Method for producing polyacid salts or mixtures thereof, and method for removing impurities

Abstract

The present invention provides a method for producing polyacid salts or mixtures thereof, wherein impurities can effectively be removed without decomposing polyacid anions, which are the anion portions of the polyacid salts or mixtures thereof, by washing polyacid salts having prescribed counter cations or mixtures of the polyacid salts with an acidic aqueous solution having a pH of 6 or less.

Description

Method for producing polyacid salts or mixtures thereof, and method for removing impurities

[0001] The present invention relates to a method for producing a polyacid salt or a mixture thereof, and a method for removing impurities.

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

[0003] Polyacids are susceptible to various chemical changes, such as pH, ionic strength, and redox potential, and these chemical changes are known to affect the structure, framework, formation mechanism, and interaction network of anionic metal oxide clusters in polyacids.

[0004] Non-Patent Document 1 states that when the pH of isopolyoxotungstic acid exceeds 5, the main isopolyoxotungstic acid species is H ｍ [W ＶＩ ７ O ２４ ] （６－ｍ）－ and paratungstate anion ([W １２ O ４２ ] type H ｍ [W ＶＩ １２ O ４０ (OH) ２ ] （１０－ｍ）－), whereas at pH less than 5, metatungstate anion (α-[H ２ W ＶＩ １２ O ４０ ] ６－ ) is the main isopolyoxotungstic acid species, and under strong acidic conditions, [W ＶＩ １０ O ３２ ] ４－ has been shown to be the predominant isopolyoxotungstate species.

[0005] Furthermore, Non-Patent Document 1 states that when the pH of silicotungstic acid is less than 4.5, [Si ＩＶ W ＶＩ １２ O ４０ ] ４－ is stable, whereas when the pH is 5-6, [Si ＩＶ W ＶＩ １１ O ３９ ] ８－ However, at around pH 8, [Si ＩＶ W ＶＩ ９ O ３４ ] １０－ have been shown to be the major tungstosilicic acid species.

[0006] In Non-Patent Document 2, it is reported that polyacids are affected by various chemical changes such as pH, ionic strength, and redox potential, and that [W １１ O ３８ ], [W １２ O ４２ ], [W ２２ O ７４ ], [W ３４ O １１６ ], [W ３６ O １２０ ], it is mentioned that the above reaction can be programmed and controlled in both the time domain and the spatial domain.

[0007] Nadia I. Gumerova et al. , “Polyoxometalates in solution: specification under spotlight”, Chem. Soc. Rev. , 2020, 49, 7568-7601. Andrew Ruiz de la Oliva et al. , “Coding the Assembly of Polyoxotungstates with a Programmable Reaction System”, Inorg. Chem. , 2017, 56, 5089-5095.

[0008] The cation moiety of a polyacid salt or a mixture thereof can be replaced with a predetermined counter cation by performing a salt exchange reaction, an ion exchange reaction, or the like. By introducing a functional cation into the cation moiety of a polyacid salt or a mixture thereof, a building block of a functional polyacid or a mixture thereof can be constructed. On the other hand, when a polyacid salt or a mixture thereof having the above-mentioned predetermined counter cation is precipitated by recrystallization or the like, the obtained polyacid salt or mixture thereof contains impurities such as metal ions that were the original counter cations. It has been difficult to remove these impurities by washing with pure water or an organic solvent.

[0009] As a result of extensive investigations aimed at solving the above-mentioned problems, the present inventors have found that when a polyacid salt having a predetermined counter cation or a mixture thereof is washed with an acidic aqueous solution having a pH of 6 or less, impurities can be effectively removed without decomposing the polyacid anion, which is the anion moiety of the polyacid salt or the mixture thereof, and have completed the present invention.

[0010] That is, the present invention relates to the following inventions: <1> A method for producing a polyacid salt or a mixture thereof, comprising a step of washing a polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein A ｍ＋are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａｍ＋ｂｎ）－ represents a polyacid anion; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.] <2> The method for producing a polyacid salt or a mixture thereof according to <1>, wherein the polyacid anion is an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxoniobate anion, or an isopolyoxotantalate anion. <3> The method for producing a polyacid salt or a mixture thereof according to <1>, wherein the polyacid anion is a heteropolyacid anion, wherein a polyatom of the heteropolyacid anion is Mo, W, V, Nb, or Ta, and a heteroatom is P, Si, B, S, or Ge. <4> The method for producing a polyacid salt or a mixture thereof according to <1>, wherein the onium cation or dication is an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication. <5> The step of washing with an acidic aqueous solution having a pH of 6 or less is carried out to remove metals or metal ions selected from Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au in the polyacid salt or mixture thereof represented by general formula (I), and the polyatoms, heteroatoms, and A in the polyacid salt or mixture thereof are removed. ｍ＋<6> A method for producing a polyacid salt or a mixture thereof, comprising the steps of: substituting a cation moiety of a polyacid salt represented by general formula (IX-1) or a mixture thereof with an ammonium ion or an ammonium cation by a salt exchange reaction; further performing salt exchange with a compound represented by general formula (IX-2); and washing the produced polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. (A' ｍ’＋ ) ａ’ (C （ａ’ｍ’）－ ) (IX-1) (B ｎ＋ ) (Y － ) ｎ (IX-2) (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein, A' ｍ’＋ are each independently H ＋ , a metal ion, or an ammonium ion; ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａ’ｍ’）－ and C （ａｍ＋ｂｎ）－ represents a polyanion; Y － represents a monovalent counter anion; m and m' are integers of 1 to 5, n is an integer of 1 or 2, a is a real number, and a' and b are real numbers greater than 0.] <7> A method for removing impurities from a polyacid salt represented by general formula (I) or a mixture thereof, the method comprising the step of washing the polyacid salt or the mixture with an acidic aqueous solution having a pH of 6 or less. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein A ｍ＋ are each independently H ＋, a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａｍ＋ｂｎ）－ represents a polyacid anion; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0011] According to the present invention, it is possible to produce a polyacid salt or a mixture thereof with a high purity and with fewer impurities. Furthermore, the method for producing a polyacid salt or a mixture thereof according to the present invention allows impurities to be effectively removed without decomposing the polyacid anion, which is the anion portion of the polyacid salt or a mixture thereof, and is therefore suitable as a method for producing a high-purity polyacid salt or a mixture thereof. Furthermore, by substituting the cation portion of the polyacid salt or a mixture thereof with an ammonium ion or an organic ammonium cation and then carrying out a salt exchange reaction with a predetermined onium cation or dication, it is possible to produce a polyacid salt represented by general formula (I) or a mixture thereof with even higher purity.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0040] As used herein, "C １－１８ The term "hydrocarbyloxycarbonylamino group" refers to a group consisting of "C １－１８"C" means a group in which a "hydrocarbyloxycarbonyl group" is bonded to an amino group. １－１８ The "hydrocarbyloxycarbonylamino group" is not particularly limited, and examples thereof include "C" such as a methoxycarbonylamino group, an ethoxycarbonylamino group, an n-propoxycarbonylamino group, an i-propoxycarbonylamino group, an n-butoxycarbonylamino group, and a t-butoxycarbonylamino group. １－１８ alkoxycarbonylamino group"; cyclopropyloxycarbonylamino group, cyclohexyloxycarbonylamino group, etc. ３－１８ alicyclic oxycarbonylamino group"; phenyloxycarbonylamino group, 1-naphthyloxycarbonylamino group, etc. ６－１８ aryloxycarbonylamino group" and the like.

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

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

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

[0044] As used herein, the term "acid-dissociable group" refers to a group that substitutes a hydrogen atom of a hydroxy group (including a phenolic hydroxy group) or a carboxy group, and that dissociates under the action of an acid. Examples of the acid-dissociable group include acid-dissociable groups G for hydroxy groups or carboxy groups, which are represented by the following general formula (G-1) or (G-2):

[0045] The acid-dissociable group G is not particularly limited as long as it dissociates under the action of an acid, and any known and commonly used group can be used. Examples of the acid-dissociable group G include "tertiary carbon-type acid-dissociable groups G" represented by the following general formula (g-1): Ａ " etc.

