Compound, acid generator, composition, cured product, method for producing cured product, pattern, and method for producing pattern

Abstract

Provided is a compound having a structure represented by general formula (A). (In formula (A), Ar is a C5-20 aromatic ring group constituting a ring, R31 represents a group represented by general formula (1), and R32 is a group represented by a formula selected from general formulas (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg), and (IVh); see description for definitions of R33 and a to c.) (See description for disclosures in formulas) (see disclosures in description for symbols in formulas.)

Description

[Technical Field]

[0001] The present disclosure relates to a compound that is suitably used as an acid generator, an acid generator containing the compound, a composition and a cured product thereof, a method for producing a cured product using the composition, a pattern, and a method for producing a pattern. [Background technology]

[0002] The acid generator is a substance that generates an acid when irradiated with energy rays such as light or when subjected to heat treatment. Patent Documents 1 and 2 disclose photoacid generators or thermal acid generators made of sulfonic acid derivative compounds as acid generators. Patent Documents 1 and 2 also describe the use of acid generators with negative resists whose solubility in a developer is reduced by the formation of chemical bonds, such as polymerization or crosslinking, due to the acid generated from the acid generator, and positive resists whose solubility in a developer is increased by the action of acid, such as cleavage of chemical bonds of ester groups or acetal groups. Specific applications of the acid generators include semiconductors, overcoats, paints, adhesives, and inks. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-169173 [Patent Document 2] US20200183271A1 Summary of the Invention [Problem to be solved by the invention]

[0004] However, these acid generators have room for improvement in terms of acid generation sensitivity.

[0005] An object of the present invention is to provide a compound having excellent acid generation sensitivity. [Means for solving the problem]

[0006] As a result of extensive research conducted by the present inventors to solve the above problems, they discovered that an oxime sulfonate compound having a specific structure has excellent acid generation sensitivity, and thus completed the present invention.

[0007] That is, the present invention is a compound having a structure represented by the following general formula (A) (hereinafter, sometimes referred to as compound A).

[0008] [ka] (wherein Ar is an aromatic ring group having 5 to 20 carbon atoms constituting the ring, R 31 represents a group represented by the following general formula (1): R 32 is a group represented by a formula selected from the following general formulae (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh), R 33 teeth, Halogen atoms, nitro groups, cyano groups, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO2R 34 , -NR 35 R 36 , -NR 35 COR 36 , -CONR 35 R 36 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the following group Ia: R 31 , R 32 or R 33 When there are multiple, they may be the same or different, R 34 , R 35 and R 36 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ia; R 34 , R 35 or R 36 When there are multiple, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: a represents an integer from 1 to 20; b represents an integer of 1 to 20; c represents an integer of 0 to 18; The sum of a, b, and c is 21 or less.) [ka] (In the formula, R 1 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: * indicates the point of attachment.) [ka] (In the formula, R 51 is OR 81 , N.R. 82 R 83 or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, R 52 and R 53 are each independently R 81 OR 81 represents R 52 and R 53 may be bonded to form a ring, R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represents an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond, R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, R 69 and R 70 are each independently R 81 OR 81 represents R 81 , R 82 and R 83 each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, * indicates the point of attachment.) (Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R”-. Group IIa: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different.

[0009] The present invention also provides an acid generator containing the compound, a composition of the compound, a cured product of the composition, a method for producing a cured product by curing the composition, a pattern using the composition, and a method for producing a pattern. [Effects of the Invention]

[0010] According to the present invention, a compound having excellent acid generation sensitivity can be provided. The compound of the present invention is also excellent in that a pattern produced from a composition using the compound has high light transmittance in the visible light region. Furthermore, the present invention provides an acid generator having high acid generation sensitivity using the compound, a composition of the compound, a cured product of the composition, a method for producing a cured product by curing the composition, a pattern using the composition, and a method for producing a pattern. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention relates to a compound, an acid generator, a composition, a cured product, a method for producing the cured product, a pattern, and a method for producing a pattern. The present invention will be described in detail below.

[0012] A. Compound First, the compound of the present invention will be described. One of the features of the compound of the present invention is that it has a structure represented by the following general formula (A): In this embodiment, the compound of the present invention is represented by the following general formula (A).

[0013] [ka] (wherein Ar is an aromatic ring group having 5 to 20 carbon atoms constituting the ring, R 31 represents a group represented by the following general formula (1): R 32 is a group represented by a formula selected from the following general formulae (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh), R 33 represents a halogen atom, a nitro group, a cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO2R 34 , -NR 35 R 36 , -NR 35 COR 36 , -CONR 35 R 36 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the following group Ia: R 31 , R 32 or R 33 When there are multiple, they may be the same or different, R 34 , R 35 and R 36each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ia; R 34 , R 35 or R 36 When there are multiple, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: a represents an integer from 1 to 20; b represents an integer of 1 to 20; c represents an integer of 0 to 18; The sum of a, b, and c is 21 or less.)

[0014] [ka] (In the formula, R 1 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: * indicates the point of attachment.) [ka] (In the formula, R 51 is OR 81 , N.R. 82 R 83 or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, R 52 and R 53 are each independently R 81 OR 81 represents R 52 and R 53 may be bonded to form a ring, R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represents an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond, R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, R 69 and R 70 are each independently R 81 OR 81 represents R 81 , R 82 and R 83 each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, * indicates the point of attachment.) (Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R”-. Group IIa: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different.

[0015] According to the present invention, the compound A has a group represented by a formula selected from the general formulae (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg), and (IVh) (hereinafter also referred to as "formulas (IVa) to (IVh)"), such as a diketone group (hereinafter sometimes referred to as "group IVa, etc."), and a group represented by the general formula (1), and therefore has excellent acid generation sensitivity. The reason why the acid generation sensitivity is excellent is not clear, but is presumed to be as follows. The compound A has a structure having an IVa group or the like and a group represented by the general formula (1) (hereinafter, this structure may be referred to as the specific structure), which increases the light absorption efficiency around 365 nm. Furthermore, the structure of formula (1) corresponding to the acid generating moiety has excellent acid generating ability. Due to these factors, the compound A has excellent acid generating efficiency. The specific structure can achieve the desired sensitivity even when added in a smaller amount than a compound that does not have a combination of an IVa group or the like and a group represented by the general formula (1). As a result, the composition has excellent acid generation sensitivity. Furthermore, the compound A has high transmittance for light in the visible light region due to the presence of IVa groups, etc., and can therefore be suitably used in resin compositions for forming parts that require transparency.

[0016] Compound A of the present invention will be explained in detail below.

[0017] Examples of the halogen atom in the general formula (A) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0018] The hydrocarbon group having 1 to 20 carbon atoms in the above general formula (A), formula (1), formulae (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and the following (A1) to (A3) is a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocyclic ring, and may have a substituent. A hydrocarbon group having a substituent is a group having a structure in which one or more hydrogen atoms in the hydrocarbon group are substituted with a substituent. Preferred examples of the unsubstituted hydrocarbon group include aliphatic hydrocarbon groups, and specific examples include alkyl groups having 1 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, and cycloalkylalkyl groups having 4 to 20 carbon atoms. Furthermore, examples of the substituted hydrocarbon group include groups in which one or more hydrogen atoms in the unsubstituted hydrocarbon group have been substituted with a substituent, and examples of the substituent include an atom or group selected from Group IIa, Group IIb, or Group IIc, i.e., a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH, or -SO3H.

[0019] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and heptyl. P Examples include tadecyl and octadecyl.

[0020] The alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may be a terminal alkenyl group having an unsaturated bond at the terminal, or an internal alkenyl group having an internal unsaturated bond. Examples of terminal alkenyl groups include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, and 4,8,12-tetradecatrienyl allyl.

[0021] Examples of the cycloalkyl group having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups are substituted with alkyl groups. Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of the saturated polycyclic alkyl group include adamantyl, decahydronaphthyl, octahydropentane, and the like. Nil and bicyclo[1.1.1]pentanyl. Examples of the alkyl group substituting a hydrogen atom in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl group having 1 to 20 carbon atoms. Examples of the group in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group are substituted with an alkyl group include a bornyl group.

[0022] The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a monocyclic cycloalkyl group include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and a polycyclic cycloalkyl group include 3-3-adamantylpropyl and decahydronaphthylpropyl.

[0023] Examples of the unsubstituted hydrocarbon group in which one or more hydrogen atoms are substituted with a substituent and the substituent is a halogen atom include halogenated alkyls such as trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, and 7H-dodecafluorohexyl, and halogenated cycloalkyls or halogenated cycloalkylalkyls such as norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2-tetrafluoropropyl, and bicyclo[2.2.1]heptane-tetrafluoromethyl.

[0024] In this specification, examples of the unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R' and R" include the same groups as those exemplified above as the hydrocarbon group having 1 to 20 carbon atoms.

