Heteropolyoxometalate having modified lacunary site, or mixture thereof

Abstract

The present invention provides a novel heteropolyoxometalate having a modified lacunary site, the heteropolyoxometalate being represented by general formula (I), wherein a plurality of polar groups having an acid-dissociable group are introduced into the anion moiety of the heteropolyoxometalate. Formula (I): (Am+)a(C(am)-)

Description

Heteropolyacid salts or mixtures thereof with modified defect sites

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

[0002] Polyacids are those having 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). The polyacid is an isopolyacid composed of the polyatom M and an oxygen acid, or a polyacid containing a different type of heteroatom 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 containing [X ｗ M ｘ O ｙ ] ｎ－ (wherein w, x, y, and n are all natural numbers)

[0003] It is also known that polyacids have multiple defect species in which 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 the 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.

[0005] U.S. Pat. No. 1,142,0871

[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.

[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 represented by general formula (I) in which the defect site is modified, or a mixture thereof. (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; （ａｍ）－ represents a heteropolyacid anion in which the defective sites have been modified, and the heteropolyacid anion in which the defective sites have been modified contains a plurality of polar groups having an acid dissociable group, and m is an integer of 1 to 5, and a is a real number greater than 0.] <2> The heteropolyacid salt or mixture thereof in which the defective sites have been modified according to <1>, wherein the acid dissociable group is a tertiary carbon-type acid dissociable group, an allyl-type or benzyl-type acid dissociable group, or an acetal-type acid dissociable group. <3> The heteropolyacid salt or mixture thereof in which the defective sites have been modified according to <1>, wherein the modification is achieved by bonding a group having one or more heteroatoms of P, Si, Ge, or Sn to which one or more organic groups are bonded to the heteropolyacid anion having the defective sites via some or all of the heteroatoms, and the organic groups contain two or more polar groups having an acid dissociable group.

[0009] <4> The organic group is C which may have a substituent. １－１８ C is a hydrocarbyl group, 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １－１８ The heteropolyacid salt or mixture thereof according to <3>, wherein two or more hydrogen atoms contained in the hydrocarbyl group are substituted by polar groups having an acid dissociable group. <5> The heteropolyacid salt or mixture thereof according to <3>, wherein the organic group is represented by general formula (VII-2). [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with ２Ｂ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0010] <6> The heteropolyacid salt or mixture thereof having modified defect sites according to <1>, wherein the polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and the heteroatom is P, Si, B, S, or Ge. <7> The heteropolyacid salt or mixture thereof having modified defect sites according to <1>, wherein the heteropolyacid anion having defective sites is a defective Keggin-type heteropolyacid anion or a defective Dawson-type heteropolyacid anion. <8> The heteropolyacid salt or mixture thereof having modified defect sites according to <7>, 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) (wherein 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 heteropolyacid salt or mixture thereof according to <7>, 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) (wherein X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; and c21- to c23- represent the number of negative charges, and c21 to c23 are natural numbers.) <10> The heteropolyacid salt or a mixture thereof, in which the defect sites are modified, according to <1>, wherein the onium cation is a sulfonium cation or an iodonium cation.

[0011] <11> A heteropolyacid salt or a mixture thereof, in which the defect site is modified and which is represented by the general formula (I'): (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [In general 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 heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the heteropolyacid anion obtained by modifying the defect site in the heteropolyacid anion having a 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.

[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.

[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. The hydrocarbylene group includes alkylene groups, arylene groups, etc. Also, "C １－１８ The divalent carbon atom at any position of the "hydrocarbylene group" may be -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). １－１８ The "hydrocarbylene group" is not particularly limited, and examples thereof include "C" 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 group"; 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,8-naphthylene group, 4,4'-biphenylene group, anthracenediyl group, phenanthrenediyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysenediyl group, etc. ６－１８ arylene group" and the like.

[0018] As used herein, "C １－１８ The term "alkyl group" means a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８The divalent carbon atom at any position excluding the terminal contained in the "alkyl group" is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ However, adjacent divalent carbon atoms may not be replaced at the same time. １－１８ The "alkyl group" is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an i-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1 , 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, n-dodecyl group, and the like. １－１８ The alkyl group may have a divalent carbon atom at any position excluding the terminal, and the divalent carbon atom may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ The group substituted with - is not particularly limited, and examples thereof include a 2-methoxyethoxymethyl group, an ethoxycarbonylmethyl group, and the like.

[0019] As used herein, "C １－１８ The term "haloalkyl group" refers to "C １－１８ "C" means a group in which one or more hydrogen atoms of an "alkyl group" are substituted with halogen atoms. １－１８The "haloalkyl group" is not particularly limited, and examples thereof include a dichloromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group.

[0020] As used herein, "C ２－１８ The term "alkenyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkenyl group having one or more double bonds, and includes alkadienyl groups, alkatrienyl groups, etc. 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 The term "alkynyl group" refers to a group having two or more carbon atoms. １－１８ "C" means an alkynyl group having one or more triple bonds in the "alkyl group." 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, etc. ３－１８ A divalent carbon atom at any position excluding the terminals contained in the "alicyclic group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２- may be substituted (however, adjacent divalent carbon atoms may not be substituted at the same time). ３－１８ The "cycloalkyl group" is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 1-i-propylcyclopentan-1-yl group, a cyclohexyl group, a t-butylcyclohexyl group, a tricyclodecanyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a 2-methyladamantan-2-yl group, a 2-i-propyladamantan-2-yl group, a bornyl group, a norbornyl group, a fenchyl group, a pinanyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group, a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a bornylmethyl group, a norbornylmethyl group, an adamantylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group.

[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 a monocyclic, polycyclic, or fused ring, 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" means 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. 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, an anthracenyl group, and the like.

[0025] As used herein, "C ７－１８ The term "aralkyl group" refers to "C １－１２ The substitutable portion of the "C alkyl group" is ２－１２ "C" means a group substituted with an "aryl group." 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 formed 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, aralkyl groups, and the like. １－１８ A divalent carbon atom at any position excluding the terminal contained in the "hydrocarbyl group" may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８ The term "C" used in the definition of "hydrocarbyloxy group" and the like is used in the definition of "C" １－１８ The same applies to "hydrocarbyl group" and the like. １－１８ The "hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８alkyl 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 The term "hydrocarbyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group." 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- "C" groups such as 2-ethylpropyloxy group, 1-ethyl-2-methylpropyloxy group, 1,1,2-trimethylpropyloxy group, 1,2,2-trimethylpropyloxy group, 1,1-dimethylbutyloxy group, 1,2-dimethylbutyloxy group, 2,2-dimethylbutyloxy group, 2,3-dimethylbutyloxy group, 1,3-dimethylbutyloxy group, 2-ethylbutyloxy group, 2-methylpentyloxy group, and 3-methylpentyloxy group １－１８ alkoxy group"; cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-methylcyclopentyloxycarbonylmethoxy group, 1-ethylcyclohexyloxycarbonylmethoxy group, 1-methyladamantyloxycarbonylmethoxy group, etc. ３－１８ alicyclic oxy group"; phenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, azulenyloxy group, pentalenyloxy group, heptalenyloxy group, indacenyloxy group, acenaphthyloxy group, phenanthrenyloxy group, anthracenyloxy group, etc. ６－１８ aryloxy group."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 The term "hydrocarbyl carbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyl group.” １－１８ The "hydrocarbyl carbonyl group" is not particularly limited, and examples thereof include "C" such as an acetyl group, a propionyl group, an isopropionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pentanoyl group, a 3-methylbutanoyl group, a pivaloyl group, a hexanoyl group, and a heptanoyl group. １－１８ alkylcarbonyl group"; cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclopentylcarbonyl group, 2-methylcyclopentylcarbonyl group, 3-methylcyclopentylcarbonyl group, cyclohexylcarbonyl group, 2-methylcyclohexylcarbonyl group, 3-methylcyclohexylcarbonyl group, 4-methylcyclohexylcarbonyl group, adamantylcarbonyl group, etc. ３－１８ alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ arylcarbonyl group" and the like.