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

[0047] "R Ａ ｇ１ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0048] R Ａ ｇ１ As the C １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－１２ an alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0049] Also, "R Ａ ｇ２ " and "R Ａ ｇ３ " are each independently a C １－１２ A hydrocarbyl group in which a divalent carbon atom at any position except the terminal is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), or R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0050] R Ａ ｇ２ and R Ａ ｇ３ As for R Ａｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and a divalent carbon atom at any position except the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ３－１８ The alicyclic group or the 3- to 18-membered non-aromatic heterocyclic group contains a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and a divalent carbon atom at any position excluding the terminal is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is more preferable that the group may be substituted with - (provided that adjacent divalent carbon atoms are not simultaneously substituted).

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

[0052] <<Tertiary carbon type acid dissociable group G Ａ１ and G Ａ２>> Also, the "tertiary carbon-type acid-dissociable group G" represented by general formula (g-1) Ａ " In R Ａ ｇ２ and R Ａ ｇ３ are combined to form C which may have a substituent. ３－１８ In the case where an alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, for example, a tertiary carbon-type acid-dissociable group G represented by the following general formula (g-1-1) is included: Ａ１ and a tertiary carbon-type oxygen-dissociating group G represented by (g-1-2): Ａ２ etc.

[0053] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1) Ａ１ >> A tertiary carbon-type acid-dissociable group G represented by the above general formula (g-1-1): Ａ１ In this case, R Ａ ｇ１１ is a C which may have a substituent １－１２ Alkyl group, C ３－１２ Alicyclic group, C ６－１２ an aryl group, or C ７－１２ An aralkyl group in which any divalent carbon atom excluding the terminal carbon atom is —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0054] Also Cy Ａ ｇ１ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0055] Cy Ａ ｇ１The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0056] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-1): Ａ１ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0057]

[0058]

[0059]

[0060] <<Tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2) Ａ２ >> In the above general formula (g-1-2), R Ａ ｇ２１ ~R Ａ ｇ２３ are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａｇ２２ and R Ａ ｇ２３ are directly connected to each other by a single bond or are divalently connected to each other by -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring.

[0061] R Ａ ｇ２１ and R Ａ ｇ２２ , and / or R Ａ ｇ２２ and R Ａ ｇ２３ Examples of the case where R 1 forms a ring together with the carbon atom contained in the ethylenically unsaturated double bond include the case where R 1 forms a cyclopentenyl group, a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group, or the like, which may have a substituent.

[0062] Also Cy Ａ ｇ２ represents a C which may have a substituent together with the tertiary carbon atom. ３－１８ An alicyclic group or a 3- to 18-membered non-aromatic heterocyclic group is formed, and any divalent carbon atom is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0063] Cy Ａ ｇ２The tertiary carbon atom may be, together with the tertiary carbon atom, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cyclododecane skeleton, a cyclopentene skeleton, a cyclohexene skeleton, a cycloheptene skeleton, a cyclooctene skeleton, a cyclodecene skeleton, a norbornane skeleton, an adamantane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a norbornene skeleton, or a tricyclodecene skeleton, and the divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, NHCO-, -S-, or -SO ２ It is preferably one which may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0064] A tertiary carbon-type acid-dissociable group G represented by general formula (g-1-2): Ａ２ Examples of the tertiary carbon-type acid-dissociable group include the following:

[0065]

[0066] As used herein, the term "hydroxy group or carboxy group having a protecting group" refers to a hydroxy group (including a phenolic hydroxy group) or a carboxy group protected with an ether-based protecting group, a silyl ether-based protecting group, an acetal-based protecting group, an acyl-based protecting group, an oxycarbonyl (alkyl)-based protecting group, an aminocarbonyl-based protecting group, or the like, or a hydroxy group (including a phenolic hydroxy group) or a carboxy group having an acid-dissociable group.

[0067] The ether-based protecting group is not particularly limited, and examples thereof include a methyl group, a benzyl group, a p-methoxybenzyl group, a t-butyl group, a triphenylmethyl group, a p-methoxyphenyldiphenylmethyl group, and a di(p-methoxyphenyl)phenylmethyl group. The silyl ether-based protecting group is not particularly limited, and examples thereof include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS). The acetal-based protecting group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxyethyl group, a 2-tetrahydropyranyl group (THP), and a methoxyethoxymethyl group. The acyl-based protecting group is not particularly limited, and examples thereof include an acetyl group, a pivaloyl group, and a benzoyl group. The oxycarbonyl (alkyl)-based protecting group is not particularly limited, and examples thereof include a t-butoxycarbonyl group. The aminocarbonyl protecting group is not particularly limited, and examples thereof include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0068] Examples of the protecting group include protecting groups P for hydroxy or carboxy groups represented by the following general formulae (P-1) and (P-2).

[0069] The protecting group P is not particularly limited, and known and commonly used protecting groups can be used. Examples of the protecting group P include, other than the above-mentioned "acid-dissociable group", "acetal-based protecting groups P" represented by the following general formula (p-1): Ａ ", "silyl ether-based protecting group P Ｂ ", "aminocarbonyl-based protecting group P Ｃ Each of these will be explained in turn below.

[0070] <Acetal-based protecting group P ＡThe protecting group P is an acetal protecting group P represented by the following general formula (p-1): Ａ A protecting group having an oxygen atom bonded to the carbon atom directly bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as:

[0071] "R Ａ ｐ１ " and "R Ａ ｐ３ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (however, adjacent divalent carbon atoms are not replaced at the same time). Ａ ｐ２ " is an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0072] R Ａ ｐ１ and R Ａ ｐ３ is a hydro group or a C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0073] R Ａ ｐ２ As the C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0074] An acetal-based protecting group P represented by general formula (p-1) Ａ Examples of the alkoxy group include a methoxymethoxy group, an ethoxymethoxy group, an n-propoxymethoxy group, an n-butoxymethoxy group, a 2,2-dimethylpropoxymethoxy group, a 2,2-dimethylbutoxymethoxy group, a cyclohexyloxymethoxy group, a 1-ethoxyethoxy group, a 1-n-butoxyethoxy group, and a 1-cyclohexyloxyethoxy group.

[0075] <Silyl ether protecting group P Ｂ The protecting group P is a silyl ether protecting group P represented by the following general formula (p-2): Ｂ A protecting group in which a silicon atom is directly bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as:

[0076] "R Ｂ ｐ１ " ~ "R Ｂ ｐ３ " each independently represents a C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0077] R Ｂ ｐ１ ~R Ｂ ｐ３ As the C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0078] A silyl ether protecting group P represented by general formula (p-2) Ｂ Examples of the silyl group include a t-butyldimethylsilyl group (TBS), a triisopropylsilyl group (TIPS), a trimethylsilyl group (TMS), a triethylsilyl group (TES), and a t-butyldiphenylsilyl group (TBDPS).

[0079]

[0080] <Aminocarbonyl protecting group P Ｃ The protecting group P is an aminocarbonyl protecting group P represented by the following general formula (p-3): Ｃ A protecting group in which an aminocarbonyl group is bonded to the oxygen atom of a hydroxy group, a phenolic hydroxy group, or a carboxy group, such as

[0081] "R Ｃ ｐ１ " and "R Ｃ ｐ２ " are each independently a hydro group or an optionally substituted C １－１２ In a hydrocarbyl group, any divalent carbon atom excluding the terminal carbon atom may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ may be replaced by - (provided that adjacent divalent carbon atoms are not replaced at the same time).