[0025] In the present invention, when a hydrogen atom in the group is substituted with a substituent, the number of carbon atoms in the group refers to the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom in the alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms of 1 to 20 refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted. Furthermore, in the present invention, the number of carbon atoms in a group in which a methylene group in a group with a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms in the group before the substitution. For example, in this specification, the number of carbon atoms in a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is replaced with a divalent group is considered to satisfy the requirement of 1 to 20, regardless of the number of carbon atoms after substitution. However, it is preferable that the number of carbon atoms in the group after substitution with a methylene group satisfies the requirement of the number of carbon atoms in the group before substitution.

[0026] The heterocycle-containing group having 2 to 20 carbon atoms in the above general formula (A), formula (1), formulae (IVa) to (IVh), (Ara), (Arb), (Ara1), and (Arb1), and the following formulae (A1) to (A3), is a heterocycle group or a group in which a heterocycle is bonded to a hydrocarbon group, and may have an aromatic hydrocarbon cycle-containing group, an aliphatic hydrocarbon group, or a substituent. In the group in which a heterocycle is bonded to a hydrocarbon group, the bond may be on the heterocycle or on the hydrocarbon group. A heterocycle-containing group having a substituent is a group in which one or more hydrogen atoms in the heterocycle-containing group are substituted with a substituent. The term "2 to 20 carbon atoms" refers to the total number of carbon atoms in the heterocycle-containing group. In the case of a group in which a heterocycle is bonded to a hydrocarbon group, the number of carbon atoms in the hydrocarbon group as well as the heterocycle is counted.

[0027] Examples of the unsubstituted heterocycle-containing group include heterocyclic groups such as a pyridyl group, a quinolyl group, a thiazolyl group, a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a thiophene group, a methylthiophene group, a hexylthiophene group, a benzothiophene group, a pyrrole group, a pyrrolidine group, an imidazole group, an imidazolidine group, an imidazoline group, a pyrazole group, a pyrazolidine group, a piperidine group, a piperazine group, a pyrimidyl group, a furyl group, a thienyl group, a benzoxazol-2-yl group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, and a morphonyl group, as well as groups in which one or more hydrogen atoms of an alkyl group are substituted with a heterocycle. Furthermore, examples of the heterocycle-containing group having a substituent include groups in which one or more hydrogen atoms in the unsubstituted heterocycle-containing group are substituted with a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH, -COOH, and -SOH.

[0028] Furthermore, the unsubstituted heterocycle-containing group may be a group in which a heterocycle and an aromatic hydrocarbon ring of a monocyclic structure are linked together, or a group in which a heterocycle and an aromatic hydrocarbon ring of a fused ring structure are linked together. Examples of the linking group linking two aromatic hydrocarbon rings include a single bond and a carbonyl group. Examples of the heterocycle-containing group in which a heterocycle and an aromatic hydrocarbon ring of a monocyclic structure are linked together include benzothiophene.

[0029] In the above general formula (A), formula (1), formulae (IVa) to (IVh), (Ara), (Arb), (Ara1) and (Arb1), and the following (A1) to (A3), the group in which one or more methylene groups in the above hydrocarbon group or the above heterocycle-containing group are replaced with a divalent group selected from the above group Ia, group Ib or group Ic does not have a structure in which multiple divalent groups are adjacent to each other. The multiple divalent groups here may be the same or different.

[0030] Examples of the hydrocarbon group in which one or more methylene groups have been replaced with a divalent group selected from Group Ia, Group Ib, or Group Ic include a 10-camphoryl group, which is a hydrocarbon group in which a methylene group in a bornyl group has been replaced with -CO-.

[0031] Examples of the unsubstituted aryl group having 6 to 20 carbon atoms in the formulae (IVa) to (IVh) include a phenyl group, a methylphenyl group, an ethylphenyl group, and a naphthyl group. Examples of the unsubstituted arylene group having 6 to 20 carbon atoms in the formulae (IVa) to (IVh) include a phenylene group, a methylphenylene group, an ethylphenylene group, and a naphthylene group. Examples of the substituent in the aryl group and arylene group having a substituent include a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH, and -SO3H.

[0032] In the general formula (A) of compound A, a is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 or 2, and most preferably 1. When a is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. In the general formula (A) of compound A, b is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 or 2, and most preferably 1. When b is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. In the general formula (A) of compound A, c is preferably 0 to 18, more preferably 0 to 10, even more preferably 0 to 3, and even more preferably 0 or 1. When c is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. The total of a, b, and c is preferably 21 or less, more preferably 10 or less, even more preferably 5 or less, and most preferably 2 or more and 3 or less, provided that the total is a number that can be bonded to the aromatic ring group Ar. This is because compound A has superior acid generation sensitivity when the total of a, b, and c is within the above range. This is also because the compound A is easily synthesized and an acid generator having superior acid generation sensitivity can be easily formed.

[0033] In formula (A), R 31 , R 32 and R 33 are all bonded to an aromatic ring constituting an aromatic ring group. In the present invention, R 31 is a group represented by the above general formula (1). R in the above general formula (1) 1 The substituents substituting one or more hydrogen atoms in the hydrocarbon group having the above substituent and the heterocycle-containing group having the above substituent, represented by the formula (I), are preferably halogen atoms, and more preferably fluorine atoms, because this facilitates the formation of an acid generator having excellent acid generation sensitivity. R in the above general formula (1) 1 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ia below, and is particularly preferably a hydrocarbon group having a substituent having 1 to 20 carbon atoms, and is particularly preferably a hydrocarbon group having a substituent having 1 to 20 carbon atoms, in which the substituent substituting one or more hydrogen atoms of the substituted hydrocarbon group is a halogen atom. This is because synthesis is easy, and an acid generator having excellent acid generation sensitivity can be easily formed. R in the above general formula (1) 1 The hydrocarbon group represented by the formula (I) is preferably a linear or branched alkyl group. R in the above general formula (1) 1The number of carbon atoms in the group represented by the formula is preferably 1 to 10, and more preferably 1 to 5. This is because synthesis is easy and an acid generator having excellent acid generation sensitivity can be easily formed. In particular, in the present invention, R 1 is preferably a halogenated alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms have been substituted with a halogen atom, and particularly preferably a halogenated alkyl group having 1 to 10 carbon atoms, in which one or more hydrogen atoms in an alkyl group having 1 to 10 carbon atoms have been substituted with a halogen atom, more preferably a perhaloalkyl group having 1 to 5 carbon atoms, in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with a halogen atom, and most preferably a perfluoroalkyl group having 1 to 5 carbon atoms, in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with a fluorine atom. 1 This is because Compound A has such a structure, and is a compound that has particularly excellent acid generation sensitivity. In particular, in the present invention, from the viewpoint of ease of synthesis and superior acid generation sensitivity, R 1 is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, particularly preferably a perfluoroalkyl group having 1 to 2 carbon atoms, and of these, particularly preferably a perfluoroalkyl group having 1 carbon atom, i.e., a trifluoromethyl group.

[0034] R in the above general formula (1) 2 The substituents substituting one or more hydrogen atoms in the hydrocarbon group having the above substituent and the heterocycle-containing group having the above substituent, represented by the formula (I), are preferably halogen atoms, more preferably fluorine atoms or chlorine atoms, and more preferably fluorine atoms, because this facilitates the formation of an acid generator having excellent acid generation sensitivity. R in the above general formula (1) 2is more preferably a cyano group, an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms, or a group in which one or more methylene groups of the hydrocarbon group have been replaced with a divalent group selected from Group Ia above, more preferably a cyano group, an unsubstituted or substituted hydrocarbon group of 1 to 20 carbon atoms having a halogen atom as a substituent, or a group in which one or more methylene groups of the unsubstituted or substituted hydrocarbon group have been replaced with -COO-, and among these, is even more preferably a cyano group, a hydrocarbon group of 1 to 20 carbon atoms having a halogen atom as a substituent, or a group in which one or more methylene groups of the unsubstituted or substituted hydrocarbon group have been replaced with -COO-, and is particularly preferably a cyano group or a hydrocarbon group of 1 to 20 carbon atoms having a halogen atom as a substituent, and among these, is particularly preferably a hydrocarbon group of 1 to 20 carbon atoms having a halogen atom as a substituent. This is because an acid generator with excellent acid generation sensitivity can be easily formed. R in the above general formula (1) 2 The hydrocarbon group represented by the formula (I) is preferably a linear or branched alkyl group. R in the above general formula (1) 2 The number of carbon atoms in the group represented by the formula is preferably 1 to 10, and more preferably 1 to 5. This is because synthesis is easy and an acid generator having excellent acid generation sensitivity can be easily formed. In particular, in the present invention, R 2is preferably a halogenated alkyl group having 1 to 20 carbon atoms, in which one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms have been substituted with a halogen atom, and among these, particularly preferred is a halogenated alkyl group having 1 to 10 carbon atoms, in which one or more hydrogen atoms in an alkyl group having 1 to 10 carbon atoms have been substituted with a halogen atom, more preferably a perhaloalkyl group having 1 to 5 carbon atoms, in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with a halogen atom, even more preferably a group in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms have been substituted with a chlorine atom or a fluorine atom, and among these, most preferably a perfluoroalkyl group having 1 to 5 carbon atoms. 2 This is because compound A has such a structure, and is a compound with superior acid generation sensitivity. In particular, in the present invention, from the viewpoint of ease of synthesis and superior acid generation sensitivity, R 2 is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, particularly preferably a perfluoroalkyl group having 1 to 2 carbon atoms, and among these, particularly preferably a perfluoroalkyl group having 1 carbon atom, i.e., a trifluoromethyl group.

