Heteropolyacid salt having modified lacunary site, mixture thereof, resist material, and pattern formation method

Abstract

The present invention provides a heteropolyacid salt having a modified lacunary site and a mixture thereof. The heteropolyacid salt having a modified lacunary site and the mixture are each characterized in that: a cation moiety of the heteropolyacid salt having the modified lacunary site includes an organic sulfonium cation; and the organic sulfonium cation has one or more iodine atoms and a polar group which has one or more acid-dissociable groups.

Description

A heteropolyate salt or mixture thereof with modified defect sites, a resist material, and a pattern forming method.

[0001] The present invention relates to a heteropolyate or mixture thereof with modified defect sites, a resist material, and a pattern forming method.

[0002] In recent years, advancements in lithography techniques such as immersion lithography and EUV lithography have led to the miniaturization of circuit patterns. This advancement in lithography technology necessitates the development of new resist materials to accommodate these changes.

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

[0004] For example, Patent Document 1 describes a core made of ZrO ２ , HfO ２ , TiO ２ A nanoparticle polymer resist is disclosed, comprising nanoparticles containing the above and a polymer. Furthermore, Patent Document 2 discloses (t-BuSn), which is an alkyltin cluster. １２ O １４ (OH) ６ (HCO ２ ) ２ A resist based on this has been disclosed.

[0005] U.S. Patent No. 9,696,624 WO2019 / 195522

[0006] The present invention aims to provide novel heteropoly salts or mixtures thereof with modified defect sites, resist materials, and pattern formation methods.

[0007] As a result of diligent research to solve the above problems, the present inventors have found that by introducing an organic sulfonium cation containing one or more acid-dissociable polar groups and one or more iodine atoms into the cation portion of a heteropoly salt or mixture thereof with modified defect sites, a heteropoly salt or mixture thereof with modified defect sites that has high sensitivity to active light and the like can be obtained, and thus the present invention has been completed.

[0008] That is, the present invention relates to the following inventions. <1> A heteropolyacid salt or a mixture thereof in which a defect site is modified, wherein the cation part of the heteropolyacid salt or the mixture thereof in which the defect site is modified contains an organic sulfonium cation, and the organic sulfonium cation has a polar group having one or more acid dissociable groups and one or more iodine atoms, and a heteropolyacid salt or a mixture thereof in which the defect site is modified. <2> The heteropolyacid salt or the mixture thereof in which the defect site is 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 the mixture thereof in which the defect site is modified according to <1> or <2>, wherein the organic sulfonium cation is a triarylsulfonium cation which may have a substituent, and one or more hydrogen atoms on one or more aryl groups of the triarylsulfonium cation are substituted with a polar group having an acid dissociable group or an organic group containing a polar group having an acid dissociable group, and one or more hydrogen atoms on one or more aryl groups of the triarylsulfonium cation are substituted with iodine atoms. <4> The heteropolyacid salt or the mixture thereof in which the defect site is modified according to any one of <1> to <3>, wherein the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (VIII). [In the formula (VIII), Ar ３Ａ ~Ar ３Ｃ each independently represents an optionally substituted C ６－１８ aryl group, and any two of the Ar ３Ａ ~Ar ３Ｃ are directly connected to each other by a single bond or are a divalent linking group C １－３ alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ - and may form a ring together with the sulfur atom in the formula (VIII), and the Ar ３Ａ , Ar ３Ｂ or Ar ３Ｃ ​​At least one of the hydrogen atoms above is substituted with a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, and the above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ At least one of the hydrogen atoms above is substituted with an iodine atom. ] <5> A heteropoly salt or mixture thereof, in which the missing site described in any of <1> to <4> is modified, wherein the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (IX-1) or (IX-2). [In formula (IX-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom; o1, p1, and q1 each represent integers from 0 to 3; r1, s1, and t1 each represent integers from 0 to 5; u1, v1, and w1 each represent integers from 0 to 5; o1 + p1 + q1 is an integer greater than or equal to 1; r1 + s1 + t1 is an integer greater than or equal to 1; and o1 + r1 + u1, p1 + s1 + v1, and q1 + t1 + w1 each represent integers from 0 to 5. [In formula (IX-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２1 represents -, o2, p2 and q2 each represent integers from 0 to 3, r2 and u2 each represent integers from 0 to 5, s2, t2, v2 and w2 each represent integers from 0 to 4, o2 + p2 + q2 is an integer of 1 or more, r2 + s2 + t2 is an integer of 1 or more, o2 + r2 + u2 is an integer from 0 to 5, and p2 + s2 + v2 and q2 + t2 + w2 are integers from 0 to 4. ] <6> A heteropoly salt or mixture thereof in which the missing site described in any of <1> to <5> is modified, wherein the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (IX-1-1) or (IX-2-1). [In formula (IX-1-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom. o11 represents an integer from 1 to 3, p11 and s11 each represent integers from 0 to 4, q11, r11, t11, and u11 each represent integers from 0 to 5, p11 + q11 + r11 is an integer greater than or equal to 1, o1 + p11 + s11 is an integer from 1 to 5, and q11 + t11 and r11 + u11 each represent integers from 0 to 5. [In formula (IX-2-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２, where o21 represents an integer from 1 to 3, p21, q21 and r21 each represent integers from 0 to 4, s21, t21 and u21 each represent integers from 0 to 4, p21 + q21 + r21 is an integer of 1 or more, o21 + p21 + s21 is an integer from 1 to 5, and q21 + t21 and r21 + u21 each represent integers from 0 to 4. ] <7> A heteropoly salt or mixture thereof with a modified defect site as described in <6>, wherein the organic sulfonium cation represented by the general formula (IX-1-1) is an organic sulfonium cation represented by the following general formula (IX-1-2) or (IX-1-3). [In formula (IX-1-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom, where o12 represents an integer of 1 or 2, p12 represents an integer from 1 to 4, q12 represents an integer from 0 to 3, r12 and s12 each represent integers from 0 to 5, and o12 + p12 + q12 is an integer from 2 to 5. [In formula (IX-1-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ ∫ represents a substituent other than an iodine atom, o13 represents an integer of 1 or 2, p13 and q13 each represent an integer from 0 to 5, r13 represents an integer from 0 to 4, p13 + q13 is an integer of 1 or more, and o13 + r13 is an integer from 1 to 5. ] <8> A heteropoly salt or mixture thereof in which the missing site described in <6> is modified, wherein the organic sulfonium cation represented by the general formula (IX-2-1) is an organic sulfonium cation represented by the following general formula (IX-2-2) or (IX-2-3). [In formula (IX-2-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４ＦEach of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ [This represents a negative value, where o22 represents an integer of 1 or 2, p22 represents an integer from 1 to 4, q22 represents an integer from 0 to 3, r22 and s22 each represent integers from 0 to 4, and o22 + p22 + q22 is an integer from 2 to 5.] [In formula (IX-2-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ represents substituents other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ - represents an integer, o23 represents an integer of 1 or 2, p23, q23 and r23 each represent an integer from 0 to 4, p23 + q23 is an integer of 1 or more, and o23 + r23 is an integer from 1 to 5. ] <9> The heteropoly salt or mixture thereof with the modified defect site is a heteropoly salt or mixture thereof with the modified defect site represented by general formula (I), as described in any of <1> to <8>. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [In formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; B ｎ＋ Each independently represents an organic sulfonium cation, the organic sulfonium cation having one or more acid-dissociable polar groups and one or more iodine atoms; C （ａｍ＋ｂｎ）－represents a heteropoly acid anion in which the missing site is modified, where m is an integer from 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0. ] <10> The organic group containing the polar group having the acid-dissociable group may have substituents C １－１８ A hydrocarbyl group in which the divalent carbon atoms at any position other than the terminals other than the bond of the organic group are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ A heteropoly salt or mixture thereof in which the defect site described in any of <3> to <8> is modified, wherein at least one hydrogen atom of the organic group is replaced by a polar group having an acid-dissociable group, and the defect site may be replaced by a (however, adjacent divalent carbon atoms may not be replaced at the same time). <11> A resist material containing (A) a heteropoly salt or mixture thereof in which the defect site described in any of <1> to <9> is modified. <12> The resist material described in <11> further contains (B) an acid diffusion control agent. <13> A pattern forming method comprising the steps of: forming a resist film using the resist material described in <11> or <12>; exposing the resist film; and developing the exposed resist film using a developer.

[0009] <14> The resist material according to <11> or <12>, further containing an organic solvent. <15> The resist material according to any one of <11>, <12>, and <14>, which is an electron beam or EUV resist material.

[0010] According to the present invention, it is possible to provide novel heteropoly salts or mixtures thereof with modified defect sites, resist materials, and pattern forming methods.

[0011] Preferred embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

[0012] In this specification, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0013] In this specification, "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0014] In this specification, for example, "C １－６ Terms such as "[...]" refer to the number of carbon atoms in the core group.

[0015] In this specification, "C １－１８ A "hydrocarbylene group" refers to a divalent hydrocarbon group produced by removing two hydrogen atoms from a hydrocarbon having 1 to 18 carbon atoms. Hydrocarbylene groups may be linear, branched, or partially or entirely cyclic. Hydrocarbylene groups include alkylene groups and arylene groups. １－１８ The divalent carbon atoms at any position in the "hydrocarbylene group" are -O-, -S-, -C(=O)-, -COO-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, -SO-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). １－１８ The "hydrocarbylene group" is not particularly limited and includes, for example, 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, oxyethyleneoxyethane-1,1-diyl group, etc. 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, phenanthrendiyl group, naphthacenediyl group, pyrenediyl group, perylenediyl group, chrysendiyl group, etc. ６－１８ Examples include the "arylene group."

[0016] In this specification, "C １－１８ "Alkyl alkyl group" refers to a linear or branched alkyl group having 1 to 18 carbon atoms. １－１８ Any divalent carbon atom in an alkyl group, excluding the terminals, is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced. However, adjacent divalent carbon atoms cannot be replaced at the same time. １－１８ The "alkyl group" is not particularly limited and includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, i-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1 Examples include 1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. １－１８ The divalent carbon atoms at any position in the alkyl group, excluding the terminals, are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ The substitutes for the hyphen are not particularly limited, and examples include the 2-methoxyethoxymethyl group and the ethoxycarbonylmethyl group.

[0017] In this specification, "C １－１８ "Haloalkyl group" refers to "C １－１８ "Alkyl group" refers to a group in which one or more hydrogen atoms are substituted with halogen atoms.１－１８ The term "haloalkyl group" is not particularly limited and includes, for example, dichloromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, etc.

[0018] In this specification, "C ２－１８ An "alkenyl group" is a group with two or more carbon atoms. １－１８ "Alkyl group" refers to an alkenyl group having one or more double bonds, and includes alkadinyl groups, alkatrienyl groups, etc. ２－１８ The "alkenyl group" is not particularly limited and includes, for example, vinyl group (ethenyl group), allyl group (2-propenyl group), 1-propenyl group, isopropenyl group (1-methylvinyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc.

[0019] In this specification, "C ２－１８ An "alkynyl group" is a group with two or more carbon atoms. １－１８ "Alkyl group" refers to an alkynyl group having one or more triple bonds. ２－１８ The "alkynyl group" is not particularly limited and includes, for example, ethynyl group, 1-propynyl group, 2-propynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desynyl group, undecynyl group, dodecynyl group, etc.

[0020] In this specification, "C ３－１８ A "cycloalicyclic group" refers to a hydrocarbon group that has a monocyclic or polycyclic cyclic structure with 3 to 18 carbon atoms, either entirely or partially. Cyclocyclic groups include cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups, monocycloalkyl groups, polycycloalkyl groups, etc. ３－１８ A divalent carbon atom at any position in an alicyclic group, excluding the terminals, is either -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or SO ２- may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). ３－１８ The term "cycloalkyl group" is not particularly limited and includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, t-butylcyclohexyl group, tricyclodecanyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, 2-methyladamantan-2-yl group, 2-i-propyladamantan-2-yl group, bornyl group, norbonyl group, fenquil group, pinanyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, cyclopropylmethyl group, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, bornylmethyl group, norbornylmethyl group, adamantylmethyl group, 1-methylcyclopentyloxycarbonylmethyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like.

[0021] In this specification, "3- to 18-membered non-aromatic heterocyclic group" means a 3- to 18-membered non-aromatic heterocyclic group containing one or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms, and may be monocyclic, polycyclic, or fused, and may be saturated or partially unsaturated. The "3- to 18-membered ring non-aromatic heterocyclic group" is not particularly limited and includes, for example, aziridinyl group, azetidyl group, pyrrolidinyl group, pyrrolyl group, piperidinyl group, piperazinyl group, morpholinyl group, thiomorpholinyl group, tetrahydrofuryl group, tetrahydropyranyl group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl group, imidazolinyl group, oxazolinyl group, 2,5-diazabicyclo[2.2.1]heptyl group, 2,5-diazabicyclo[2.2.2]octyl group, 3,8-diazabicyclo[3.2.1]octyl group, 1,4-diazabicyclo[4.3.0]nonyl group, 1-azadamantyl group, 2-azadamantyl group, etc.

[0022] In this specification, "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, one or more heteroatoms selected from the group consisting of carbon atoms having 2 to 10 carbon atoms and nitrogen atoms, oxygen atoms and sulfur atoms form a ring, and each may be a monocyclic, polycyclic or condensed ring. "C ２－１８ The "aryl group" is not particularly limited, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an azulene group, a pentalenyl group, a heptalenyl group, an indacenyl group, an acenaphthyl group, a phenanthrenyl group, an anthracenyl group and the like.

[0023] In this specification, "C ７－１８ The term "aralkyl group" means a group in which a substitutable part in the "C １－１２ alkyl group" is substituted with the above-mentioned "C ２－１２ aryl group". The "C ７－１８ 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, a 2-naphthylmethyl group and the like.

[0024] In this specification, "C １－１８ The term "hydrocarbyl group" means a monovalent group formed by removing one hydrogen atom from a hydrocarbon having 1 to 18 carbon atoms. The hydrocarbyl group includes an alkyl group, an alkenyl group, an alkynyl group, an alicyclic group, an aryl group, an aralkyl group and the like. Also, any divalent carbon atom at a position other than the terminal contained in the "C １－１８ hydrocarbyl group" may be replaced by -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (however, it is assumed that two adjacent divalent carbon atoms are not simultaneously replaced). This point also applies to the "C １－１８ hydrocarbyl group" and the like used in the description of the definitions such as the following "C １－１８ hydrocarbyloxy group". The "C １－１８ hydrocarbyl group" is not particularly limited, and examples thereof include "C １－１８"Alkyl alkyl group", "C ２－１８ "Alkenyl group", "C ２－１８ "Alkynyl group", "C ３－１８ “Alicyclic group”, “C ２－１８ "Aryl group", "C ７－１８ Examples include the "aralkyl group."

[0025] In this specification, "C １－１８ "Hydrocarbyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl group". １－１８ The term "hydrocarbyloxy group" is not particularly limited and includes, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, i-pentoxy group, sec-pentoxy group, n-hexoxy group, i-hexoxy group, 1,1-dimethylpropyloxy group, 1,2-dimethylpropyloxy group, 2,2-dimethylpropyloxy group, 1-methyl- C １－１８ "Alkoxy group"; such as 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, pentarenyloxy group, heptarenyloxy group, indacenyloxy group, acenaphthyloxy group, phenantrenyloxy group, anthracenyloxy group, etc. ６－１８ Examples include "aryloxy group".１－１８ As for the "hydrocarbyl oxy group", C １－１８ It is preferable that the divalent carbon atoms at any position other than the terminals in the "hydrocarbyl group" are 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 substituted ethylcyclopentyloxy, methyladamantyloxy, ethyladamantyloxy, t-butyloxy, etc.

[0026] In this specification, "C １－１８ The term "hydrocarbyl carbonyl group" refers to "C １－１８ This refers to 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 includes, for example, acetyl group, propionyl group, isopropionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pentanoyl group, 3-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanol group, etc. １－１８ "Alkyl carbonyl group"; cyclopropyl carbonyl group, cyclobutyl carbonyl group, cyclopentyl carbonyl group, 2-methylcyclopentyl carbonyl group, 3-methylcyclopentyl carbonyl group, cyclohexyl carbonyl group, 2-methylcyclohexyl carbonyl group, 3-methylcyclohexyl carbonyl group, 4-methylcyclohexyl carbonyl group, adamantyl carbonyl group, etc. ３－１８ "Alicyclic carbonyl group"; "C" such as benzoyl group, 1-naphthoyl group, 2-naphthoyl group, etc. ６－１８ Examples include "arylcarbonyl group," etc.

[0027] In this specification, "C １－１８ "Hydrocarbylcarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyl carbonyl group". １－１８The "hydrocarbylcarbonyloxy group" is not particularly limited and includes, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, isopentylcarbonyloxy group, hexylcarbonyloxy group, etc. １－１８ "Alkyl carbonyloxy group"; such as cyclopropyl carbonyloxy group, cyclobutyl carbonyloxy group, cyclopentyl carbonyloxy group, cyclohexyl carbonyloxy group, etc. ３－１８ "Alicyclic carbonyloxy group"; such as phenylcarbonyloxy group, naphthylcarbonyloxy group, acenaphthylcarbonyloxy group, phenantrenylcarbonyloxy group, anthracenylcarbonyloxy group, etc. ６－１８ Examples include "arylcarbonyloxy group," etc.

[0028] In this specification, "C １－１８ The term "hydrocarbyloxycarbonyl group" refers to "C １－１８ This refers to 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 includes, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neopentyloxycarbonyl group, etc. １－１８ "Alkoxycarbonyl group"; such as cyclopropyloxycarbonyl group, cyclobutyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 2-methylcyclopentyloxycarbonyl group, 3-methylcyclopentyloxycarbonyl group, 2-methylcyclohexyloxycarbonyl group, 3-methylcyclohexyloxycarbonyl group, 4-methylcyclohexyloxycarbonyl group, etc. ３－１８"Alicyclic oxycarbonyl group"; such as phenoxycarbonyl group, naphthoxycarbonyl group, acenaphthyloxycarbonyl group, phenantrenyloxycarbonyl group, anthracenyloxycarbonyl group, etc. ６－１８ Examples include "aryloxycarbonyl group," etc.

[0029] In this specification, "C １－１８ The term "hydrocarbyloxycarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbyloxycarbonyl group". １－１８ The "hydrocarbyloxycarbonyloxy group" is not particularly limited and includes, for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propyloxycarbonyloxy group, i-propyloxycarbonyloxy group, n-butoxycarbonyloxy group, i-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, t-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group, i-pentyloxycarbonyloxy group, n-hexyloxycarbonyloxy group, etc. １－１８ "Alkoxycarbonyloxy group"; such as cyclopropyloxycarbonyloxy group, cyclobutyloxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, etc. ３－１８ "Alicyclic oxycarbonyloxy group"; such as phenoxycarbonyloxy group, naphthoxycarbonyloxy group, acenaphthyloxycarbonyloxy group, phenantrenyloxycarbonyloxy group, anthracenyloxycarbonyloxy group, etc. ６－１８ Examples include "aryloxycarbonyloxy group".

[0030] In this specification, "C １－１８ A "hydrocarbylamino group" is a single "C" １－１８ A "hydrocarbyl group" refers to a group in which an amino group is bonded. １－１８The "hydrocarbylamino group" is not particularly limited and includes, for example, methylamino group, ethylamino group, n-propylamino group, i-propylamino group, n-butylamino group, i-butylamino group, sec-butylamino group, t-butylamino group, n-pentylamino group, i-pentylamino group, neopentylamino group, n-hexylamino group, etc. 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"; such as phenylamino group, 1-naphthylamino group, 2-naphthylamino group, etc. ６－１８ Examples include "arylamino group," etc.

[0031] In this specification, "Di C １－１８ A "hydrocarbylamino group" is two identical or different "C" groups. １－１８ "Hydrocarbyl group" refers to a group in which a hydroxyl group is bonded to an amino group. １－１８ The term "hydrocarbylamino group" is not particularly limited and includes, for example, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, diisobutylamino group, di-t-butylamino group, di-n-pentylamino group, di-n-hexylamino group, N-ethyl-N-methylamino group, N-methyl-N-n-propylamino group, N-isopropyl-N-methylamino group, N-n-butyl-N-methylamino group, N DiC groups such as -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, etc. １－１８"Alkylamino group"; dicyclopropylamino group, dicyclobutylamino group, dicyclopentylamino group, dicyclohexylamino group, etc. ３－１８ "Alicyclic amino group"; such as diphenylamino group, phenylnaphthylamino group, etc. ６－１８ "Arylamino group"; "N-C" such as N-methylcyclopentaneamino group and N-methylcyclohexylamino group. １－１８ Alkyl-N-C ３－１８ "Cycloalkylamino group"; "N-C" such as N-methyl-2-phenylethylamino group, N-ethyl-N-(4-methylphenyl)amino group １－１８ Alkyl-N-C ６－１８ Examples include "arylamino group," etc.