[0082] R Ｃ ｐ１ and R Ｃ ｐ２ is a hydro group or an optionally substituted C １－１２ Alkyl group or C ３－１２ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and １－６ Alkyl group or C ３－８ In an alicyclic group, any divalent carbon atom excluding the terminal carbon atoms may be —O—, —C(═O)—, —C(═O)O—, —OCO—, —CONH—, NHCO—, —S—, or —SO ２ It is more preferred that it may be substituted with - (provided that adjacent divalent carbon atoms are not substituted at the same time).

[0083] An aminocarbonyl-based protecting group P represented by general formula (p-3)Ｃ Examples of the aminocarbonyl group include a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a diisopropylaminocarbonyl group, and an N-phenyl-N-methyl-aminocarbonyl group.

[0084]

[0085] In this specification, the term "optionally having a substituent" is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the "substituent" include (1) a halogen atom, (2) a haloalkyl group, (3) a hydroxy group, (4) a thiol group, (5) a nitro group, (6) a cyano group, (7) a carboxy group, (8) an amino group, (9) a sulfo group, (10) a vinyl group, (11) an allyl group, (12) a (meth)acryloyl group, (13) a (meth)acryloyloxy group, (14) a (meth)acrylamide group, (15) a styryl group, (16) an epoxy group, (17) a glycidyl group, (18) an amide group, (19) a hydroxy group or a carboxy group having a protecting group, or (20) a C group in which at least a part of the hydrogen atoms may be substituted with the above (1) to (19). １－１８ Hydrocarbyl group, C １－１８ Hydrocarbyloxy group, C １－１８ Hydrocarbyl carbonyl group, C １－１８ Hydrocarbylcarbonyloxy group, C １－１８ Hydrocarbyloxycarbonyl group, C １－１８ Hydrocarbyloxycarbonyloxy group, C １－１８ Hydrocarbylamino group, diC １－１８ Hydrocarbylamino group, C １－１８ Hydrocarbylaminocarbonyl group, diC １－１８ Hydrocarbylaminocarbonyl group, C １－１８ Hydrocarbylcarbonylamino group, C １－１８ Hydrocarbylaminocarbonyloxy group, diC １－１８ Hydrocarbylaminocarbonyloxy group, C １－１８ Hydrocarbylaminocarbonylamino group, diC １－１８ Hydrocarbylaminocarbonylamino group, C １－１８ Hydrocarbyloxycarbonylamino group, C１－１８ Hydrocarbylthio group, C １－１８ Hydrocarbylsulfinyl group, C １－１８ A hydrocarbylsulfonyl group, in which a divalent carbon atom at any position except the terminal of the substituent is -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S-, or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time), etc.

[0086] [1. Method for Producing Polyacid Salt or a Mixture Thereof] The method for producing a polyacid salt or a mixture thereof according to this embodiment includes a step of washing a polyacid salt represented by the following general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａｍ＋ｂｎ）－ represents a polyacid anion; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

[0087] Hereinafter, the terms "polyacid anion," "onium cation or dication (B ｎ＋ )," "Other counter cations (A ｍ＋ After explaining the above, a method for producing the polyacid salt represented by the general formula (I) or a mixture thereof will be explained in order.

[0088] [1-2. Polyacid Anion] As the polyacid anion according to this embodiment, an isopolyacid anion or a heteropolyacid anion can be used.

[0089] [1-2-1. Isopolyacid Anion] The isopolyacid anion according to this embodiment is not particularly limited, and examples thereof include isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion.

[0090] Examples of the isopolyoxomolybdate anion include [MoO ４ ] ２－ , [Mo ７ O ２４ ] ６－ , [Mo ８ O ２６ ] ４－ Examples of the isopolyoxotungstate anion include [W ４ O １３ ] ２－ , [W ５ O １６ ] ２－ , [W ６ O １９ ] ２－ , [W ７ O ２２ ] ２－ , [W ７ O ２４ ] ６－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (wherein z represents an integer of 1 to 4), [W １０ O ３２ ] ４－ , [H ４ W １１ O ３８ ] ６－ , [H ７ W １１ O ４０ ] ７－ , [HW ５ O １９ ] ７－ , [H ３ W １１ O ２２ ] ５－ Examples of the isopolyoxovanadate anion include [V ４ O １２ ] ４－ , [V１０ O ２８ ] ６－ Examples of the isopolyoxoniobate anion include [Nb ６ O １９ ] ８－ , [Nb １０ O ２８ ] ６－ Examples of the isopolyoxotantalate anion include [Ta ６ O １９ ] ８－ , [Ta ８ O ２１ ] ２－ etc.

[0091] The above-mentioned isopolyoxomolybdate anion, isopolyoxotungstate anion, isopolyoxovanadate anion, isopolyoxoniobate anion, and isopolyoxotantalate anion include various isomers.

[0092] The isopolyoxotungstate anion may be selected from the group consisting of [W ４ O １３ ] ２－ , [W ５ O １６ ] ２－ , [W ６ O １９ ] ２－ , [W ７ O ２２ ] ２－ , [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (wherein z represents an integer of 1 to 4), [H ４ W １１ O ３８ ] ６－ , [H ７ W １１ O ４０ ] ７－ , [HW ５ O １９ ] ７－ , [H ３ W１１ O ２２ ] ５－ , [H ４ W ２２ O ７４ ] １２－ , or [H １０ W ３４ O １１６ ] １８－ It is preferable that [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ｚ W １２ O ４０ ] －（８－ｚ） (where z represents an integer of 1 to 4), and more preferably [W ７ O ２４ ] ６－ , [W １０ O ３２ ] ４－ , [H ２ W １２ O ４０ ] ６－ It is more preferable that:

[0093] [1-2-2. Heteropolyacid Anion] Examples of the heteropolyacid anion according to this embodiment include heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, heteropolyoxoniobate anion, heteropolyoxotantalate anion, etc. The polyatom of the heteropolyacid anion is preferably Mo, W, V, Nb, or Ta, and more preferably Mo or W.

[0094] Examples of the heteropolyoxomolybdate anion include phosphomolybdate anion, silicomolybdate anion, boromolybdate anion, sulfur molybdate anion, phosphotungstomolybdate anion, cobalt molybdate anion, arsenic molybdate anion, germanium molybdate anion, etc. Examples of the heteropolyoxotungstate anion include phosphotungstate anion, silicotungstate anion, borotungstate anion, sulfur tungstate anion, cobalt tungstate anion, arsenic tungstate anion, germanium tungstate anion, etc. Examples of the heteropolyoxovanadate anion include phosphomolybdovanadate anion, boromolybdovanadate anion, boromolybdotungstovanadate anion, etc. The heteroatom of the heteropolyacid anion is preferably P, Si, Ge, B, S, Co or As, and more preferably P, Si, B, S or Ge.

[0095] The heteropolyoxomolybdate anion, heteropolyoxotungstate anion, heteropolyoxovanadate anion, etc. include Keggin type, Dawson type, Anderson type, and isomers thereof.

[0096] The heteropolyoxotungstate anion may be [PW １２ O ４０ ] ３－ , [SiW １２ O ４０ ] ４－ , [B.W. １２ O ４０ ] ５－ , [SW １２ O ４０ ] ２－ , [P ２ W １８ O ６２ ] ６－ , [Si ２ W １８ O ６２ ] ８－ It is preferable that:

[0097] [1-3. Onium cation or dication (B ｎ＋ ) )] As the onium cation or onium dication according to this embodiment, an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication can be used.

[0098] [1-3-1. Organic sulfonium cation] The organic sulfonium cation is not particularly limited, and any known or commonly used organic sulfonium cation can be used. Examples of the organic sulfonium cation include organic sulfonium cations represented by the following general formula (II):

[0099] In formula (II), R １Ａ , R １Ｂ and R １Ｃ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, １Ａ , R １Ｂ and R １Ｃ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); １Ａ , R １Ｂ and R １Ｃ Any two of these are directly connected to each other by a single bond, or are divalent linking groups -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (II).