[0035] R 32 is preferably a group represented by a formula selected from the above general formulas (IVa), (IVf), and (IVh), and is particularly preferably a group represented by general formula (IVf). This is because compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it becomes easy to form an acid generator with superior acid generation sensitivity. R of the above general formula (IVf) 67 is preferably a single bond, because compound A will have superior acid generation sensitivity. In addition, it is easy to synthesize and will facilitate the formation of an acid generator with superior acid generation sensitivity. Also, R 68is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and is most preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. This is because compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity. Also R 33 In terms of ease of imparting various functions to compound (A), it is preferable that one or more of the following represent an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been substituted with a divalent group selected from the following group Ia:

[0036] The aromatic ring in the aromatic ring group Ar having 5 to 20 carbon atoms constituting the ring may be a 5- to 7-membered monocyclic ring or a fused ring. Examples of the monocyclic ring include monocyclic cycloalkanes such as cyclopentane, cyclohexane, and cyclopentene, monocyclic aromatic rings such as benzene, and monocyclic heterocyclic rings such as pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone rings, and lactam rings. Examples of the fused ring include naphthalene, anthracene, carbazole, and fluorene. The aromatic ring group Ar may have a linked ring structure in which multiple aromatic rings are linked by a direct bond, -S-, -O-, a nitrogen atom, or the like. For example, in the case of a linked ring, the 5 to 20 carbon atoms constituting the ring may be bonded to each other. elementary atoms The number of carbon atoms constituting all rings contained in Ar is the total number of carbon atoms constituting all rings contained in Ar. For example, the number of carbon atoms constituting a carbazole ring is 12, and the number of carbon atoms constituting a fluorene ring is 13. When the aromatic ring group Ar has a condensed ring, R 31 , R 32 , R 33 is preferably bonded.

[0037] The aromatic ring group Ar is preferably an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb), because this makes the compound A a compound with superior acid generation sensitivity.

[0038] [ka] (In the formula, X 1 is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 and X 2 is an oxygen atom, a sulfur atom, a selenium atom, a CR 41 R 42 , CO, NR 43 or PR 44 and X 3 is NR 53 and R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ib; R 41 , R 42 , R 43 and R 44 When there are multiple, they may be the same or different, R 53 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111 , -NR 112 R 113 , -NR 112 COR113 , -CONR 112 R 113 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ib: R 111 , R 112 and R 113 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ib; R 111 , R 112 and R 113 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the following group IIb: ( Group Ib: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group IIb: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different.

[0039] In addition, from the viewpoint of further increasing the acid generation sensitivity of compound A, it is preferable that in the above general formula (A), a is 1, b is 1, and the following partial structure (Aα) in general formula (A) is a group represented by the following general formula (Ara1) or (Arb1).

[0040] [ka] (In the formula, Ar, R 33 and c are the same as in formula (A). *1 is R 31 *2 indicates the bond with R 32 )

[0041] [ka] (In the formula, X 1 , X 2 , X 3 are the same as those in the general formulae (Ara) and (Arb), respectively, R 141 , R 142 , R 151 and R 152 each independently represents a halogen atom, a nitro group, a cyano group, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121 , -SR 121 , -SOR 121 , -SO2R 121 , -NR 122 R 123 , -NR 122 COR 123 , -CONR 122 R 123 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the following Group Ic: R 121 , R 122 and R 123each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ic; R 121 , R 122 and R 123 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIc: a1 is 0 to 3, a2 is 0 to 3, c1 is 0 to 3, c2 is between 0 and 1, *1 is R 31 represents the point of attachment to *2 is R 32 ) ( Group Ic: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group IIc: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different.

[0042] X in the above general formulas (Ara) and (Ara1) 1 is a single bond, no bond, CR 41 R 42 , CO, or NR 43Preferably, X is a single bond or no bond, and most preferably a single bond. This is because compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity. "No bond" means that X 1 For example, in the following general formula (A1), R 11 and R 20 is not bonded.

[0043] X in the above general formula (Ara) and (Ara1) 2 is a sulfur atom, CR 41 R 42 or NR 43 It is preferable that CR 41 R 42 or NR 43 is preferable because Compound A is a compound with superior acid generation sensitivity, and is easy to synthesize, making it easy to form an acid generator with superior acid generation sensitivity.

[0044] X in the above general formulas (Ara) and (Ara1) 2 R used in 41 , R 42 is preferably a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ib above, and is particularly preferably a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and is particularly preferably a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. This is because Compound A will be a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity. X in the above general formulas (Ara) and (Ara1) 2 R used in 41 , R 42The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 5. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, this is because it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed.

[0045] R in the above general formulas (Ara) and (Ara1) 43 From the viewpoints of ease of synthesis and excellent acid generation sensitivity, is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ib above, and among these, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms is preferred, and an unsubstituted hydrocarbon group having 1 to 20 carbon atoms is particularly preferred. R in the above general formulas (Ara) and (Ara1) 43 From the viewpoints of ease of synthesis and excellent acid generation sensitivity, the hydrocarbon group represented by the following formula preferably has 1 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 9 carbon atoms. R in the above general formulas (Ara) and (Ara1) 43 From the viewpoints of ease of synthesis and excellent acid generation sensitivity, the aliphatic hydrocarbon group represented by the formula (I) is preferably a linear or branched alkyl group, and more preferably a branched alkyl group. In the case of a branched alkyl group, it is particularly preferred that the number of carbon atoms is 3 to 9.

[0046] In the general formula (Ara1), a1 is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. When a1 is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. In the general formula (Ara1), a2 is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. When a2 is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. In the general formula (Arb1), c1 is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0. When c1 is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. In the general formula (Arb1), c2 is preferably 0 to 1, and particularly preferably 0. When c2 is within the above range, compound A becomes a compound with superior acid generation sensitivity. In addition, this is because synthesis is easy, and an acid generator with superior acid generation sensitivity can be easily formed.

[0047] In the present invention, X in the above general formula (Ara) or (Ara1) 2 is preferably a sulfur atom, and X in (Ara1) 2 is a sulfur atom, a1=0, a2=0 are particularly preferred. In the above general formula (Ara) or (Ara1), X 2 When is a sulfur atom, it is particularly preferable that compound A has a structure represented by the following general formula (A1). This is because Compound A has excellent acid generation sensitivity due to its structure, and is easy to synthesize, making it easy to form an acid generator with excellent acid generation sensitivity.

[0048] [ka] (In the formula, R 11 and R 20 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , -OCOR 90 , -COOR 90, -SR 90 , -SOR 90 , -SO2R 90 , -NR 91 R 92 , -NR 91 COR 92 , -CONR 91 R 92 , a group represented by the following general formula (1), a group represented by a formula selected from the above formulas (IVa) to (IVh), an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the above group Ia, or R 11 and R 20 Single bonds formed by bonding -O-, -S-, -Se-, -CR 41 R 42 -, -CO-, -NR 43 - or -PR 44 - represents R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , -OCOR 90 , -COOR 90 , -SR 90 , -SOR 90 , -SO2R 90 , -NR 91 R 92 , -NR 91 COR 92 , -CONR 91 R 92, a group represented by the above general formula (1), a group represented by a formula selected from the above formulae (IVa) to (IVh), an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the above group Ia, R 90 , R 91 and R 92 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the above group Ia; R 90 , R 91 and R 92 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the above group IIa. However, R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 At least one of the above is a group represented by the general formula (1), and at least one of the remaining is a group represented by a formula selected from the above formulas (IVa) to (IVh).

[0049] R in the above general formula (A1) 11 and R 20 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group are replaced by a divalent group selected from the group Ia above, or R 11 and R 20 are combined formed , single bond, -O-, -S-, -Se-, -CR 41 R 42 -, -CO-, -NR 43 - or -PR 44 - is preferred, and among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, or R 11 and R 20 A single bond, -O- or -NR 43 -, and in particular a hydrogen atom or R 11 and R 20 is preferably a single bond formed by bonding the following: Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize and makes it easy to form an acid generator with superior acid generation sensitivity. 。

[0050] R in the above general formula (A1) 11 , R 20 are bonded to each other to form -NR 43 -If R 43 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ib above, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and is particularly preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed. R in the above general formula (A1) 43The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 5. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, this is because it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed. R in the above general formula (A1) 43 The hydrocarbon group represented by the formula (I) is preferably a linear or branched alkyl group, and more preferably a linear alkyl group. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, this is because it is easy to synthesize, and it becomes easy to form an acid generator with superior acid generation sensitivity.