[0029] As used herein, "C １－１８ The term "hydrocarbylcarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group." １－１８The "hydrocarbylcarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, an isopentylcarbonyloxy group, and a hexylcarbonyloxy group. １－１８ alkylcarbonyloxy group"; cyclopropylcarbonyloxy group, cyclobutylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, etc. ３－１８ alicyclic carbonyloxy group"; "C" such as a phenylcarbonyloxy group, a naphthylcarbonyloxy group, an acenaphthylcarbonyloxy group, a phenanthrenylcarbonyloxy group, an anthracenylcarbonyloxy group, etc. ６－１８ arylcarbonyloxy group" and the like.

[0030] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbyloxy group.” 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"; "C" such as a cyclopropyloxycarbonyl group, a cyclobutyloxycarbonyl group, a cyclopentyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-methylcyclopentyloxycarbonyl group, a 3-methylcyclopentyloxycarbonyl group, a 2-methylcyclohexyloxycarbonyl group, a 3-methylcyclohexyloxycarbonyl group, and a 4-methylcyclohexyloxycarbonyl group; ３－１８alicyclic oxycarbonyl group"; "C" such as a phenoxycarbonyl group, a naphthoxycarbonyl group, an acenaphthyloxycarbonyl group, a phenanthrenyloxycarbonyl group, an anthracenyloxycarbonyl group, etc. ６－１８ aryloxycarbonyl group" and the like.

[0031] As used herein, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group." 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"; "C" such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ alicyclic oxycarbonyloxy group"; "C" such as a phenoxycarbonyloxy group, a naphthoxycarbonyloxy group, an acenaphthyloxycarbonyloxy group, a phenanthrenyloxycarbonyloxy group, an anthracenyloxycarbonyloxy group, etc. ６－１８ aryloxycarbonyloxy group" and the like.

[0032] As used herein, "C １－１８ The term "hydrocarbylamino group" refers to a group consisting of one "C １－１８ "C" means a group bonded to an amino group. １－１８The "hydrocarbylamino group" is not particularly limited, and examples thereof include a "C hydrocarbylamino group" such as a 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, and an n-hexylamino group. 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 The term "hydrocarbylamino group" refers to two identical or different "C １－１８ "DiC" means a group in which a "hydrocarbyl group" is bonded to an amino group. １－１８ The "hydrocarbylamino group" is not particularly limited, and examples thereof include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a diisobutylamino group, a di-t-butylamino group, a di-n-pentylamino group, a di-n-hexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-n-propylamino group, an N-isopropyl-N-methylamino group, an N-n-butyl-N-methylamino group, an N N-isobutyl-N-methylamino group, N-t-butyl-N-methylamino group, N-methyl-N-n-pentylamino group, N-n-hexyl-N-methylamino group, N-ethyl-N-n-propylamino group, N-ethyl-N-isopropylamino group, N-n-butyl-N-ethylamino group, N-ethyl-N-isobutylamino group, N-t-butyl-N-ethylamino group, N-ethyl-N-n-pentylamino group, N-ethyl-N-n-hexylamino group, and other "di-C １－１８alkylamino group"; "di-C" such as dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ alicyclic amino group"; "di-C" such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "N-C arylamino group" such as N-methylcyclopentanamino group, N-methylcyclohexylamino group, etc. １－１８ Alkyl-N—C ３－１８ cycloalkylamino group"; "N-C cycloalkylamino group" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group, etc. １－１８ Alkyl-N—C ６－１８ arylamino group" and the like.

[0034] As used herein, "C １－１８ The term "hydrocarbylaminocarbonyl group" refers to a group consisting of "C １－１８ It means a group in which a carbonyl group (—C(═O)—) is bonded to a “hydrocarbylamino group.” １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyl group, an ethylaminocarbonyl group, an n-propylaminocarbonyl group, an i-propylaminocarbonyl group, an n-butylaminocarbonyl group, a sec-butylaminocarbonyl group, a t-butylaminocarbonyl group, an n-pentylaminocarbonyl group, a 2-pentylaminocarbonyl group, a neopentylaminocarbonyl group, a 4-methyl-2-pentylaminocarbonyl group, an n-hexylaminocarbonyl group, and a 3-methyl-n-pentylaminocarbonyl group. １－１８ alkylaminocarbonyl group"; cyclopropylaminocarbonyl group, cyclobutylaminocarbonyl group, cyclopentylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-methylcyclopentylaminocarbonyl group, 3-methylcyclopentylaminocarbonyl group, 2-methylcyclohexylaminocarbonyl group, 3-methylcyclohexylaminocarbonyl group, 4-methylcyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ arylaminocarbonyl group.

[0035] As used herein, "diC １－１８ The term "hydrocarbylaminocarbonyl group" refers to a "diC １－１８ "DiC" means a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group." １－１８ The "hydrocarbylaminocarbonyl group" is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a di-n-propylaminocarbonyl group, a diisopropylaminocarbonyl group, a di-n-butylaminocarbonyl group, a diisobutylaminocarbonyl group, a di-t-butylaminocarbonyl group, a di-n-pentylaminocarbonyl group, a di-n-hexylaminocarbonyl group, an N-ethyl-N-methylaminocarbonyl group, an N-methyl-N-n-propylaminocarbonyl group, an N-isopropyl-N-methylaminocarbonyl group, an N-n-butyl-N-methylaminocarbonyl group, an N-isobutyl-N-methylaminocarbonyl group, an N-t-butyl-N-methylaminocarbonyl group, an N-methyl-N-n-pentylaminocarbonyl group, an N-n-hexyl-N-methylaminocarbonyl group, "diC" groups such as an N-ethyl-N-n-propylaminocarbonyl group, an N-ethyl-N-isopropylaminocarbonyl group, an N-n-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-isobutylaminocarbonyl group, an N-t-butyl-N-ethylaminocarbonyl group, an N-ethyl-N-n-pentylaminocarbonyl group, and an N-ethyl-N-n-hexylaminocarbonyl group １－１８ alkylamino group"; "di-C" such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ alicyclic aminocarbonyl group"; "di-C" such as diphenylaminocarbonyl group, phenylnaphthylaminocarbonyl group, etc. ６－１８ arylaminocarbonyl group" and the like.

[0036] As used herein, "C １－１８ The term "hydrocarbylcarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which an amino group is bonded to a "hydrocarbyl carbonyl group." １－１８ The "hydrocarbylcarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, i-propylcarbonylamino group, n-butylcarbonylamino group, i-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino group, i-pentylcarbonylamino group, and n-hexylcarbonylamino group. １－１８ alkylcarbonylamino group"; cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ alicyclic carbonylamino group"; "C" such as 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 a group consisting of "C １－１８ "C" means a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "C" such as a methylaminocarbonyloxy group, an ethylaminocarbonyloxy group, and an n-propylaminocarbonyloxy group. 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 The term "hydrocarbylaminocarbonyloxy group" refers to a "diC １－１８"DiC" means a group in which an oxygen atom (—O—) is bonded to a "hydrocarbylaminocarbonyl group." １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, and di-n-propylaminocarbonyloxy group. １－１８ alkylaminocarbonyloxy group" and the like.

[0039] As used herein, "C １－１８ The term "hydrocarbylaminocarbonylamino group" refers to a group consisting of "C １－１８ "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "C" such as methylaminocarbonylamino group, ethylaminocarbonyloxy group, and n-propylaminocarbonylamino group. 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 "Hydrocarbylaminocarbonyl group" means a group bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited, and examples thereof include "diC" such as dimethylaminocarbonylamino group, diethylaminocarbonylamino group, and di-n-propylaminocarbonylamino group. １－１８ alkylaminocarbonylamino group, etc.

[0041] As used herein, "C １－１８ The term "hydrocarbyloxycarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a t-butoxycarbonylamino group. 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 The term "hydrocarbylthio group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group." １－１８ The "hydrocarbylthio group" is not particularly limited, and examples thereof include a "C 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, an n-hexylthio group, etc. 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"; "C" such as a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, an acenaphthylthio group, a phenanthrenylthio group, an anthracenylthio group, etc. ６－１８ arylthio group" and the like.