[0032] In this specification, "C １－１８ "Hydrocarbylaminocarbonyl group" refers to "C １－１８ This refers to 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 includes, for example, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, i-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, t-butylaminocarbonyl group, n-pentylaminocarbonyl group, 2-pentylaminocarbonyl group, neopentylaminocarbonyl group, 4-methyl-2-pentylaminocarbonyl group, n-hexylaminocarbonyl group, 3-methyl-n-pentylaminocarbonyl group, etc. 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"; such as phenylaminocarbonyl group, 1-naphthylaminocarbonyl group, 2-naphthylaminocarbonyl group, etc.６－１８ An example is the "arylaminocarbonyl group."

[0033] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonyl group" refers to "diC １－１８ This refers to a group in which a carbonyl group (-C(=O)-) is bonded to a "hydrocarbylamino group". １－１８ The term "hydrocarbylaminocarbonyl group" is not particularly limited and includes, for example, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, diisopropylaminocarbonyl group, di-n-butylaminocarbonyl group, diisobutylaminocarbonyl group, di-t-butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, N-ethyl-N-methylaminocarbonyl group, N-methyl-N-n-propylaminocarbonyl group, N-isopropyl-N-methylaminocarbonyl group, N-n-butyl-N-methylaminocarbonyl group. DiC １－１８ "Alkylamino group"; such as dicyclopropylaminocarbonyl group, dicyclobutylaminocarbonyl group, dicyclopentylaminocarbonyl group, dicyclohexylaminocarbonyl group, etc. ３－１８ "Alicyclic aminocarbonyl group"; "DiC" such as diphenylaminocarbonyl group and phenylnaphthylaminocarbonyl group. ６－１８ Examples include "arylaminocarbonyl group," etc.

[0034] In this specification, "C １－１８ "Hydrocarbylcarbonylamino group" refers to "C １－１８This refers to a group in which an amino group is bonded to a "hydrocarbyl carbonyl group". １－１８ The "hydrocarbonylamino group" is not particularly limited and includes, for example, 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, n-hexylcarbonylamino group, etc. １－１８ "Alkylcarbonylamino group"; such as cyclopropylcarbonylamino group, cyclobutylcarbonylamino group, cyclopentylcarbonylamino group, cyclohexylcarbonylamino group, etc. ３－１８ "Alicyclic carbonylamino group"; such as phenylcarbonylamino group, naphthylcarbonylamino group, acenaphthylcarbonylamino group, phenantrenylcarbonylamino group, anthracenylcarbonylamino group, etc. ６－１８ Examples include "arylcarbonylamino group," etc.

[0035] In this specification, "C １－１８ "Hydrocarbylaminocarbonyloxy group" refers to "C １－１８ This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, methylaminocarbonyloxy group, ethylaminocarbonyloxy group, n-propylaminocarbonyloxy group, etc. １－１８ "Alkylaminocarbonyloxy group"; "C" such as cyclopropylaminocarbonyloxy group, cyclohexylaminocarbonyloxy group, etc. ３－１８ "Alicyclic aminocarbonyloxy group"; "C" such as phenylaminocarbonyloxy group, 1-naphthylaminocarbonyloxy group ６－１８ Examples include "arylaminocarbonyloxy group".

[0036] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonyloxy group" is a "diC １－１８This refers to a group in which an oxygen atom (-O-) is bonded to a "hydrocarbylaminocarbonyl group". １－１８ The "hydrocarbylaminocarbonyloxy group" is not particularly limited and includes, for example, dimethylaminocarbonyloxy group, diethylaminocarbonyloxy group, di-n-propylaminocarbonyloxy group, etc. １－１８ Examples include "alkylaminocarbonyloxy group," etc.

[0037] In this specification, "C １－１８ "Hydrocarbylaminocarbonylamino group" refers to "C １－１８ "Hydrocarbylaminocarbonyl group" refers to a group in which an amino group is bonded. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, methylaminocarbonylamino group, ethylaminocarbonyloxy group, n-propylaminocarbonylamino group, etc. １－１８ "Alkylaminocarbonylamino group"; "C" such as cyclopropylaminocarbonylamino group, cyclohexylaminocarbonylamino group, etc. ３－１８ "Alicyclic aminocarbonylamino group"; "C" such as phenylaminocarbonylamino group, 1-naphthylaminocarbonylamino group, etc. ６－１８ Examples include "arylaminocarbonylamino group," etc.

[0038] In this specification, "Di C １－１８ "Hydrocarbylaminocarbonylamino group" refers to "diC １－１８ "DiC" refers to a group in which a "hydrocarbylaminocarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbylaminocarbonylamino group" is not particularly limited and includes, for example, dimethylaminocarbonylamino group, diethylaminocarbonylamino group, di-n-propylaminocarbonylamino group, etc. １－１８ Examples include "alkylaminocarbonylamino group," etc.

[0039] In this specification, "C １－１８ "Hydrocarbyloxycarbonylamino group" is "C １－１８This refers to a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited and includes, for example, methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group, n-butoxycarbonylamino group, t-butoxycarbonylamino group, etc. １－１８ "Alkoxycarbonylamino group"; "C" such as cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ "Alicyclic oxycarbonylamino group"; "C" such as phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ Examples include "aryloxycarbonylamino group," etc.

[0040] In this specification, "C １－１８ A "hydrocarbylthio group" is a "C １－１８ This refers to a group in which a sulfur atom (-S-) is bonded to a "hydrocarbyl group". １－１８ The "hydrocarbylthio group" is not particularly limited and includes, for example, methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, t-butylthio group, n-pentylthio group, 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"; such as phenylthio group, 1-naphthylthio group, 2-naphthylthio group, acenaphthylthio group, phenantrenylthio group, anthracenylthio group, etc. ６－１８ Examples include "arylthio group," etc.

[0041] In this specification, "C １－１８ The term "hydrocarbyl sulfinyl group" refers to "C １－１８ This refers to a group in which a sulfinyl group (-S (=O)-) is bonded to a hydrocarbyl group.１－１８ The "hydrocarbyl sulfinyl group" is not particularly limited and includes, for example, methyl sulfinyl group, ethyl sulfinyl group, n-propyl sulfinyl group, i-propyl sulfinyl group, n-butyl sulfinyl group, t-butyl sulfinyl group, pentyl sulfinyl group, hexyl sulfinyl group, etc. １－１８ "Alkyl sulfinyl group"; cyclopropyl sulfinyl group, cyclobutyl sulfinyl group, cyclopentyl sulfinyl group, cyclohexyl sulfinyl group, 2-methylcyclopentyl sulfinyl group, 3-methylcyclopentyl sulfinyl group, 2-methylcyclohexyl sulfinyl group, 3-methylcyclohexyl sulfinyl group, 4-methylcyclohexyl sulfinyl group, etc. ３－１８ "Alicyclic sulfinyl group"; such as phenylsulfinyl group, naphthylsulfinyl group, acenaphthylsulfinyl group, phenantrenylsulfinyl group, anthracenylsulfinyl group, etc. ６－１８ Examples include "aryl sulfinyl group," etc.

[0042] In this specification, "C １－１８ The term "hydrocarbyl sulfonyl group" refers to "C １－１８ A sulfonyl group (-SO) attached to a hydrocarbyl group. ２ It means a group to which -) is attached. １－１８ The "hydrocarbyl sulfonyl group" is not particularly limited and includes, for example, methyl sulfonyl group, ethyl sulfonyl group, n-propyl sulfonyl group, i-propyl sulfonyl group, n-butyl sulfonyl group, t-butyl sulfonyl group, pentyl sulfonyl group, etc. １－１８ "Alkyl sulfonyl group"; cyclopropyl sulfonyl group, cyclobutyl sulfonyl group, cyclopentyl sulfonyl group, cyclohexyl sulfonyl group, 2-methylcyclopentyl sulfonyl group, 3-methylcyclopentyl sulfonyl group, 2-methylcyclohexyl sulfonyl group, 3-methylcyclohexyl sulfonyl group, 4-methylcyclohexyl group, etc. ３－１８ "Alicyclic sulfonyl group"; such as phenylsulfonyl group, naphthylsulfonyl group, acenaphthylsulfonyl group, phenantrenylsulfonyl group, anthracenylsulfonyl group, etc. ６－１８Examples include "aryl sulfonyl group," etc.

[0043] In this specification, "acid-dissociable group" means a polar group that substitutes a hydrogen atom, such as a hydroxyl group (including phenolic hydroxyl groups, etc.), a carboxyl group, an amino group, or a sulfo group, which dissociates upon the action of an acid. Compounds having the above-mentioned acid-dissociable group can increase their polarity by dissociating the acid-dissociable group upon the action of an acid, thereby generating the above-mentioned 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 increases relatively, while when a less polar organic developer is used as the developer, the solubility of the compound in the developer decreases relatively. Preferred polar groups are hydroxyl groups (including phenolic hydroxyl groups, etc.) and carboxyl groups.

[0044] The above-mentioned acid-dissociable group is not particularly limited, and any known and conventional acid-dissociable group usable in chemically amplified resists can be used. Examples of acid-dissociable groups include the acid-dissociable group G for polar groups having an acid-dissociable group represented by the following general formulas (G-1) to (G-4).

[0045] The above-mentioned acid-dissociable group G is not particularly limited as long as it dissociates upon the action of an acid, and known and commonly used groups can be used. For example, the acid-dissociable group G is the "tertiary carbon type acid-dissociable group G" represented by the following general formula (g-1). Ａ ", and "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2) Ｂ " and "acetal-type acid-dissociating group G" represented by the following general formula (g-3) Ｃ These are some examples. Each of these will be explained in turn below.

[0046] <Tertiary carbon type acid dissociable group G Ａ> The above acid-dissociating group G is the "tertiary carbon type acid-dissociating group G" represented by the following general formula (g-1) Ａ As shown above, the carbon is directly bonded to a polar group, and R Ａ ｇ１ ~R Ａ ｇ３ An acid-dissociable group can be used in which the bonded carbon is a tertiary carbon atom.

[0047] "R Ａ ｇ１ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0048] R Ａ ｇ１ C may have substituents. １－１２ Alkyl alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１２ Alkyl alkyl group, or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0049] Also, "R Ａ ｇ２ " and "R Ａ ｇ３Each of these C atoms may independently have substituents. １－１２ A hydrocarbyl group in which the divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms may not be replaced at the same time), or R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0050] R Ａ ｇ２ and R Ａ ｇ３ For example, R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atom may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously), and furthermore, it may have the above substituent. ３－１８The alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group includes a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, and tricyclodecene skeleton, and the divalent carbon atoms at any position except the terminals are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0051] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) Ａ Examples include t-butyl group, t-amyl group, 1,1-dimethylpropyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, and 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group.

[0052] Tertiary carbon type acid-dissociable group G represented by general formula (g-1) Ａ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0053]

[0054] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２ >> Also, the "tertiary carbon type acid-dissociable group G" represented by the general formula (g-1) Ａ In ", R Ａ ｇ２ and R Ａ ｇ３ These are combined and may have substituents. ３－１８In cases 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) Ａ１ , and the tertiary carbon-type oxygen dissociable group G represented by (g-1-2) Ａ２ These are some examples.

[0055] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) Ａ１ >> The tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1) Ａ１ In R Ａ ｇ１１ C may have substituents. １－１２ Alkyl alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0056] Also CC Ａ ｇ１ This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0057] Cy Ａ ｇ１These may have substituents along with the above-mentioned tertiary carbon atoms to form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the atoms may be replaced by ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0058] The tertiary carbon type acid-dissociable group G, represented by the general formula (g-1-1). Ａ１ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0059]

[0060]

[0061]

[0062]

[0063] <<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 Each of these may independently have a hydro group or a substituent. １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time), R Ａ ｇ２１ and R Ａｇ２２ , and / or, R Ａ ｇ２２ and R Ａ ｇ２３ These are linked directly by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring.

[0064] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or, R Ａ ｇ２２ and R Ａ ｇ２３ Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include the formation of a cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, etc., which may have substituents.

[0065] Also CC Ａ ｇ２ This is a C atom that may have substituents, along with the tertiary carbon atom mentioned above. ３－１８ It forms an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0066] Cy Ａ ｇ２These may have substituents along with the above-mentioned tertiary carbon atoms to form a cyclopentane skeleton, cyclohexane skeleton, cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cyclododecane skeleton, cyclopentene skeleton, cyclohexene skeleton, cycloheptene skeleton, cyclooctene skeleton, cyclodecene skeleton, norbornane skeleton, adamantane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, norbornene skeleton, or tricyclodecene skeleton, and any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the atoms may be replaced by ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0067] Tertiary carbon type acid-dissociable group G represented by general formula (g-1-2) Ａ２ Examples of such groups include the following tertiary carbon-type acid-dissociating groups.

[0068]

[0069]

[0070]

[0071] <Allyl or benzyl acid-dissociating group G> Ｂ > The above acid-dissociating group G is an "allyl-type or benzyl-type acid-dissociating group G" represented by the following general formula (g-2). Ｂ As shown above, an acid-dissociable group can be used in which the carbon directly bonded to the polar group is located at the allylic or benzyl position.

[0072] "R Ｂ ｇ１ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0073] R Ｂ ｇ１ C may have substituents. １－１２ Alkyl alkyl group, C ３－１２ Alicyclic group, C ６－１２ Aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１２ Alkyl alkyl group, or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0074] Also, "R Ｂ ｇ２ "~"R Ｂ ｇ４ Each of these may independently have a hydro group or a substituent. １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0075] R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or, R Ｂ ｇ３ and R Ｂ ｇ４These are linked directly by single bonds, or by divalent bonds such as -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring.

[0076] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) Ｂ In R Ｂ ｇ１ and R Ｂ ｇ２ , R Ｂ ｇ２ and R Ｂ ｇ３ , and / or, R Ｂ ｇ３ and R Ｂ ｇ４ Examples of cases where a ring is formed together with the carbon atom included in the ethylenically unsaturated double bond include cases where a cyclic cyclopentenyl group, cyclohexenyl group, cyclopentylideneethenyl group, cyclohexyllideneethenyl group, benzyl group, or 2,3-dihydro-1H-indanyl group, which may have substituents, are formed.

[0077] Allyl or benzyl acid-dissociable group G represented by general formula (g-2) Ｂ Examples of such groups include 1-methyl-2-propenyl group, 1-cyclohexyl-2-propenyl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-methyl-2-cyclohexen-1-yl group, and 1-indanyl group.

[0078] Allyl or benzyl acid-dissociating group G Ｂ Specifically, the following allyl or benzyl acid-dissociating groups can be cited as examples.

[0079]

[0080] <Acetal-type acid-dissociating group G> Ｃ > The above acid-dissociating group G is the "acetal-type acid-dissociating group G" represented by the following general formula (g-3). Ｃ As shown above, an acid-dissociable group can be used in which an oxygen atom is bonded to a carbon atom that is directly bonded to the polar group.

[0081] "R Ｃ ｇ１ " and "R Ｃ ｇ３ Each of these may independently have a hydro group or a substituent. １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0082] R Ｃ ｇ１ and R Ｃ ｇ３ This may include a hydro group or a C which may have a substituent. １－１２ Alkyl or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the C group may be replaced by a ⁻ (however, adjacent divalent carbon atoms may not be replaced simultaneously), and may have a hydro group or substituent. １－６ Alkyl or C ３－８ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0083] Also, "R Ｃ ｇ２ " may have substituents C １－１２ A hydrocarbyl group in which any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0084] R Ｃ ｇ２ C may have substituents. １－１２ Alkyl alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－６ Alkyl alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom other than the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0085] Acetal-type acid-dissociable group G represented by general formula (g-3) Ｃ Examples include methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, n-butoxymethoxy group, 2,2-dimethylpropoxymethoxy group, 2,2-dimethylbutoxymethoxy group, cyclohexyloxymethoxy group, 1-ethoxyethoxy group, 1-n-butoxyethoxy group, and 1-cyclohexyloxyethoxy group.

[0086] In this specification, "hydroxyl group or carboxyl group having a protecting group" means a hydroxyl group (including phenolic hydroxyl group) or carboxyl group that is protected by an ether protecting group, a silyl ether protecting group, an acyl protecting group, an aminocarbonyl protecting group, or the like.

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

[0088] In this specification, "may have substituents" is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Examples of substituents include: (1) halogen atoms, (2) haloalkyl groups, (3) hydroxyl groups, (4) thiol groups, (5) nitro groups, (6) cyano groups, (7) carboxyl groups, (8) amino groups, (9) sulfo groups, (10) vinyl groups, (11) allyl groups, (12) (meth)acryloyl groups, (13) (meth)acryloyloxy groups, (14) (meth)acrylamide groups, (15) styryl groups, (16) epoxy groups, (17) glycidyl groups, (18) amide groups, (19) hydroxyl or carboxyl groups having a protecting group, (20) polar groups having an acid-dissociable group, or (21) C in which at least one part of the hydrogen atoms is substituted with (1) to (20) above. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyl sulfinyl group, C １－１８ A hydrocarbyl sulfonyl group in which the divalent carbon atoms at any position other than the terminals of the substituent are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ Examples include the possibility of substitution with - (however, adjacent divalent carbon atoms cannot be replaced simultaneously).

[0089] [1. Heteropolyates or mixtures thereof with modified defect sites] The heteropolyates or mixtures thereof with modified defect sites according to this embodiment are characterized in that the cationic portion contains an organic sulfonium cation, and the organic sulfonium cation has one or more acid-dissociable polar groups and one or more iodine atoms.

[0090] By including an organic sulfonium cation in the cation portion of a heteropolyate or mixture thereof with a modified defect site, it can function as an acid generator that generates acid upon exposure to active light (including visible light, ultraviolet light, DUV, XUV, EUV, X-rays, electron beams, alpha rays, beta rays, gamma rays, etc.).

[0091] Furthermore, by including one or more iodine atoms in the above-mentioned organic sulfonium cation, sensitivity to active light and the like can be improved.

[0092] Furthermore, if the above-mentioned organic sulfonium cation contains one or more acid-dissociable polar groups, the acid-dissociable polar groups can be dissociated by the action of an acid, thereby changing the solubility in the developer and other properties. In addition, if the above-mentioned organic sulfonium cation contains one or more acid-dissociable polar groups, the compounds formed after it has acted as an acid generator can be easily removed using a polar solvent or the like. Similarly, if the above-mentioned organic sulfonium cation contains one or more iodine atoms, the compounds formed after it has acted as an acid generator can be even more easily removed using a polar solvent or the like.

[0093] In the following, the anionic and cationic portions of the heteropoly salt or mixture thereof modified with the defective portion according to this embodiment will be described, respectively.

[0094] [1-1. Anionic portion of heteropoly acid salts or mixtures thereof with modified defect sites] As the anionic portion of heteropoly acid salts or mixtures thereof with modified defect sites according to this embodiment, a heteropoly acid anion with a modified defect site can be used, in which the terminal oxygen atom at the defect site of a heteropoly acid anion having a defect site is modified with a P, Si, Ge, or Sn compound having one or more organic groups.

[0095] [1-1-1. Heteropoly acid anions having a defect] The heteropoly acid anion having a defect according to this embodiment is not particularly limited, and a defect species in which a part of the basic skeleton of the above heteropoly acid anion is missing can be used, and any of the 1-defect species, 2-defect species, 3-defect species, etc. can be used. Examples of the above heteropoly acid anion having a defect include a Keggin-type heteropoly acid anion with a defect, a Dawson-type heteropoly acid anion with a defect, and the like.

[0096] <Deficient Keggin-type heteropoly acid anions> Examples of the above-mentioned deficient Keggin-type heteropoly acid anions include the 1-deficient Keggin-type heteropoly acid anion represented by the following general formula (II-1), the 2-deficient Keggin-type heteropoly acid anion represented by the following general formula (II-2), and the 3-deficient Keggin-type heteropoly acid 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) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c11- to c13- represent the negative charge number, and c11- to c13 are natural numbers.)