[0051] R in the above general formula (A1) 12 , R 14 , R 15 , R 16 , R 17 and R 19 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ic above, and among these, a hydrogen atom, a nitro group, or a cyano group is preferred, and a hydrogen atom is particularly preferred. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity.

[0052] R in the above general formula (A1) 13 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group are replaced with a divalent group selected from Group Ic above, a group represented by General Formula (1) above, or a group represented by Formulas (IVa) to (IVh) above is preferred, and among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by General Formula (1) above, or a group represented by a formula selected from Formulas (IVa) to (IVh) above is preferred, and a hydrogen atom, a group represented by General Formula (1) above, or a group represented by a formula selected from Formulas (IVa) to (IVh) above is preferred, and a group represented by General Formula (1) above is particularly preferred. This is because Compound A becomes a compound with superior acid generation sensitivity. Furthermore, it is easy to synthesize, and acid generators with excellent acid generation sensitivity can be easily formed.

[0053] R in the above general formula (A1) 18 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from group Ic above, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above, and among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above is preferred, a hydrogen atom, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above is preferred, and a group represented by a formula selected from formulas (IVa) to (IVh) above is particularly preferred.

[0054] In addition, in the above general formula (A1), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20At least one of the groups may be a group represented by the general formula (1), 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 At least one of the groups may be a group represented by a formula selected from the above formulas (IVa) to (IVh). 13 and R 18 It is preferable that one group of R in the general formula (A1) is a group represented by the above general formula (1), and the other group is a group represented by a formula selected from the above formulas (IVa) to (IVh). 13 is a group represented by the general formula (1), and R 18 is preferably a group represented by a formula selected from the above formulas (IVa) to (IVh). This is because Compound A has excellent acid generation sensitivity due to its structure, and is easy to synthesize, making it easy to form an acid generator with excellent acid generation sensitivity.

[0055] Among the groups represented by a formula selected from general formulae (IVa) to (IVh), groups represented by a formula selected from general formulae (IVa), (IVf), and (IVh) are preferred, and a group represented by general formula (IVf) is particularly preferred. This is because compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it becomes easy to form an acid generator with superior acid generation sensitivity.

[0056] R of the above general formula (IVf) 67 is preferably a single bond. 68is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and is preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed.

[0057] In the present invention, X in the above general formula (Ara) or (Ara1) 1 is a single bond and X 2 NR 43 In the formula (Ara) or (Ara1), X 1 is a single bond and X 2 NR 43 It is particularly preferable that a1 = 0 and a2 = 0. This is because compound A becomes a compound with superior acid generation sensitivity. In the above general formula (Ara) or (Ara1), X 1 is a single bond and X 2 NR 43 In the case where the compound A is a compound represented by the formula (A2), it is particularly preferable that the compound A has a structure represented by the following formula (A2). This is because Compound A has excellent acid generation sensitivity due to its structure, and is easy to synthesize, making it easy to form an acid generator with excellent acid generation sensitivity.

[0058] [ka] (R 12' 、 R 13' , R 14' , R 15' , R 16' , R 17' , R 18' and R 19' are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90, -COR 90 , -OCOR 90 , -COOR 90 , -SR 90 , -SOR 90 , -SO2R 90 , -NR 91 R 92 , -NR 91 COR 92 , -CONR 91 R 92 , a group represented by the above general formula (1), a group represented by a formula selected from the above formulae (IVa) to (IVh), an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the above group Ia, R 90 , R 91 and R 92 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the above group Ia; R 90 , R 91 and R 92 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the above group IIa. However, R 12' 、 R 13' , R 14' , R 15' , R 16' , R 17' , R 18' and R 19' At least one of the above is a group represented by the general formula (1), and at least one of the remaining is a group represented by a formula selected from the above formulas (IVa) to (IVh).

[0059] R in the above general formula (A2) 12' , R 14' , R 15' , R 16' , R 17' and R 19' are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ic above, and among these, a hydrogen atom, a nitro group, or a cyano group is preferred, and a hydrogen atom is particularly preferred. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity.

[0060] R in the above general formula (A2) 13' represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group are replaced with a divalent group selected from Group Ic above, a group represented by General Formula (1) above, or a group represented by Formulas (IVa) to (IVh) above is preferred, and among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by General Formula (1) above, or a group represented by a formula selected from Formulas (IVa) to (IVh) above is preferred, and a hydrogen atom, a group represented by General Formula (1) above, or a group represented by a formula selected from Formulas (IVa) to (IVh) above is preferred, and a group represented by General Formula (1) above is particularly preferred. This is because Compound A becomes a compound with superior acid generation sensitivity. Furthermore, it is easy to synthesize, and acid generators with excellent acid generation sensitivity can be easily formed.

[0061] R in the above general formula (A2) 18' represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from group Ic above, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above, and among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above is preferred, a hydrogen atom, a group represented by general formula (1) above, or a group represented by a formula selected from formulas (IVa) to (IVh) above is preferred, and a group represented by a formula selected from formulas (IVa) to (IVh) above is particularly preferred.

[0062] In addition, in the general formula (A2), R 12' , R 13' , R 14' , R 15' , R 16' , R 17' , R 18' and R 19' At least one of the groups may be a group represented by the general formula (1), 12' , R 13' , R 14' , R 15' , R 16' , R 17' , R 18' and R 19' At least one of the groups may be a group represented by a formula selected from the above formulas (IVa) to (IVh). 13' and R 18' It is preferable that one group of R in the general formula (A2) is a group represented by the above general formula (1), and the other group is a group represented by a formula selected from the above formulas (IVa) to (IVh). 13' is a group represented by the general formula (1), and R 18' is preferably a group represented by a formula selected from the above formulas (IVa) to (IVh). This is because Compound A has excellent acid generation sensitivity due to its structure, and is easy to synthesize, making it easy to form an acid generator with excellent acid generation sensitivity.

[0063] Among the groups represented by a formula selected from general formulae (IVa) to (IVh), groups represented by a formula selected from general formulae (IVa), (IVf), and (IVh) are preferred, and a group represented by general formula (IVf) is particularly preferred. This is because compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it becomes easy to form an acid generator with superior acid generation sensitivity.

[0064] R of the above general formula (IVf) 67 is preferably a single bond. 68 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 5 carbon atoms, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 3 carbon atoms, and is preferably an unsubstituted hydrocarbon group having 1 to 3 carbon atoms. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed.

[0065] R in the above general formula (A2) 43 is preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ib above, and is particularly preferably an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and is particularly preferably an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed. R in the above general formula (A2) 43The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 1 to 15, more preferably 2 to 10, and particularly preferably 2 to 9. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed. R in the above general formula (A2) 43 The hydrocarbon group represented by the formula (I) is preferably a linear or branched alkyl group, and particularly preferably a branched alkyl group. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it becomes easy to form an acid generator with superior acid generation sensitivity. Furthermore, it has good solubility in solvents.

[0066] In the present invention, X in the above general formula (Ara) or (Ara1) 1 is a single bond and X 2 is CR 41 R 42 In the above general formula (Ara) or (Ara1), X 1 is a single bond and X 2 is CR 41 R 42 It is particularly preferable that a1 = 0 and a2 = 0. This is because compound A becomes a compound with superior acid generation sensitivity. In the above general formula (Ara) or (Ara1), X 1 is a single bond and X 2 is CR 41 R 42 In the case where compound A is a compound represented by the formula (A3), it is particularly preferable that compound A has a structure represented by the following formula (A3). This structure makes Compound A a compound with superior acid generation sensitivity. Furthermore, it is easy to synthesize and to form an acid generator with superior acid generation sensitivity. Furthermore, the skeleton of formula (A3) has the advantage of easily achieving solvent solubility.

[0067] [ka] (R 12'', R 13'' , R 14'' , R 15'' , R 16'' , R 17'' , R 18'' and R 19'' represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 , -OCOR 90 , -COOR 90 , -SR 90 , -SOR 90 , -SO2R 90 , -NR 91 R 92 , -NR 91 COR 92 , -CONR 91 R 92 , a group represented by the above general formula (1), a group represented by a formula selected from the above formulae (IVa) to (IVh), an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the above group Ia, R 90 , R 91 and R 92 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group have been replaced with a divalent group selected from the above group Ia; R 90 , R 91 and R 92 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the above group IIa. However, R 12'' , R 13'' , R 14'' , R 15'' , R 16'' , R 17'', R 18'' and R 19'' At least one of the above is a group represented by the general formula (1), and at least one of the remaining is a group represented by a formula selected from the above formulas (IVa) to (IVh).

[0068] R 41 , R 42 is preferably a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ib above, and is particularly preferably a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and is particularly preferably a hydrogen atom or an unsubstituted hydrocarbon group having 1 to 20 carbon atoms. This is because Compound A will be a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity. R in the above general formula (A3) 41 , R 42 The number of carbon atoms in the hydrocarbon group represented by the formula (I) is preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 5. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, this is because it is easy to synthesize, and an acid generator with superior acid generation sensitivity can be easily formed.