[0043] As used herein, "C １－１８ The term "hydrocarbylsulfinyl group" refers to a group consisting of "C １－１８ "C" means a group in which a sulfinyl group (-S(=O)-) is bonded to a "hydrocarbyl group."１－１８ The "hydrocarbylsulfinyl group" is not particularly limited, and examples thereof include "C" such as methylsulfinyl group, ethylsulfinyl group, n-propylsulfinyl group, i-propylsulfinyl group, n-butylsulfinyl group, t-butylsulfinyl group, pentylsulfinyl group, and hexylsulfinyl group. 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"; "C" such as a phenylsulfinyl group, a naphthylsulfinyl group, an acenaphthylsulfinyl group, a phenanthrenylsulfinyl group, an 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 The hydrocarbyl group may be a sulfonyl group (-SO ２ -) is bonded to the group. １－１８ The "hydrocarbylsulfonyl group" is not particularly limited, and examples thereof include "C" such as a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an i-propylsulfonyl group, an n-butylsulfonyl group, a t-butylsulfonyl group, and a pentylsulfonyl group. １－１８ alkylsulfonyl group"; "C" such as cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, 2-methylcyclopentylsulfonyl group, 3-methylcyclopentylsulfonyl group, 2-methylcyclohexylsulfonyl group, 3-methylcyclohexylsulfonyl group, and 4-methylcyclohexyl group; ３－１８ alicyclic sulfonyl group"; "C" such as a phenylsulfonyl group, a naphthylsulfonyl group, an acenaphthylsulfonyl group, a phenanthrenylsulfonyl group, an anthracenylsulfonyl group, etc. ６－１８arylsulfonyl group" and the like.

[0045] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom of a polar group, such as a hydroxy group (including a phenolic hydroxy group), a carboxy group, an amino group, or a sulfo group, and dissociates under the action of an acid. A 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 a developer. More specifically, when a highly polar developer, such as an alkaline aqueous solution, is used as the developer, the solubility of the compound in the developer relatively increases, while when a less polar organic developer is used as the developer, the solubility of the compound in the developer relatively decreases. Preferred polar groups are hydroxy groups (including a phenolic hydroxy group) and carboxy groups.

[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 an acid-dissociable group G for a polar group having an acid-dissociable group represented by the following general formulas (G-1) to (G-4).

[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.

[0048] <Tertiary carbon type acid dissociable group G ＡThe acid-dissociable group G is 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 atom to which the group is bonded is a tertiary carbon atom can be used.

[0049] "R Ａ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0050] R Ａ ｇ１ As the C １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0051] Also, "R Ａ ｇ２ " and "R Ａ ｇ３" are each independently a C １－１２ A hydrocarbyl group in which a divalent carbon atom at any position except the terminal is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), or R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be substituted with - (provided that adjacent divalent carbon atoms are not substituted 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 An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８The 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, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[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 the tertiary carbon-type acid-dissociable group include the following:

[0055]

[0056] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２ >> Also, 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. ３－１８In 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 included: 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 >> A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1): Ａ１ In this case, R Ａ ｇ１１ is a C which may have a substituent 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 is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0058] Also Cy Ａ ｇ１ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0059] Cy Ａ ｇ１The tertiary carbon atom may be, together with the tertiary carbon atom, 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, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0060] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): Ａ１ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0061]

[0062]

[0063]

[0064]

[0065] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), R Ａ ｇ２１ and R Ａｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ are directly connected to each other by a single bond or are divalently connected to each other by -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 each of these groups forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where each of these groups 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 represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0068] Cy Ａ ｇ２The tertiary carbon atom may be, together with the tertiary carbon atom, 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, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0069] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): Ａ２ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0070]

[0071]

[0072]

[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:

[0074] "R Ｂ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (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 ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0076] Also, "R Ｂ ｇ２ " ~ "R Ｂ ｇ４ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (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 ｇ４are directly connected to each other by a single bond or are divalently connected to each other by -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 this case, 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, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, a benzyl group, or a 2,3-dihydro-1H-indanyl group, which may have a substituent.

[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]

[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

[0082] "R Ｃ ｇ１ " and "R Ｃ ｇ３ " are each independently a hydro group or an optionally substituted C １－１２In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (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 a C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0084] Also, "R Ｃ ｇ２ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (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 ３－１２In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[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-based 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-based protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The aminocarbonyl-based 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 １－１８Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino 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 A hydrocarbylsulfonyl group, in which a divalent carbon atom at any position except the terminal of the substituent is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time), etc.

[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 general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; （ａｍ）－ represents a heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the defect site being modified in the heteropolyacid anion having a defect site, the heteropolyacid anion having a defect site and modified in the heteropolyacid anion having a defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer of 1 to 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 moiety (C （ａｍ）－ Since the anion moiety 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, 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 preferably, for example, 2 to 12, more preferably 4 to 10, and even more preferably 4 to 8. From the viewpoint of ease of synthesis, the number of polar groups having an acid-dissociable group contained in the anion moiety is preferably 2, 4, 6, 8, 10, or 12, more preferably 4, 6, 8, or 10, and even more preferably 4, 6, or 8. Furthermore, by adjusting the bulkiness, hydrophobicity, liposolubility, etc. of the acid-dissociable group, it is possible to adjust the range of change in physical properties, such as solubility in a developer, between the exposed portion to actinic rays or the like and the unexposed portion.

[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 Moiety of Heteropolyacid Salt Having Modified Defect Sites or a Mixture Thereof] The anion moiety of the heteropolyacid salt having modified defect sites or a mixture thereof 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 anion having a defect site] 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. Deficient Keggin type heteropolyacid anion] Examples of the defective Keggin type heteropolyacid anion include a mono-deficient Keggin type heteropolyacid anion represented by the following general formula (II-1), a di-deficient Keggin type heteropolyacid anion represented by the following general formula (II-2), and a tri-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) [XM ９ O ３４ ] ｃ１３－(II-3) (wherein, 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 formulas (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－ , [P.W. 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－ , [B.W. 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－ , [P.W. １０ O ３６ ] ７－ ) and when X is Si and M is Mo or W, c12 is 8 ([SiMo １０ O ３６ ] ８－ , [SiW１０ O ３６ ] ８－ ) and when X is B and M is Mo or W, c12 is 9 ([BMo １０ O ３６ ] ９－ , [B.W. 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 ([PMo ９ O ３４ ] ９－ , [P.W. ９ O ３４ ] ９－ ) and when X is Si and M is Mo or W, c13 is 10 ([SiMo ９ O ３４ ] １０－ , [SiW ９ O ３４ ] １０－ ) and when X is S and M is Mo or W, c13 is 8 ([SMo ９ O ３４ ] ８－ , [SW ９ O ３４ ] ８－ ) and when X is Ge and M is Mo or W, c13 is 10 ([GeMo ９ O ３４ ] １０－ , [GeW ９ O ３４ ] １０－ )

[0100] The defect Keggin type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structure of the one defect Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １１ O ３９ ] ７－ , [β-PW １１ O ３９ ] ７－ , [γ-PW１１ 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－ The isomer structure of the two-deficient Keggin type heteropoly acid anion represented by the general formula (II-1) is preferably [α-PW １０ O ３６ ] ７－ , [β-PW １０ O ３６ ] ７－ , [γ-PW １０ O ３６ ] ７－ , [α-PMo １０ O ３６ ] ７－ , [β-PMo １０ O ３６ ] ７－ , [γ-PW １０ O ３６ ]７－ , [α-SiW １０ O ３６ ] ８－ , [β-SiW １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ , [α-SiMo １０ O ３６ ] ８－ , [β-SiMo １０ O ３６ ] ８－ , [γ-SiW １０ O ３６ ] ８－ is preferred, and [γ-PW １０ O ３６ ] ７－ , [γ-PMo １０ O ３６ ] ７－ , [γ-SiW １０ O ３６ ] ８－ , [γ-SiMo １０ O ３６ ] ８－ Further, the isomeric structure of the 3-deficient Keggin type heteropoly acid anion represented by the general formula (III-1) is preferably [α-PW ９ O ３４ ] ９－ , [β-PW ９ O ３４ ] ９－ , [γ-PW ９ O ３４ ] ９－ , [α-PMo ９ O ３４ ] ９－ , [β-PMo ９ O ３４ ] ９－ , [γ-PW ９ O ３４ ] ９－ , [α-SiW ９ O ３４ ] １０－ , [β-SiW ９ O ３４ ] １０－ , [γ-SiW ９ O ３４ ] １０－ , [α-SiMo ９O ３４ ] １０－ , [β-SiMo ９ O ３４ ] １０－ , [γ-SiW ９ O ３４ ] １０－ is preferred.