[0097] In general formulas (II-1) to (II-3), the values ​​of c11 to c13 change depending on the types of X and M. For example, in general formula (II-1), when X is P and M is Mo or W, c11 is 7 ([PMo １１ O ３９ ] ７－ [PW １１ O ３９ ] ７－ ) and when X is Si and M is Mo or W, c11 is 8 ([SiMo １１ O ３９ ] ８－ [SiW １１ O ３９ ] ８－ ) and if X is S and M is Mo or W, then c11 is 6 ([SMo １１ O ３９ ] ６－ [SW １１ O ３９ ] ６－ ) and if X is B and M is Mo or W, then c11 is 9 ([BMo １１ O ３９ ] ９－ [BW １１ O ３９ ] ９－) and if X is Ge and M is Mo or W, then c11 is 8 ([GeMo １１ O ３９ ] ８－ [GeW １１ O ３９ ] ８－ ) becomes. Also, in general formula (II-2), when X is P and M is Mo or W, c12 is 7 ([PMo １０ O ３６ ] ７－ [PW １０ O ３６ ] ７－ ) and when X is Si and M is Mo or W, c12 is 8 ([SiMo １０ O ３６ ] ８－ [SiW １０ O ３６ ] ８－ ) and if X is B and M is Mo or W, then c12 is 9 ([BMo １０ O ３６ ] ９－ [BW １０ O ３６ ] ９－ ) and if X is Ge and M is Mo or W, then c12 is 8 ([GeMo １０ O ３６ ] ８－ [GeW １０ O ３６ ] ８－ Furthermore, in general formula (II-3), for example, when X is P and M is Mo or W, c13 is 9 ([PMo ９ O ３４ ] ９－ [PW 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 if X is S and M is Mo or W, then c13 is 8 ([SMo ９ O ３４ ] ８－ [SW ９ O ３４ ] ８－) and if X is Ge and M is Mo or W, then c13 is 10 ([GeMo ９ O ３４ ] １０－ [GeW ９ O ３４ ] １０－ )

[0098] The above-mentioned deficient Keggin-type heteropoly acid anion is preferably an isomer structure of the α-form, β-form, or γ-form. The isomer structure of the 1-deficient Keggin-type heteropoly acid anion represented by general formula (II-1) is [α-PW １１ O ３９ ] ７－ [β-PW １１ O ３９ ] ７－ [γ-PW １１ O ３９ ] ７－ [α-PMo １１ O ３９ ] ７－ [β-PMo １１ O ３９ ] ７－ [γ-PW １１ O ３９ ] ７－ [α-SiW] １１ O ３９ ] ８－ [β-SiW] １１ O ３９ ] ８－ [γ-SiW １１ O ３９ ] ８－ [α-SiMo １１ O ３９ ] ８－ [β-SiMo １１ O ３９ ] ８－ [γ-SiW １１ O ３９ ] ８－ Preferably, [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 more preferable is the isomer structure of the two-deficient Keggin-type heteropoly acid anion represented by the general formula (II-2), which is [α-PW １０ O ３６ ] ７－ [β-PW １０ O ３６ ] ７－ [γ-PW １０ O ３６ ] ７－ [α-PMo １０ O ３６ ] ７－ [β-PMo １０ O ３６ ] ７－ [γ-PW １０ O ３６ ] ７－ [α-SiW] １０ O ３６ ] ８－ [β-SiW] １０ O ３６ ] ８－ [γ-SiW １０ O ３６ ] ８－ [α-SiMo １０ O ３６ ] ８－ [β-SiMo １０ O ３６ ] ８－ [γ-SiW １０ O ３６ ] ８－ Preferably, [γ-PW １０ O ３６ ] ７－ [γ-PMo １０ O ３６ ] ７－ [γ-SiW １０ O ３６ ] ８－ [γ-SiMo １０ O ３６ ] ８－ This is more preferable. Furthermore, the isomer structure of the 3-deficient Keggin-type heteropoly acid anion represented by general formula (II-3) is [α-PW ９ O ３４ ] ９－ [β-PW ９ O ３４ ] ９－ [γ-PW９ 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 ９ O ３４ ] １０－ [β-SiMo ９ O ３４ ] １０－ [γ-SiW ９ O ３４ ] １０－ It is preferable.

[0099] <Deficient Dawson-type heteropoly acid anions> Examples of the above-mentioned deficient Dawson-type heteropoly acid anions include the 1-deficient Dawson-type heteropoly acid anion represented by the following general formula (III-1), the 2-deficient Dawson-type heteropoly acid anion represented by the following general formula (III-2), and the 3-deficient Dawson-type heteropoly acid 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) (In the formula, X represents a heteroatom of P, Si, B, S, or Ge; M represents a polyatom of Mo, W, V, Nb, or Ta; c21- to c23- represent the negative charge number, and c21- to c23 are natural numbers.)

[0100] In general formulas (III-1) to (III-3), the values ​​of c21 to c23 change depending on the types of X and M. For example, in 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, then c21 is 8([S ２ W １７ O ６１ ] ８－ ) And in general formula (III-2), when X is Ge and M is Mo, c22 is 12([Ge ２ Mo １６ O ５８ ] １２－ Furthermore, in 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－ )

[0101] The above-mentioned deficient Dawson-type heteropoly acid anion is preferably an isomer structure of the α-form, β-form, or γ-form. The isomer structure of the deficient Dawson-type heteropoly acid anion represented by general formulas (III-1) to (III-3) is [α-P ２ W １７ O ６１ ] １０－ [α-P ２ W １５ O ５６ ] １２－ [α-S ２ W １７ O ６１ ] ８－ These can be suitably used.

[0102] [1-1-2. Modification of Defect Sites] The modification of the defective site in the heteropoly acid anion having a defective site according to this embodiment is performed by reacting the terminal oxygen atom at the defective site of the heteropoly acid anion with a P, Si, Ge, or Sn compound having one or more organic groups and two or more leaving groups to modify the defective site. Through the above reaction, the terminal oxygen atom at the defective site of the heteropoly acid anion is bonded to a group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded, via part or all of the heteroatom, thereby modifying the defective site.

[0103] <Bonding format and notation of the defective site> In the heteropoly acid anion modified with a defective site according to this embodiment, the terminal oxygen atom of the defective site of the heteropoly acid anion having a defective site is modified by a group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded.

[0104] The bonding configuration between the terminal oxygen atom of the vacant site of the heteropoly acid anion and the group having a heteroatom P, Si, Ge, or Sn to which one or more organic groups are bonded is not particularly limited and can be represented, for example, by the following general formulas (IV-1) to (IV-5). [In formulas (IV-1) to (IV-5), X' represents Si or Ge; X'' represents a heteroatom of Si, Ge, or Sn; R １Ａ１ ~R １Ｅ１ Each of these may independently have substituents. １－１８ Represents a hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, and the above R １Ａ１ ~R １Ｅ１ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and the above R １Ａ１~R １Ｅ１ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups with protecting groups, or (t) polar groups with acid-dissociable groups; * indicates the bond site with the terminal oxygen atom of the deficiency site of the heteropoly acid anion.

[0105] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-1) are bonded may be represented as shown 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, X, M, X', R １Ａ１ and R １Ａ２ (This is the same as above.) Also, R １Ａ１ and R １Ａ２ If they are the same, then R １Ａ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ａ X') ２ O] ｃ－ (V-1')

[0106] A heteropoly acid anion modified with a defect site represented by the general formula (V-1) or (V-1') is not particularly limited, and for example, a heteropoly acid anion having a defect site and (R １Ａ ) X'Y ３ (Y represents a leaving group, for example, a halogen atom, a hydroxyl group, an alkoxy group (C) １－４It is preferably an alkoxy group, C １－２ It is more preferable that it be an alkoxy group, (C) alkylcarbonyloxy group １－４ Preferably, it is an alkylcarbonyloxy group.), hydrocarbyl sulfonyloxy group (C １－６ Alkyl or C ７－１０ It is preferable that it be an aralkylsulfonyloxy group. Examples include a methanesulfonyloxy group and a p-toluenesulfonyloxy group. It can be obtained by reacting it with ().

[0107] Similarly, in this specification, for the convenience of use, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-2) are bonded may be expressed as shown 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, X, M, X', R １Ｂ１ , R １Ｂ２ , R １Ｂ３ and R １Ｂ４ (This is the same as above.) Also, R １Ｂ１ R １Ｂ２ and R １Ｂ３ R １Ｂ４ If they are the same, they can be expressed as shown in the following general formula (V-2'). [X ｗ M ｘ O ｙ (R １Ｂ１ R １Ｂ２ X') ２ ] ｃ－ (V-2')

[0108] A heteropoly acid anion modified with a defect site represented by the general formula (V-2) or (V-2') is not particularly limited, and for example, a heteropoly acid anion having a defect site and (R １Ｂ１ ) (Caution １Ｂ２ ) X'Y ２It can be obtained by reacting it with (Y represents a leaving group as described above).

[0109] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having a heteroatom Si or Ge to which one or more organic groups represented by general formula (IV-3) are bonded may be represented as shown in the following general formula (V-3). [X ｗ M ｘ O ｙ (R １Ｃ１ X'O) (R １Ｃ２ X'O) (R １Ｃ３ X'O) (R １Ｃ４ X'O) ｃ－ (V-3) (In the formula, w, x, y, and c are all natural numbers, and X, M, X', R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ (This is the same as above.) Also, R １Ｃ１ , R １Ｃ２ , R １Ｃ３ and R １Ｃ４ If they are the same, then R １Ｃ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ｃ X'O) ４ ] ｃ－ (V-3')

[0110] The heteropoly acid anions modified by the deletion site represented by the general formula (V-3) or (V-3') are not particularly limited, and for example, two-deleted Keggin-type or Dawson-type heteropoly acid anions and R １Ｃ X'Y ３ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0111] In this specification, for convenience, heteropoly acid anions in which the deficiency site of the heteropoly acid anion is modified by a group having a heteroatom P to which one or more organic groups represented by general formula (IV-4) are bonded may be represented as shown in the following general formula (V-4). [X ｗ M ｘ Oｙ (R １Ｄ１ P = O) (R １Ｄ２ P = O) ｃ－ (V-4) (In the formula, w, x, y, and c are all natural numbers, and X, M, R １Ｄ１ and R １Ｄ２ (This is the same as above.) Also, R １Ｄ１ and R １Ｄ２ If they are the same, then R １Ｄ It can be expressed as follows: [X ｗ M ｘ O ｙ (R １Ｄ P = O) ２ )] ｃ－ (V-4')

[0112] A heteropoly acid anion modified with a defect site represented by the general formula (V-4) or (V-4') is not particularly limited, and for example, a heteropoly acid anion having a defect site and R １Ｄ P(=O)Y ２ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0113] In this specification, for convenience, heteropoly acid anions in which the vacant site of the heteropoly acid anion is modified by a group having one or more organic groups represented by general formula (IV-5) bonded to a heteroatom Si, Ge, or Sn may be represented as shown 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 same applies as above.) Also, the above (V-5) may be expressed as the general formula (V-5') below in some cases. Note that R １Ｅ is R １Ｅ１ The same definition is used. [X ｗ M ｘ O ｙ (R １Ｅ X'')] ｃ－ (V-5')

[0114] A heteropoly acid anion modified with a defect site represented by the general formula (V-5) or (V-5') is not particularly limited, and for example, a heteropoly acid anion having a defect site and R １Ｅ X''Y ３ It can be obtained by reacting it with (Y represents a leaving group as described above).

[0115] Among heteropoly acid anions modified with the defect sites represented by the general formulas (V-1) to (V-5) and (V-1') to (V-5'), heteropoly acid anions modified with the defect sites represented by the following general formulas (VI-1) to (VI-12) are particularly preferred from the viewpoint of being relatively stable and allowing for controllable 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 R １Ｂ２ 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) (wherein 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 of these may independently have substituents. １－１８ Represents a hydrocarbyl group, a 3-18 membered non-aromatic heterocyclic group, or a 5-18 membered aromatic heterocyclic group, and the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and the above R １Ａ ~R １ＥThe hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups with protecting groups, or (t) polar groups with acid-dissociable groups; c31, c32, and c33 are natural numbers.

[0116] In heteropolyacid anions with modified defect sites, the four terminal oxygen atoms of the defect site are modified. Therefore, the value of c31 is usually c11-4 (where c11 represents the absolute value of the number of negative charges in a one-defective Keggin-type heteropolyacid anion represented by general formula (II-1)), the value of c32 is c12-4 (where c12 represents the absolute value of the number of negative charges in a two-defective Keggin-type heteropolyacid anion represented by general formula (II-2)), and the value of c33 is c21-4 (where c21 represents the absolute value of the number of negative charges in a one-defective Dawson-type heteropolyacid anion represented by general formula (III-1)). On the other hand, for example, if the organic group contains an amino group which is protonated to form an ammonium cation, or if the organic group contains a carboxyl group which is formed to form a carboxyl anion, the values ​​of c31 to c33 will differ from the above values.

[0117] <Organic group> The above R １Ａ , R １Ｂ１ and R １Ｂ２ , R １Ｃ , R １Ｄ , and also, R １Ｅ The organic group represented by is not particularly limited, and any known and commonly used one can be used. １Ａ ~R １Ｅ As an example of an organic group represented by R, １Ａ ~R １Ｅ However, C may have substituents. １－１８represents a hydrocarbyl group, a 3- to 18-member non-aromatic heterocyclic group, or a 5- to 18-member aromatic heterocyclic group; the above R １Ａ to R １Ｅ Any divalent carbon atom at an arbitrary position except for the terminals of may be replaced by -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); the hydrogen atoms contained in the above R １Ａ to R １Ｅ are preferably replaced by (a) a halogen atom, (b) a haloalkyl group, (c) a hydroxy group, (d) a thiol group, (e) a nitro group, (f) a cyano group, (g) a carboxy group, (h) an amino group, (i) a sulfo group, (j) a vinyl group, (k) an allyl group, (l) a (meth)acryloyl group, (m) a (meth)acryloyloxy group, (n) a (meth)acrylamide group, (o) a styryl group, (p) an epoxy group, (q) a glycidyl group, (r) an amide group, (s) a hydroxy group or carboxy group having a protecting group, or (t) a polar group having an acid dissociable group, and is a C １－１８ hydrocarbyl group which may have a substituent; any divalent carbon atom at an arbitrary position except for the terminals of the above R １Ａ to R １Ｅ may be replaced by -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); the above R １Ａ to R １ＥThe hydrogen atoms contained in C may more preferably be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group, and C may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in are more preferably replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group.

[0118] Also, the above R １Ａ ~R １ＥFrom the viewpoint of providing a functional building block in which the physical properties such as solubility in developing solutions differ between the exposed and unexposed portions of the active light, the organic group represented is preferably an organic group having one or more polar groups having acid-dissociable groups. The number of polar groups having acid-dissociable groups included in the above organic group is not particularly limited, but for example, it is preferably 1 to 6, more preferably 1 to 5, and even more preferably 1 to 4.

[0119] <<An organic group having one or more polar groups with acid-dissociable groups>> The above R １Ａ ~R １Ｅ From the viewpoint of changing the solubility in the developing solution by the action of an acid, etc., it is preferable that the organic group represented by the above contains one or more polar groups having an acid-dissociable group.

[0120] R is an organic group having one or more of the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, R １Ａ ~R １Ｅ However, C may have substituents. １－１８ It is a hydrocarbyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R１Ｅ Preferably, at least one hydrogen atom of the C is replaced by a polar group having a (t) acid-dissociable group, and the C may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R １Ｅ It is more preferable that at least one hydrogen atom of the C is replaced by a polar group having an acid-dissociable group, and the C may have substituents. １－１８ Alkyl alkyl group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １ＥIt is even more preferable that at least one hydrogen atom is replaced by a polar group having a (t) acid-dissociable group.

[0121] The above R １Ａ ~R １Ｅ It is characterized by containing one or more polar groups having acid-dissociable groups, for example, polar groups such as hydroxyl groups, carboxyl groups, amino groups, or sulfo groups having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R containing one or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0122] [* indicates a bond between a heteroatom P, Si, Ge, or Sn to an organic group containing one or more acid-dissociable polar groups.]

[0123] Furthermore, the organic group having one or more polar groups having acid-dissociable groups according to another embodiment is not particularly limited, and examples include the organic group represented by general formula (VII-1).

[0124] [In general formula (VII-1), L ２Ａ１ C may have substituents. １－１２ In a hydrocarbyl group, one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are R ２Ａ１ Represents a group substituted with the L ２Ａ１ The terminal and R ２Ａ１ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ１each independently represents a polar group having an acid dissociable group; x represents an integer of 1 to 6; * represents a bonding portion between the organic group and a hetero atom P, Si, Ge or Sn.

[0125] In the organic group represented by the general formula (VII-1), L ２Ａ１ is, for L ２Ａ１ a C ２－１０ hydrocarbyl group which may have a substituent, and one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are replaced by R ２Ａ１ : for the above L ２Ａ１ except for the terminal of and the carbon atom to which R ２Ａ１ is bonded, the divalent carbon atoms at any position may be replaced by -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), preferably, L ２Ａ１ is, for a C ２－１０ alkyl group, C ３－１０ alicyclic group, C ６－１０ aryl group, or C ６－１０ aralkyl group which may have a substituent, and one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are replaced by R ２Ａ１ : for the above L ２Ａ１ except for the terminal of and the carbon atom to which R ２Ａ１ is bonded, the divalent carbon atoms at any position may be replaced by -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), more preferably, L ２Ａ１ is, for a C ２－８ alkyl group, C ３－８ alicyclic group, C ６－８ aryl group, or C ６－８ aralkyl group which may have a substituent, and one or more hydrogen atoms in total on the same or different carbon atoms at any position including the terminal are each replaced by R２Ａ１ The group substituted for: the above L ２Ａ１ The terminal and R ２Ａ１ It is even more preferable that any divalent carbon atoms at any position other than the carbon atom to which the compound is bonded may be replaced with -O- or -S- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0126] R in an organic group represented by general formula (VII-1) ２Ａ１ For example, R ２Ａ１ However, each is preferably independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group, R ２Ａ１ However, each is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ Allyl or benzyl acid-dissociating group G Ｂ , or acetal-type acid-dissociating group G Ｃ It is more preferable that R ２Ａ１ However, each is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ It is even more preferable that this be the case.

[0127] The x represented by the general formula (VII-1) is preferably an integer from 1 to 6, and may also be an integer from 2 to 4. The organic group represented by the general formula (VII-1) is R ２Ａ１ It contains one or more of the following: R ２Ａ１ When two or more are included, the R ２Ａ１ These may all be polar groups having the same acid-dissociating group, or they may each be polar groups having different acid-dissociating groups.

[0128] <<An organic group having two or more polar groups with acid-dissociable groups>> The above R １Ａ ~R １Ｅ From the viewpoint of drastically changing the solubility in the developing solution through the action of an acid, etc., it is preferable that the organic group represented by the above contains two or more polar groups having acid-dissociable groups.

[0129] R is an organic group containing two or more polar groups having the above-mentioned acid-dissociable group. １Ａ ~R １Ｅ For example, R １Ａ ~R １Ｅ However, C may have substituents. １－１８ It is a hydrocarbyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ The hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R １Ｅ Preferably, at least two hydrogen atoms of the C are replaced by polar groups having (t) acid-dissociable groups, and the C may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １ＥThe hydrogen atoms contained in may be replaced by (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, or (t) polar groups having an acid-dissociable group; the above R １Ａ ~R １Ｅ It is more preferable that at least two hydrogen atoms of the C are replaced by polar groups having (t) acid-dissociable groups, and the C may have substituents. １－１８ Alkyl alkyl group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １Ａ ~R １Ｅ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １Ａ ~R １Ｅ It is even more preferable that at least two hydrogen atoms are replaced by polar groups having (t) acid-dissociable groups.

[0130] The above R １Ａ ~R １Ｅ It is characterized by containing two or more polar groups having acid-dissociable groups, for example, polar groups such as a hydroxyl group, carboxyl group, amino group, or sulfo group having acid-dissociable groups are introduced. Examples of the above acid-dissociable groups include a tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include R containing two or more polar groups having the above-mentioned acid-dissociable groups. １Ａ ~R １Ｅ For example, the following can be cited:

[0131] [G represents an acid-dissociable group G, and * indicates the bond between the organic group and the heteroatom P, Si, Ge, or Sn.]

[0132] [* indicates organic group R] １Ａ ~R １Ｅ This refers to the bond with the heteroatom P, Si, Ge, or Sn to which it is bonded.