[0069] R in the above general formula (A3) 12'' , R 15'' , R 16'' and R 19'' are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from Group Ic above, and among these, a hydrogen atom, a nitro group, or a cyano group is preferred, and a hydrogen atom is particularly preferred. This is because Compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with superior acid generation sensitivity.

[0070] R in the above general formula (A3) 13'' and R 14'' At least one of the groups is a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90 a hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are replaced by a divalent group selected from group Ic above, a group represented by general formula (1) above, or a group selected from formulas (IVa) to (IVh) above formula Among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above general formula (1), or a group selected from the above formulas (IVa) to (IVh) is preferred. formula and is preferably a group represented by the formula (1) above, or a group selected from the formulae (IVa) to (IVh) above. formula It is particularly preferred that the group be a group represented by the general formula (1) above. 14'' However, it is preferable that Compound A satisfies these conditions, because Compound A will be a compound with superior acid generation sensitivity, and because it is easy to synthesize, making it easy to form an acid generator with superior acid generation sensitivity.

[0071] In the above general formula (A3), R 17'' and R 18'' At least one of the groups is a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 90 , -COR 90a hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are replaced by a divalent group selected from group Ic above, a group represented by general formula (1) above, or a group selected from formulas (IVa) to (IVh) above formula Among these, a hydrogen atom, a halogen atom, a nitro group, a cyano group, a group represented by the above general formula (1), or a group selected from the above formulas (IVa) to (IVh) is preferred. formula and is preferably a group represented by the formula (1) above, or a group selected from the formulae (IVa) to (IVh) above. formula In particular, it is preferably a group represented by the formula (IVa) to (IVh) above. formula In particular, R 17'' However, it is preferable that Compound A satisfies these conditions, because Compound A will be a compound with superior acid generation sensitivity, and because it is easy to synthesize, making it easy to form an acid generator with superior acid generation sensitivity.

[0072] In addition, in general formula (A3), R 12'' , R 13'' , R 14'' , R 15'' , R 16'' , R 17'' , R 18'' and R 19'' At least one of the groups may be a group represented by the general formula (1), 12'' , R 13'' , R 14'' , R 15'' , R 16'' , R 17'' , R 18'' and R 19'' At least one of the above is selected from the formulas (IVa) to (IVh). formula Among them, R 13'' and R 18'' one group is a group represented by the above general formula (1), and the other group is selected from the above formulas (IVa) to (IVh), formula or R 14'' and R 17''one group is a group represented by the above general formula (1), and the other group is selected from the above formulas (IVa) to (IVh), formula In particular, R in the above general formula (A3) is preferably a group represented by 14'' is a group represented by the general formula (1), and R 17'' is selected from the above formulas (IVa) to (IVh) formula It is preferable that the group is a group represented by the following formula: This is because Compound A has excellent acid generation sensitivity due to its structure, and is easy to synthesize, making it easy to form an acid generator with excellent acid generation sensitivity.

[0073] In the general formula (A3), a compound selected from the general formulae (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh) is formula Among the groups represented by the formulae (IVa), (IVf) and (IVh), groups represented by the formulae (IVa), (IVf) and (IVh) are preferred, and groups selected from the formula (IVf) are particularly preferred. formula The compound A is preferably a group represented by the formula (I) because it is easy to synthesize and makes it easy to form an acid generator having excellent acid generation sensitivity.

[0074] Specific examples of the compound A include compounds represented by the following Nos. 1 to 58.

[0075] [ka]

[0076] [ka]

[0077] [ka]

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] [ka]

[0084] The method for producing the compound A may be any method that can obtain a compound of the desired structure, and can be synthesized by applying well-known chemical reactions. For example, the method shown in the following scheme can be mentioned. Specifically, a known ketone compound is reacted with hydroxylamine hydrochloride to obtain an oxime compound. Subsequently, the oxime compound is reacted with sulfonic acid anhydride. Next, R 32 In one example, a compound having a group represented by the formula (I) is reacted with a diketone such as chloroglyoxylic acid to obtain Compound A. The reaction conditions in the production method, such as the reaction temperature, reaction time, and amount of raw materials used, are not particularly limited, and known conditions may be used.

[0085] [ka] (The symbols in the formula have the same meanings as in the above general formula (1), (IVf), and (Ara).)

[0086] The compound A has the function of generating an acid. The method for generating an acid from the compound A can be a method generally used for acid generators, such as a method of irradiating with energy rays, a method of heat treatment, or a method of performing these methods simultaneously or sequentially. Examples of the energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible light, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle rays. Examples of light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, and lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium-cadmium lasers, etc.). The heating temperature in the heat treatment is preferably, for example, 70°C or higher and 450°C or lower, and more preferably 100°C or higher and 300°C or lower, and may be 150°C or higher. The heating time in the heat treatment is preferably, for example, 1 minute or higher and 100 minutes or lower. This is because the above heat treatment conditions can effectively exert the effect of obtaining a composition with little color change.

[0087] The compound A can be used as an acid generator, more specifically as a photoacid generator that generates an acid upon irradiation with energy rays, or as a thermal acid generator that generates an acid upon heat treatment. Furthermore, the acid generator can be used as an additive to a composition containing a resin component. The compositions can be used in applications such as optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, and print substrates. board, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic EL devices, optical elements, electrical insulation, electronic components, separation membranes, etc., molding materials, putty, glass fiber impregnation agents, fillers, passivation films for semiconductors, solar cells, etc., interlayer insulating films used in thin film transistors (TFTs), liquid crystal displays, organic EL displays, printed circuit boards, etc., surface protection films, printed circuit boards, color televisions, PC monitors, personal digital assistants, color filters for CCD image sensors, electrode materials for plasma display panels, printing inks, dental compositions, stereolithography resins, both liquid and dry films, micromachine parts, glass fiber cable coatings, holographic recording materials, magnetic recording materials, optical switches, plating masks, etching masks, screen printing stencils, touch panels such as transparent conductive films, MEMS elements, nanoimprint materials, photofabrication such as two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, engineering Nails, glass substitute optical films, electronic paper, optical discs, microlens arrays used in projectors, lasers for optical communications, etc., prism lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens for projection televisions, etc., lens parts of lens sheets such as lenticular lens sheets, or backlights using such sheets, optical lenses such as microlenses and imaging lenses, optical elements, optical connectors, optical waveguides, insulating packing, heat-shrinkable rubber tubes, O-rings, sealants for display devices, They can be used for a variety of purposes, including, but not limited to, protective materials, optical fiber protective materials, adhesives, die bonding agents, high heat dissipation materials, high heat resistant sealing materials, solar cell, fuel cell, and secondary battery components, solid electrolytes for batteries, insulating coating materials, photosensitive drums for copiers, gas separation membranes, civil engineering and construction materials such as concrete protective materials, linings, soil injection agents, sealants, cold and heat storage materials, glass coatings, and foams, tubes, sealants, coating materials, sealants for sterilization treatment equipment, contact lenses, oxygen enrichment membranes, medical materials such as biochips, automotive parts, and various machine parts. From the viewpoint of more effectively exerting the effect of the excellent acid generation sensitivity of the present invention, the above-mentioned use is preferably for a pattern-forming composition, for example, for a negative composition used together with an acid-hardening component, or for a positive composition used together with an acid-decomposable component (also referred to as an "acid-decomposable resin component"). More specifically, the use is preferably for a composition used in forming an optical lens, an optical element, an optical connector, an optical waveguide, or an interlayer insulating film used in a liquid crystal display device, an organic EL display device, a printed circuit board, etc., which require high acid generation sensitivity.

[0088] B. Acid generator One of the characteristics of the acid generator of the present invention is that it contains the compound A described above. By including Compound A in the acid generator, an acid generator having excellent acid generation sensitivity can be easily obtained.

[0089] 1. Compound A The type of the compound A used in the acid generator of the present invention may be any type as long as an acid generator having excellent acid generation sensitivity can be easily obtained, and the acid generator may contain only one type or two or more types.