[0101] [1-1-1-2. Deficient Dawson type heteropolyacid anion] Examples of the deficient Dawson type heteropolyacid anion include a mono-deficient Dawson type heteropolyacid anion represented by the following general formula (III-1), a di-deficient Dawson type heteropolyacid anion represented by the following general formula (III-2), and a tri-deficient Dawson type heteropolyacid anion represented by the following general formula (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) (wherein 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 formulas (III-1) to (III-3), the values ​​of c21 to c23 vary 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 ([P ２ Mo １７ O ６１ ] １０－ , [P ２ W １７ O ６１ ] １０－ ), and if X is S and M is W, c21 is 8([S ２ W １７ O ６１ ] ８－ In addition, in the general formula (III-2), when X is Ge and M is Mo, c22 is 12 ([Ge２ Mo １６ O ５８ ] １２－ Furthermore, in the general formula (III-3), when X is P and M is Mo or W, c23 is 12 ([P ２ Mo １５ O ５６ ] １２－ , [P ２ W １５ O ５６ ] １２－ )

[0103] The deficient Dawson type heteropoly acid anion preferably has an isomeric structure of α-, β-, or γ-form. The isomeric structures of the deficient Dawson type heteropoly acid anions represented by the general formulae (III-1) to (III-3) include [α-P ２ W １７ O ６１ ] １０－ , [α-P ２ W １５ O ５６ ] １２－ , [α-S ２ W １７ O ６１ ] ８－ etc. can be suitably used.

[0104] [1-1-2. Modification of Defect Sites] The modification of the defect sites of the heteropolyacid anion having defect sites according to this embodiment is achieved by reacting a terminal oxygen atom at the defect site of the heteropolyacid anion 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. Through this reaction, the terminal oxygen atom at the defect site of the heteropolyacid anion bonds to a group having a P, Si, Ge, or Sn heteroatom to which one or more organic groups are bonded, via some or all of the heteroatom, thereby modifying the defect site.

[0105] [1-1-2-1. Bonding Form of Defect Site and Its Notation] In the heteropolyacid anion modified at a defect site according to this embodiment, the terminal oxygen atom at 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 heteropolyacid 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). [In the general 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 １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ１ ~R １Ｅ１ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ１ ~R １Ｅ１ a hydrogen atom contained in the R may be substituted with (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; １Ａ１ ~R １Ｅ１ Two or more hydrogen atoms contained in (t) are replaced by a polar group having an acid-dissociable group; * represents a bond with a terminal oxygen atom of a vacant site of the heteropolyacid anion.]

[0107] In this specification, for convenience, a heteropolyacid anion in which the vacant 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) (wherein 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 they are the same, call this R １Ａ can be expressed as in the following general formula (V-1'): [X ｗ M ｘ O ｙ (R １Ａ X') ２ O] 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'Y ３ (Y represents a leaving group, for example, 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.), 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 vacant 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) (wherein 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 in the following general formula (V-2'): 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'Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0111] In this specification, for convenience, a heteropolyacid anion in which the vacant 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) (R１Ｃ４ X'O)] ｃ－ (V-3) (wherein 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 they are the same, call this R １Ｃ can be expressed as in 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 defect sites represented by general formula (V-3) or (V-3′) is not particularly limited, and may be, for example, a heteropoly acid anion of two defect Keggin type or Dawson type and R １Ｃ X'Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0113] In this specification, for convenience, a heteropolyacid anion in which the vacant 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) (wherein 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 they are the same, call this R １Ｄ can be expressed as in 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 P(=O)Y ２ (wherein Y represents a leaving group as above) to obtain the compound.

[0115] In this specification, for convenience, a heteropolyacid anion in which the vacant 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 in the following general formula (V-5): [X ｗ M ｘ O ｙ (R １Ｅ１ X'') ｃ－ (V-5) (wherein w, x, y, and c are all natural numbers, and X, M, X″, and R １Ｅ１ 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 as for [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 X''Y ３ (wherein Y represents a leaving group as above) to obtain the compound.

[0117] Among the heteropolyacid anions having modified defect sites represented by the general formulae (V-1) to (V-5) and (V-1') to (V-5'), heteropolyacid anions having modified defect sites represented by the following general formulae (VI-1) to (VI-12) are preferred, from the viewpoint of being relatively stable and capable of controlling the reactivity. [XM １１ O ３９ (R １Ａ X') ２ O] 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 １０ O ３６ (R １Ａ X') ２ O] 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) [X ２ M １７ O ６１ (R １Ａ X') ２ O] ｃ３３－ (VI-9) [X ２ M １７ O ６１ (R １Ｂ１ R１Ｂ２ X') ２ ] ｃ３３－ (VI-10) [X ２ M １７ O ６１ (R １Ｄ P=O) ２ ] ｃ３３－ (VI-11) [X ２ M １７ O ６１ (R １Ｅ X'') ｃ３３－ (VI-12) (In the general 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 １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ ~R １Ｅ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １Ａ ~R １Ｅ a hydrogen atom contained in the R may be substituted with (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 １Ｅtwo or more hydrogen atoms contained in (t) are replaced by a polar group having an acid-dissociable group; and 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. Therefore, the value of c31 is usually c11-4 (c11 represents the absolute value of the number of negative charges in the mono-vacant Keggin-type heteropolyacid anion represented by general formula (II-1)), the value of c32 is c12-4 (c12 represents the absolute value of the number of negative charges in the di-vacant Keggin-type heteropolyacid anion represented by general formula (II-2)), and the value of c33 is c21-4 (c21 represents the absolute value of the number of negative charges in the mono-vacant Dawson-type heteropolyacid anion represented by general formula (III-1)). On the other hand, the values ​​of c31 to c33 will differ from the above values, for example, when the organic group contains an amino group which is protonated to form an ammonium cation, or when the organic group contains a carboxy group which is formed into a carboxy anion.

[0119] [1-1-2-2. Organic group] The 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 or 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 or the like, between the exposed and unexposed portions of the actinic ray, the organic group is preferably an organic group having two or more polar groups 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 is, for example, preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4.

[0120] an organic group R having two or more polar groups having the acid-dissociable group; １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １ＥAs for R １Ａ ~R １Ｅ C which may have a substituent １－１８ is a hydrocarbyl group; １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ one or more hydrogen atoms contained in the R may be substituted with (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 R are replaced by (t) a polar group having an acid-dissociable group, 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 an aralkyl group; １Ａ ~R １Ｅ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅa hydrogen atom contained in the above R may be substituted with (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 More preferably, at least two hydrogen atoms of R are replaced by (t) a polar group having an acid-dissociable group, １Ａ ~R １Ｅ C which may have a substituent １－１８ Alkyl group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; １Ａ ~R １Ｅ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ ~R １Ｅ More preferably, at least two hydrogen atoms of (t) are replaced by a polar group having an acid-dissociable group.