[0100] Specific examples of the organic sulfonium cation include dibutyl(pentyl)sulfonium cation, triethylsulfonium cation, (2-carboxyethyl)dimethylsulfonium cation, trimethylsulfonium cation, dimethylphenacylsulfonium cation, 1-(4-hydroxynaphthalen-1-yl)hexahydrothiopyrylium cation, dimethylphenylsulfonium cation, triphenylsulfonium cation, tris(4-methylphenyl)sulfonium cation, 4-methoxyphenyldiphenylsulfonium cation, 4-iodophenyldiphenylsulfonium cation, tris(4-fluorophenyl)sulfonium cation, 1-phenylhexahydrothiopyrylium cation, di(naphthalen-1-yl)(phenyl)sulfonium cation, phenylbis(2-(trifluoromethyl)phenyl)sulfonium cation, cation, mesitylbis(2-(trifluoromethyl)phenyl)sulfonium cation, bis(3,5-difluorophenyl)(phenyl)sulfonium cation, tris(3,5-difluorophenyl)sulfonium cation, (4-(dodecanoyloxy-3,5-dimethylphenyl))diphenylsulfonium cation, diphenyl(3-(trifluoromethoxy)phenyl)sulfonium cation, (4-(1-adamantylcarbonyloxy)phenyl)diphenylsulfonium cation, (4-phenylthiophenyl)diphenylsulfonium cation, 5-phenyl-5H-thianthren-5-ium cation, 5-(2,5-dimethylphenyl)thianthren-5-ium cation, 5-phenyl-5H-dibenzo[b,d]thiophen-5-ium cation, 5-(3-(trifluoromethyl)phenyl)-5H-dibenzo[b,Examples of the thiophene-5-ium cation include 1-(4-(t-butyl)phenyl)-1H-benzo[b]thiophen-1-ium cation, methyldiphenylsulfonium cation, (2-bromoethyl)diphenylsulfonium cation, (3-chloropropyl)diphenylsulfonium cation, benzyl(4-hydroxyphenyl)methylsulfonium cation, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium cation, 4-hydroxyphenyldimethylsulfonium cation, diphenyl(methyl)sulfonium cation, diphenyl(4-(phenylthio)phenyl)sulfonium cation, (2-bromoethyl)diphenylsulfonium cation, dimesityl(trifluoromethyl)sulfonium cation, tri-p-tolylsulfonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)dimethylsulfonium cation, (4-(methacryloyloxy)phenyl)dimethylsulfonium cation, and dimethyl(4-(nonanoyloxy)phenyl)sulfonium cation.

[0101] [1-3-2. Organic sulfonium dication] The organic sulfonium dication is not particularly limited, and known and commonly used ones can be used. Examples of the organic sulfonium dication include the organic sulfonium dication represented by formula (III):

[0102] In formula (III), R ２Ａ , R ２Ｂ , R ２Ｃ and R ２Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ２Ａ , R ２Ｂ , R ２Ｃ and R ２Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２- may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); K ２Ａ , K. ２Ｂ and L ２Ａ each independently represents a C １－１８ represents a hydrocarbylene group, ２Ａ , K. ２Ｂ and L ２Ａ The divalent carbon atom at any position in ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ２Ａ , R ２Ｂ and K. ２Ａ and / or R ２Ｃ , R ２Ｄ and K. ２Ｂ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the sulfur atom in formula (III).

[0103] Specific examples of the organic sulfonium dication include (ethane-1,2-diylbisoxy)bis(4,1-phenylene)bis(diphenylsulfonium) dication, (thiodi-4,1-phenylene)bis(diphenylsulfonium) dication, and the like.

[0104] [1-3-3. Organic iodonium cation] The organic iodonium cation is not particularly limited, and known and commonly used ones can be used. Examples of the organic iodonium cation include the organic iodonium cation represented by formula (IV).

[0105] In general formula (IV), R ３Ａ and R ３Ｂ each independently represents a C １－１８represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ３Ａ and R ３Ｂ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ３Ａ and R ３Ｂ are directly connected to each other by a single bond, or are connected to each other by a divalent linking group, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the iodine atom in formula (IV).

[0106] Specific examples of the organic iodonium cation include ethynyl(phenyl)iodonium cation, bis(pyridine)iodonium cation, bis(2,4,6-trimethylpyridine)iodonium cation, diphenyliodonium cation, bis(4-(t-butyl)phenyl)iodonium cation, (2-carboxyphenyl)(phenyl)iodonium cation, (4-nitrophenyl)(phenyl)iodonium cation, (3-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, )iodonium cation, bis(4-fluorophenyl)iodonium cation, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium cation, bis(2,4,6-trimethylphenyl)iodonium cation, 4-isopropyl-4'-methyldiphenyliodonium cation, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium cation, ((4 (4-trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (5-fluoro-2-nitrophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (3-bromophenyl)(mesityl)iodonium cation, bis(4-bromophenyl)iodonium cation, (3,5-dichlorophenyl)(2,4,6-trimethoxyphenyl)iodonium cation, (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium cation, (3-methylphenyl)(mesityl)iodonium cation, Examples include (4-((diisopropylcarbamoyl)oxy)phenyl)(phenyl)iodonium cation, (4-(methacryloyloxy)phenyl)(phenyl)iodonium cation, (4-(nonanoyloxy)phenyl)(phenyl)iodonium cation, and the like.

[0107] [1-3-4. Organic Ammonium Cation] The organic ammonium cation is not particularly limited, and known and commonly used cations can be used. The organic ammonium cation is not particularly limited, and examples thereof include organic primary ammonium cations (NH ３ (R ４Ａ ) ＋ )), organic secondary ammonium cations (NH ２ (R ４Ａ ) (R ４Ｂ )) ＋ ), organic tertiary ammonium cation (NH(R ４Ａ ) (R ４Ｂ ) (R ４Ｃ ) ＋ ), organic quaternary ammonium cation (N(R ４Ａ ) (R ４Ｂ ) (R ４Ｃ ) (R ４Ｄ ) ＋ ) can be mentioned. ４Ａ ~R ４Ｄ represents the same as defined below. The organic ammonium cation is preferably a quaternary ammonium cation, and particularly preferably an organic quaternary ammonium cation represented by the following general formula (V):

[0108] In general formula (V), R ４Ａ ~R ４Ｄ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ４Ａ ~R ４Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), and ４Ａ ~R ４Ｄ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (V).

[0109] Specific examples of the organic quaternary ammonium cation include diallyldimethylammonium cation, (3-acrylamidopropyl)trimethylammonium cation, trimethyl-2-methacryloyloxyethylammonium cation, N-(2-acryloyloxyethyl)-N-benzyl-N,N-dimethylammonium cation, trimethylvinylammonium cation, N-4-vinylbenzyltriallylammonium cation, 3-hydroxypropyltriallylammonium cation, 2-trifluoromethylbenzyltriallylammonium cation, di-2-(N-methylacrylamido)ethyldimethylammonium cation, allyltrimethylammonium cation, butyl(2-methacryloyloxyethyl)dimethylammonium cation, ethoxycarbonylmethyltriethylammonium cation, 2-hydroxyethyltrimethylammonium cation, 2-acetylethyltrimethylammonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)trimethylammonium cation, (4-(methacryloyloxy)phenyl)trimethylammonium cation, trimethyl(4-(nonanoyloxy)phenyl)ammonium cation, and the like.

[0110] [1-3-5. Organic Ammonium Dication] The organic ammonium dication is not particularly limited, and any known and commonly used organic ammonium dication can be used. Examples of the organic ammonium dication include organic quaternary ammonium dications represented by the following general formula (VI):

[0111] In general formula (VI), R ５Ａ ~R ５Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ５Ａ ~R ５ＦThe divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); ５Ａ is an optionally substituted C １－１８ represents a hydrocarbylene group, ５Ａ The divalent carbon atom at any position in ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ５Ａ ~R ５Ｆ and L ５Ａ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the nitrogen atom in formula (VI).

[0112] Specific examples of the organic quaternary ammonium cation 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.