[0133] The organic group containing two or more polar groups having acid-dissociable groups according to another embodiment is not particularly limited, and examples include the organic group represented by general formula (VII-2). [In formula (VII-2), L ２Ａ２ C may have substituents. １－１２ In the hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R ２Ａ２ and R ２Ｂ２ Represents a group substituted with the L ２Ａ２ A divalent carbon atom at any position other than the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ２Ａ２ and R ２Ｂ２ Each of these independently represents a polar group having an acid-dissociable group, and * represents the bond between the organic group and the heteroatom P, Si, Ge, or Sn.

[0134] L in an organic group represented by general formula (VII-2) ２Ａ２ L ２Ａ２ However, C may have substituents. ２－１０ In the hydrocarbyl group, hydrogen atoms on carbon atoms at any position including the terminals are each R ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ２ The terminal and R ２Ａ２ or R ２Ｂ２A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), L ２Ａ２ However, C may have substituents. ２－１０ Alkyl alkyl group, C ３－１０ Alicyclic group, C ６－１０ Aryl group, or C ６－１０ In an aralkyl group, hydrogen atoms on carbon atoms at any position, including terminals, are each R ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ２ The terminal and R ２Ａ２ or R ２Ｂ２ A divalent carbon atom at any position other than the carbon atom to which it is bonded is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), L ２Ａ２ However, C may have substituents. ２－８ Alkyl alkyl group, C ３－８ Alicyclic group, C ６－８ Aryl group, or C ６－８ In an aralkyl group, hydrogen atoms on carbon atoms at any position, including terminals, are each R ２Ａ２ and R ２Ｂ２ The group substituted for: the above L ２Ａ２ The terminal and R ２Ａ２ or R ２Ｂ２ It is even more preferable that any divalent carbon atoms at any position other than the carbon atom to which the compound is bonded may be replaced with -O- or -S- (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0135] R in an organic group represented by general formula (VII-2) ２Ａ２ and R ２Ｂ２ For example, R ２Ａ２ and R２Ｂ２ Each of these is preferably an acid-dissociable hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group, R ２Ａ２ and R ２Ｂ２ Each of these is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; and the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ Allyl or benzyl acid-dissociating group G Ｂ , or acetal-type acid-dissociating group G Ｃ It is more preferable that R ２Ａ２ and R ２Ｂ２ Each of these is independently a hydroxyl group (including a phenolic hydroxyl group) or a carboxyl group having an acid-dissociable group; the above acid-dissociable group is a tertiary carbon type acid-dissociable group G Ａ It is even more preferable that this be the case.

[0136] [1-2. Cationic portion of heteropoly salt or mixture thereof modified with a defect site] The cationic portion of heteropoly salt or mixture thereof modified with a defect site according to this embodiment is characterized by containing an organic sulfonium cation into which one or more acid-dissociable polar groups and one or more iodine atoms are introduced.

[0137] Examples of polar groups having the above-mentioned acid-dissociable group include hydroxyl groups, carboxyl groups, amino groups, or sulfo groups having the acid-dissociable group. Furthermore, an example of the above-mentioned acid-dissociable group is the tertiary carbon type acid-dissociable group G described above. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ Examples include the tertiary carbon type acid-dissociating group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G ＣPreferably, it is a tertiary carbon-type acid-dissociable group G such as t-butyl group, t-amyl group, 1,1-dimethylpropyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-(1-methoxy-2-methylpropan-2-yl)cyclopentyl group, 1-(1-ethoxy-2-methylpropan-2-yl)cyclopentyl group. Ａ Allyl or benzyl acid-dissociable groups G such as 1-methyl-2-propenyl group, 1-cyclohexyl-2-propenyl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-methyl-2-cyclohexen-1-yl group, and 1-indanyl group. Ｂ Acetal-type acid-dissociable groups G such as methoxymethoxy group, ethoxymethoxy group, n-propoxymethoxy group, n-butoxymethoxy group, 2,2-dimethylpropoxymethoxy group, 2,2-dimethylbutoxymethoxy group, cyclohexyloxymethoxy group, 1-ethoxyethoxy group, 1-n-butoxyethoxy group, and 1-cyclohexyloxyethoxy group. Ｃ It is preferable that it be so.

[0138] The above-mentioned organic sulfonium cation contains one or more polar groups having acid-dissociable groups, and in some cases, it may contain two or three polar groups having acid-dissociable groups.

[0139] The above-mentioned organic sulfonium cation contains one or more iodine atoms. From the viewpoint of increasing the absorption coefficient of the organic sulfonium cation to active light and improving its sensitivity, it is preferable that it contains two or more iodine atoms.

[0140] Furthermore, the organic sulfonium cation in this embodiment may have a hydroxyl group, a thiol group, an amino group, or a substituent, from the viewpoint of improving sensitivity to active light and the like. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbylamino group, diC １－１８Hydrocarbylamino group, or C １－１８ Electron-donating groups such as hydrocarbylthio groups; fluorine atom, chlorine atom, bromine atom, C １－５ C may have a haloalkyl group, a nitro group, a sulfo group, or a substituent. １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbyl sulfinyl group, or C １－１８ The group may contain electron-withdrawing groups such as hydrocarbyl sulfonyl groups.

[0141] [1-2-1. Triarylsulfonium Cation] Examples of the organic sulfonium cation according to this embodiment include the triarylsulfonium cation represented by the following general formula (VIII).

[0142] In general formula (VIII), Ar ３Ａ ~Ar ３Ｃ Each of these may independently have substituents. ６－１８ Represents an aryl group, as shown above Ar ３Ａ ~Ar ３Ｃ Any two of these are directly linked by a single bond, or are divalent linking groups C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ - may be connected via and form a ring with the sulfur atom in formula (VIII), and the Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ At least one of the hydrogen atoms above is substituted with a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, and the above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ At least one of the hydrogen atoms above is substituted with an iodine atom.

[0143] In the triarylsulfonium cation represented by general formula (VIII), the above Ar ３Ａ ~Ar ３Ｃ This is not particularly limited, and may include, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenantrenyl group, an anthracenyl group, etc., which may have substituents. ６－１８ It is preferably an aryl group, and more preferably a phenyl group, 1-naphthyl group, or 2-naphthyl group, which may have substituents.

[0144] Furthermore, in the triarylsulfonium cation represented by general formula (VII), the above Ar ３Ａ ~Ar ３Ｃ Any two of these are directly linked by a single bond, or are divalent linking groups C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ Examples of structures where the atoms are linked via a - and form a ring with the sulfur atom in formula (VIII) include those having a 9-thia-9H-fluorene-9-ium skeleton, a 9-thia-9,10-dihydroanthracene-9-ium skeleton, a 10H-phenoxatiyne-10-ium skeleton, a 5H-thianthrene-5-ium skeleton, a 9-thia-9,10-dihydroanthracene-9-ium-10-one skeleton, and a 5,10-dihydrothianthrene-5-ium-10,10-dione skeleton. More specifically, examples include those having the following skeletons. Note that in the following chemical structural formulas, * indicates Ar that is not involved in ring formation. ３Ａ Ar ３Ｂ This represents the bond with the sulfur atom in general formula (VII).

[0145]

[0146] <Polar group having an acid-dissociable group or organic group containing a polar group having an acid-dissociable group> In the triarylsulfonium cation represented by general formula (VIII), the above Ar ３Ａ Ar ３Ｂ or Ar ３ＣAt least one of the hydrogen atoms above is substituted with a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group.

[0147] The above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ An example of a case where at least one of the above hydrogen atoms is substituted with a polar group having an acid-dissociable group is the above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ Examples include cases where the hydrogen atoms on the aryl group above are substituted with hydroxyl or carboxyl groups, and further, the hydrogen atoms of the hydroxyl and carboxyl groups are substituted with acid-dissociable groups. In the above case, an example of an acid-dissociable group is a tertiary carbon type acid-dissociable group G. Ａ Allyl or benzyl acid-dissociating group G Ｂ Acetal-type acid-dissociating group G Ｃ The following can be used.

[0148] Also, the above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ At least one of the hydrogen atoms above is an organic group "R" which contains a polar group having an acid-dissociable group. ３ In cases where it is substituted with the above organic group R, ３ However, C may have substituents. １－１８ A hydrocarbyl group, R ３ A divalent carbon atom at any position other than the terminals outside the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time), R ３ One example is when at least one hydrogen atom is replaced by a polar group having an acid-dissociable group.

[0149] Organic group R containing the polar group having the above-mentioned acid-dissociating group ３ For example, C which may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８Aryl group, or C ７－１８ It is an aralkyl group; the above R ３ A divalent carbon atom at any position other than the terminals outside the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３ It is more preferable that at least one hydrogen atom of the C is replaced by a polar group having an acid-dissociable group, and the C may have substituents. １－１８ Alkyl alkyl group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R ３ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ３ It is even more preferable that at least one hydrogen atom is replaced by a polar group having an acid-dissociable group.

[0150] The triarylsulfonium cation represented by general formula (VIII) contains one or more polar groups having acid-dissociable groups, and may contain two or three polar groups having acid-dissociable groups.

[0151] <Iodine atom> In the triarylsulfonium cation represented by general formula (VIII), the above Ar ３Ａ Ar ３Ｂ or Ar ３Ｃ At least one of the hydrogen atoms above is substituted with an iodine atom. From the viewpoint of increasing the absorption coefficient of the triarylsulfonium cation to active light and improving its sensitivity, it is preferable that the triarylsulfonium cation contains two or more iodine atoms.

[0152] <Examples of Triarylsulfonium Cations> Examples of triarylsulfonium cations represented by the above general formula (VIII) include (4-iodophenyl)(phenyl)(4-(1-i-propylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, (4-(t-butyloxycarbonylmethyloxy)phenyl)(3-iodophenyl)(phenyl)sulfonium cation, diphenyl(2-iodo-4-(1-i-propylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(3,4-Diiodophenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, (3-t-butyloxycarbonyl-4-methoxyphenyl)(4-iodophenyl)(phenyl)sulfonium cation, bis(4-iodophenyl)(3-(1-ethylcyclopentyloxycarbonyl)-4-methoxyphenyl)sulfonium cation, bis(4-iodophenyl)(3-(t-butyloxycarbonyl)-5-iodo-4-methoxyphenyl)sulfonium cation Honium cation, bis(4-iodophenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-methylphenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-t-butylphenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, (4-(1-ethylcyclopentyloxy Bis(2-naphthyl)sulfonium cation, bis(4-methoxyphenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-3-iodophenyl)sulfonium cation, bis(4-acetylphenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-(methyloxycarbonyl)phenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-3-iodophenyl)sulfonium cation, bis(4-fluorophenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-3-iodophenyl)sulfonium cation, bis(4-fluorophenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-bromophenyl)(4-(t-butyloxycarbonylmethyloxy)-3-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl) sulfonium cation, bis(3-(trifluoromethyl)phenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl) sulfonium cation, bis(3-fluoro-5-(trifluoromethyl)phenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl) sulfonium cation, bis(3,4-bis(trifluoromethyl)phenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-3-iodophenyl) sulfonium cation, bis(3,4-bis(trifluoromethyl)phenyl)(3-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl) sulfonium cation, bis(3,5-difluorophenyl)(4-(1-ethenylcyclopentyloxycarbonylmethyloxy)-2-iodophenyl) sulfonium Sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(1-(1-methylethenyl)cyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(1-ethynylcyclopentyloxycarbonylmethyloxy)-3-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(1-(1-propynyl)cyclopentyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(1-ethylcyclohexyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium cation, bis(4-fluorophenyl)(3-iodo-4-(1-phenylcyclohexyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(2-cyclopentene-1-yloxycarbonylmethyloxy)-2-iodophenyl)sulfonium cation, bis(4-(trifluoromethyl)phenyl)(4-(1-indanyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(1-methyl-1-indanyloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(4-fluorophenyl)(3-iodo-4-(1-methyl-2- Cyclopenten-1-yloxycarbonylmethyloxy)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(2-cyclohexene-1-yloxycarbonylmethyloxy)-2-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(3-methyl-2-cyclohexene-1-yloxycarbonylmethyloxy)phenyl)sulfonium cation, (2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)(4- Trophenyl)(phenyl)sulfonium cation, bis(4-iodophenyl)(4-(t-butyloxycarbonyl)phenyl)sulfonium cation, bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium cation, (4-(1-ethylcyclopentyloxycarbonyl)phenyl)bis(3-iodophenyl)sulfonium cation, bis(4-iodophenyl)(4-(1-i-propylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis( 4-iodophenyl)(4-(1-t-butylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(4-(trifluoromethyl)phenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(3,5-diiodophenyl)(4-(1-ethylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(3-iodophenyl)(4-(1-i-propylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(1-ethenylcyclopentyloxycarbonyl)-2-iodophenyl)sulfonium cation, bis(4-fluorophenyl)(2-iodo-4-(1-(1-methylethenyl)cyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(3-(trifluoromethyl)phenyl)(4-(1-ethynylcyclopentyloxycarbonyl)-2-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(1-(1-P Ropinyl)cyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(4-fluorophenyl)(2-iodo-4-(1-phenylcyclopentyloxycarbonyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(1-ethylcyclohexyloxycarbonyl)-2-iodophenyl)sulfonium cation, bis(4-(trifluoromethyl)phenyl)(2-iodo-4-(1-phenylcyclohexyloxycarbonyl)phenyl)sulfonium cation , bis(3,5-difluorophenyl)(4-(2-cyclopentene-1-yloxycarbonyl)-3-iodophenyl) sulfonium cation, bis(3,5-difluorophenyl)(4-(1-indanyloxycarbonyl)-3-iodophenyl) sulfonium cation, bis(3-fluorophenyl)(3-iodo-4-(1-methyl-1-indanyloxycarbonyl)phenyl) sulfonium cation, bis(3,5-difluorophenyl)(3-iodo-4-(1-methyl-2-cyclopentene- Examples include 1-yloxycarbonyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(4-(2-cyclohexene-1-yloxycarbonyl)-3-iodophenyl)sulfonium cation, bis(3,5-difluorophenyl)(2-iodo-4-(3-methyl-2-cyclohexene-1-yloxycarbonyl)phenyl)sulfonium cation, and (4-(t-butyloxycarbonyl)-2-iodophenyl)(3-nitrophenyl)(phenyl)sulfonium cation.

[0153] The following are specific examples of the above-mentioned triarylsulfonium cations.

[0154]

[0155]

[0156]

[0157] [1-2-2. Triphenylsulfonium Cation] An example of an organic sulfonium cation according to another embodiment is an organic sulfonium cation represented by the following general formula (IX-1) or (IX-2).

[0158] <Organosulfonium cation represented by general formula (IX-1)> An organosulfonium cation represented by general formula (IX-1) comprises a polar group having one or more acid-dissociable groups or an organic group containing a polar group having an acid-dissociable group, and one or more iodine atoms. In the general formula (IX-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom, o1, p1, and q1 each represent integers from 0 to 3, r1, s1, and t1 each represent integers from 0 to 5, u1, v1, and w1 each represent integers from 0 to 5, o1 + p1 + q1 is an integer of 1 or more, r1 + s1 + t1 is an integer of 1 or more, and o1 + r1 + u1, p1 + s1 + v1, and q1 + t1 + w1 are integers from 0 to 5.

[0159] Examples of polar groups having acid-dissociable groups or organic groups containing polar groups having acid-dissociable groups are similar to those exemplified in the section on "triarylsulfonium cations." The number of polar groups having acid-dissociable groups or organic groups containing polar groups having acid-dissociable groups contained in the organic sulfonium cation represented by general formula (IX-1) is at least one, and may include two or three in some cases.

[0160] The number of iodine atoms contained in the organic sulfonium cation represented by the general formula (IX-1) is at least one, and preferably two or more.

[0161] Also, the above R ４Ａ , R ４Ｂ and R ４Ｃ Other substituents besides the iodine atom represented by include, for example, a hydroxyl group, a thiol group, an amino group, or a C atom which may have substituents. １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, or C １－１８ Electron-donating groups such as hydrocarbylthio groups; fluorine atom, chlorine atom, bromine atom, C １－５ C may have a haloalkyl group, a nitro group, a sulfo group, or a substituent. １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbyl sulfinyl group, or C １－１８ Examples include electron-withdrawing groups such as hydrocarbyl sulfonyl groups.

[0162] <<Organosulfonium cation represented by general formula (IX-1-1)>> The above organosulfonium cation represented by general formula (IX-1) may also be an organosulfonium cation represented by the following general formula (IX-1-1). In the general formula (IX-1-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４ＣEach of these independently represents a substituent other than the iodine atom, o11 represents an integer from 1 to 3, p11 and s11 each represent an integer from 0 to 4, q11, r11, t11 and u11 each represent an integer from 0 to 5, p11 + q11 + r11 is an integer of 1 or more, o1 + p11 + s11 is an integer from 1 to 5, and q11 + t11 and r11 + u11 each represent an integer from 0 to 5.

[0163] Examples of polar groups having the above-mentioned acid-dissociable group or organic groups containing a polar group having the above-mentioned acid-dissociable group and their number, iodine atoms and their number, and substituents other than iodine atoms include those similar to those exemplified in the section on "Organosulfonium cations represented by general formula (IX-1)".

[0164] <<Organosulfonium cation represented by general formula (IX-1-2) or (IX-1-3)>> Furthermore, the organosulfonium cation represented by the above general formula (IX-1-1) may also be an organosulfonium cation represented by the following general formula (IX-1-2) or (IX-1-3). In the general formula (IX-1-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom, o12 represents an integer of 1 or 2, p12 represents an integer from 1 to 4, q12 represents an integer from 0 to 3, r12 and s12 each represent integers from 0 to 5, and o12 + p12 + q12 is an integer from 2 to 5. In the general formula (IX-1-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ represents a substituent other than the iodine atom, o13 represents an integer of 1 or 2, p13 and q13 each represent an integer from 0 to 5, r13 represents an integer from 0 to 4, p13 + q13 is an integer of 1 or more, and o13 + r13 is an integer from 1 to 5.

[0165] Examples of substituents other than iodine atoms in the organic sulfonium cations represented by general formulas (IX-1-2) and (IX-1-3) include the polar group having the above-mentioned acid-dissociable group or the organic group containing the polar group having the acid-dissociable group and its number, the iodine atom and its number, and the substituents other than iodine atoms, similar to those exemplified in the section on "Organosulfonium cations represented by general formula (IX-1)".

[0166] <Organosulfonium cation represented by general formula (IX-2)> An organosulfonium cation represented by general formula (IX-2) comprises a polar group having one or more acid-dissociable groups or an organic group containing a polar group having an acid-dissociable group, and one or more iodine atoms. In the general formula (IX-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ The expression represents -, o2, p2, and q2 each represent integers from 0 to 3, r2 and u2 each represent integers from 0 to 5, s2, t2, v2, and w2 each represent integers from 0 to 4, o2 + p2 + q2 is an integer greater than or equal to 1, r2 + s2 + t2 is an integer greater than or equal to 1, o2 + r2 + u2 is an integer from 0 to 5, and p2 + s2 + v2 and q2 + t2 + w2 are integers from 0 to 4.

[0167] Examples of polar groups having acid-dissociable groups or organic groups containing polar groups having acid-dissociable groups are the same as those exemplified in the section on "triarylsulfonium cations." The number of polar groups having acid-dissociable groups or organic groups containing polar groups having acid-dissociable groups in the organic sulfonium cation represented by general formula (IX-2) is at least one, and may include two or three in some cases. Furthermore, the number of iodine atoms in the organic sulfonium cation represented by general formula (IX-2) is at least one, and preferably two or more.

[0168] Also, the above R ４Ｄ , R ４Ｅ and R ４Ｆ Examples of substituents other than the iodine atom represented by the formula (IX-1) include those similar to those exemplified in the section on "Organosulfonium cations represented by general formula (IX-1)".

[0169] <<Organosulfonium cation represented by general formula (IX-2-1)>> The organosulfonium cation represented by the above general formula (IX-2) may also be an organosulfonium cation represented by the following general formula (IX-2-1). In the general formula (IX-2-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ The expression represents a negative value, o21 represents an integer from 1 to 3, p21, q21, and r21 each represent integers from 0 to 4, s21, t21, and u21 each represent integers from 0 to 4, p21 + q21 + r21 is an integer greater than or equal to 1, o21 + p21 + s21 is an integer from 1 to 5, and q21 + t21 and r21 + u21 each represent integers from 0 to 4.