[0121] The 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 allyl or benzyl acid-dissociable group G Ｂ , acetal-type acid-dissociable group GＣ Examples of the acid-dissociable group G include the following. １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and R １Ｅ For example, the following can be exemplified:

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

[0123] [* means 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-1). [In general formula (VII-1), L ２Ａ is an optionally substituted C １－１２ In the hydrocarbyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ represents a group substituted with ２Ａ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ａ and R ２Ｂ each independently represents a polar group having an acid-dissociable group, and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0125] L in the organic group represented by general formula (VII-1) ２Ａ As for L ２Ａ C which may have a substituent ２－１０In the hydrocarbyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２Ａ and the end of R ２Ａ or R ２Ｂ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ａ 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 the aralkyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２Ａ and the end of R ２Ａ or R ２Ｂ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ａ 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 the aralkyl group, the hydrogen atoms on the carbon atoms at any positions including the terminals are each R ２Ａ and R ２Ｂ is a group substituted with the above L ２Ａ and the end of R ２Ａ or R ２Ｂis 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-1) ２Ａ and R ２Ｂ As for R ２Ａ and R ２Ｂ are preferably each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group, 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 , an allyl 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] The organic group having two or more polar groups having an acid-dissociable group according to yet another embodiment is not particularly limited, and examples thereof include an organic group represented by general formula (VII-2).

[0128] [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with ２Ｂ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

[0129] L in the organic group represented by formula (VII-2) ２Ｂ As for L ２Ｂ C which may have a substituent ２－１０ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ｂ 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 the aralkyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminal, are R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and L ２Ｂ C which may have a substituent ２－８ Alkyl group, C ３－８ Alicyclic group, C ６－８ an aryl group, or C６－８ In the aralkyl group, two or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminals are each R ２Ｃ is a group substituted with the above L ２Ｂ and the end of R ２Ｃ 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).

[0130] R in the organic group represented by general formula (VII-2) ２Ｃ As for R ２Ｃ are each independently a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group, and R ２Ｃ 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 allyl or benzyl acid-dissociable group G Ｂ or an acetal-type acid-dissociable group G Ｃ More preferably, R ２Ｃ 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 It is more preferable that:

[0131] x in the general formula (VII-2) is preferably an integer of 2 to 6, and may be an integer of 2 to 4. The organic group represented by the general formula (VII-2) may include R ２Ｃ Contains two or more R ２Ｃ may all be polar groups having the same acid-dissociable group, or may each be a polar group having a different acid-dissociable group.

[0132] [1-2. Cation Moiety of Heteropolyacid Salt or Mixture Thereof Having Modified Defect Sites] As the cation moiety of the heteropolyacid salt or mixture thereof having modified defect sites according to this embodiment, H ＋, metal ions, onium cations or onium dications can be used.

[0133] [1-2-1. Metal Ion] The metal ion that can be used as the cation moiety of the heteropolyacid salt or mixture thereof whose defect site is modified is not particularly limited, and examples thereof include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ Metal ions include Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ is preferred, and Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Ca ２＋ , Al ３＋ , Co ３＋ These metal ions may be used alone or in combination of two or more.

[0134] [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 known and commonly used ones 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.

[0135] The onium cation or onium dication is preferably a sulfonium cation, a sulfonium dication, or an 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.

[0136] [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 ion (NH ４ ＋ ), primary ammonium cation (NH ３ (R ３Ａ ) ＋ )), secondary ammonium cation (NH ２ (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.

[0137] The ammonium cation is ammonium ion (NH ４ ＋ ), and quaternary ammonium cations are preferred, and in particular, ammonium ions (NH ４ ＋ ), and organic quaternary ammonium cations represented by the following general formula (VIII-1) are more preferred.

[0138] In general formula (VIII-1), R ３Ａ ~R ３Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ ~R ３Ｄ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), 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 groups in which at least a portion 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 １－１８Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); 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 general formula (VIII-1).

[0139] 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 thereof include ammonium cation, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamide)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.

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

[0141] In general formula (VIII-2), R ４Ａ ~R ４Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ４Ａ ~R ４Ｆ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ４ is an optionally substituted C １－１８ represents a hydrocarbylene group, ４ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); 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 groups in which at least a portion 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 １－１８Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted 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 general formula (VIII-2).

[0142] The organic quaternary ammonium dication represented by 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.

[0143] [1-2-2-3. Phosphonium Cation] The phosphonium cation is not particularly limited, and any known or commonly used phosphonium cation can be used. Examples of the phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VIII-3):

[0144] In general formula (VIII-3), R ５Ａ ~R ５Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ５Ａ ~R ５Ｄ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５Ｄ 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 groups in which at least a portion 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 １－１８Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ５Ａ ~R ５Ｄ 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 general formula (VIII-3).

[0145] 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. phenyl)phosphonium 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.

[0146] [1-2-2-4. Phosphonium dication] The phosphonium dication is not particularly limited, and any known or commonly used phosphonium dication can be used. Examples of the phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VIII-4):

[0147] In general formula (VIII-4), R ６Ａ ~R ６Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ６Ａ ~R ６ＦThe 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), L ６ is an optionally substituted C １－１８ represents a hydrocarbylene group, ６ The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); 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 groups in which at least a portion 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 Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C１－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted 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 general formula (VIII-4).

[0148] The organic quaternary phosphonium dication represented by 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.

[0149] [1-2-2-5. Sulfonium Cation] The sulfonium cation is not particularly limited, and any known or commonly used sulfonium cation can be used. Examples of the sulfonium cation include organic sulfonium cations represented by the following general formula (VIII-5):

[0150] In general formula (VIII-5), R ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ７Ａ , R ７Ｂ and R ７Ｃ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced); 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 groups in which at least a portion 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 Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ７Ａ , R ７Ｂ and R ７Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -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 general formula (VIII-5).

[0151] In the organic sulfonium cation represented by general formula (VIII-5), the R ７Ａ , R ７Ｂ and R ７Ｃ As for R ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８ is a hydrocarbyl group; ７Ａ , R ７Ｂ and R ７Ｃ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８an aralkyl group; ７Ａ , R ７Ｂ and R ７Ｃ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ７Ａ , R ７Ｂ and R ７Ｃ each independently represents a C 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 groups in which at least a portion 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 a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0152] Also R ７Ａ , R ７Ｂ and R ７Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ Examples of the case where R is linked via an alkylene group to form a ring together with the sulfur atom in general formula (VIII-5) include those 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 be exemplified. Note that * indicates that R is not involved in ring formation. ７Ａ , R ７Ｂ or R ７Ｃ It means the junction with.

[0153]

[0154] 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.

[0155] The sulfonium dication is not particularly limited, and any known or commonly used sulfonium dication can be used. Examples of the sulfonium dication include organic sulfonium dications represented by the following general formula (VIII-6):

[0156] In general formula (VIII-6), R ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ８Ａ , R ８Ｂ , R ８Ｃ and R ８Ｄ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ８ is an optionally substituted C １－１８ represents a hydrocarbylene group, ８The divalent carbon atom at any position in ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); 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 groups in which at least a portion 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 Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８A divalent carbon atom at any position excluding the terminal of these substituents may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ８Ａ , R ８Ｂ and L ８ 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 general formula (VIII-6).

[0157] [1-2-2-7. Iodonium cation] The iodonium cation is not particularly limited, and any known or commonly used iodonium cation can be used. Examples of the iodonium cation include organic iodonium cations represented by the following general formula (VIII-7):

[0158] In general formula (VIII-7), R ９Ａ and R ９Ｂ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ９Ａ and R ９Ｂ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ９Ａ and R ９ＢThe 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 groups in which at least a portion 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 Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ a hydrocarbyloxycarbonylamino group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ９Ａ and R ９Ｂare 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 general formula (VIII-7).

[0159] 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 a C １－１８ is a hydrocarbyl group; ９Ａ and R ９Ｂ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ９Ａ and R ９Ｂ each independently represents a C １－１８ Alkyl group, C ３－１８ Alicyclic group, C ６－１８ an aryl group, or C ７－１８ an aralkyl group; ９Ａ and R ９Ｂ 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ９Ａ and R ９Ｂ each independently represents a C ６－１８ is an aryl group; ９Ａ and R ９ＢThe 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 groups in which at least a portion 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 a hydrocarbyloxycarbonyloxy group, or C １－１８ The divalent carbon atom at any position of these substituents, excluding the terminals, may be replaced by a hydrocarbylthio group, and may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, —NHCO—, —NH(C═O)O—, —S—, or —SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

[0160] 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 (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-methylphenyl)(mesityl)iodonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation, and the like.