[0113] [1-3-6. Organic phosphonium cation] The organic phosphonium cation is not particularly limited, and any known or commonly used organic phosphonium cation can be used. Examples of the organic phosphonium cation include organic quaternary phosphonium cations represented by the following general formula (VII):

[0114] In general formula (VII), R ６Ａ ~R ６Ｄeach independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group; ６Ａ ~R ６Ｄ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO ２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced); ６Ａ ~R ６Ｄ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VII).

[0115] Specific examples of the organic quaternary phosphonium cation include tributylcyanomethylphosphonium cation, methyltriphenylphosphonium cation, ethyltriphenylphosphonium cation, cyanomethyltriphenylphosphonium cation, formylmethyltriphenylphosphonium cation, methoxymethyltriphenylphosphonium cation, chloromethyltriphenylphosphonium cation, acetonyltriphenylphosphonium cation, tributyl-1,3-dioxan-2-ylmethylphosphonium cation, triphenylpropargylphosphonium cation, allyltriphenylphosphonium cation, cyclopropyltriphenylphosphonium cation, benzyltriphenylphosphonium cation, tetrakis(hydroxymethyl)phosphonium cation, 2-carboxyethyltriphenylphosphonium cation, methoxycarbonylmethyltriphenylphosphonium cation, t-butoxycarbonylmethyltriphenylphosphonium cation, (4-((diisopropylcarbamoyl)oxy)phenyl)triphenylphosphonium cation, (4-(methacryloyloxy)phenyl)triphenylphosphonium cation, triphenyl(4-(nonanoyloxy)phenyl)phosphonium cation, and the like.

[0116] [1-3-7. Organic phosphonium dication] The organic phosphonium dication is not particularly limited, and known and commonly used organic phosphonium dications can be used. Examples of the organic phosphonium dication include organic quaternary phosphonium dications represented by the following general formula (VIII):

[0117] In general formula (VIII), R ７Ａ ~R ７Ｆ each independently represents a C １－１８ represents a hydrocarbyl group, a 3- to 18-membered non-aromatic heterocyclic group, or a 5- to 18-membered aromatic heterocyclic group, ７Ａ ~R ７Ｆ The divalent carbon atom at any position excluding the terminal may be -O-, -C(=O)-, -C(=O)O-, -OCO-, -CONH-, -NHCO-, -NH(C=O)O-, -S- or -SO２ - (provided that adjacent divalent carbon atoms are not simultaneously replaced), L ７Ａ is an optionally substituted C １－１８ represents a hydrocarbylene group, ７Ａ The divalent carbon atom at any position in ２ - may be substituted (provided that adjacent divalent carbon atoms are not substituted at the same time); R ７Ａ ~R ７Ｆ and L ７Ａ Any two of these are directly connected to each other by a single bond, or are connected to each other by a divalent linking group -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -C(=O)O-, or C １－３ They may be linked via an alkylene group to form a ring together with the phosphorus atom in formula (VIII).

[0118] Specific examples of the organic quaternary phosphonium dication include trans-2-butene-1,4-bis(triphenylphosphonium) dication, ethylenebis(triphenylphosphonium) dication, and pentamethylenebis(triphenylphosphonium) dication.

[0119] [1-4. Other counter cations (A ｍ＋ Other counter cations according to this embodiment (A ｍ＋ ) is H ＋ , metal ions, or ammonium ions (NH ４＋ ) represents

[0120] "A ｍ＋ The metal ions that can be used as " are not particularly limited, and for example, Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋, Al ３＋ , Co ３＋ , Bi ３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ These metal ions may be used alone or in combination of two or more.

[0121] "A ｍ＋ " as H ＋ , Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Al ３＋ , Co ３＋ , N.H. ４＋ is preferred, and H ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Ca ２＋ , Al ３＋ , Co ３＋ , N.H. ４＋ is more preferred.

[0122] [1-5. A ｍ＋ and B ｎ＋ In the following general formula (I), m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) The mixture of polyacid salts also contains A ｍ＋ and B ｎ＋ In this case, the values ​​of a and b can be determined by, for example, NMR analysis, XRF analysis, XPS analysis, or the like.

[0123] The ratio of a to b is as follows: ｍ＋ , B ｎ＋Although it depends on the types of compounds, a:b is preferably 0-3:3-12, more preferably 0-2:2-8, and even more preferably 0-1:1-4. In particular, when the value of am+bn is an integer of 2 to 8 and m and n are 1, it is preferable that a is a real number of 0 to 3 and b is a real number of 1 to 7, and it is more preferable that a is a real number of 0 to 2 and b is a real number of 2 to 7.

[0124] [1-6. Method for Producing Polyacid Salt Represented by General Formula (I) or a Mixture Thereof] The polyacid salt represented by general formula (I) according to this embodiment or a mixture thereof can be produced by any known or commonly used method without any particular limitation. Examples of methods for producing the polyacid salt or a mixture thereof include a salt exchange method and an ion exchange method.

[0125] [1-6-1. Salt Exchange Step] The method for producing a polyacid salt represented by general formula (I) or a mixture thereof according to this embodiment may include a salt exchange step of reacting a compound having a polyacid anion represented by the following general formula (IX-1) with a compound having a predetermined onium cation or dication represented by general formula (IX-2): (A' ｍ’＋ ) ａ’ (C （ａ’ｍ’）－ ) (IX-1) (B ｎ＋ ) (Y － ) ｎ (IX-2) [wherein, A' ｍ’＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａ’ｍ’）－ represents a polyanion; Y － represents a monovalent counter anion; m' is an integer of 1 to 5, n is an integer of 1 or 2, and a' is a real number greater than 0.

[0126] According to another embodiment, a method for producing a polyacid salt represented by general formula (I) or a mixture thereof may include a step of reacting a compound having a polyacid anion represented by general formula (IX-1) with a compound having a specific onium cation or dication represented by general formula (IX-2) to perform salt exchange, and a step of removing the compound represented by general formula (VI-3) from the resulting compounds represented by general formulas (I) and (IX-3). ｍ’＋ ) (Y － ) ｍ’ (IX-3) [wherein, A' ｍ’＋ are each independently H ＋ , a metal ion, or an ammonium ion; Y － represents a monovalent counter anion; and m′ is an integer of 1 to 5.

[0127] Furthermore, as a method for producing a polyacid salt represented by general formula (I) or a mixture thereof, a production method involving the following two-stage salt exchange reaction process may be used. That is, in another embodiment of a method for producing a polyacid salt represented by general formula (I) or a mixture thereof, the cation moiety of the polyacid salt or a mixture thereof is converted into an ammonium ion (NH ４＋ ) or an organic ammonium cation, and then further replacing it with a predetermined metal ion, or an onium cation or dication, thereby producing a polyacid salt or a mixture thereof represented by general formula (I) with fewer impurities. The organic ammonium cation may be the aforementioned organic primary ammonium cation (NH ３ (R ４Ａ ) ＋ )), organic secondary ammonium cations (NH ２ (R ４Ａ ) (R ４Ｂ )) ＋ ), organic tertiary ammonium cation (NH(R ４Ａ ) (R ４Ｂ) (R ４Ｃ ) ＋ ), organic quaternary ammonium cation (N(R ４Ａ ) (R ４Ｂ ) (R ４Ｃ ) (R ４Ｄ ) ＋ ) can be used.

[0128] More specifically, a method for producing a polyacid represented by general formula (I) or a mixture thereof can be used, which comprises the steps of reacting a compound having a polyacid anion represented by general formula (IX-1) with a compound having an ammonium ion or organic ammonium cation represented by general formula (IX-4) to effect salt exchange, and further reacting the resulting compound represented by general formula (IX-5) with a compound having a predetermined metal ion, onium cation, or dication represented by general formula (IX-2). (A ’’＋ ) (Y － ) ｎ (IX-4) (A ’’＋ ) ａ’’ (C ａ’’－ ) (IX-5) [wherein, A ’’＋ represents an ammonium ion or an organic ammonium cation; ａ’’－ represents a polyanion; Y － represents a monovalent counter anion; and a″ is a real number greater than 0.] Examples of the compound represented by general formula (IX-4) include salts of ammonium chloride, ammonium bromide, and any of the above-mentioned organic quaternary ammonium cations exemplified above with a halide ion.