[0170] Examples of polar groups having the above-mentioned acid-dissociable group or organic groups containing a polar group having the above-mentioned acid-dissociable group and their number, iodine atoms and their number, and substituents other than iodine atoms include those similar to those exemplified in the section on "Organosulfonium cations represented by general formula (IX-2)".

[0171] <<Organosulfonium cation represented by general formula (IX-2-2) or (IX-2-3)>> Furthermore, the organosulfonium cation represented by the above general formula (IX-2-1) may also be an organosulfonium cation represented by the following general formula (IX-2-2) or (IX-2-3). In the general formula (IX-2-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ ∫ represents -, o22 represents an integer of 1 or 2, p22 represents an integer from 1 to 4, q22 represents an integer from 0 to 3, r22 and s22 each represent integers from 0 to 4, and o22 + p22 + q22 is an integer from 2 to 5. In the general formula (IX-2-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ represents substituents other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ The negative sign represents a negative value, o23 represents an integer of 1 or 2, p23, q23, and r23 each represent integers from 0 to 4, p23 + q23 is an integer greater than or equal to 1, and o23 + r23 is an integer from 1 to 5.

[0172] Examples of substituents other than iodine atoms in the organosulfonium cations represented by general formulas (IX-2-2) and (IX-2-3) include the polar group having the above-mentioned acid-dissociable group or the organic group containing the polar group having the acid-dissociable group and its number, the iodine atom and its number, and the substituents other than iodine atoms, similar to those exemplified in the section on "Organosulfonium cations represented by general formula (IX-2-1)".

[0173] [1-3. Heteropolyates or mixtures thereof with modified defect sites] The heteropolyates or mixtures thereof with modified defect sites according to this embodiment are characterized in that the cationic portion contains an organic sulfonium cation, and the organic sulfonium cation has one or more acid-dissociable polar groups and one or more iodine atoms, and the heteropolyates or mixtures thereof with modified defect sites represented by the following general formula (I) may also be used. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [In formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; B ｎ＋ Each independently represents an organic sulfonium cation, the organic sulfonium cation having one or more acid-dissociable polar groups and one or more iodine atoms; C （ａｍ＋ｂｎ）－ [wherein, m is an integer between 1 and 5, n is an integer between 1 and 2, a is a real number, and b is a real number greater than 0.]

[0174] [1-3-1. Metal Ions] In heteropoly salts or mixtures thereof in which the defect site represented by the above general formula (I) is modified, the metal ions that can be used are not particularly limited, for example, Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Be ２＋ Mg２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Al ３＋ Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ Examples include Li ＋ Na ＋ _K ＋ , Rb ＋ , Cs ＋ Mg ２＋ Ca ２＋ , Sr ２＋ Ba ２＋ Al ３＋ Co ３＋ Na is preferred. ＋ _K ＋ , Rb ＋ , Cs ＋ Ca ２＋ Al ３＋ Co ３＋ This is more preferable. These metal ions may be present individually or in combination of two or more.

[0175] [1-3-2. Onium Cation or Onium Dication] The onium cation or onium dication that can be used as the cation portion of a heteropoly salt or mixture thereof modified with the missing site represented by the above general formula (I) is not particularly limited, and known and commonly used ones can be used. Examples of onium cations or onium dications include ammonium cation, ammonium dication, phosphonium cation, phosphonium dication, sulfonium cation, sulfonium dication, iodonium cation, etc. These onium cations or onium dications may be used individually or in combination of two or more types.

[0176] <Ammonium Cation> In heteropoly salts or mixtures thereof in which the missing site represented by the above general formula (I) is modified, the ammonium cation that can be used is not particularly limited, and known and commonly used ones can be used. The above ammonium cation is not particularly limited, for example, primary ammonium cation (NH ３ (R ６Ａ ) ＋ )), secondary ammonium cation (NH ２ (R ６Ａ ) (Caution ６Ｂ )) ＋ ), tertiary ammonium cation (NH(R ６Ａ ) (Caution ６Ｂ ) (Caution ６Ｃ ) ＋ ), quaternary ammonium cation (N(R ６Ａ ) (Caution ６Ｂ ) (Caution ６Ｃ ) (Caution ６Ｄ ) ＋ ) are listed above. ６Ａ ~R ６Ｄ This shall represent something equivalent to what is defined below.

[0177] The ammonium cation is preferably a quaternary ammonium cation, and more preferably an organic quaternary ammonium cation represented by the following general formula (XI-1).

[0178] In general formula (XI-1), R ６Ａ ~R ６Ｄ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ６Ａ ~R ６Ｄ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time), and the above R ６Ａ ~R ６ＤThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R ６Ａ ~R ６ＤAny two of these are linked to each other by a single bond, directly, or by the divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the nitrogen atom in formula (XI-1).

[0179] Specific examples of the above organic quaternary ammonium cations 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-methacroyloxyethylammonium cation, and N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium Examples include ammonium cations, 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, etc.

[0180] <Ammonium Dication> The ammonium dication is not particularly limited, and known and commonly used ones can be used. Examples of ammonium dications include the organic quaternary ammonium dication represented by the following general formula (XI-2).

[0181] In general formula (XI-2), R ７Ａ ~R ７Ｆ Each of these may independently have substituents. １－１８ The above R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ７Ａ ~R ７Ｆ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); L ７ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L ７ The divalent carbon atoms at any position are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ７Ａ ~R ７Ｆ and L ７ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ７Ａ ~R ７Ｆ Any two of these are linked to each other by a single bond, directly, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring with the nitrogen atom in formula (XI-2).

[0182] The organic quaternary ammonium dication represented by the above general formula (XI-2) is not particularly limited, and examples 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)acrylamideethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium.

[0183] <Phosonium Cation> The phosphonium cation is not particularly limited, and known and commonly used cations can be used. Examples of phosphonium cations include the organic quaternary phosphonium cation represented by the following general formula (XI-3).

[0184] In general formula (XI-3), R ８Ａ ~R ８Ｄ Each of these may independently have substituents. １－１８ Represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; the above R ８Ａ ~R ８Ｄ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ８Ａ ~R ８ＤThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R ８Ａ ~R ８ＤAny two of these are linked to each other by a single bond, directly, or by the divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the phosphorus atom in formula (XI-3).

[0185] The organic quaternary phosphonium cation represented by the above general formula (XI-3) is not particularly limited, and includes, for example, 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, and allyltriphenyl Examples include phosphonium cations, cyclopropyltriphenylphosphonium cations, benzyltriphenylphosphonium cations, tetrakis(hydroxymethyl)phosphonium cations, 2-carboxyethyltriphenylphosphonium cations, methoxycarbonylmethyltriphenylphosphonium cations, t-butoxycarbonylmethyltriphenylphosphonium cations, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cations, (4-(methacryloyloxy)phenyl)triphenylphosphonium cations, and triphenyl(4-(nonanoyloxy)phenyl)phosphonium cations.

[0186] <Phosphonium Dication> The phosphonium dication is not particularly limited, and known and commonly used ones can be used. Examples of phosphonium dications include the organic quaternary phosphonium dication represented by the following general formula (XI-4).

[0187] In general formula (XI-4), R ９Ａ ~R ９ＦEach of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. ９Ａ ~R ９Ｆ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time), L ９ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L ９ The divalent carbon atoms at any position are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R ９Ａ ~R ９Ｆ and L ９ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R ９Ａ ~R ９Ｆ Any two of these are linked to each other by a single bond, directly, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring with the phosphorus atoms in formula (XI-4).

[0188] The organic quaternary phosphonium dication represented by the above general formula (XI-4) is not particularly limited, and examples include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, pentamethylenebis(triphenylphosphonium) dication, and the like.

[0189] <Sulfonium Cation> The sulfonium cation is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium cations include the organic sulfonium cation represented by the following general formula (XI-5).

[0190] In general formula (XI-5), R １０Ａ , R １０Ｂ and R １０Ｃ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. １０Ａ , R １０Ｂ and R １０Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １０Ａ , R １０Ｂ and R １０Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 １－１８Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R １０Ａ , R １０Ｂ and R １０Ｃ Any two of these are directly linked 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 alkylene groups and form a ring together with the sulfur atoms in general formula (XI-5).

[0191] In an organic sulfonium cation represented by the general formula (XI-5), the above R １０Ａ , R １０Ｂ and R １０Ｃ For example, R １０Ａ , R １０Ｂ and R １０Ｃ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R １０Ａ , R １０Ｂ and R １０Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), R １０Ａ , R １０Ｂ and R １０ＣHowever, each C may independently have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １０Ａ , R １０Ｂ and R １０Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), R １０Ａ , R １０Ｂ and R １０Ｃ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R １０Ａ , R １０Ｂ and R １０Ｃ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is even more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0192] Also R １０Ａ , R １０Ｂ and R １０Ｃ Any two of these are directly linked 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 structures that are linked via alkylene groups and form a ring with the sulfur atom in general formula (XI-5) include those having the thian-1-ium skeleton, thiophene-1-ium skeleton, 1,4-oxatian-4-ium skeleton, 1,4-dithian-1-ium skeleton, 1H-thiophene-1-ium skeleton, benzo[b]thiophene-1-ium skeleton, dibenzothiophenium skeleton, 9,10-dihydrothioxanthilium skeleton, 10H-phenoxatiyne-10-ium skeleton, 5H-thiantrene-5-ium skeleton, and the following are examples. Note that * indicates that the sulfur atom is not involved in ring formation. １０Ａ , R １０Ｂ or R １０Ｃ It means the connection point.

[0193]

[0194] Examples of the above organic sulfonium cations include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalene-1-yl)hexahydrothiopyrillium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrillium cation, di(naphthalene-1-yl)(phenyl)sulfonium cation, and phenylbis(2-(trifluoromethyl)phenyl)sulfonium Mu 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-thianthrene-5-ium cation, 5-(2,5-dimethylphenyl)thianthrene-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophene-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,Examples include [d] thiophene-5-ium cation, 1-(4-(t-butyl)phenyl)-1H-benzo[b] thiophene-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, dimethyl(trifluoromethyl)sulfonium cation, tri-p-tolylsulfonium cation, etc.

[0195] <Sulfonium Dication> The sulfonium dication is not particularly limited, and known and commonly used ones can be used. Examples of sulfonium dications include the organic sulfonium dication represented by the following general formula (XI-6).

[0196] In general formula (XI-6), R １１Ａ , R １１Ｂ , R １１Ｃ and R １１Ｄ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. １１Ａ , R １１Ｂ , R １１Ｃ and R １１Ｄ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); L １１ C may have substituents. １－１８ Represents a hydrocarbylene group, and the above L １１The divalent carbon atoms at any position are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １１Ａ , R １１Ｂ , R １１Ｃ , R １１Ｄ , and L １１ The hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C １－１８The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R １１Ａ , R １１Ｂ and L １１ Any two of the following, and / or R １１Ｃ , R １１Ｄ and L １１ Any two of these are directly linked by a single bond, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring together with the sulfur atoms in general formula (XI-6).

[0197] <Iodonium Cation> The iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of iodonium cations include the organic iodonium cation represented by the following general formula (XI-7).

[0198] In general formula (XI-7), R １２Ａ and R １２Ｂ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. １２Ａ and R １２Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms may not be replaced at the same time); the above R １２Ａ and R １２ＢThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy 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 Hydrocarbyloxycarbonylamino group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time); further R １２Ａ and R １２ＢThese are linked directly by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the iodine atom in general formula (XI-7).

[0199] In the organic iodonium cation represented by the general formula (XI-7), R １２Ａ and R １２Ｂ For example, R １２Ａ and R １２Ｂ However, each C may independently have substituents. １－１８ It is a hydrocarbyl group; the above R １２Ａ and R １２Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), R １２Ａ and R １２Ｂ However, each C may independently have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ It is an aralkyl group; the above R １２Ａ and R １２Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time), R １２Ａ and R １２Ｂ However, each C may independently have substituents. ６－１８ It is an aryl group; the above R １２Ａ and R １２ＢThe hydrogen atoms contained in C may be (a) halogen atoms, (b) haloalkyl groups, (c) hydroxyl groups, (d) thiol groups, (e) nitro groups, (f) cyano groups, (g) carboxyl 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) hydroxyl or carboxyl groups having a protecting group, (t) polar groups having an acid-dissociable group, or (u) C in which at least one part of the hydrogen atoms may be substituted with the above (a) to (t). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyl oxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, or C １－１８ The groups may be replaced by hydrocarbylthio groups, and the divalent carbon atoms at any position other than the terminals of these substituents are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ It is even more preferable that it may be replaced by - (however, adjacent divalent carbon atoms may not be replaced at the same time).

[0200] Examples of the above organic iodonium cations 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, and (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl) ) Iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 (Trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl) Examples include (2,4,6-trimethylphenyl)iodonium cation, (2-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, phenyl(2,4,6-trimethoxyphenyl)iodonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, and (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation.

[0201] [1-3-3. Organic sulfonium cation (B ｎ＋)] In the above general formula (I), "B ｎ＋ As the organic sulfonium cation represented by ", examples such as the "triarylsulfonium cation" and "triphenylsulfonium cation" mentioned above, which are organic sulfonium cations having one or more acid-dissociable polar groups and one or more iodine atoms, can be used as appropriate.

[0202] [1-3-4. Heteropolyate anions having a defect site in which the defect site is modified] As heteropolyate anions having a defect site represented by the above general formula (I) in which the defect site is modified, a heteropolyate anion with a modified defect site can be used, in which the terminal oxygen atom at the defect site of the heteropolyate anion having a defect site is modified with a P, Si, Ge, or Sn compound having one or more organic groups. Furthermore, from the viewpoint of drastically changing the solubility in the developer, a heteropolyate anion with a modified defect site can be suitably used by having a group having a heteroatom P, Si, Ge, or Sn to which an "organic group containing one or more polar groups having an acid-dissociable group" or an "organic group containing two or more polar groups having an acid-dissociable group" is bonded to the terminal oxygen atom at the defect site of the heteropolyate anion having a defect site via some or all of the heteroatoms.

[0203] [1-3-5. Composition] A heteropoly salt or mixture thereof in which the defect site represented by the above general formula (I) is modified, comprising multiple types of A ｍ＋ and B ｎ＋ It may include [the specified element]. In the above case, the values ​​of a and b can be determined by performing NMR analysis, XRF analysis, XPS analysis, etc.

[0204] The ratio of a to b is A ｍ＋ , B ｎ＋ , C （ａｍ＋ｂｎ）－Depending on the type, etc., it is preferable that a:b = 0 to 8:1 to 12, more preferably 0 to 4:2 to 8, and even more preferably 0 to 2:1 to 4. In particular, when the value of am + bn is an integer from 2 to 8, and m and n are 1, it is preferable that a is a real number from 0 to 7 and b is a real number from 1 to 8, and more preferably that a is a real number from 0 to 4 and b is a real number from 2 to 8.

[0205] [2. Resist Material] The resist material according to this embodiment contains a heteropolyate or mixture thereof modified with (A) a defect site, wherein the cationic portion of the heteropolyate or mixture thereof modified with (A) a defect site contains an organic sulfonium cation, and the organic sulfonium cation has one or more acid-dissociable polar groups and one or more iodine atoms. The resist material according to this embodiment may also contain an acid diffusion control agent, an organic solvent, an acid generator, or other components as optional components.

[0206] [2-1. (A) Heteropolyate salts or mixtures thereof with modified defect sites] As (A) heteropolyate salts or mixtures thereof with modified defect sites according to this embodiment, the above "1. Heteropolyate salts or mixtures thereof with modified defect sites" can be used. The above heteropolyate salts or mixtures thereof with modified defect sites are characterized in that the cationic portion contains an organic sulfonium cation, and the organic sulfonium cation has one or more acid-dissociable polar groups and one or more iodine atoms.

[0207] As described above, by including an organic sulfonium cation in the cation portion of a heteropolyate or mixture thereof with a modified defect site, it can function as an acid generator that produces acid upon exposure to active light or the like. Furthermore, by including one or more iodine atoms in the organic sulfonium cation, the absorption coefficient to active light and the like can be increased, resulting in improved sensitivity.

[0208] Furthermore, if the above-mentioned organic sulfonium cation contains one or more acid-dissociable polar groups, the acid-dissociable polar groups can be dissociated by the action of an acid, thereby generating the polar groups and changing the solubility of the resist material in the developer.

[0209] In addition, because the above-mentioned organic sulfonium cation contains one or more polar groups having acid-dissociable groups and one or more iodine atoms, the by-products generated after the organic sulfonium cation has acted as an acid generator can be easily removed with a polar solvent or the like.

[0210] Therefore, the resist material containing component (A) above has improved sensitivity, and it is possible to reduce foreign matter and defects on the surface of the coated film after development in the resist film made using this resist material.

[0211] The content of component (A) in the resist material is not particularly limited and can be appropriately set depending on the method of coating the resist material onto the substrate, the film thickness to be coated, etc. The content of component (A) in the resist material is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass, when the resist material is considered to be 100% by mass.

[0212] [2-2. (B) Acid Diffusion Control Agent] The resist material according to this embodiment may contain (B) an acid diffusion control agent as an optional component in addition to component (A). By including (B) an acid diffusion control agent in the resist material, the acid generated by exposure can be trapped and the diffusion of the acid can be controlled. Component (B) is not particularly limited, and known and commonly used components can be used. Examples of acid diffusion control agents include (B1) a photodegradable base that decomposes upon exposure and loses its acid diffusion control properties, and (B2) a nitrogen-containing organic compound that does not fall under component (B1). These may be used individually or in combination of two or more.

[0213] [2-2-1. (B1) Photodecayable Bases] (B1) Photodecayable bases lose their ability to control acid diffusion when decomposed by exposure to active light, etc., but in unexposed areas they act as acid quenchers and can control acid diffusion. For this reason, by including (B1) photodecayable bases in the resist material, properties such as increased sensitivity, reduced roughness, and suppression of coating defects can be improved.

[0214] The above-mentioned photodecayable base is not particularly limited, and known and commonly used bases can be used. For example, the photodecayable base is "carboxylate compound B" represented by the following general formula (XII-1). Ａ ", represented by the following general formula (XII-2), "sulfonate compound B" Ｂ ", and "sulfonylamide salt compound B" represented by the following general formula (XII-3) Ｃ Examples include the following: carboxylate anions, sulfonate anions, sulfonylamide anions, onium cations, or onium dication D. ｐ＋ I will explain in that order.

[0215] [2-2-1-1. Carboxylate Compound B] Ａ The above (B1) photodecayable base is "carboxylate compound B" represented by the following general formula (XII-1). Ａ " and onium cation or dication (D ｐ＋ ) and salt can be used.

[0216] "R Ａ ｂ１ " may have substituents C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0217] R Ａ ｂ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0218] <Carboxylate compound B> Ａ１ > Carboxylate compound B represented by the above general formula (XII-1) Ａ This is carboxylate compound B, represented by the following general formula (XII-1-1). Ａ１ That's fine.

[0219] "X Ａ ｂ１ " may have substituents C １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0220] X Ａ ｂ１ C may have substituents.３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８ An aryl group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0221] "L Ａ ｂ１ " is X Ａ ｂ１ to-COO － A base that connects and the following general formula (L ｂ -1) to (L ｂ A linking group represented by -7) can be used. [In the formula, L ｂ１ and L ｂ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ａ ｂ１ The connection part is, *2 is -COO － This represents the connection point.

[0222] L ｂ１ and L ｂ２ This may consist of a single bond or a C that may have a substituent. １－８ Alkylene group or C ６－８ It is preferably an arylene group, and may have a single bond or a substituent.１－８ It is more preferable that the group be an alkylene group.

[0223] <Example of a carboxylate anion> The above carboxylate salt compound B Ａ or B Ａ１ The carboxylic acid anions are not particularly limited, and examples include trifluoroacetate anion, pentafluoropropionate anion, 2-methoxyacetate anion, 2-methoxy-2-methylpropionate anion, 2-hydroxyacetate anion, 2-hydroxy-2-methylpropionate anion, 2-acetoxyacetate anion, adamantane-1-carboxylic acid anion, 9,10-dihydro-9,10-ethanoanthracene-11-carboxylic acid anion, 9,10-dihydro-9,10-[1,2]benzenoanthracene-9-carboxylic acid anion, benzoate anion, salicylate anion, 3-hydroxybenzoate anion, 3-trifluoromethylbenzoate anion, and the like.

[0224]

[0225]

[0226]

[0227] [2-2-1-2. Sulfonate Compound B] Ｂ The above (B1) photodecayable base is "sulfonate compound B" represented by the following general formula (XII-2). Ｂ " and sulfonate anion and onium cation or dication (D ｐ＋ ) and salt can be used.