[0161] [2. Heteropolyacid salt having modified defect sites or a mixture thereof (general formula (I'))] As a heteropolyacid salt having modified defect sites or a mixture thereof according to another embodiment of the present invention, a heteropolyacid salt having modified defect sites represented by the following general formula (I') or a mixture thereof can be used. (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [In general 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 heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the heteropolyacid anion obtained by modifying the defect site in the heteropolyacid anion having a 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.

[0162] 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 in which the defect sites have been modified" can be appropriately selected from those described above.

[0163] The heteropolyacid salt or mixture thereof in which the deficiency sites represented by the above general formula (I') have been modified 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.

[0164] The mixture of heteropolyacid salts having modified defect sites represented by general formula (I') contains A' ｍ’＋ and B ｎ＋In this case, the values ​​of a′ and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0165] The ratio of a' to b is as follows: A' is a heteropoly acid anion whose defect site is modified; ｍ’＋ , B ｎ＋ Although it depends on the types of compounds, 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 2-8 and m' and n are 1, it is preferable that a' is a real number of 0-7 and b is a real number of 1-8, and it is more preferable that a' is a real number of 0-4 and b is a real number of 2-8.

[0166] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0167] [1. Synthesis of Polyacid Salt] <Production Example 1: Potassium undecatungstosilicate (α-K ８ [SiW １１ O ３９ ]) > Production of tungstosilicic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ４ [SiW １２ O ４０ ]・xH ２ To 63 g of 1M acetic acid (C10), 380 g was added, and the reaction solution was heated to 45 ° C. Potassium bicarbonate (52 g) was added so that the pH was 6.0. The reaction solution was then cooled to room temperature and filtered off by suction, yielding 56 g of a crude product. 216 g of purified water was added to the resulting crude product, which was then redissolved by heating to 73 ° C. The solution was cooled at 4 ° C. for 16 hours to recrystallize, which was then filtered off by suction and dried in vacuo to yield 34 g of the target compound. ２９ Si-NMR (119.22MHz, D ２ O): δ (ppm) = -84.6 (s, 1Si). １８３ W-NMR (20.84MHz, D ２O): 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).

[0168] <Production Example 2: Production of di(1-methylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound B)>

[0169] 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 ice-cooled with stirring. Fumaryl chloride (10.3 g) was added thereto and stirred for 1 hour. Thereafter, a 5% aqueous potassium carbonate solution (60 g) was charged and stirred. After stirring was stopped, the aqueous layer was removed and washed with ultrapure water (60 g). The organic layer was concentrated under reduced pressure, yielding 14.5 g of Compound A.

[0170] 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 charged in this order and stirred. Thereafter, the temperature was raised from room temperature to 90°C and the mixture was stirred for 7 hours. The reaction liquid 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).

[0171] <Production Example 3: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D)>

[0172] Production Example 3-1: Production of di(1-t-butylcyclopentyl)(2E)-but-2-enedioate (Compound C) Compound C was obtained in the same manner as 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).

[0173] Production Example 3-2: Production of di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound D) Compound D was obtained by changing Compound A to Compound C in Production Example 2-2. 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).

[0174] <Production Example 4: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F)>

[0175] 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. １ H-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).

[0176] Production Example 4-2: Production of di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound F) Compound F was obtained by changing Compound A in Production Example 2-2 to Compound E. １H-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).

[0177] <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))>

[0178] 5.6 g of Compound B was added to a mixed solvent of 402 g of acetonitrile and 184 g of pure water, and the mono-defective Keggin-type potassium undecatungstosilicate (α-K ８ [SiW １１ O ３９ 10.9 g of bis(2-trifluoromethylphenylphenylsulfonium chloride) was added to the concentrate. The pH was adjusted to 1.8 with 1 M hydrochloric acid, and the mixture was stirred for 2 hours. The filtrate was then concentrated to approximately 200 g. To this concentrated solution, 9.9 g (18.2 mol) of bis(2-trifluoromethylphenylphenylsulfonium chloride) and 40 g of pure water were added to precipitate a powder. The precipitated powder was separated by filtration, washed three times with 180 mL of pure water, and separated by filtration. The mixture was then thoroughly dried under vacuum to obtain 15.8 g of polyacid salt (A-1). 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), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋) NEGATIVE m / z 864.1 (median) ([C ３８ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0179] <Synthesis Example 2: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-t-butylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-2))>

[0180] In Synthesis Example 1, compound B was changed to compound D, thereby obtaining polyacid salt (A-2). 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). ２９ Si-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 F ６ S] ＋ ) NEGATIVE m / z 906.2 (median) ([C ５０ H ８６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0181] <Synthesis Example 3: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-3))>

[0182] In Synthesis Example 1, compound B was changed to compound F, and polyacid salt (A-3) was 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0183] <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))>

[0184] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to (4-(1-ethylcyclopentyloxycarbonylmethoxy)-3,5-dimethylphenyl)diphenylsulfonium bromide, thereby obtaining 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 461.2 ([C ２９ H ３３ O ３ S] ＋ ) NEGATIVE m / z 864.1 (median) ([C ３８ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0185] <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))>

[0186] In Synthesis Example 1, bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to triphenylsulfonium chloride to obtain polyacid salt (A-5). 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), 7.78-7.87 (m, 60H). ２９ Si-NMR (119.22 MHz, 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 S ２ Si ３ W １１ ] ４－ )

[0187] Synthesis Example 6: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)silicate (polyacid salt (A-6))

[0188] 37.26 g of bis(2-trifluoromethylphenyl)phenylsulfonium chloride was dissolved in 50 g of cyclohexanone, and silicotungstic acid (H ４ [SiW １２ O ４０ ]・26H ２ 41.06 g of methyl 2-hydroxybenzoate (A-1) was added, and the reaction solution was stirred at room temperature for 2 hours. The reaction solution was filtered, and the obtained 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 (20.84 MHz, DMSO-d6): δ (ppm) = -92.7 (s12W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ )

[0189] <Production Example 5: Production of 3-(2-(1-methylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane (Compound G)>

[0190] 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).

[0191] <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))>

[0192] In Synthesis Example 1, compound B was changed to compound G, thereby obtaining polyacid salt (A-7). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 1.49 (s, 6H), 1.54-1.71 (m, 16H) , 1.99-2.08 (m, 4H), 2.49 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 801.1 (median) ([C ２４ H ４２ O ４４ S ２ Si ３ W １１ ] ４－ )

[0193] <Synthesis Example 8: Synthesis of tetrakis(bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (Polyacid Salt (A-8))> In Synthesis Example 1, Compound B was changed to Compound F and bis(2-trifluoromethylphenyl)phenylsulfonium chloride was changed to bis(3,5-difluorophenyl)(4-iodophenyl)sulfonium triflate to obtain polyacid salt (A-8). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.62-1.82 (m, 20H), 1.90-2.10 (m, 8H), 2.20-2. 32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 6.75-6.81 (m, 24H), 7.10-7.39 (m, 28H), 7.77 (d, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 460.9 ([C １８ H １０ F ４ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0194] <Production Example 6: Production of bis(3,5-difluorophenyl)(3,4-diiodophenyl)sulfonium triflate> 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 the mixture was stirred at room temperature for 1 hour. 10 g of pure water was added and the mixture was stirred at room temperature for 30 minutes, after which the organic layer was separated and isolated. This organic layer was washed three times with pure water in the same manner, 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).

[0195] <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))> 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). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 586.8 ([C １８ H ９ F ４I ２ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0196] <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))> 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 425.0 ([C １８ H １２ F ２ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0197] <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))> 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 550.9 ([C １８ H １１ F ２ I ２ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0198] <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))> 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 525.0 ([C ２０ H １２ F ６ IS] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0199] <Production Example 7: Production of (3,5-dimethyl-4-((3-methyl-2-cyclohexen-1-yloxycarbonyl)methyloxy)phenyl)di(phenyl)sulfonium bromide> 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 then 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 off, washed with methyl t-butyl ether, and thoroughly dried in vacuo 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).