[0090] The content of the compound A in the acid generator of the present invention may be any amount that allows an acid generator with excellent acid generation sensitivity to be easily obtained, and is appropriately set depending on the type of acid generator, etc. The content of the compound A in the acid generator of the present invention may be, for example, 100 parts by mass per 100 parts by mass of the solid content of the acid generator, i.e., the solid content of the acid generator may consist solely of the compound A. The content of the compound A in the acid generator of the present invention may be less than 100 parts by mass per 100 parts by mass of the solid content of the acid generator, i.e., the acid generator may be a composition containing the compound A and other components, and may be, for example, more than 20 parts by mass but not more than 99.99 parts by mass. This is because an acid generator with excellent acid generation sensitivity can be easily obtained when the content of the compound A is in the above-mentioned range. When the acid generator of the present invention contains components other than the compound A, from the viewpoint of more easily obtaining an acid generator with excellent acid generation sensitivity, the lower limit of the content of compound A in the acid generator of the present invention is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 90 parts by mass or more, per 100 parts by mass of the solid content of the acid generator. This is because an acid generator with excellent acid generation sensitivity can be easily obtained by setting the upper limit of the content of compound A within the above-mentioned range. Furthermore, from the viewpoint of facilitating control of the particle size of the acid generator, etc., the upper limit of the content of compound A in the acid generator of the present invention is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, and even more preferably 90 parts by mass or less, per 100 parts by mass of the solid content of the acid generator. This is because an acid generator with excellent acid generation sensitivity can be easily obtained by setting the content of compound A within the above-mentioned range. The solid content includes all components other than the solvent. Furthermore, when two or more types of compound A are contained, the content of compound A indicates the total amount of compound A.

[0091] The compound A can be the same as that described in the section "A. Compound" above, and therefore the description here will be omitted.

[0092] 2. Other ingredients The acid generator may contain other components in addition to the compound A. Such other components may include, for example, a solvent. The solvent is capable of dissolving or dispersing each component of the acid generator. Therefore, even if the solvent is liquid at room temperature (25°C) under atmospheric pressure, the compound A is not included in the solvent. Either water or an organic solvent can be used as the solvent. In the present invention, the solvent is preferably an organic solvent, as this makes it easier to dissolve or disperse the compound A.

[0093] Examples of the organic solvent include carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and the monomethyl ether or monophenyl ether of dipropylene glycol monoacetate; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene; and lactones such as γ-caprolactone and δ-caprolactone.

[0094] The content of the solvent in the acid generator can be 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the acid generator.

[0095] Examples of other components besides the compound A and the solvent include those described in the sections "2. Resin component" and "3. Other components" in "C. Composition" below. The other components include known compounds used as acid generators. The content of the other components can be appropriately set depending on the application of the acid generator, and can be, for example, less than 50 parts by mass, and more preferably 10 parts by mass or less, per 100 parts by mass of the solid content of the acid generator, because this makes it easier to increase the content of compound A in the acid generator, and makes it easier to obtain an acid generator with excellent acid generation sensitivity.

[0096] 3.Other The acid generator may be produced by any method as long as it contains the compound A in the desired amount. When the acid generator contains compound A and other components, a method using a known mixing means can be used.

[0097] The acid generator may be used in the form of an additive to a composition containing a resin component, and specifically, the same applications as those described in the section "A. Compound" above may be used.

[0098] C. Composition One of the characteristics of the composition of the present invention is that it contains the above-mentioned compound A and a resin component. By including the compound A, the resulting composition etc. will have excellent acid generation sensitivity.

[0099] 1. Compound A The type of compound A used in the composition of the present invention may be any type that can exhibit the effect of excellent acid generation sensitivity, and the composition may contain only one type or two or more types.

[0100] The content of the compound A in the composition of the present invention may be any amount that can exhibit the effect of excellent acid generation sensitivity, and is appropriately set depending on the type of resin component used, etc. The content of compound A in the composition of the present invention is, for example, preferably 0.05 parts by mass or more and 100 parts by mass or less, and more preferably 0.05 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the resin component. This is because a composition that can exhibit the effect of excellent acid generation sensitivity can be easily obtained. Also, this is because it is easy to form a composition that is suppressed in coloration. The content of compound A in the composition of the present invention is preferably, for example, 0.001 to 20 parts by mass per 100 parts by mass of the solid content of the composition. This is because a composition that can exhibit the effect of excellent acid generation sensitivity can be easily obtained. Also, this is because it is easy to form a composition that is suppressed in coloration. The content of the compound A in the composition of the present invention is preferably, for example, 0.001 to 20 parts by mass per 100 parts by mass of the composition. This is because a composition that can exhibit the effect of excellent acid generation sensitivity can be easily obtained. Also, this is because a composition that is suppressed in coloration can be easily formed. The content of the compound A indicates the total amount of the compound A when two or more types of compound A are contained.

[0101] The compound A can be the same as that described in the section "A. Compound" above, and therefore will not be described here.

[0102] 2. Resin component As the resin component, a polymer compound or a component that can become a polymer compound can be used. Furthermore, the resin component may be an acid-reactive component having a structure capable of reacting with the acid generated from compound A, or a non-acid-reactive component that does not react with the acid generated from compound A. However, it is preferable that the resin component be an acid-reactive component. This is because, when the resin component is an acid-reactive component, the composition can easily achieve the effect of excellent acid generation sensitivity possessed by compound A. This is also because it is easy to form a composition in which coloration is suppressed.

[0103] As such an acid-reactive component, it is preferable to use an acid-hardening component that hardens by polymerization or crosslinking due to the acid generated from compound A, or an acid-decomposable component whose solubility in a developer increases due to the acid generated from compound A. In the present invention, when the resin component is an acid-hardening component, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-hardening component can be easily hardened. Furthermore, when the resin component is an acid-decomposable component, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-decomposable component can be easily decomposed. Furthermore, a composition can be obtained in which coloring is suppressed in non-developed areas that do not undergo a change in solubility in the developer.

[0104] The acid-hardening component may include a cationically polymerizable compound. Examples of the cationically polymerizable compound include cyclic ether compounds such as epoxy compounds and oxetane compounds, vinyl ether compounds, vinyl compounds, styrenes, spiro orthoesters, bicyclo orthoesters, spiro orthocarbonates, lactones, oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, and aryldialdehydes, as well as polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in their side chains. These compounds may be used alone or in combination of two or more. Specific examples of such cationically polymerizable compounds that can be used include the acid-reactive organic substances described in WO 2017 / 130896 and the compounds described as cationically polymerizable compounds in WO 2014 / 084269, WO 2016 / 132413, etc.

[0105] The acid-hardening component may also be a mixture of a crosslinkable resin and a crosslinking agent. Examples of the crosslinkable resin include polyhydroxystyrene and derivatives thereof; polyacrylic acid and derivatives thereof; polymethacrylic acid and derivatives thereof; copolymers of two or more selected from hydroxystyrene, acrylic acid, methacrylic acid, and derivatives thereof; copolymers of two or more selected from hydroxystyrene, styrene, and derivatives thereof; copolymers of three or more selected from cycloolefins and derivatives thereof, maleic anhydride, and acrylic acid and derivatives thereof; copolymers of three or more selected from cycloolefins and derivatives thereof, maleimide, and acrylic acid and derivatives thereof; polynorbornene; one or more types of high molecular weight polymers selected from the group consisting of metathesis ring-opening polymers; polymers having alkoxysilyl groups; and high molecular weight polymers obtained by partially substituting these high molecular weight polymers with acid labile groups having alkali solubility controllability. Examples of the polymer containing a structural unit derived from hydroxystyrene, such as the polyhydroxystyrene, include the phenolic hydroxyl group-containing resin (QN) described in JP-A-2018-112670. Examples of the crosslinkable resin that can be used include the resist base resin described in WO 2017 / 130896, the resin whose solubility in an alkaline developer changes due to the action of the acid of component (A) described in JP 2003-192665 A, claim 3 of JP 2004-323704 A, and the alkali-soluble resin described in JP 10-10733 A. As the polymer having an alkoxysilyl group, for example, a compound in which the alkoxysilyl group is not directly bonded to an aromatic ring can be used.

[0106] The crosslinking agent may be any agent capable of crosslinking the crosslinkable resins together in the presence of an acid, and may be a compound capable of reacting with an acidic group, such as a phenolic hydroxyl group or a carboxyl group, contained in the resin, such as an epoxy group-containing compound, a hydroxyl group-containing compound, an alkoxy group-containing compound, a methylol group-containing compound, or a carboxymethyl group-containing compound, in the presence of an acid. More specifically, examples of the crosslinking agent include the crosslinking agents described in JP-A-2016-169173 and JP-A-2018-112670.

[0107] The acid-decomposable component may be any component whose solubility in a developer is increased by the acid generated from compound A. Examples of the acid-decomposable component include resins having acidic groups such as phenolic hydroxyl groups, carboxyl groups, sulfonyl groups, and silanol groups, in which some or all of the hydrogen atoms of the acidic groups are protected with protecting groups. Examples of resins having such acidic groups include the crosslinkable resins used together with the crosslinking agent as the acid-hardening component described above. The positive-type chemically amplified resins described in JP 2018-112670 A can also be used. The protecting group may be any group capable of protecting the acidic group, and examples thereof include the protecting groups described in JP 2016-169173 A, the acid-labile groups described in WO 2017 / 130896 A, and the acid-dissociable groups described in JP 2018-112670 A. Examples of the silanol group protected by a protecting group include alkoxysilyl groups. Examples of polymers having alkoxysilyl groups used as acid-decomposable components include those described in JP 2019-66828 A as "polymer component (A) having a structural unit (I) containing an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring, and a structural unit (II) containing an acidic group." Examples of the developer include the developer described in the section "G. Pattern manufacturing method" below.