[0228] "R Ｂ ｂ１ " may have substituents C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0229] R Ｂ ｂ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0230] <Sulfonate compound B> Ｂ１ > Sulfonate compound B represented by the above general formula (XII-2) Ｂ However, sulfonate compound B, represented by the following general formula (XII-2-1) Ｂ１ That's fine.

[0231] "X Ｂ ｂ１ " may have substituents C １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0232] X Ｂ ｂ１ C may have substituents. ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８ An aryl group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0233] "L Ｂ ｂ１ " is X Ｂ ｂ１ to-SO ２ -O － A base that connects and the above general formula (L ｂ -1) to (L ｂ A linking group represented by -7) can be used. In this case, the general formula (L ｂ -1) to (L ｂ -7) Medium, L ｂ１ and L ｂ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｂ ｂ１ The connection point is, *2 is -SO ２ -O － This represents the connection point.

[0234] L ｂ１ and L ｂ２ This may consist of a single bond or a C that may have a substituent. １－８ Alkylene group or C６－８ It is preferably an arylene group, and may have a single bond or a substituent. １－８ It is more preferable that the group be an alkylene group.

[0235] <Example of sulfonate anion> The above sulfonate compound B Ｂ or B Ｂ１ The sulfonate anions are not particularly limited and include, for example, camphor sulfonate anion, (adamantan-1-yl)methanesulfonate anion, (adamantan-1-carbonyloxy)ethane-1-sulfonate anion, cyclohexanesulfonate anion, 2-(cyclohexanecarbonyloxy)ethane-1-sulfonate anion, bicyclo[2.2.1]heptane-2-sulfonate anion, benzenesulfonate anion, 4-methylbenzenesulfonate anion, and the like.

[0236]

[0237] [2-2-1-3. Sulfonylamide salt compound B] Ｃ ] The above (B1) photodecayable base is "sulfonylamide compound B" represented by the following general formula (XII-3). Ｃ " and a sulfonylamide anion and an onium cation or dication (D ｐ＋ ) and salt can be used.

[0238] "R Ｃ ｂ１ " may have substituents C １－１８ A hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, wherein any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ - may be replaced (however, adjacent divalent carbon atoms cannot be replaced at the same time). Ｃ ｂ２ " may have substituents C １－１８A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0239] R Ｃ ｂ１ C may have substituents. １－１８ A hydrocarbyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0240] R Ｃ ｂ２ C may have substituents. １－１８ Alkyl alkyl group, C ３－１８ In an alicyclic group, any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that it may be replaced by - (however, adjacent divalent carbon atoms will not be replaced at the same time), C １－１２ It is more preferably a haloalkyl group, C １－５ It is even more preferable that the alkyl group is a fluorinated alkyl group.

[0241] <Sulfonylamide compound B> Ｃ１ > Sulfonylamide salt compound B represented by the above general formula (XII-3) Ｃ However, sulfonylamide salt compound B, represented by the following general formula (XII-3-1) Ｃ１ That's fine.

[0242] "X Ｃ ｂ１ " may have substituents C １－１８ Alkyl alkyl group, C ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It may be replaced by - (however, adjacent divalent carbon atoms cannot be replaced at the same time).

[0243] X Ｃ ｂ１ C may have substituents. ３－１８ Alicyclic group, C ６－１８ Aryl group, or C ７－１８ An aralkyl group in which any divalent carbon atom other than the terminals other than the bond is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by - (however, adjacent divalent carbon atoms may not be replaced simultaneously), and the carbon atoms may have substituents. ３－１８ Alicyclic group, or C ６－１８ An aryl group in which any divalent carbon atom, excluding the terminals other than the bond, is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or -SO ２ It is preferable that the carbon atoms may be replaced by a negative (however, adjacent divalent carbon atoms may not be replaced simultaneously).

[0244] "L Ｃ ｂ１ " is X Ｃｂ１ to-N － -SO ２ -R Ｃ ｂ２ A base that connects and the above general formula (L ｂ -1) to (L ｂ A linking group represented by -7) can be used. In this case, the general formula (L ｂ -1) to (L ｂ -7) Medium, L ｃ１ and L ｃ２ C may have a single bond or a substituent. １－８ This represents a hydrocarbylene group, and *1 is X Ｃ ｂ１ The connection point is, *2 is -N － -SO ２ -R Ｃ ｂ２ This represents the connection point.

[0245] L ｂ１ and L ｂ２ This may consist of a single bond or a C that may have a substituent. １－１２ Alkylene group, C １－１２ Cycloalkylene group or C ６－１２ It is preferably an arylene group, and may have a single bond or a substituent. １－８ Alkylene group or C １－８ It is more preferable that the group be a cycloalkylene group.

[0246] <Example of sulfonylamide anion> The above sulfonylamide salt compound B Ｃ or B Ｃ１The sulfonylamide anion is not particularly limited, and includes, for example, methyl((trifluoromethyl)sulfonyl)amide anion, i-propyl((trifluoromethyl)sulfonyl)amide anion, methacryloyloxy((trifluoromethyl)sulfonyl)amide anion, 2-(methacryloyloxy)ethyl((trifluoromethyl)sulfonyl)amide anion, cyclohexyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclopentanecarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-((cyclohesanylcarbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1 Examples include heptane-2-ylmethyl((trifluoromethyl)sulfonyl)amide anion, bicyclo[2.2.1]heptane-7-ylmethyl((trifluoromethyl)sulfonyl)amide anion, 2-((adamantane-1-carbonyl)oxy)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(adamantane-1-carboxamide)ethyl((trifluoromethyl)sulfonyl)amide anion, 2-(4-((adamantane-1-carbonyl)oxy)cyclohexyl)ethyl((trifluoromethyl)sulfonyl)amide anion, and 4-((adamantane-1-carbonyl)oxy)phenyl((trifluoromethyl)sulfonyl)amide anion.

[0247]

[0248]

[0249]

[0250] [2-2-1-4. Onium cation or onium dication (D ｐ＋ )] The cation portion of the above (B1) photodecayable base is an onium cation or an onium dication (D ｐ＋ ) can be used. Here, the general formulas (XII-1) to (XII-3) represent "(D ｐ+ ) １／ｐIn this expression, D represents an onium cation or onium dication, and p represents an integer of 1 or 2. The onium cation or onium dication is not particularly limited, and organic sulfonium cations, organic sulfonium dications, organic iodonium cations, etc., can be used.

[0251] The above onium cation or dication (D ｐ＋ For example, an organic sulfonium cation represented by the following general formula (XIII-1) can be used.

[0252] In general formula (XIII-1), R Ｄ １Ａ , R Ｄ １Ｂ and R Ｄ １Ｃ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. Ｄ １Ａ , R Ｄ １Ｂ and R Ｄ １Ｃ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R Ｄ １Ａ , R Ｄ １Ｂ and R Ｄ １Ｃ Any two of these are directly linked 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 alkylene groups and form a ring together with the sulfur atom in formula (XIII-1).

[0253] Also, the above onium cation or dication (D ｐ＋For example, an organic sulfonium dication represented by the following general formula (XIII-2) can be used. In general formula (XIII-2), R Ｄ ２Ａ , R Ｄ ２Ｂ , R Ｄ ２Ｃ and R Ｄ ２Ｄ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. Ｄ ２Ａ , R Ｄ ２Ｂ , R Ｄ ２Ｃ and R Ｄ ２Ｄ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); L Ｄ ２ Each of these may independently have substituents. １－１８ Represents a hydrocarbylene group, and the above L Ｄ ２ The divalent carbon atoms at any position are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -S-, or SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R Ｄ ２Ａ , R Ｄ ２Ｂ and L Ｄ ２ Any two of the following, and / or R Ｄ ２Ｃ , R Ｄ ２Ｄ and L Ｄ ２Any two of these are directly linked by a single bond, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups to form a ring together with the sulfur atoms in formula (XIII-2).

[0254] The above onium cation or dication (D ｐ＋ For example, an organic iodonium cation represented by the following general formula (XIII-3) can be used.

[0255] In general formula (XIII-3), R Ｄ ３Ａ and R Ｄ ３Ｂ Each of these may independently have substituents. １－１８ R represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group. Ｄ ３Ａ and R Ｄ ３Ｂ Any divalent carbon atom at any position except the terminals is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be replaced by (however, adjacent divalent carbon atoms cannot be replaced at the same time); R Ｄ ３Ａ and R Ｄ ３Ｂ These are linked directly by single bonds, or by divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via alkylene groups and form a ring together with the iodine atom in formula (XIII-3).

[0256] [2-2-2. (B2) Nitrogen-containing organic compounds] Other (B) acid diffusion control agents may include nitrogen-containing organic compounds that do not fall under (B2) or (B1). The nitrogen-containing organic compounds are not particularly limited, and for example, aliphatic amines, aromatic amines, heterocyclic amines, etc., can be used.

[0257] Examples of nitrogen-containing organic compounds include aliphatic amines such as n-hexylamine, n-heptylamine, diethylamine, di-n-propylamine, di-n-butylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-octylamine; aromatic amines such as aniline, N-methylaniline, N-ethylamine, N,N-dimethylaniline, 4-methylaniline, and pyrrole; and heterocyclic amines such as pyridine, imidazole, benzimidazole, piperidine, piperazine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane. These nitrogen-containing organic compounds may be used individually or in combination of two or more.

[0258] [2-2-3. Amount of Component (B)] The amount of acid diffusion control agent (B) contained in the resist material according to this embodiment is not particularly limited and can be appropriately selected depending on the content and type of component (A). The content of component (B) in the resist material is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 25 parts by mass, and even more preferably 0.5 to 20 parts by mass, per 100 parts by mass of component (A).

[0259] [2-3. Organic Solvents] The resist material according to this embodiment may further contain an organic solvent. The organic solvent is not particularly limited, and known and commonly used solvents can be used. The organic solvent is preferably one that can be uniformly dissolved or dispersed when prepared with component (A).

[0260] Examples of organic solvents include polar solvents such as alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, nitrile-based solvents, and aproton-based polar solvents, and examples of non-polar solvents such as hydrocarbon-based solvents. These organic solvents may be used individually or in combination of two or more.

[0261] Specific examples of the above polar solvents include, for example, alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), diacetone alcohol (DAA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); ether-based solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methylisopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; Examples of organic solvents include: amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); nitrile solvents such as acetonitrile, propionitrile, and benzonitrile; and aprotic polar solvents such as γ-butyrolactone, δ-valerolactone, γ-lactam, δ-lactam, dimethyl sulfoxide (DMSO), sulfolane, 1,3-dimethyl-2-imidazolidinone, and tetramethylurea. Nonpolar solvents include hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. The above organic solvents may be used individually or in combination of two or more.

[0262] The organic solvent to be included in the resist material according to this embodiment is preferably a polar solvent in terms of coatability, and more preferably an amide solvent, ester solvent, alcohol solvent, or ketone solvent in terms of solubility. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent or alcohol solvent is preferably one having an ester bond and / or a hydroxyl group in terms of solubility, and among the above, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate, and propylene glycol monomethyl ether acetate.

[0263] The content of the organic solvent in the resist material is not particularly limited and can be appropriately set depending on the method of applying the resist material to the substrate, the film thickness to be applied, etc. Preferably, the solid content of the organic solvent in the resist material is 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.2 to 10% by mass.

[0264] [2-4. Others] The resist material according to this embodiment may optionally contain additional miscible additives, such as additional resins to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halation agents, dyes, etc.

[0265] [3. Pattern Forming Method] The pattern forming method according to this embodiment comprises the steps of: applying a resist material to a substrate; exposing the resist film formed by the application step to light; and developing the exposed resist film.

[0266] [3-1. Coating Process] The pattern formation method according to this embodiment includes a step of coating a resist material onto a substrate.

[0267] <Substrate> The substrate used in this embodiment is not particularly limited, and known and commonly used substrates can be used. For example, a substrate for electronic components or a substrate with a predetermined wiring pattern formed on it may be used. The material of the substrate is not particularly limited, and examples include silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and inorganic substrates such as glass, titanium oxide, and silicon dioxide. The size and shape of the substrate are not particularly limited, and the surface of the substrate may be smooth, curved, or uneven, or it may be a thin, flake-shaped substrate.

[0268] The surface of the substrate may be surface-treated as needed. In the case of a substrate having hydroxyl groups on its surface, surface treatment of the substrate using a silane-based coupling agent that reacts with hydroxyl groups can change the surface of the substrate from hydrophilic to hydrophobic, thereby improving the adhesion between the substrate and the metal compound-containing film. Examples of the silane-based coupling agent include hexamethyldisilazane (HMDS).

[0269] <Coating Method> The method for coating the resist material onto the substrate is not particularly limited, and known and conventional methods can be used. Dry coating methods include, for example, CVD methods (chemical vapor deposition) such as thermal CVD, plasma CVD, and photo-CVD; and PVD methods (physical vapor deposition) such as vacuum deposition, plasma-assisted deposition, sputtering, and ion plating. Wet coating methods include, for example, spin coating, bar coating, roll coating, flow coating, dip coating, spray coating, inkjet printing, and screen printing.

[0270] As a method for applying the resist material according to this embodiment onto a substrate, it is preferable to use a wet method such as spin coating or screen printing, and more preferably to use spin coating, from the viewpoint of forming a uniform film thickness. After forming the coated film, backside rinsing, edge bead removal steps, etc., can be performed to remove edge beads.

[0271] The method for drying the resist film formed by coating a resist material onto a substrate is not particularly limited and can be carried out using, for example, a heating device such as a hot plate (post-application bake (PAB)), a vacuum device, etc. The baking conditions are not particularly limited and can be set appropriately according to the type of resist film, application, etc. The baking temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C. The baking time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0272] The thickness of the resist film after drying is not particularly limited, but is preferably 0.5 to 100 nm, more preferably 1 to 75 nm, and even more preferably 1 to 60 nm.

[0273] [3-2. Exposure Step] The pattern formation method according to this embodiment includes a step of exposing the resist film formed by the coating step described above.

[0274] For example, an ArF exposure apparatus, electron beam lithography apparatus, EUV exposure apparatus, etc., can be used as the exposure apparatus in the resist film exposure process. In the exposure process, exposure may be performed through a mask (mask pattern) on which a predetermined pattern is formed, or selective exposure may be performed by direct irradiation with an electron beam or the like without using a mask pattern.

[0275] The wavelength used for exposure is not particularly limited, and includes ArF excimer laser (wavelength 193 nm), KrF excimer laser (248 nm), and F ２ Radiation such as excimer lasers (wavelength 157 nm), EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays may also be used.

[0276] For ArF or KrF excimer lasers, the exposure dose to the resist film is 1 to 200 mJ / cm². ２ Preferably, the concentration is 20 to 60 mJ / cm². ２It is more preferable that this is the case. Also, in the case of extreme ultraviolet light, the exposure amount is, for example, 500 mJ / cm². ２ The following applies: 0.1 to 200 mJ / cm² ２ Preferably, it is 3 to 100 mJ / cm². ２ It is more preferable that the concentration be 5 to 50 mJ / cm². ２ It is even more preferable that the voltage is 3 μC / cm at 50 kV in the case of an electron beam. ２ ~2 mC / cm ２ It is preferable to expose with a dose of 10 μC / cm². ２ ~1.5 mC / cm ２ Exposure at this dose is more preferable.

[0277] After exposure to the resist film, a bake (post-exposure bake (PEB)) treatment may or may not be performed. The bake conditions are not particularly limited and can be set appropriately depending on the type of resist film, application, etc. The bake temperature is preferably 80 to 300°C, more preferably 80 to 200°C, and even more preferably 80 to 130°C, using a heating device such as a hot plate. The bake time is preferably 10 to 300 seconds, more preferably 20 to 180 seconds, and even more preferably 30 to 120 seconds.

[0278] [3-3. Development Process] The pattern formation method according to this embodiment includes a step of developing the exposed resist film. In the development process, a pattern can be formed by developing the exposed resist film with a developer. When the exposed area remains as a pattern after development, it is a negative-type pattern formation process, and when the exposed area is removed after development, it is a positive-type pattern formation process. Whether to form a positive or negative pattern can be appropriately selected depending on the resist material or developer. After development, the film may be washed with a rinsing solution and then dried, and in some cases, a baking process may be performed further.

[0279] The developer used in this embodiment may be an alkaline developer for the alkaline development process, or a developer containing an organic solvent (organic developer) for the organic solvent development process.

[0280] <Alkaline Development Process> With conventional metal oxide resist materials, it has been difficult to form positive-type patterns with good resolution using the alkaline development process. In contrast, the resist material according to this embodiment can form patterns with good resolution using a water-containing developer.

[0281] The alkaline developer used in the alkaline development process is not particularly limited, and any known and commonly used one may be used. Examples of the above-mentioned alkaline developer include quaternary ammonium salts such as tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and aqueous solutions containing one or more alkanolamines such as dimethylethanolamine and triethanolamine.

[0282] The method for developing the exposed resist film using the above-mentioned alkaline developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0283] Furthermore, pure water can be used as the rinsing solution in the alkaline development process.

[0284] <Organic Solvent Development Process> Examples of developers used in the organic solvent development process include developers containing one or more organic solvents such as polar solvents like ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, or hydrocarbon solvents.

[0285] Specific examples of organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, acetophenone, propylene carbonate, and furfural; ester solvents such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate (PGMEA); alcohol solvents such as methanol, ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and propylene glycol monomethyl ether (PGME); and nitrile solvents such as acetonitrile, propionitrile, and benzonitrile. Examples include amide solvents such as N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylpyrrolidone, 1-ethyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone; ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran, anisole, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; and hydrocarbon solvents such as n-pentane, n-hexane, toluene, and xylene. These may be used individually or in combination of two or more.

[0286] Among these, the organic solvent used in the developer is preferably a polar solvent, and more preferably contains amide solvents, alcohol solvents, ester solvents, and ketone solvents. The amide solvent is preferably at least one selected from the group consisting of N,N-dimethylformamide, N,N-diethylformamide, acetamide, and N-methylpyrrolidone. The ester solvent is preferably one or more selected from the group consisting of methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and propylene glycol monomethyl ether acetate. The alcohol solvent is preferably at least one selected from the group consisting of ethanol, isopropyl alcohol (IPA), 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 4-methyl-2-pentanol, benzyl alcohol, and 4-methylbenzyl alcohol. Furthermore, the ketone solvent is preferably at least one selected from the group consisting of acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone.

[0287] When the developer contains either an amide-based solvent or an ester-based solvent and an alcohol-based solvent, the mixing ratio (by weight) of the amide-based solvent or ester-based solvent to the alcohol-based solvent is preferably 5:95 to 95:5, and more preferably 10:90 to 90:10.

[0288] The method for developing the exposed resist film using the above-mentioned developer is not particularly limited, and known and conventional methods can be used. Examples of methods for developing using the above-mentioned developer include immersing the substrate having the exposed resist film in the developer for a certain period of time (dip method), spraying the developer onto the surface of the exposed resist film (spray method), and dispensing the developer from a discharge nozzle at a constant speed toward the surface of the exposed resist film on a substrate rotating at a constant speed (dynamic dispensing method).

[0289] The process may include a step of washing with a rinsing solution after development with the above-mentioned developer solution. The rinsing solution is not particularly limited, and any known and commonly used solution can be used. As the rinsing solution, a suitable choice can be made from the water or organic solvent contained in the above-mentioned developer solution that does not easily dissolve the resist pattern.

[0290] The rinsing solution is not particularly limited, and for example, at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents can be used. Among these, it is preferable to use at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents as the rinsing solution, more preferably at least one selected from the group consisting of alcohol solvents and ester solvents, and even more preferably at least one alcohol solvent.

[0291] As the alcohol-based solvent used in the rinsing solution, a monohydric alcohol having 2 to 8 carbon atoms is preferred, and the monohydric alcohol may be linear, branched, or cyclic. Specific examples of the above monohydric alcohols include ethanol, isopropyl alcohol (IPA), butanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, and the like. These organic solvents may be used individually or in combination of two or more.

[0292] The method for cleaning the resist pattern with the above-mentioned rinsing solution is not particularly limited, and known and conventional methods can be used. Examples of methods for cleaning using the above-mentioned rinsing solution include immersing the resist pattern in the rinsing solution for a certain period of time (dip method), spraying the rinsing solution onto the surface of the resist pattern (spray method), and dispensing the rinsing solution from a discharge nozzle at a constant speed toward the surface of a resist pattern rotating at a constant speed (dynamic dispensing method).