[0129] When the compound represented by general formula (IX-5) is reacted with a compound having a predetermined metal ion, an onium cation, or a dication, represented by general formula (IX-2), a salt exchange reaction can be carried out using a two-phase system of organic solvent and water. By using a two-phase system of organic solvent and water, the polyacid salt represented by general formula (I) or a mixture thereof is contained in the organic layer, and the by-products ((IX-3), (IX-4)) are mainly contained in the aqueous layer. This makes it possible to produce a polyacid salt represented by general formula (I) or a mixture thereof with fewer impurities. Examples of the organic solvent that can be used include methanol, ethanol, 1,4-dioxane, acetonitrile, 1-propanol, 2-propanol, ethyl acetate, acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide, and diethyl ether. Ethyl acetate, dichloromethane, chloroform, and diethyl ether are preferred.

[0130] [1-6-1-1. Compounds Having Polyacid Anions Represented by General Formula (IX-1)] Compounds having polyacid anions represented by general formula (IX-1) can be used as raw materials in the production of polyacid salts represented by general formula (I) or mixtures thereof. (A' ｍ’＋ ) ａ’ (C （ａ’ｍ’）－ ) (IX-1) [wherein, A' ｍ’＋ are each independently H ＋ , a metal ion, or an ammonium ion; （ａ’ｍ’）－ represents a polyacid anion; m' is an integer of 1 to 5, and a' is a real number greater than 0.

[0131] A' ｍ’＋ is not particularly limited, and can be, for example, H ＋ , Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ , Be ２＋ , Mg ２＋ , Ca ２＋ , Sr ２＋ , Ba ２＋ , Co ３＋ , Bi３＋ , Zr ４＋ , Hf ４＋ , Bi ５＋ , N.H. ４＋ or a combination thereof. ｍ’＋ From the viewpoint of promoting the salt exchange reaction, ＋ , Na ＋ , K. ＋ , Mg ２＋ , Ca ２＋ , N.H. ４＋ or a combination thereof, and H ＋ , Na ＋ , K. ＋ , N.H. ４＋ or a combination thereof is more preferable.

[0132] Specific examples of the compound having the polyacid anion represented by the general formula (IX-1) include ammonium metatungstate hydrate, sodium polytungstate, phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・nH ２ O), tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H ２ O) and the like can be exemplified.

[0133] [1-6-1-2. Compounds Having a Specified Metal Ion, or an Onium Cation or Dication Represented by General Formula (IX-2)] The compounds having a specified metal ion, or an onium cation or dication, represented by general formula (IX-2) can be used as raw materials in the production of polyacid salts represented by general formula (I) or mixtures thereof. (B ｎ＋ ) (Y － ) ｎ (IX-2) [wherein, B ｎ＋ each independently represents an onium cation or a dication; Y － represents a monovalent counter anion; and n is an integer of 1 or 2.

[0134] Above B ｎ＋As the cation, the above-mentioned onium cation or dication can be used.

[0135] Above Y － From the viewpoint of promoting the salt exchange reaction, Br － , Cl － , I － , O.H. － , C.F. ３ SO ３ － , C ２ F ５ SO ３ － , C ３ F ７ SO ３ － , C ４ F ９ SO ３ － , p-CH ３ (C ６ H ４ ) SO ３ － , ClSO ３ － , ClO ４ － , (C ６ F ５ ) ４ B-, BF ４ － , P.F. ６ － , SbF ６ － , AlCl ４ － , BiF ６ － , AsF ６ － Preferably, Br － , Cl － , I － , O.H. － , C.F. ３ SO ３ － , C ４ F ９ SO ３ － , B.F. ４ － , P.F. ６ － , SbF ６ －More preferably, Br － , Cl － , C.F. ３ SO ３ － , B.F. ４ － , P.F. ６ － , SbF ６ － It is more preferable that:

[0136] Specific examples of the compound having a predetermined onium cation or dication represented by the general formula (IX-2) include WPAG-336 (diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate), WPAG-367 (diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate), WPAG-370 (diphenyl(4-methoxyphenyl)sulfonium trifluoromethanesulfonate), WPAG-469 (4-methylphenyldiphenylsulfonium nonafluorobutanesulfonate), and WPAG-638 (tris(4-methylphenyl)sulfonium nonafluorobutanesulfonate), all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; benzyl(4-hydroxyphenyl)methylsulfonium hexafluoroantimonate, diphenyl(methyl)sulfonium tetrafluoroborate, trimethylsulfonium bromide, 4-hydroxyphenyldimethylsulfonium methylsulfate, and (2-bromoethyl)diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium bromide, trimethylsulfonium hydroxide, triphenylsulfonium nonafluoro-1-butanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluoroantimonate, diphenyl(4-(phenylthio)phenyl)sulfonium hexafluorophosphate, (3-chloropropyl)diphenylsulfonium tetrafluoroborate, (2-carboxyethyl)dimethylsulfonium chloride, (2-carboxyethyl)dimethylsulfonium bromide, tri-p-tolylsulfonium trifluoromethanesulfonate, (difluoromethyl)bis(2,5-dimethylphenyl)sulfonium tetrafluoroborate, (4-hydroxyphenyl)methyl(2-methylbenzyl)sulfonium hexafluoroantimonate, tributylsulfonium iodide, (thiodi-4,1-phenylene)bis(diphenylsulfonium)bis(hexafluorophosphate), 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, (4-(bromomethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, 4-biphenylyl(2,4,6-trimethoxyphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium hexafluorophosphate, bis(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, bis(2,4,6-trimethylpyridine)iodonium Examples of iodonium compounds include iodonium hexafluorophosphate, bis(4-fluorophenyl)iodonium trifluoromethanesulfonate, ethynyl(phenyl)iodonium tetrafluoroborate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethoxyphenyl)iodonium p-toluenesulfonate, (4-(trifluoromethyl)phenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate, diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium hexafluorophosphate, and diphenyliodonium trifluoromethanesulfonate.

[0137] [1-6-1-3. Molar ratio of compounds represented by general formulas (IX-1) and (IX-2)] The molar ratio of the compound having a polyacid anion represented by general formula (IX-1) to the compound having a predetermined onium cation or dication represented by general formula (IX-2) is not particularly limited, and may be determined based on the molar ratio of the compound having a predetermined onium cation or dication contained in the target polyacid salt or a mixture thereof. ｍ＋ and B ｎ＋ The molar ratio of the compounds represented by general formulas (IX-1) and (IX-2) is preferably 1-3:1-20, more preferably 1-3:1-18, and even more preferably 2:1-15, where the molar ratio is the ratio of the compound represented by formula (IX-1):the compound represented by formula (IX-2).

[0138] [1-6-1-4. Reaction of Compounds Represented by General Formulae (IX-1) and (IX-2)] The reaction conditions for the compounds represented by general formulae (IX-1) and (IX-2) are not particularly limited, and the reaction can be carried out under known and commonly used reaction conditions. The type of solvent, reaction temperature, reaction time, pressure, and the like can be set appropriately. The type of solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 1,4-dioxane, acetonitrile, 1-propanol, 2-propanol, ethyl acetate, acetonitrile, acetone, dichloromethane, chloroform, dimethylformamide, and diethyl ether. These solvents may be used alone or in combination. The reaction temperature is not particularly limited, and the reaction may be carried out at room temperature or with heating, for example. The reaction time is not particularly limited, and is preferably 1 minute to 24 hours, and more preferably 1 minute to 5 hours. The pressure is not particularly limited, and the reaction may be carried out at normal pressure or under pressure.