[0108] The acid-reactive component may be, in addition to the acid-hardening component and the acid-decomposable component, a component that reacts with acid. For example, a resin having an alkali-soluble group that is insolubilized by acid may also be used. Specific examples include acid-insolubilized resins that undergo intramolecular or intermolecular crosslinking reactions due to acid-catalyzed dehydration condensation between hydroxyl groups and carboxyl groups, or between carboxyl groups as exemplified below. Examples of acid-insolubilized resins that undergo acid-catalyzed dehydration condensation between carboxyl groups include resins having a phthalic acid structure that undergo dehydration condensation between carboxyl groups in the presence of acid, as shown below.

[0109] [ka]

[0110] The non-acid-reactive component may be one that does not react with the acid generated from compound A, more specifically, one that does not harden, decompose, or undergo a change in solubility in an alkaline developer due to the acid generated from compound A. Examples of the non-acid-reactive component include thermoplastic resins such as polyolefin resins, polybutadiene resins, polystyrene resins, polystyrene-butadiene resins, and polystyrene-olefin resins.

[0111] The content of the resin component in the composition of the present invention may be any amount that can provide the effect of providing excellent acid generation sensitivity, and is appropriately set depending on the type of resin component used, etc. The content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more, preferably 30 parts by mass or more and 99.9 parts by mass or less, and more preferably 50 parts by mass or more and 99 parts by mass or less, per 100 parts by mass of the solid content of the composition, because this effectively achieves the effect of obtaining a composition with excellent acid generation sensitivity. The content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more, more preferably 30 parts by mass or more and 99.9 parts by mass or less, and particularly preferably 50 parts by mass or more and 96 parts by mass or less, per 100 parts by mass of the composition, because this effectively achieves the effect of obtaining a composition with excellent acid generation sensitivity.

[0112] 3. Solvent The composition may include a solvent. The solvent is capable of dispersing or dissolving each component in the composition. Therefore, even if the solvent is liquid at room temperature (25°C) and atmospheric pressure, the compound A and the resin component are not included in the solvent. The solvent may be either water or an organic solvent. In the present invention, the solvent is preferably an organic solvent, since it is easy to dissolve or disperse the compound A in the organic solvent. The organic solvent may be the same as that described in the section "B. Acid Generator." Furthermore, the content of the solvent in the composition of the present invention is appropriately set depending on the intended use of the composition, and can be, for example, 1 part by mass or more and 99 parts by mass or less per 100 parts by mass of the composition.

[0113] 4. Other ingredients The composition may contain other ingredients as needed. Such other components can be selected depending on the intended use of the composition, and examples thereof include benzotriazole-based, triazine-based, and benzoate-based ultraviolet absorbers; phenol-based, phosphorus-based, and sulfur-based antioxidants; antistatic agents such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants; flame retardants such as halogen-based compounds, phosphate ester-based compounds, phosphoric acid amide-based compounds, melamine-based compounds, fluororesins or metal oxides, (poly)melamine phosphate, and (poly)piperazine phosphate; and hydrocarbon-based, fatty acid-based, and aliphatic alcohols. lubricants based on aliphatic esters, aliphatic amides, or metal soaps; colorants such as dyes, pigments, and carbon black; silicic acid-based inorganic additives such as fumed silica, fine particle silica, silica stone, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, minesotite, pyrophyllite, and silica; fillers such as glass fiber and calcium carbonate; crystallization agents such as nucleating agents and crystallization accelerators, rubber elasticity-imparting agents such as silane coupling agents and flexible polymers, and sensitizers. The other components may also include an acid diffusion controller such as an amine compound, an amide group-containing compound, a urea compound, or a nitrogen-containing heterocyclic compound. Examples of the sensitizer include compounds described as spectral sensitizers in JP-A-2008-506749. Examples of the acid diffusion controller include compounds described as “[D] acid diffusion controller” in JP-A-2019-8300. The content of these other components in the composition of the present invention can be 50 parts by mass or less per 100 parts by mass of the composition.

[0114] 5.Other The composition can be produced by any known method as long as it is capable of mixing the components in the desired amounts. For example, there can be mentioned a method in which the compound A is dissolved or dispersed in a solvent, and then the resin component is added to the solvent.

[0115] D. Cured product The cured product of the present invention is a cured product of the above-described composition. The resin component contained in the composition is an acid-hardening component.

[0116] According to the present invention, by using the above-mentioned composition, a cured product is obtained in which the acid-curable component has been sufficiently cured.

[0117] The cured product of the present invention uses the above-described composition. The resin component is an acid-curable component. The cured product is formed by curing the acid-curable component, and includes a polymer formed by polymerizing or crosslinking the acid-curable components together. The contents of such compositions can be the same as those described in the above section "C. Composition," and therefore, a description thereof will be omitted here.

[0118] The shape of the cured product in plan view can be appropriately set depending on the application of the cured product, and can be, for example, a pattern such as a dot shape or a line shape.

[0119] The uses of the cured product can be the same as those described in the section "A. Compounds" above.

[0120] The method for producing the cured product is not particularly limited as long as it is a method that can form the cured product of the composition into a desired shape. As such a production method, for example, the production method described in the section "E. Production method of cured product" below can be used.

[0121] E. Manufacturing method of cured product Next, the method for producing the cured product of the present invention will be described. One of the features of the method for producing a cured product of the present invention is that it includes a curing step of curing the above-mentioned composition. The resin component contained in the composition is an acid-hardening component.

[0122] According to the present invention, by using the above-described composition, the effect of excellent acid generation sensitivity can be effectively exhibited, and a cured product in which the acid-curing component has sufficiently progressed in curing can be easily formed.

[0123] 1.Curing process The curing step in the present invention is a step of curing the above-mentioned composition. The method for curing the composition may be any method that can cure the acid-curable component, and a method in which an acid is generated from compound A can be used. The method for generating an acid from compound A may be any method that can generate a desired amount of acid from compound A, and examples thereof include a method of irradiating with energy rays, a method of heat treatment, and a method of performing these simultaneously or sequentially. Examples of such methods of irradiating with energy rays and methods of heat treatment include the same methods as those described in the above section "A. Compound." In this step, it is particularly preferable that the method for generating the acid includes a method of irradiating with energy rays, because this can effectively exhibit the effect of excellent acid generation sensitivity and effectively cure the acid-curable component. The composition contains an acid-curable component as a resin component. The content of such a composition can be the same as that described in the above section "C. Composition," and therefore, a description thereof will be omitted here.

[0124] 2. Other processes The method for producing a cured product of the present invention may include other steps in addition to the curing step, if necessary. Examples of the other steps include a developing step in which unpolymerized portions in the coating film of the composition are removed after the curing step to obtain a patterned cured product; a post-baking step in which the cured product is heat-treated after the curing step; a pre-baking step in which the composition is heat-treated to remove the solvent in the composition before the curing step; and a step in which a coating film of the composition is formed before the curing step. In the present invention, the other steps preferably include a post-baking step, because this allows the acid generated from compound A to be effectively diffused, facilitating the formation of a cured product in which the acid-curing component has been sufficiently cured.

[0125] As a method for removing the unpolymerized portions in the development step, for example, a method of applying a developer such as an alkaline developer to the unpolymerized portions can be mentioned. As the alkaline developer, those generally used as alkaline developers such as an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of potassium hydroxide, an aqueous solution of potassium carbonate, etc. can be used. As the developer, a solvent developer such as propylene glycol monomethyl ether acetate (PEGMEA) or cyclohexanone that is generally used can be used. The developing method using the developer may be any method that can bring the developer into contact with the area to be developed, and known methods such as showering, spraying, and immersion can be used. The developing step may be carried out at any time after the curing step. The heating conditions in the post-baking step may be any conditions that can improve the strength of the cured product obtained in the curing step, and may be, for example, 200° C. or higher and 250° C. or lower for 20 to 90 minutes. The heating conditions in the pre-baking step may be any conditions that can remove the solvent in the composition, and may be, for example, at 70° C. or higher and 150° C. or lower for 30 to 300 seconds. In the step of forming the coating film, the composition can be applied by any known method such as using a spin coater, roll coater, bar coater, die coater, curtain coater, various types of printing, or dipping. The coating film can be formed on a substrate. The substrate can be appropriately selected depending on the intended use of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. Furthermore, after the cured product is formed on a substrate, it may be peeled off from the substrate and used, or may be transferred from the substrate to another adherend and used.

[0126] F. Pattern The pattern of the present invention is produced using a positive resist comprising the above-mentioned composition. The resin component contained in the composition is an acid-decomposable component.

[0127] According to the present invention, by using the above-described composition, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-decomposable component can be easily decomposed, thereby facilitating the formation of a pattern with excellent dimensional accuracy.