[0200] <Production Example 8: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I)>

[0201] Production Example 8-1: Production of di(1-phenylcyclohexyl)(2E)-but-2-enedioate (Compound H) Compound H was obtained by changing 1-methylcyclopentanol to 1-phenylcyclohexanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(12H), 1.86 (m, 4H), 2.12 (m, 4H), 6.31 (s, 2H), 7.17 (m, 2H), 7.30 (t, 4H), 7.54 (dd, 4H).

[0202] Production Example 8-2: Production of di(1-phenylcyclohexyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound I) Compound I was obtained by changing Compound A to Compound H and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. 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).

[0203] <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))> 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, thereby obtaining 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 O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0204] <Production Example 9: Production of (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> 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).

[0205] <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))> Polyacid salt (A-14) was obtained in Synthesis Example 1 by changing Compound B to Compound I and by changing bis(2-trifluoromethylphenyl)phenylsulfonium chloride to (4-((2-cyclopenten-1-yloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide. １H-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 O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0206] <Production Example 10: Production of (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide> 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. １ H-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).

[0207] <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))> Polyacid salt (A-15) was obtained by changing Compound I instead of Compound B and changing bis(2-trifluoromethylphenyl)phenylsulfonium chloride to (4-((1-indanyloxycarbonyl)methyloxy)-3,5-dimethylphenyl)di(phenyl)sulfonium bromide in Synthesis Example 1. 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 (119.22 MHz, 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 O ３ S] ＋ ) NEGATIVE m / z 963.4 (median) ([C ６４ H ８２ O ４８ S ４ Si ３ W １１ ] ４－ )

[0208] <Production Example 11: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K)>

[0209] 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).

[0210] Production Example 11-2: Production of di(2-cyclopenten-1-yl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound K) Compound K was obtained by changing Compound A in Production Example 2-2 to Compound J. 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).

[0211] <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))> 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). ２９Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 847.9 (median) ([C ３４ H ４６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0212] <Production Example 12: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M)>

[0213] 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).

[0214] Production Example 12-2: Production of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanedioate (Compound M) Compound M was obtained by changing Compound A in Production Example 2-2 to Compound L. 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).

[0215] <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))> 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 F ６ S] ＋ ) NEGATIVE m / z 898.4 (median) ([C ５０ H ５４ O ４８ S ２ Si ３ W １１ ] ４－ )

[0216] <Production Example 13: Potassium undecatungstophosphate (α-K ７ [P.W. １１ O ３９ ]) > Preparation of phosphotungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ３ [P.W. １２ O ４０ ]・xH ２To 63 g of acetic acid (C10), 380 g of 1 M acetic acid was added, and the reaction solution was heated to 45°C. Sodium bicarbonate (43 g) was added so that the pH was 4.8. The reaction solution was then cooled to room temperature. 41 g of potassium chloride was added to the resulting solution, and the solution was redissolved by heating to 73°C. The solution was cooled at 4°C for 16 hours to allow recrystallization, which was filtered off by suction filtration and dried in vacuo to obtain 38 g of the target compound. ３１ P-NMR (242.92MHz, D ２ O): δ (ppm) = 10.08 (s, 1P).

[0217] <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))> In Synthesis Example 1, Compound B was changed to Compound I, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, 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 F ６ S] ＋ ) NEGATIVE m / z 1285.6 (median) ([C ６４ H ８２ O ４８ P.S.４ Si ２ W １１ ] ３－ )

[0218] <Production Example 14: Production of di(1-methylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound N)>

[0219] 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).

[0220] <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))> In Synthesis Example 1, Compound B was changed to Compound N, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, 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 H１３ F ６ S] ＋ ) NEGATIVE m / z 1184.2 (median) ([C ４０ H ６６ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0221] <Production Example 15: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P)>

[0222] Production Example 15-1: Production of di(1-ethylcyclopentyl) (2E)-but-2-enedioate (Compound O) Compound O was obtained by changing 1-methylcyclopentanol to 1-ethylcyclopentanol in Production Example 2-1. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 6H), 1.49-1.81 (m, 20H), 6.31 (s, 2H).

[0223] Production Example 15-2: Production of di(1-ethylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound P) Compound P was obtained by changing Compound A to Compound O and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. 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).

[0224] <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))> In Synthesis Example 1, Compound B was changed to Compound P, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, DMSO-d6): δ (ppm) = -54.05 (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 F ６ S] ＋ ) NEGATIVE m / z 1202.2 (median) ([C ４４ H ７４ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0225] <Production Example 16: Production of di(1-phenylcyclopentyl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound Q)> 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).

[0226] <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))> In Synthesis Example 1, Compound B was changed to Compound Q, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, 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 F ６ S] ＋ ) NEGATIVE m / z 1266.2 (median) ([C ６０ H ７４ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0227] <Production Example 17: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S)>

[0228] 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. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.60-2.01 (m, 18H), 5.13 (q, 2H), 5.37 (d, 2H), 6.31 (s, 2H).

[0229] Production Example 17-2: Production of di(3-methyl-2-cyclohexen-1-yl) 2-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)butanedioate (Compound S) Compound S was obtained by changing 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane and compound A to compound R in Production Example 2-2. 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).

[0230] <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))> In Synthesis Example 1, Compound B was changed to Compound S, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a polyacid salt (A-22). １H-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 (119.22 MHz, 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 F ６ S] ＋ ) NEGATIVE m / z 1200.2 (median) ([C ４４ H ６６ O ４８ P.S. ４ Si ２ W １１ ] ３－ )

[0231] <Production Example 18: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U)>

[0232] 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 solution was stirred at room temperature for 12 hours, and the solvent was distilled off from the resulting reaction solution 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 changed to trans-aconitic acid chloride. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 9H), 1.63-1.81 (m, 24H), 3.58 (s, 2H), 6.79 (s, 1H).

[0233] Production Example 18-2: Production of tri(1-methylcyclopentyl) 1-(3-(trimethoxysilyl)propylthio)-1,2,3-propanetricarboxylate (Compound U) Compound U was obtained by changing Compound A in Production Example 2-2 to Compound T. １ H-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).

[0234] <Synthesis Example 23: Synthesis of tetrakis(bis(2-trifluoromethylphenyl)phenylsulfonium)(1,3-bis(3-(1,2,3-tris(1-methylcyclopentyloxycarbonyl)propylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungstosilicate (polyacid salt (A-23))> In Synthesis Example 1, compound B was changed to compound U to obtain polyacid salt (A-23). １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 18H), 1.56-1.81 ( m, 52H), 2.60-2.69 (m, 6H), 2.94 (m, 2H), 3.86-3.90 (m, 4H), 7.65-8.35 (m, 52H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 934.7 (median) ([C ５４ H ８６ O ５２ S ２ Si ３ W１１ ] ４－ )

[0235] <Production Example 19: Production of tri(1-methylcyclopentyl) 1-(2-(2-(trimethoxysilyl)ethylthio)ethylthio)-1,2,3-propanetricarboxylate (Compound V)> Compound V was obtained by changing Compound A to Compound T and 3-mercaptopropyltrimethoxysilane to (2-(2-mercaptoethylthio)ethyl)trimethoxysilane in Production Example 2-2. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.95 (t, 2H), 1.39 (s, 9H), 1.56-1.81 (m, 24H), 2 .40 (t, 2H), 2.69 (m, 1H), 2.81 (s, 4H), 2.94 (m, 1H), 3.55 (s, 9H), 3.86-3.90 (m, 2H).

[0236] <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))> In Synthesis Example 1, Compound B was changed to Compound V, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, 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 H１３ F ６ S] ＋ ) NEGATIVE m / z 1277.6 (median) ([C ５６ H ９０ O ５２ P.S. ４ Si ２ W １１ ] ３－ )

[0237] <Production Example 20: Production of di(1-phenylcyclohexyl) 2-(2-(1,2-bis(1-phenylcyclohexyloxycarbonyl)ethyloxycarbonyl)-1-(3-(trimethoxysilyl)propylthio)ethylcarbonyloxy)butanedioate (Compound Y)>

[0238] Production Example 20-1: Production of di(1,2-bis(methyloxycarbonyl)ethyl)(2E)-but-2-enedioate (Compound W) Compound W was obtained in the same manner as in Production Example 2-1, except that 1-methylcyclopentanol was changed to dimethyl DL-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).