[0293] [4. Patterned Structure] The patterned structure according to this embodiment is obtained by forming a pattern on a substrate using the pattern formation method described above.

[0294] The average thickness of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. The patterned structure preferably has an average thickness portion of 1 to 100 nm, more preferably a portion of 5 to 75 nm, and even more preferably a portion of 10 to 60 nm.

[0295] Furthermore, the pitch of part or all of the patterned structure according to this embodiment is not particularly limited and can be set as appropriate depending on the intended use. It is preferable that the patterned structure has a portion with a pitch of 100 nm or less, more preferably a portion with a pitch of 50 nm or less, and even more preferably a portion with a pitch of 20 nm or less. By patterning the resist material according to this embodiment using the pattern formation method described above, it is possible to create portions with pitches of 50 nm, 20 nm, and 15 nm in part or all of the patterned structure.

[0296] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0297] [1. Synthesis of heteropolyates with modified defect sites (hereinafter also referred to as "polyates")] <Production example 1: Potassium undecatungus silicate (α-K ８ [SiW １１ O ３９ ])> Silicate tungstic acid hydrate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.: H ４ [SiW １２ O ４０ ]・xH ２O) 63 g was mixed with 380 g of 1 M acetic acid, and the reaction mixture was heated to 45°C. Potassium bicarbonate was added (52 g) to bring the pH to 6.0. The reaction mixture was then cooled to room temperature and filtered by suction filtration to obtain 56 g of crude product. 216 g of pure water was added to the obtained crude product and heated to 73°C to redissolve it. The solution was cooled at 4°C for 16 hours to recrystallize it, filtered by suction filtration, and vacuum dried to obtain 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 ２ O): 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).

[0298] <Production Example 2: 2-(1-methylcyclopentyloxycarbonyl)ethyltrimethoxysilane> 6.1 g of trimethoxysilane and 6.4 g of 1-methylcyclopentyl acrylate were added, and the mixture was stirred at room temperature. Then, 100 μL of a 1 M isopropyl alcohol solution of hexachloroplatinic acid was added. After the reaction started, the reaction mixture was heated to 60°C and then allowed to cool to room temperature. The reaction mixture was stirred at room temperature for 72 hours, filtered by Celite, and the resulting filtrate was thoroughly vacuum-dried to obtain 13.1 g of the target compound as a colorless oily liquid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.97 (t, 2H), 1.39 (s, 3H), 1.56-1.81 (m, 8H), 2.21 (t, 2H), 3.55 (s, 9H).

[0299] <Manufacturing Example 3: Bis(4-iodophenyl)(4-carboxyphenyl)sulfonium bromide> 10 g of 4-iodobenzoic acid was dissolved in 150 mL of anhydrous THF, and 1.8 g of sodium hydride was added. The mixture was then stirred for 10 minutes and cooled to -40°C. Next, 30 mL of 15% isopropylmagnesium bromide solution in THF was added dropwise, and the mixture was stirred at -10°C for 3 hours. In a separate container, 43.9 g of bis(4-iodophenyl) sulfoxide was dissolved in 50 mL of THF, cooled to -40°C, and then 21.3 g of trimethylsilyl bromide was added dropwise. After stirring at -40°C for 30 minutes, the former reaction solution was added. The mixture was then stirred at -20°C for 3 hours, cooled to -70°C, and 100 mL of 20% hydrochloric acid aqueous solution was added. The mixture was warmed to room temperature, and 300 mL of diethyl ether and 200 mL of 20% hydrochloric acid aqueous solution were added. The mixture was then stirred for one hour, and the aqueous layer was extracted with diethyl ether and dichloromethane by liquid-liquid extraction. The aqueous layer was then combined with the organic layer and concentrated. The mixture was purified by silica gel column chromatography, yielding 21.6 g of the target product as a white solid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 7.10 (d, 4H), 7.54 (d, 2H), 7.77 (d, 4H), 8.17 (d, 2H), 12.71 (s, 1H).

[0300] <Production Example 4: Bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide> Under a nitrogen atmosphere, 1.5 g (15 mmol) of 1-methylcyclopentanol was dissolved in 100 mL of anhydrous THF. Then, it was dissolved in 20 mL of anhydrous THF. 2.04 g (12.6 mmol) of carbonyldiimidazole was slowly added dropwise at room temperature. After stirring the reaction mixture for 3 hours, 8.56 g (12.6 mmol) of bis(4-iodophenyl)(4-carboxyphenyl)sulfonium bromide, dissolved in 20 mL of anhydrous THF, was slowly added dropwise under reflux. The reaction mixture was then stirred under reflux for 12 hours and cooled to room temperature. Liquid-liquid extraction was then performed with ethyl acetate and pure water, and the organic layer was washed three times with pure water. The solvent was evaporated using a rotary evaporator, and recrystallization was performed to obtain 5.7 g of the target compound. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 3H), 1.63-1.75 (m, 8H), 7.10 (d, 4H), 7.44 (d, 2H), 7.77 (d, 4H), 8.03 (d, 2H).

[0301] <Synthesis Example 1: Synthesis of Tetrakis(bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-1))> 95g of pure water, one-deficient Keggin-type potassium undecatungus silicate (α-K ８ [SiW １１ O ３９ 3.8 g (1.3 mmol) of ) was added. After stirring, 1.7 g (6.3 mmol) of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane was added, followed by the addition of 10.5 g of 1 M hydrochloric acid, and the mixture was stirred for 20 hours. The unreacted powder was filtered by suction filtration, and an aqueous solution of 5.48 g (7.6 mmol) of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide dissolved in 44 g of pure water was added to precipitate the powder. The precipitated powder was poured into a suction funnel with a small amount of pure water, filtered by suction filtration, and washed with 151 g of isopropanol. Further vacuum drying was performed to obtain 6.1 g of the target compound as a white powder. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.39 (s, 12H), 1.49-2.00 (m , 54H), 2.37-2.42 (m, 4H), 7.10 (d, 16H), 7.44 (d, 8H), 7.77 (d, 16H), 8.03 (d, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 641.2 ([C ２５ H ２３ I ２ O ２ S] ＋) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0302] <Manufacturing Example 5: Bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide> 17.85 g (74.9 mmol) of bis(4-fluorophenyl) sulfoxide and 16.48 g (74.9 mmol) of 3-iodophenol were dissolved in 200 mL of dichloromethane, and Eaton's reagent (100 mL) was added dropwise at 0°C. The reaction was heated to room temperature, stirred for 4 hours, then cooled to 0°C, and 200 mL of water was slowly added to quench the reaction. The reaction temperature was maintained below 20°C. The aqueous layer was extracted with ethyl acetate, and 50 mL of an aqueous solution containing 17.9 g (150 mmol) of potassium bromide was added to the aqueous layer with vigorous stirring. The slurry was stirred at room temperature for 1 hour, filtered, washed with water and methyl-t-butyl ether, and thoroughly vacuum-dried to obtain 13.7 g of the target compound as a white solid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.80 (d, 1H), 6.93 (d, 1H), 7.19-7.20 (m, 5H), 7.31 (m, 4H), 9.45 (s, 1H).

[0303] <Manufacturing Example 6: Bis(4-fluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide> 8.13 g (15.6 mmol) of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide and 10.15 g (31.1 mmol) of cesium carbonate were dissolved in 150 mL of dimethylformamide, and 3.78 g (17.1 mmol) of 1-methylcyclopentyl 2-bromoacetate was added dropwise at 0°C under a nitrogen atmosphere. The solution was gradually warmed to room temperature and stirred for 16 hours, after which 400 mL of water and 400 mL of dichloromethane were added. The organic layer was separated, and the aqueous layer was extracted with dichloromethane. The combined organic layers were extracted with water, dried over sodium sulfate, and concentrated to a volume of 100 mL. When 700 mL of methyl-t-butyl ether was added to this solution, a precipitate formed. The precipitate was filtered off, washed with methyl-t-butyl ether, and thoroughly vacuum-dried to obtain 9.90 g of the target compound as a white solid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 3H), 1.56-1.81 (m, 8H), 4.99 (s, 2H), 6.95 (d, 1H), 7.10 (d, 1H), 7.20-7.34 (m, 9H).

[0304] <Synthesis Example 2: Synthesis of Tetrakis(bis(4-fluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-2))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(4-fluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.39 (s, 12H), 1.49-1. 84 (m, 54H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.95 (d, 4H), 7.10-7.34 (m, 40H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 581.0 ([C ２６ H ２４ F ２ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0305] <Production Example 7: Bis(4-fluorophenyl)(2-iodo-4-(1-phenylcyclohexyloxycarbonylmethyloxy)phenyl)sulfonium bromide> In Production Example 6, the target compound was obtained by the same method as described above, except that 2-1-phenylcyclohexyl bromoacetate was used as the starting material instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.43-1.53 ​​(m, 6H), 1.86-2.12 (m, 4H), 4.99 (s, 2H), 6.95 (d, 1H), 7.10 (d, 1H), 7.17-7.34 (m, 12H), 7.54 (d, 2H).

[0306] <Synthesis Example 3: Synthesis of Tetrakis(bis(4-fluorophenyl)(2-iodo-4-(1-phenylcyclohexyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-3))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(4-fluorophenyl)(2-iodo-4-(1-phenylcyclohexyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.49-2.17 (m, 62H), 2. 37-2.42 (m, 4H), 4.99 (s, 8H), 6.95 (d, 4H), 7.10-7.34 (m, 52H), 7.54 (d, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 657.1 ([C ３２ H ２８ F ２ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0307] <Production Example 8: Bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide> In Production Example 5, the target compound was obtained in the same manner as described above, except that bis(3,5-difluorophenyl) sulfoxide was used as the raw material compound instead of bis(4-fluorophenyl) sulfoxide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 6.75-6.81 (m, 7H), 6.93 (d, 1H), 7.19 (s, 1H), 9.45 (s, 1H).

[0308] <Production Example 9: Bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide> In Production Example 6, the target compound was obtained in the same manner as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used as the raw material compound instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.39 (s, 3H), 1.56-1.81 (m, 8H), 4. 99 (s, 2H), 6.75-6.81 (d, 6H), 6.95 (d, 1H), 7.10 (d, 1H), 7.34 (s, 1H).

[0309] <Synthesis Example 4: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-4))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.39 (s, 12H), 1.49-1.84 (m, 5 4H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 617.0 ([C ２６ H ２２ F ４ IO ３ S] ＋) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0310] <Manufacturing Example 10: 3-(2-(1-t-butylcyclopentyloxycarbonyl)ethylthio)propyltrimethoxysilane> 9.6 g of 1-t-butylcyclopentyl acrylate and 9.8 g of 3-mercaptopropyltrimethoxysilane were mixed with 20 mL of methyl ethyl ketone, and 0.3 g of 1,1'-azobis(cyclohexane-1-carbonitride) was added and the mixture was stirred uniformly. Then, nitrogen was blown in for 30 minutes to perform nitrogen bubbling. After that, the reaction mixture was heated in nitrogen from room temperature to 90°C over 30 minutes. It was then maintained at 90°C for 7 hours. The methyl ethyl ketone was removed from the reaction mixture using a rotary evaporator. Further vacuum drying was performed to obtain 17.9 g of the target compound as a colorless liquid. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 0.89 (s, 9H), 1.56-1.81 (m, 10H), 2.42 (t, 2H), 2.58 (t, 2H), 2.83 (t, 2H), 3.55 (s, 9H).

[0311] <Synthesis Example 5: Synthesis of Tetrakis(bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium))(1,3-bis(3-(2-(1-t-butylcyclopentyloxycarbonyl)ethylthio)propyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-5))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that (3-(2-(1-t-butylcyclopentyloxycarbonyl)ethylthio)propyl)trimethoxysilane was used as the starting compound instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.67 (t, 4H), 0.89 (s, 18H), 1.39 (s, 12H), 1.56-2.00 (m, 52H) , 2.42 (t, 4H), 2.58 (t, 4H), 2.67 (t, 4H), 7.10 (d, 16H), 7.44 (d, 8H), 7.77 (d, 16H), 8.03 (d, 8H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.04 (s, 1Si). ESI-MS: POSITIVE m / z 641.2 ([C ２５ H ２３ I ２ O ２ S] ＋ ) NEGATIVE m / z 822.1 (median) ([C ３０ H ５４ O ４４ S ２ Si ３ W １１ ] ４－ )

[0312] <Manufacturing Example 11: Di(1-t-butylcyclopentyl) (2E)-buta-2-engioate> 1-t-butylcyclopentanol (20.0 g), dichloromethane (60 g), and triethylamine (21.3 g) were charged and cooled with ice while stirring. Fumaryl chloride (10.3 g) was added and stirred for 1 hour. Then, 5% potassium carbonate aqueous solution (60 g) was charged and stirred. After stopping stirring, the aqueous layer was removed and washed with ultrapure water (60 g). The organic layer was concentrated under reduced pressure to obtain 18.9 g of the target compound. 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).

[0313] <Manufacturing Example 12: Di(1-t-butylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanediate> In Production Example 10, the target compound was obtained by the same method as described above, except that di(1-t-butylcyclopentyl)(2E)-buta-2-engioate was used as the raw material compound instead of 1-t-butylcyclopentyl acrylate. 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).

[0314] <Synthesis Example 6: Synthesis of Tetrakis(bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-t-butylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-6))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(1-t-butylcyclopentyl)2-(3-(trimethoxysilyl)propylthio)butanediate was used as the starting compound instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 0.95 (s, 36H), 1.39 (s, 12H), 1.62-1.82 (m, 52H), 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 (d, 16H), 7.44 (d, 8H), 7.77 (d, 16H), 8.03 (d, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.05 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 641.2 ([C ２５ H ２３ I ２ O ２ S] ＋) NEGATIVE m / z 906.2 (median) ([C ５０ H ８６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0315] <Manufacturing Example 13: Di(1-phenylcyclopentyl)(2E)-buta-2-engioate> In Production Example 11, the target compound was obtained by the same method as described above, except that 1-phenylcyclopentanol was used instead of 1-t-butylcyclopentanol as the raw material compound. 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).

[0316] <Manufacturing Example 14: Di(1-phenylcyclopentyl) 2-(3-(trimethoxysilyl)propylthio)butanediate> In Production Example 10, the target compound was obtained by the same method as described above, except that di(1-phenylcyclopentyl)(2E)-buta-2-engioate was used as the raw material compound instead of 1-t-butylcyclopentyl acrylate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 2H), 1.62-1.82 (m, 10H), 1.90-2.10 ( m, 4H), 2.20-2.32 (m, 4H), 2.50-2.80 (m, 4H), 3.45-3.50 (m, 10H), 7.10-7.39 (m, 10H).

[0317] <Synthesis Example 7: Synthesis of Tetrakis(bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium)(1,3-bis(3-(1,2-bis(1-phenylcyclopentyloxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-7))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(1-phenylcyclopentyl)2-(3-(trimethoxysilyl)propylthio)butanediate was used as the starting compound instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 12H), 1.62-1.82 (m, 52H), 1.90-2.10 (m, 8H) , 2.20-2.32 (m, 8H), 2.50-2.80 (m, 8H), 3.45-3.50 (m, 2H), 7.10-7.44 (m, 44H), 7.77 (d, 16H), 8.03 (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 641.2 ([C ２５ H ２３ I ２ O ２ S] ＋ ) NEGATIVE m / z 926.2 (median) ([C ５８ H ７０ O ４８ S ２ Si ３ W １１ ] ４－ )

[0318] <Synthesis Example 8: Synthesis of Tetrakis(bis(4-iodophenyl)(phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-8))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(4-iodophenyl)(phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.49-1.84 (m, 22H), 2.37-2.42 (m, 4H), 7.10 (d, 16H), 7.36 (m, 20H), 7.77 (d, 16H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 514.9 ([C １８ H １３ I ２ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0319] <Production Example 15: Diphenyl (4-(1-ethylcyclopentyloxycarbonyl)phenyl) sulfonium chloride> Under a nitrogen atmosphere, 1.71 g (15 mmol) of 1-ethylcyclopentanol was dissolved in 100 mL of anhydrous THF. Then, 2.04 g (12.6 mmol) of carbonyldiimidazole, dissolved in 20 mL of anhydrous THF, was slowly added dropwise at room temperature. After stirring the reaction mixture for 3 hours, 4.3 g (12.6 mmol) of 4-carboxyphenyldiphenylsulfonium chloride, dissolved in 20 mL of anhydrous THF, was slowly added dropwise under reflux. The reaction mixture was then stirred under reflux for 12 hours and cooled to room temperature. Next, liquid-liquid extraction was performed with ethyl acetate and pure water, and the organic phase was washed three times with pure water. The solvent was evaporated using a rotary evaporator, and 2.48 g of the target compound was obtained by recrystallization. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 3H), 1.63-2.00 (m, 10H), 7.33-7.36 (m, 10H), 7.44 (d, 2H), 8.03 (d, 2H).

[0320] <Synthesis Example 9: Synthesis of Tetrakis(diphenyl(4-(1-ethylcyclopentyloxycarbonyl)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-9))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that diphenyl(4-(1-ethylcyclopentyloxycarbonyl)phenyl)sulfonium chloride was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide as the starting compound. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 0.90 (t, 12H), 1.49-2. 00 (m, 62H), 2.37-2.42 (m, 4H), 7.33-7.36 (m, 40H), 7.44 (d, 8H), 8.03 (d, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 403.2 ([C ２６ H ２７ O ２ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0321] <Synthesis Example 10: Synthesis of Tetrakis(bis(4-fluorophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-10))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(4-fluorophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.39 (s, 12H), 1.49-1. 84 (m, 54H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.96 (d, 8H), 7.20-7.33 (m, 40H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 455.1 ([C ２６ H ２５ F ２ O ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0322] <Production Example 16: Bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide> In Production Example 6, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide as the starting compound, and 2-t-butyl bromoacetate was used instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.42 (s, 9H), 4.99 (s, 2H), 6.75-6.95 (m, 7H), 7.10 (d, 1H), 7.34 (s, 1H).

[0323] <Synthesis Example 11: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-11))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.42 (s, 36H), 1.49-1.84 (m, 2 2H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 591.0 ([C ２４ H ２０ F ４ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0324] <Production Example 17: Bis(3,5-difluorophenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide> In Production Example 6, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide as the starting compound, and 2-1-ethylcyclopentyl bromoacetate was used instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.90 (t, 3H), 1.49-1.81 (m, 10H), 4 99 (s, 2H), 6.75-6.81 (m, 6H), 6.95 (d, 1H), 7.10 (d, 1H), 7.34 (s, 1H).

[0325] <Synthesis Example 12: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-12))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-(1-ethylcyclopentyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 0.90 (t, 12H), 1.49-1.84 (m, 6 2H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 631.0 ([C ２７ H ２４ F ４IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0326] <Production Example 18: Bis(3,5-difluorophenyl)(2-iodo-4-(1-i-propylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide> In Production Example 6, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide as the starting compound, and 2-1-i-propylcyclopentyl bromoacetate was used instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.88 (d, 6H), 1.56-1.81 (m, 8H), 2.09 (qq, 1H), 4.99 (s, 2H), 6.75-6.81 (m, 6H), 6.95 (d, 1H), 7.10 (d, 1H), 7.34 (s, 1H).

[0327] <Synthesis Example 13: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-i-propylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-13))> The target compound was obtained by the same method as described above, except that in Synthesis Example 1, bis(3,5-difluorophenyl)(2-iodo-4-(1-i-propylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 0.88 (d, 24H), 1.49-1.84 (m, 54H), 2. 09 (sep, 4H), 2.37-2.42 (m, 4H), 4.99 (s, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 645.1 ([C ２８ H ２６ F ４ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0328] <Production Example 19: Bis(3,5-difluorophenyl)(2-iodo-4-(1-phenylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide> In Production Example 6, the target compound was obtained in the same manner as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide as the starting compound, and 2-1-phenylcyclopentyl bromoacetate was used instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.63-2.17 (m, 8H), 4.99 (s, 2H), 6.75-6.95 (m, 7H), 7.10-7.34 (m, 5H), 7.54 (d, 2H).