[0139] [1-6-1-5. Step of Removing the Compound Represented by General Formula (IX-3)] The method for removing the compound represented by general formula (IX-3) is not particularly limited, and examples thereof include a method of extracting the by-produced compound represented by general formula (IX-3) into an aqueous layer and removing it, a method of precipitating it as an inorganic salt and filtering it off, and a method of crystallizing the target compound represented by general formula (I) or a solvate thereof and filtering it off. When the by-produced compound represented by general formula (IX-3) is extracted into an aqueous layer and removed, an organic solvent such as ethyl acetate, dichloromethane, or chloroform can be used as the organic layer containing the polyacid salt or a mixture thereof.

[0140] [1-6-1-6. Step of Obtaining Polyacid Salt Represented by General Formula (I) or a Mixture Thereof] The method for producing a polyacid salt represented by general formula (I) or a mixture thereof according to this embodiment may further include a step of obtaining a polyacid salt represented by general formula (I) or a mixture thereof.

[0141] The method for obtaining the polyacid salt represented by general formula (I) or a mixture thereof is not particularly limited, and examples thereof include a method of crystallizing the polyacid salt or a mixture thereof and collecting the resultant by filtration. The method for crystallizing the polyacid salt or a mixture thereof is not particularly limited, and examples thereof include a method of heating the target substance to dissolve it in a solvent and then slowly cooling the solution to precipitate crystals, and a method of crystallizing the target substance by combining a poor solvent and a good solvent. The poor solvent can be appropriately selected depending on the target substance, and examples of suitable solvents include diethyl ether, dipropyl ether, ethyl acetate, butyl acetate, hexane, toluene, 2-propanol, ethanol, and methanol. The good solvent can be appropriately selected depending on the target substance, and examples of suitable solvents include water, methanol, ethanol, 1,4-dioxane, dimethylformamide, chloroform, and dichloromethane.

[0142] [1-6-2. Step of Removing Impurities] The method for producing the polyacid salt represented by general formula (I) or a mixture thereof according to this embodiment includes a step of washing the polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less as a step of removing impurities.

[0143] The step of washing the polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less may be performed by extracting the by-product compound represented by general formula (IX-3) into an aqueous layer in the step of removing the compound represented by general formula (IX-3) and then washing the obtained organic layer containing the polyacid salt or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. Alternatively, the step may be performed by precipitating the polyacid salt or a mixture thereof by recrystallization or the like, and washing the obtained polyacid salt or a mixture thereof with an acidic aqueous solution having a pH of 6 or less.

[0144] Furthermore, the step of washing the polyacid salt represented by the general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less can be carried out by salt-exchanging the cation moiety of the polyacid salt or a mixture thereof with an ammonium ion or an organic ammonium cation, and then washing the organic layer obtained by salt-exchange reaction with a compound having a predetermined onium cation or dication represented by the general formula (IX-2) with an acidic aqueous solution having a pH of 6 or less, thereby making it possible to obtain a polyacid salt or a mixture thereof with fewer impurities.

[0145] The pH of the acidic aqueous solution is preferably 6 or less, more preferably −1 to 5.8, more preferably −0.5 to 4.5, even more preferably 0 to 3.5, and even more preferably 0 to 2.0.

[0146] Examples of the acid contained in the acidic aqueous solution include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; organic acids having a carboxy group such as tartaric acid, oxalic acid, formic acid, malic acid, citric acid, succinic acid, maleic acid, fumaric acid, glycolic acid, trifluoroacetic acid, and trichloroacetic acid; and organic acids having a sulfo group such as methanesulfonic acid, ethanesulfonic acid, sulfosuccinic acid, metatoluenesulfonic acid, and paratoluenesulfonic acid. These acids may be used alone or in combination of two or more. The acid is preferably hydrochloric acid, sulfuric acid, tartaric acid, formic acid, citric acid, succinic acid, or malic acid.

[0147] The acid concentration (w / w %) of the acidic aqueous solution can be appropriately set depending on the type of acid, etc.

[0148] It is preferable to include a step of washing the organic layer containing the polyacid salt or the mixture thereof and the precipitate of the polyacid salt or the mixture thereof multiple times with pure water or the like, after the step of washing the polyacid salt represented by the general formula (I) or the mixture thereof with an acidic aqueous solution having a pH of 6 or less.

[0149] In a method for producing a polyacid salt or a mixture thereof, the method includes a step of washing a polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less, whereby metals or metal ions contained as impurities, such as Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au (provided that the polyatoms, heteroatoms, and Au in the polyacid salt or the mixture thereof are not included). ｍ＋ (excluding metals or metal ions contained in the above) can be removed, and the content of each can be reduced to a value of less than 100 ppb.

[0150] The content of metals or metal ions contained as impurities in the polyacid or mixture thereof can be measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0151] Although the mechanism by which the content of metal or metal ions as impurities can be effectively reduced by including a step of washing the polyacid salt represented by the above general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less is not clear, it is thought that exposing the polyacid salt or a mixture thereof to an acidic aqueous solution having a pH of 6 or less loosens the structure / frame, formation mechanism, interaction network, etc. of the polyacid salt or a mixture thereof, and makes it possible to effectively wash out and remove the metal or metal ions as impurities that have been clinging to the structure / frame or interaction network of the polyacid salt or a mixture thereof.

[0152] [2. Method for Removing Impurities] The method for removing impurities from a polyacid salt represented by general formula (I) or a mixture thereof according to this embodiment includes a step of washing the polyacid salt or the mixture with an acidic aqueous solution having a pH of 6 or less.

[0153] The above-mentioned method for removing impurities can effectively remove metal or metal ions as impurities without decomposing the polyacid anion in the anion portion of the polyacid salt represented by general formula (I) or a mixture thereof, and is therefore suitable as a method for removing impurities from polyacids or mixtures thereof.

[0154] EXAMPLES The present invention will be specifically explained below by showing examples, but the present invention is not limited to these examples.

[0155] [1. Production of Polyacid Salts] Polyacid salts M-1 to M-4 and M'-1 were each produced by the production method described below.

[0156] [Production Example 1: Tris((3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium)phosphotungstate (Polyacid Salt M-1)] 43.81 g of (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride was dissolved in 50 g of dichloromethane and 50 g of pure water, and phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ 41.97 g of methyl tert-butyl ether (M-1) was added, and the reaction solution was stirred at room temperature for 1 hour. The aqueous layer was then removed, and 50 g of 1% hydrochloric acid (pH approximately 0.5) was added to the resulting organic layer, followed by stirring for 10 minutes. After stirring, the aqueous layer was removed, and the resulting organic layer was washed three times with 50 g of pure water. After washing, 400 mL of methyl t-butyl ether was added to the resulting dichloromethane solution of the organic layer, and the precipitated powder was separated by suction filtration. The resulting powder was thoroughly dried under vacuum to obtain the target compound, polyacid salt M-1. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.79-7.93 (m, 36H), 2.73 (t, 6H), 2.19 (s, 18H), 1.65-1.72 (m, 6H), 1.25-1.38 (m, 42H), 0.85 (t, 9H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis S:W (molar ratio of S to W) = 3:12

[0157] [Production Example 2: Tetrakis((3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium)silicate (Polyacid Salt M-2)] In Production Example 1, phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ Instead of tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H ２ The target compound, polyacid salt M-2, was obtained in the same manner as above, except that methyl methyl acrylate (M-1) was used instead. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.79-7.93 (m, 48H), 2.73 (t, 8H), 2.19 (s, 24H), 1.65-1.72 (m, 8H), 1.25-1.38 (m, 56H), 0.85 (t, 12H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0158] [Production Example 3: Tris((4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium)silicate (Polyacid Salt M-3)] In Production Example 1, (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride was replaced with (4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)diphenylsulfonium chloride as the raw material compound, and phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ Instead of tungstosilicic acid (H ４ [SiW １２ O ４０ ]・26H２ The target compound, polyacid salt M-3, was obtained in the same manner as above, except that methyl methyl acrylate (M-3) was used instead. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.76-7.82 (m, 40H), 7.59 (s, 8H), 4.55 (s, 8 H), 2.29 (m, 24H), 1.90-1.93 (m, 16H), 1.48-1.75 (m, 24H), 0.77-0.81 (t, 12H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -92.7 (s, 12 W). ESI-MS: NEGATIVE m / z 718.5 (median) ([SiW １２ O ４０ ] ４－ ) XPS analysis S:W (molar ratio of S to W) = 4:12