[0239] 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. Thereafter, the pH of the aqueous layer was 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 operation was repeated five times, and the resulting organic layer was concentrated using a rotary evaporator and dried in vacuo to obtain a carboxylic acid. Thereafter, in Production Example 18-1, trans-aconitic acid was changed to the carboxylic acid obtained above, and this was converted into carboxylic acid chloride. Then, in Production Example 2-1, fumaryl chloride was changed to the carboxylic acid chloride and 1-methylcyclopentanol was changed to 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).

[0240] 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) Compound Y was obtained by changing Compound A in Production Example 2-2 to Compound X. １H-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).

[0241] <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))> 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 (119.22 MHz, DMSO-d6): δ (ppm) = -53.03 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 399.1 ([C ２０ H １３ F ６ S] ＋ ) NEGATIVE m / z 1214.8 (median) ([C １２６ H １５０ O ６４ S ２ Si ３ W １１ ] ４－ )

[0242] <Production Example 21: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-(3-(trimethoxysilyl)propylthio)propylthio)butanedioate (Compound AA)>

[0243] Production Example 21-1: Production of di(1-ethylcyclopentyl) 2-(2-(1,2-bis(1-ethylcyclopentyloxycarbonyl)ethylthio)-3-hydroxypropylthio)butanedioate (Compound Z) 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).

[0244] 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) To a DCM solution of Compound Z and pyridine, tosyl chloride was added dropwise at 0°C. The mixture was then stirred at room temperature for 18 hours, and the resulting crude product was purified by column chromatography. Thereafter, the resulting tosylate ester was 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).

[0245] <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))> In Synthesis Example 1, Compound B was changed to Compound AA, and potassium undecatungstosilicate was changed to potassium undecatungstophosphate, to obtain a 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 (119.22 MHz, 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 F ６ S] ＋ ) NEGATIVE m / z 1448.7 (median) ([C ８４ H １３８ O ５６ P.S. ６ Si ２ W １１ ] ３－ )

[0246] [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) at the contents (unit: parts by mass) shown in Tables 1 to 3 below.

[0247]

[0248]

[0249]

[0250] [3. Formation of Test Films and Evaluation Thereof] 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) treatment was performed on a hot plate at a temperature of 120°C for 60 seconds, followed by drying to prepare a resist film with a thickness of 50 nm. The thickness of the formed test films (M-1) to (M-26) was measured using a film thickness measuring device ("M-2000D" manufactured by J.A. Woollam Co.).

[0251] <Evaluation of Film Remaining Rate Before Exposure and After Development> The above test films (M-1) to (M-26) were subjected to alkaline development for 60 seconds using a 2.38% by mass aqueous solution of TMAH (trade name "NMD-3", manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C. Thereafter, the test films were rinsed with pure water for 15 seconds. The film thickness (average thickness) of each test film after development was measured using the above film thickness measuring device, and the film thickness reduction rate before and after development was calculated according to the following formula. The film thickness remaining rate before exposure 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) × 100 (%) A: Film thickness reduction rate is 0% or more but less than 10% B: Film thickness reduction rate is 10% or more but less than 20% C: Film thickness reduction rate is 20% or more

[0252] <Evaluation of Film Remaining Rate After Exposure and Development> The test films (M-1) to (M-26) were subjected to 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 After the exposure, a post-exposure bake (PEB) treatment was carried out at 100° C. for 60 seconds.

[0253] After the PEB treatment, each test film was subjected to alkaline development for 60 seconds at 23°C using a 2.38% by mass TMAH aqueous solution (trade name "NMD-3", manufactured by Tokyo Ohka Kogyo Co., Ltd.). Then, the test film was rinsed for 15 seconds using pure water. The film thickness (average thickness) of each test film after development was measured using the film thickness measuring device, and the residual film ratio of the test film after development was calculated according to the following formula. The residual 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 ratio after development = (film thickness after development / film thickness before development) x 100 (%) A: Residual film ratio after development is 0% or more and less than 10% B: Residual film ratio after development is 10% or more and less than 20% C: Residual film ratio after development is 20% or more

[0254]

[0255]

[0256]

[0257] From the results in Tables 4 to 6, it can be seen that the solubility in the developer before and after exposure changes dramatically in all cases, including 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 at defect sites by introducing four polar groups having an acid dissociable group, as in the test films (M-23) and (M-24) containing polyacid salts (A-23) or (A-24) having heteropolyacid anions modified at defect sites by introducing six polar groups having an acid dissociable group, as in the test films (M-25) and (M-26) containing polyacid salts (A-25) or (A-26) having heteropolyacid anions modified at defect sites by introducing eight polar groups having an acid dissociable group. On the other hand, when the test film (M-6) contained 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 ratio after exposure and development was not good, and it was found that the residual film ratio after development was 20% or more.

[0258] 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 at defect sites by the introduction of two polar groups having an acid-dissociable group, the film remaining 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.

[0259] Furthermore, the above results show that in heteropolyacid salts in which vacant 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.

[0260] 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 vacancy sites have been modified, as in the polyacid salts (A-8) to (A-12).

[0261] 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.

[0262] In addition, it was found that 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), organic / inorganic hybrid structures of polyacid having similar functionality can be provided.

[0263] From the above, it can be seen that a heteropolyacid salt in which four or more polar groups having an acid-dissociable group have been introduced to modify the defect sites can drastically change the physical properties, such as solubility in a developer, between the exposed and unexposed areas to actinic rays, etc., and is useful as a functional building block having the above-mentioned functions.

Claims

1. A heteropolyacid salt or a mixture thereof in which the defect site is modified, represented by general formula (I). (A ｍ＋ ) ａ (C （ａｍ）－ ) (I) [In general formula (I), A ｍ＋ are each independently H ＋ , metal ions, NH ４ ＋ , an onium cation, or an onium dication; （ａｍ）－ represents a heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the defect site being modified in the heteropolyacid anion having a defect site, the heteropolyacid anion having a defect site and modified in the heteropolyacid anion having a defect site contains a plurality of polar groups having an acid-dissociable group, m is an integer of 1 to 5, and a is a real number greater than 0.] 2. A heteropolyacid salt or a mixture thereof in which the defective site is modified and which is represented by the general formula (I'). (A' ｍ’＋ ) ａ’ (B ｎ＋ ) ｂ (C'(a'm'+bn)-) (I') [In general 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 heteropolyacid anion obtained by modifying a heteropolyacid anion having a defect site, the heteropolyacid anion obtained by modifying the defect site in the heteropolyacid anion having a 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.

3. The heteropolyacid salt or mixture thereof having a modified defect site 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 heteropolyacid salt or mixture thereof in which the defective sites have been modified according to claim 1 or 2, wherein 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 heteropolyacid anion having the defective sites via some or all of the heteroatoms, and the organic group contains two or more polar groups having an acid-dissociable group.

5. The organic group is C, which may have a substituent. １－１８ C is a hydrocarbyl group, 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 - (provided that adjacent divalent carbon atoms are not simultaneously replaced), １－１８ The heteropolyacid salt or a mixture thereof having modified defect sites according to claim 4, wherein two or more hydrogen atoms contained in the hydrocarbyl group are substituted with polar groups having an acid-dissociable group.

6. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 4, wherein the organic group is represented by general formula (VII-2). [In general formula (VII-2), L ２Ｂ is an optionally substituted C １－１２ In the hydrocarbyl group, a total of two or more hydrogen atoms on the same or different carbon atoms at any position, including the terminals, are R ２Ｃ represents a group substituted with ２Ｂ 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 substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ｃ each independently represents a polar group having an acid-dissociable group; x represents an integer of 2 to 6; and * represents a bond between the organic group and a heteroatom such as P, Si, Ge, or Sn.

7. 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. The heteropolyacid salt or mixture thereof having modified defect sites according to claim 1 or 2, 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 general 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 general 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. 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.

Images