mentioned functions.

Claims

1. A heteropolyacid salt having a modified defect site 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.

2. A heteropolyacid salt having a modified defect site 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.

3. 3. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 1 or 2, 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. 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 contains two or more polar groups having an acid-dissociable group; The heteropolyacid salt or a mixture thereof, wherein the defect site is modified according to claim 1 or 2.

5. 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 heteropolyacid salt or a mixture thereof, wherein the defect site is modified according to claim 4 .

6. The heteropolyacid salt or a mixture thereof having modified defect sites according to claim 4 , 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.]

7. 3. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 1 or 2, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge.

8. 3. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 1, wherein the heteropolyacid anion having defect sites is a defective Keggin type heteropolyacid anion or a defective Dawson type heteropolyacid anion.

9. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 8, 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.

10. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 8, wherein the defective Dawson type heteropolyacid 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.

11. 3. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 1 or 2, wherein the onium cation is a sulfonium cation or an iodonium cation.

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