[0159] [Production Example 4: Production of tris((3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium)phosphotungstate (polyacid salt M-4) via tris(triethylammonium)phosphotungstate (m-4)] 13.3 g of triethylamine was dissolved in 50 g of pure water, and phosphotungstic acid (H ３ [P.W. １２ O ４０ ]・30H ２ To the resulting solution, 41.97 g of (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride and 50 g of dichloromethane were added, and the reaction solution was stirred at room temperature for 1 hour. Thereafter, the aqueous layer was removed, and 50 g of 1% hydrochloric acid was added to the resulting organic layer, followed by stirring for 10 minutes. After stirring, the aqueous layer was removed, and the resulting organic layer was washed three times with 50 g of pure water. After washing, 400 mL of methyl t-butyl ether was added to the dichloromethane solution of the resulting organic layer, and the precipitated powder was separated by suction filtration. The resulting powder was thoroughly dried under vacuum to obtain the target compound, polyacid salt M-4. １H-NMR (400MHz, DMSO-D6): δ (ppm) = 7.79-7.93 (m, 36H), 2.73 (t, 6H), 2.19 (s, 18H), 1.65-1.72 (m, 6H), 1.25-1.38 (m, 42H), 0.85 (t, 9H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis S:W (molar ratio of S to W) = 3:12

[0160] [Production Example 5: Production of tris(bis(4-t-butylphenyl)iodonium)phosphotungstate (polyacid salt M-5) via tris(triethylammonium)phosphotungstate (m-4)] The target compound, polyacid salt M-5, was obtained in the same manner as in Production Example 4, except that bis(4-t-butylphenyl)iodonium methyl sulfate was used instead of (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride as the raw material compound. １ H-NMR (400MHz, DMSO-D6): δ (ppm) = 1.25 (s, 54H), 7.56 (d, 12H), 8.18 (d, 12H). １８３ W-NMR (20.84 MHz, DMSO-D6): δ (ppm) = -86.7 (s, 12 W). ESI-MS: NEGATIVE m / z 959 (median) ([PW １２ O ４０ ] ３－ ) XPS analysis I:W (molar ratio of I to W) = 3:12

[0161] Comparative Production Example 1: Tris((3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium)phosphotungstate (polyacid salt M'-1) 43.81 g of (3,5-dimethyl-4-(undecanoyloxy)phenyl)diphenylsulfonium chloride was dissolved in 50 g of dichloromethane and 50 g of pure water to obtain phosphotungstic acid (H ３ [P.W. １２ O ４０]・30H ２ 41.97 g of methyl tert-butyl ether was added, and the reaction solution was stirred at room temperature for 1 hour. The aqueous layer was then removed, and the resulting organic layer was washed three times with 50 g of pure water. After washing, 400 mL of methyl t-butyl ether was added to the resulting dichloromethane solution of the organic layer, and the precipitated powder was separated by suction filtration. The resulting powder was thoroughly dried under vacuum to obtain the target compound, polyacid salt M'-1.

[0162] [2. Measurement of Metal or Metal Ion Content] The amounts of metals or metal ions (Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au) contained in the polyacid salts M-1 to M-5 and M′-1 were measured using an inductively coupled plasma mass spectrometer (ICP-MS, Agilent 8900, manufactured by Agilent Technologies). Among the metals or metal ions, excluding the metals or metal ions contained in the polyatom (tungsten), heteroatom, and cation portion of the isopolyacid salt or heteropolyacid salt, if the content of the metal or metal ion with the highest content was less than 100 ppb, it was evaluated as A, and if it was 100 ppb or more, it was evaluated as B.

[0163]

[0164] The results in Table 1 show that by providing a step of washing the organic layer containing the polyacid salts M-1 to M-5 with 1% hydrochloric acid, the content of metals or metal ions contained as impurities in the polyacid salts can be reduced compared to the case of washing only with pure water (polyacid salt M'-1).

[0165] Furthermore, as in the case of polyacid salts M-4 and M-5, polyacid salts with even fewer impurities could be prepared by undergoing a two-step salt exchange reaction in which the cation moiety of a polyacid salt or a mixture thereof was first replaced with an organic ammonium cation and then with a specific sulfonium cation or iodonium cation.

Claims

1. A method for producing a polyacid salt or a mixture thereof, comprising a step of washing a polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａｍ＋ｂｎ）－ represents a polyacid anion; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

2. The method for producing a polyacid salt or a mixture thereof according to claim 1, wherein the polyacid anion is an isopolyoxomolybdate anion, an isopolyoxotungstate anion, an isopolyoxoniobate anion, or an isopolyoxotantalate anion.

3. The method for producing a polyacid salt or a mixture thereof according to claim 1, wherein the polyacid anion is a heteropolyacid anion, the polyatom of the heteropolyacid anion being Mo, W, V, Nb or Ta, and the heteroatom being P, Si, B, S or Ge.

4. The method for producing a polyacid salt or a mixture thereof according to claim 1, wherein the onium cation or dication is an organic sulfonium cation, an organic sulfonium dication, an organic iodonium cation, an organic ammonium cation, an organic ammonium dication, an organic phosphonium cation, or an organic phosphonium dication.

5. The step of washing with an acidic aqueous solution of pH 6 or less is carried out by removing metals or metal ions of Li, Na, Mg, Al, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Zr, Mo, Ag, Cd, Sn, Sb, Ba, W, Pb, and Au in the polyacid salt or mixture thereof represented by general formula (I), and removing polyatoms, heteroatoms, and Au in the polyacid salt or mixture thereof. ｎ＋ The method for producing a polyacid salt or a mixture thereof according to claim 1, further comprising the step of adjusting the content of each of the metals or metal ions excluding the metal or metal ion contained in the above-mentioned salt to less than 100 ppb.

6. A method for producing a polyacid salt or a mixture thereof, comprising the steps of: replacing the cationic portion of a polyacid salt represented by general formula (IX-1) or a mixture thereof with an ammonium ion or an ammonium cation by a salt exchange reaction; further performing salt exchange with a compound represented by general formula (IX-2); and washing the resulting polyacid salt represented by general formula (I) or a mixture thereof with an acidic aqueous solution having a pH of 6 or less. (A' ｍ’＋ ) ａ’ (C （ａ’ｍ’）－ ) (IX-1) (B ｎ＋ ) (Y － ) ｎ (IX-2) (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein, A ｍ＋ are each independently H ＋ A represents a metal ion or an ammonium ion; ｍ’＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａ’ｍ’）－ and C （ａｍ＋ｂｎ）－ represents a polyacid anion; Y － represents a monovalent counter anion; m and m' are integers from 1 to 5, n is an integer of 1 or 2, a is a real number, and a' and b are real numbers greater than 0.

7. A method for removing impurities from a polyacid salt represented by general formula (I) or a mixture thereof, comprising a step of washing the polyacid salt or the mixture with an acidic aqueous solution having a pH of 6 or less. (A ｍ＋ ) ａ (B ｎ＋ ) ｂ (C （ａｍ＋ｂｎ）－ ) (I) [wherein A ｍ＋ are each independently H ＋ , a metal ion, or an ammonium ion; B ｎ＋ each independently represents an onium cation or a dication; （ａｍ＋ｂｎ）－ represents a polyacid anion; m is an integer of 1 to 5, n is an integer of 1 or 2, a is a real number, and b is a real number greater than 0.

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