[0329] <Synthesis Example 14: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-phenylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-14))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(2-iodo-4-(1-phenylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.49-2.17 (m, 54H), 2.37- 2.42 (m, 4H), 4.99 (s, 8H), 6.75-6.95 (m, 28H), 7.10-7.34 (m, 20H), 7.54 (d, 8H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 679.0 ([C ３１ H ２４ F ４ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0330] <Production Example 20: Bis(3,5-difluorophenyl)(2-iodo-4-(3-methyl-2-cyclohexene-1-yloxycarbonylmethyloxy)phenyl)sulfonium bromide> In Production Example 6, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide was used instead of bis(4-fluorophenyl)(4-hydroxy-2-iodophenyl)sulfonium bromide as the starting compound, and 3-methyl-2-cyclohexenyl bromoacetate was used instead of 1-methylcyclopentyl bromoacetate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 1.60-2.01 (m, 9H), 4.90 (s, 2H), 5. 13 (m, 1H), 5.37 (d, 1H), 6.75-6.95 (m, 7H), 7.10 (d, 1H), 7.34 (s, 1H).

[0331] <Synthesis Example 15: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(3-methyl-2-cyclohexen-1-yloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(2-(1-methylcyclopentyloxycarbonyl)ethyl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-15))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that bis(3,5-difluorophenyl)(2-iodo-4-(3-methyl-2-cyclohexen-1-yloxycarbonylmethyloxy)phenyl)sulfonium bromide was used as the starting compound instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.77-0.81 (m, 4H), 1.49-2.01 (m, 58H), 2.37-2.42 (m, 4H) H), 4.90 (s, 8H), 5.13 (m, 4H), 5.37 (d, 4H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.12 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 629.0 ([C ２７H ２２ F ４ IO ３ S] ＋ ) NEGATIVE m / z 764.4 (median) ([C １８ H ３０ O ４４ Si ３ W １１ ] ４－ )

[0332] <Manufacturing Example 21: Manufacturing of di(3-methyl-2-cyclohexen-1-yl)(2E)-buta-2-engioate> In Production Example 11, the target compound was obtained by the same method as described above, except that 3-methyl-2-cyclohexen-1-ol was used as the raw material compound instead of 1-t-butylcyclopentanol. 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).

[0333] <Manufacturing Example 22: Manufacturing of di(3-methyl-2-cyclohexen-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediote> In Production Example 10, the target compound was obtained by the same method as described above, except that di(3-methyl-2-cyclohexen-1-yl)(2E)-buta-2-engioate was used instead of 1-t-butylcyclopentyl acrylate. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.56 (t, 2H), 1.62-2.01 (m, 20H), 2.60 (t, 2H) , 2.85 (m, 1H), 3.10 (m, 1H), 3.55 (s, 9H), 4.00 (t, 1H), 5.13 (q, 2H), 5.37 (d, 2H).

[0334] <Synthesis Example 16: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(3-(1,2-bis((3-methyl-2-cyclohexen-1-yl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-16))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(3-methyl-2-cyclohexen-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 12H), 1.56-2.01 (m, 72H), 2.60 (t, 4H), 2.85 (m, 2H) , 3.10 (m, 2H), 4.00 (t, 2H), 4.99 (s, 8H), 5.13 (q, 4H), 5.37 (d, 4H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.03 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 617.0 ([C ２６ H ２２ F ４ IO ３ S] ＋ ) NEGATIVE m / z 876.4 (median) ([C ４２ H ６２ O ４８ S ２ Si ３ W １１ ] ４－ )

[0335] <Synthesis Example 17: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis((3-methyl-2-cyclohexen-1-yl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-17))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(3-methyl-2-cyclohexen-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.42 (s, 36H), 1.62-2.01 (m, 40H), 2.60 (t, 4H), 2.85 (m, 2H) , 3.10 (m, 2H), 4.00 (t, 2H), 4.99 (s, 8H), 5.13 (q, 4H), 5.37 (d, 4H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (d, 4H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.03 (s, 2Si), -85.02 (s, 1Si). ESI-MS: POSITIVE m / z 591.0 ([C ２４ H ２０ F ４ IO ３ S] ＋ ) NEGATIVE m / z 876.4 (median) ([C ４２ H ６２ O ４８ S ２ Si ３ W １１ ] ４－)

[0336] <Manufacturing Example 23: Manufacturing of di(2-cyclopenten-1-yl)(2E)-buta-2-engioate> In Production Example 11, the target compound was obtained in the same manner as described above, except that 2-cyclopenten-1-ol was used as the raw material compound instead of 1-t-butylcyclopentanol. 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).

[0337] <Manufacturing Example 24: Manufacturing of di(2-cyclopenten-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediote> In Production Example 10, the target compound was obtained by the same method as described above, except that di(2-cyclopenten-1-yl)(2E)-buta-2-engioate was used instead of 1-t-butylcyclopentyl acrylate. 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).

[0338] <Synthesis Example 18: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(3-(1,2-bis((2-cyclopenten-1-yl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-18))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(2-cyclopenten-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 12H), 1.56-1.81 (m, 36H), 2.02-2.33 (m, 16H), 2.60 (t, 4H), 2.85 (m, 2H), 3.10 (m, 2H), 4.00 (t, 2H), 4.99 (s, 8H), 5.45 (m, 4H), 5.60-5.61 (m, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (d, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 617.0 ([C ２６ H ２２ F ４ IO ３ S] ＋ ) NEGATIVE m / z 847.9 (median) ([C ３４ H ４６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0339] <Synthesis Example 19: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis((2-cyclopenten-1-yl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-19))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(2-cyclopenten-1-yl)2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.42 (s, 36H), 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), 4.99 (s, 8H), 5.45 (m, 4H), 5.60-5.61 (m, 8H), 6.75-6.95 (m, 28H), 7.10 (d, 4H), 7.34 (s, 4H). ２９ Si-NMR (119.22 MHz, DMSO-d6): δ (ppm) = -53.02 (s, 2Si), -85.01 (s, 1Si). ESI-MS: POSITIVE m / z 591.0 ([C ２４ H ２０ F ４ IO ３ S] ＋ ) NEGATIVE m / z 847.9 (median) ([C ３４ H ４６ O ４８ S ２ Si ３ W １１ ] ４－ )

[0340] <Manufacturing Example 25: Manufacturing of di(1-indanyl)(2E)-buta-2-engioate> In Production Example 11, the target compound was obtained in the same manner as described above, except that 1-indanol was used instead of 1-t-butylcyclopentanol as the raw material compound. 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).

[0341] <Manufacturing Example 26: Manufacturing of di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanediote> In Production Example 10, the target compound was obtained in the same manner as described above, except that di(1-indanyl)(2E)-buta-2-engioate was used instead of 1-t-butylcyclopentyl acrylate. 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).

[0342] <Synthesis Example 20: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium)(1,3-bis(3-(1,2-bis((1-indanyl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungus silicate (polyate (A-20))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(2-iodo-4-(1-methylcyclopentyloxycarbonylmethyloxy)phenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.39 (s, 12H), 1.56-1.81 (m, 36H), 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), 4.99 (s, 8H), 6.08 (t, 4H), 6.75-6.95 (m, 28H), 7.06-7.34 (m, 24H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 617.0 ([C ２６ H ２２ F ４ IO ３ S] ＋ ) NEGATIVE m / z 898.4 (median) ([C ５０ H ５４ O ４８ S ２ Si ３ W １１ ] ４－ )

[0343] <Synthesis Example 21: Synthesis of Tetrakis(bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium)(1,3-bis(3-(1,2-bis((1-indanyl)oxycarbonyl)ethylthio)propan-1-yl)disiloxane-1,1,3,3-tetrayl)undecatungustosilicate(polyate (A-21))> In Synthesis Example 1, the target compound was obtained by the same method as described above, except that di(1-indanyl) 2-(3-(trimethoxysilyl)propylthio)butanediate was used instead of (2-(1-methylcyclopentyloxycarbonyl)ethyl)trimethoxysilane as the starting compound, and bis(3,5-difluorophenyl)(4-(t-butyloxycarbonylmethyloxy)-2-iodophenyl)sulfonium bromide was used instead of bis(4-iodophenyl)(4-(1-methylcyclopentyloxycarbonyl)phenyl)phenyl)sulfonium bromide. １ H-NMR (400MHz, DMSO-d6): δ (ppm) = 0.52-0.68 (m, 4H), 1.42 (s, 36H), 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), 4.99 (s, 8H), 6.08 (t, 4H), 6.75-6.95 (m, 28H), 7.06-7.34 (m, 24H). ２９ Si-NMR (119.22MHz, DMSO-d6): δ (ppm) = -53.04 (s, 2Si), -85.03 (s, 1Si). ESI-MS: POSITIVE m / z 591.0 ([C ２４ H ２０ F ４ IO ３ S] ＋ ) NEGATIVE m / z 898.4 (median) ([C ５０ H ５４ O ４８ S ２ Si ３ W １１ ] ４－ )

[0344] [2. Preparation of Test Resist Materials] As test resist materials, the poly salts (A-1) to (A-21) synthesized above, the acid diffusion control agents (B-1) to (B-3) shown below, and organic solvents (γ-butyrolactone, cyclopentanone) were blended in the amounts shown in Tables 1 to 3 below (unit: parts by mass) to prepare test resist materials (R-1) to (R-23).

[0345] Furthermore, the following acid diffusion control agents (B-1) to (B-3) were used as the (B) acid diffusion control agents listed in Tables 1 to 3. • Acid diffusion control agent (B-1): An acid diffusion control agent which is a salt of a triphenylsulfonium cation represented by the following formula (B-1) and a salicylate anion. • Acid diffusion control agent (B-2): An acid diffusion control agent that is a salt of the (4-(1-ethylcyclopentyloxycarbonylmethyloxy)-3,5-dimethylphenyl)diphenylsulfonium cation, represented by the following formula (B-2), and the salicylate anion. • Acid diffusion control agent (B-3): An acid diffusion control agent which is a salt of the triphenylsulfonium cation represented by (B-3) below and the heptafluorobutyrate anion.

[0346]

[0347]

[0348]

[0349] [3. Formation of Resist Patterns] Each test resist material (R-1) to (R-23) was applied to an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner. A post-application bake (PAB) treatment was performed on a hot plate at 120°C for 60 seconds, followed by drying to produce a resist film with a thickness of 50 nm. The thickness of the formed resist film was measured using a film thickness measuring device (M-2000D, manufactured by J.A. Wollam). The resist film was then subjected to drawing (exposure) using an electron beam lithography system F7000S-VD2 (manufactured by Advantest Corporation) at an acceleration voltage of 50 kV, with a target size of a 1:1 line-and-space pattern (hereinafter also referred to as "LS pattern") with a line width of 50 nm. Subsequently, a post-exposure heating (post-exposure bake (PEB)) treatment was performed at 90°C for 60 seconds. Next, development was performed at 23°C using a developer (NMD-W (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) for 60 seconds, followed by rinsing with pure water for 60 seconds. As a result, a 1:1 LS pattern with a line width of 50 nm was formed, and test LS patterns (LS-1) to (LS-23) corresponding to each test resist material (R-1) to (R-23) were obtained. All of the above test LS patterns are positive type patterns.

[0350] [4. Evaluation of Test LS Patterns] <Evaluation of Sensitivity> The optimal exposure dose Eop (μC / cm²) for forming a 1:1 LS pattern with a line width of 50 nm using the above method for forming test LS patterns is obtained. ２ The values ​​for each were calculated. The results are shown in Table 4.

[0351] <Evaluation of Defects> For the above test LS patterns, the total number of defects in the wafer was measured using a surface defect observation device (product name: KLA2905, manufactured by KLA-Tencor). The defects were limited to foreign matter and defects on the surface of the coated film with a size of 1 μm or larger, and the average value of 10 measurements per sample was defined as the "number of defects". The number of defects for each test LS pattern was divided by the number of defects for test LS pattern LS-10 and evaluated according to the following evaluation criteria. The results are shown in Table 4. A: Less than 0.2 B: 0.2 or more and less than 0.5 C: 0.5 or more and less than 1.0 D: 1.0 or more

[0352]

[0353] From the results in Table 4, compared to test resist materials R-11 and R-12 containing polyates (A-9) or (A-10) that have polar groups with acid-dissociable groups but do not contain an iodine atom, test resist materials R-1 to R-9 and R-13 to R-23 containing polyates (A-1) to (A-7) or (A-11) to (A-21) that have polar groups with acid-dissociable groups and contain an iodine atom-containing organic sulfonium cation yielded a lower optimal exposure dose Eop (μC / cm²). ２ The value of ) is given, and it can be seen that the sensitivity is good.

[0354] Furthermore, the results in Table 4 show that, compared to test LS pattern LS-10, which contains polyates (A-8) containing an organic sulfonium cation that has an iodine atom but does not have a polar group with an acid-dissociable group, test LS patterns LS-1 to LS-9 and LS-13 to LS-23, which contain polyates (A-1) to (A-7) or (A-13) to (A-21) that have a polar group with an acid-dissociable group and an organic sulfonium cation containing an iodine atom, all gave good defect evaluations, indicating a reduction in foreign matter and defects on the surface of the coated film after development.

[0355] Furthermore, the results in Table 4 show that the defect evaluation is very good for test LS patterns LS-6, LS-7, and LS-18 to LS-23, which contain polyate salts having four polar groups with acid-dissociable groups in the anionic portion, such as polyate salts (A-6), (A-7), and (A-16) to (A-21).

Claims

1. A heteropolyate or mixture thereof modified with a defect site, wherein the cation portion of the heteropolyate or mixture thereof modified with a defect site contains an organic sulfonium cation, and the organic sulfonium cation has one or more acid-dissociable polar groups and one or more iodine atoms.

2. A heteropoly salt or mixture thereof, in which the defective site is modified according to claim 1, wherein the acid-dissociable group is a tertiary carbon type acid-dissociable group, an allyl type or benzyl type acid-dissociable group, or an acetal type acid-dissociable group.

3. The heteropoly salt or mixture thereof with a modified defect site according to claim 1, wherein the organic sulfonium cation is a triarylsulfonium cation which may have substituents, one or more hydrogen atoms on one or more aryl groups of the triarylsulfonium cation are substituted with a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, and one or more hydrogen atoms on one or more aryl groups of the triarylsulfonium cation are substituted with an iodine atom.

4. The heteropolyacid salt or a mixture thereof, in which the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (VIII), with the defect site modified as described in claim 1. [In formula (VIII), Ar ３Ａ ~Ar ３Ｃ each independently represents a C ６－１８ aryl group which may have a substituent; any two of the above Ar ３Ａ ~Ar ３Ｃ are directly linked to each other by a single bond or through a divalent linking group which is a C １－３ alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ -, and may form a ring together with the sulfur atom in formula (VIII); at least one or more hydrogen atoms on the above Ar ３Ａ , Ar ３Ｂ or Ar ３Ｃ are substituted by a polar group having an acid dissociable group or an organic group containing a polar group having an acid dissociable group; at least one or more hydrogen atoms on the above Ar ３Ａ , Ar ３Ｂ or Ar ３Ｃ are substituted by iodine atoms. ] 5. The heteropoly salt or mixture thereof with a modified defect site according to claim 1, wherein the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (IX-1) or (IX-2). [In formula (IX-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom; o1, p1, and q1 each represent integers from 0 to 3; r1, s1, and t1 each represent integers from 0 to 5; u1, v1, and w1 each represent integers from 0 to 5; o1 + p1 + q1 is an integer greater than or equal to 1; r1 + s1 + t1 is an integer greater than or equal to 1; and o1 + r1 + u1, p1 + s1 + v1, and q1 + t1 + w1 each represent integers from 0 to 5. [In formula (IX-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ The expression represents -, where o2, p2, and q2 each represent integers from 0 to 3, r2 and u2 each represent integers from 0 to 5, s2, t2, v2, and w2 each represent integers from 0 to 4, o2 + p2 + q2 is an integer greater than or equal to 1, r2 + s2 + t2 is an integer greater than or equal to 1, o2 + r2 + u2 is an integer from 0 to 5, and p2 + s2 + v2 and q2 + t2 + w2 are integers from 0 to 4.

6. The heteropoly salt or mixture thereof with a modified defect site according to claim 1, wherein the organic sulfonium cation is an organic sulfonium cation represented by the following general formula (IX-1-1) or (IX-2-1). [In formula (IX-1-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom. o11 represents an integer from 1 to 3, p11 and s11 each represent integers from 0 to 4, q11, r11, t11, and u11 each represent integers from 0 to 5, p11 + q11 + r11 is an integer greater than or equal to 1, o1 + p11 + s11 is an integer from 1 to 5, and q11 + t11 and r11 + u11 each represent integers from 0 to 5. [In formula (IX-2-1), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ [This represents a negative value, where o21 represents an integer between 1 and 3, p21, q21, and r21 each represent integers between 0 and 4, s21, t21, and u21 each represent integers between 0 and 4, p21 + q21 + r21 is an integer greater than or equal to 1, o21 + p21 + s21 is an integer between 1 and 5, and q21 + t21 and r21 + u21 each represent integers between 0 and 4.] 7. The heteropoly salt or mixture thereof with a modified defect site according to claim 6, wherein the organic sulfonium cation represented by the general formula (IX-1-1) is an organic sulfonium cation represented by the following general formula (IX-1-2) or (IX-1-3). [In formula (IX-1-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ , R ４Ｂ and R ４Ｃ Each of these independently represents a substituent other than the iodine atom, where o12 represents an integer of 1 or 2, p12 represents an integer from 1 to 4, q12 represents an integer from 0 to 3, r12 and s12 each represent integers from 0 to 5, and o12 + p12 + q12 is an integer from 2 to 5. [In formula (IX-1-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ａ 'x' represents a substituent other than the iodine atom, 'o13' represents an integer of 1 or 2, 'p13' and 'q13' each represent an integer from 0 to 5, 'r13' represents an integer from 0 to 4, 'p13 + q13' is an integer of 1 or more, and 'o13 + r13' is an integer from 1 to 5.

8. The heteropoly salt or mixture thereof with a modified defect site according to claim 6, wherein the organic sulfonium cation represented by the general formula (IX-2-1) is an organic sulfonium cation represented by the following general formula (IX-2-2) or (IX-2-3). [In formula (IX-2-2), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ , R ４Ｅ and R ４Ｆ Each of these independently represents a substituent other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ [This represents a negative value, where o22 represents an integer of 1 or 2, p22 represents an integer from 1 to 4, q22 represents an integer from 0 to 3, r22 and s22 each represent integers from 0 to 4, and o22 + p22 + q22 is an integer from 2 to 5.] [In formula (IX-2-3), ADG each independently represents a polar group having an acid-dissociable group or an organic group containing a polar group having an acid-dissociable group, I represents an iodine atom, and R ４Ｄ represents substituents other than the iodine atom, Z represents a single bond, C １－３ Alkylene group, -O-, -S-, -C(=O)-, -C(=O)-O-, -O(C=O)-, -CONH-, -NHCO-, -S(=O)-, or -SO ２ [This represents a negative value, o23 represents an integer of 1 or 2, p23, q23, and r23 each represent integers from 0 to 4, p23 + q23 is an integer greater than or equal to 1, and o23 + r23 is an integer from 1 to 5.] 9. The heteropoly salt or mixture thereof with a modified defect site, as described in claim 1, wherein the heteropoly salt or mixture thereof with a modified defect site is represented by general formula (I). (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [In formula (I), A ｍ＋ Each of them independently, H ＋ , metal ions, NH ４ ＋ , represents an onium cation or onium dication; B ｎ＋ Each independently represents an organic sulfonium cation, the organic sulfonium cation having one or more acid-dissociable polar groups and one or more iodine atoms; C （ａｍ＋ｂｎ）－ [wherein, m is an integer between 1 and 5, n is an integer between 1 and 2, a is a real number, and b is a real number greater than 0.] 10. The organic group containing the acid-dissociable polar group may have substituents. １－１８ A hydrocarbyl group in which the divalent carbon atoms at any position other than the terminals other than the bond of the organic group are -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ A heteropoly salt or mixture thereof, in which the defective site is modified according to any one of claims 3 to 8, wherein at least one hydrogen atom of the organic group is replaced by a polar group having an acid-dissociable group, even if it is replaced by a negative (provided that adjacent divalent carbon atoms are not replaced at the same time).

11. (A) A resist material containing a heteropolyate or a mixture thereof in which the defective site described in any one of claims 1 to 9 is modified.

12. The resist material according to claim 11, further comprising (B) an acid diffusion control agent.

13. A pattern forming method comprising the steps of: forming a resist film using the resist material described in claim 11; exposing the resist film; and developing the exposed resist film using a developer.

Images