[0128] The pattern of the present invention uses the above-described composition. The resin component is an acid-decomposable component. The pattern is formed by forming a coating film using the above-described composition and then removing unnecessary portions. Specifically, the pattern is formed by forming a coating film, irradiating it with energy rays through a predetermined mask or the like, generating acid in the irradiated portions to increase their solubility in a developer, and then removing the irradiated portions through a development process. The contents of such compositions can be the same as those described in the above section "C. Composition," and therefore, a description thereof will be omitted here.

[0129] The shape of the pattern in plan view can be appropriately set depending on the application of the pattern, and can be, for example, a dot-like, line-like or other pattern shape.

[0130] The use of the pattern can be the same as that described in the above section "A. Compounds."

[0131] The method for producing the pattern is not particularly limited as long as it is a method that can form the composition into a desired shape. As such a manufacturing method, for example, the manufacturing method described in the section "G. Method for manufacturing a pattern" below can be used.

[0132] G. Pattern manufacturing method Next, a method for producing a pattern according to the present invention will be described. The method for producing a pattern of the present invention includes the steps of forming a coating film using the above-mentioned composition, generating an acid from a compound contained in the formed coating film, and developing the coating film after the step of generating an acid from the compound to remove a portion of the coating film and form a pattern. The resin component contained in the composition is an acid-decomposable component.

[0133] According to the present invention, by using the above-mentioned composition, a pattern excellent in dimensional accuracy can be obtained.

[0134] 1. Acid generation process The step of generating an acid in the present invention is a step of generating an acid from the compound A contained in the coating film formed using the above-mentioned composition. In this step, the method for generating an acid from the compound A may be any method that can generate a desired amount of acid from the compound A, and examples thereof include a method of irradiating with energy rays, a method of heat treatment, and a method of performing these simultaneously or sequentially. Examples of such methods of irradiating with energy rays and a method of heat treatment include the same methods as those described in the section "A. Compound" above. In this step, it is particularly preferable that the method for generating the acid includes a method of irradiating with energy rays, since this can effectively exert the effect of obtaining a pattern with excellent dimensional accuracy and the like. In this step, the portion of the coating film where the acid is generated is preferably a part of the coating film in plan view, because this makes it easier to carry out the step of forming a pattern, which will be described later. The planar shape and thickness of the coating film are appropriately determined depending on the application of the pattern coating film. The composition contains an acid-decomposable component as a resin component. The content of such a composition can be the same as that described in the above section "C. Composition," and therefore, a description thereof will be omitted here.

[0135] 2. Pattern formation process The step of forming a pattern in the present invention is a step of developing the coating film and removing a portion thereof to form a pattern after the step of generating an acid from the compound. The development method in this step may be a method using a developer. Such a developer and developing method can be the same as those described in the above section "E. Method for producing a cured product."

[0136] 3. Other processes The pattern manufacturing method of the present invention includes the above-mentioned step of generating an acid and step of forming a pattern, but may also include other steps as necessary. Examples of such other steps include a step of forming a coating film of the composition before the step of generating the acid, and a pre-baking step of removing the solvent in the coating film by heat treatment after the step of forming the coating film. In the present invention, the other steps preferably include a post-exposure bake step, because this allows the acid generated from compound A to be effectively diffused, thereby allowing the decomposition of the acid-decomposable component to proceed more effectively. The step of forming the coating film and the pre-baking step can be the same as those described in the section "E. Method for producing a cured product." The post-exposure bake step may be carried out under conditions of, for example, 70° C. or higher and 150° C. or lower for 30 to 300 seconds.

[0137] 4.Other The pattern produced by the above production method and its uses can be the same as those described in the section "A. Composition" above.

[0138] The present disclosure includes the following aspects: 。 [1] A compound having a structure represented by the following general formula (A): [ka] (wherein Ar is an aromatic ring group having 5 to 20 carbon atoms constituting the ring, R 31 represents a group represented by the following general formula (1): R 32 is a group represented by a formula selected from the following general formulae (IVa), (IVb), (IVc), (IVd), (IVe), (IVf), (IVg) and (IVh), R 33 represents a halogen atom, a nitro group, a cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , -SR 34 , -SOR 34 , -SO2R 34 , -NR 35 R 36 , -NR 35 COR 36 , -CONR 35 R 36 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the following group Ia: R 31 , R 32 or R 33 When there are multiple, they may be the same or different, R 34 , R 35 and R 36 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ia; R 34 , R 35 or R 36When there are multiple, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: a represents an integer from 1 to 20; b represents an integer of 1 to 20; c represents an integer of 0 to 18; The sum of a, b, and c is 21 or less.) [ka] (In the formula, R 1 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: * indicates the point of attachment.) [ka] (In the formula, R 51 is OR 81 , N.R. 82 R 83 or an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, R 52 and R 53 are each independently R 81 OR 81represents R 52 and R 53 may be bonded to form a ring, R 55 , R 56 , R 58 , R 59 , R 61 , R 62 , R 64 , R 65 , R 71 and R 73 each independently represents an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, R 54 , R 57 , R 60 , R 63 , R 66 , R 67 and R 72 each independently represents an unsubstituted or substituted arylene group having 6 to 20 carbon atoms or a single bond, R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, R 69 and R 70 are each independently R 81 OR 81 represents R 81 , R 82 and R 83 each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, * indicates the point of attachment.) ( Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R”-. Group IIa: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different. [2] The compound according to [1], wherein the aromatic ring group Ar is an aromatic ring group having a structure represented by the following general formula (Ara) or (Arb): [ka] (In the formula, X 1 is a single bond, no bond, oxygen atom, sulfur atom, selenium atom, CR 41 R 42 , CO, NR 43 or PR 44 and X 2 is an oxygen atom, a sulfur atom, a selenium atom, a CR 41 R 42 , CO, NR 43 or PR 44 and X 3 is NR 53 and R 41 , R 42 , R 43 and R 44 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ib; R 41 , R 42 , R 43 and R 44 When there are multiple, they may be the same or different, R 53 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 111 , -COR 111 , -OCOR 111 , -COOR 111 , -SR 111 , -SOR 111 , -SO2R 111, -NR 112 R 113 , -NR 112 COR 113 , -CONR 112 R 113 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ib: R 111 , R 112 and R 113 each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ib; R 111 , R 112 and R 113 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the following group IIb: ( Group Ib: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group IIb: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different. [3] a is 1, The b is 1, The compound according to [2], wherein the following partial structure (Aα) in the general formula (A) is a group represented by the following general formula (Ara1) or (Arb1): [ka] (In the formula, Ar, R 33 and c are the same as in formula (A). *1 is R 31 *2 indicates the bond with R 32 ) [ka] (In the formula, X 1 , X 2 and X 3 are the same as those in the general formulae (Ara) and (Arb), R 141 , R 142 , R 151 and R 152 are each independently, Halogen atoms, nitro groups, cyano groups, -OR 121 , -COR 121 , -OCOR 121 , -COOR 121 , -SR 121 , -SOR 121 , -SO2R 121 , -NR 122 R 123 , -NR 122 COR 123 , -CONR 122 R 123 an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are replaced by a divalent group selected from the following Group Ic: R 121 , R 122 and R 123each independently represents a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocyclic ring-containing group are substituted with a divalent group selected from the following group Ic; R 121 , R 122 and R 123 When there are a plurality of each of the groups, they may be the same or different, The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIc: a1 is 0 to 3, a2 is 0 to 3, c1 is 0 to 3, c2 is between 0 and 1, *1 is R 31 represents the point of attachment to *2 is R 32 ) ( Group Ic: -O-, -COO-, -OCO-, -CO-, -CO-CO-, -CO-CO-O-, -CS-, -S-, -SO-, -SO2-, -NR'-, -NR'-CO-, -CO-NR'-, -NR'-COO-, -OCO-NR'- or -SiR'R"-. Group IIc: a halogen atom, a cyano group, a nitro group, -CO-H, -OH, -SH, -NH2, -COOH or -SO3H. R' and R" each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when there are multiple R's or R"s, they may be the same or different. [4] R 32 is a group represented by any one of general formulas (IVa), (IVf) and (IVh). [5] R 1 is a hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom as a substituent, R2 is a cyano group, a hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom as a substituent, or a group in which one or more methylene groups of a hydrocarbon group having 1 to 20 carbon atoms and being unsubstituted or having a halogen atom as a substituent are substituted with -COO-. [6] An acid generator comprising the compound according to any one of [1] to [5]. [7] The compound according to any one of [1] to [5], A resin component, A composition comprising: [8] The composition according to [7], wherein the resin component is an acid-hardening resin component. [9] A cured product of the composition described in [8].

[10] [8] A method for producing a cured product, comprising a curing step of curing the composition according to [8].

[11] The composition according to [7], wherein the resin component is an acid-decomposable resin component.

[12] A pattern produced from the composition described in

[11] .

[13] forming a coating film using the composition according to

[11] , and generating an acid from the compound contained in the formed coating film; a step of developing the coating film after the step of generating an acid from the compound to remove a portion of the coating film and form a pattern; A method for manufacturing a pattern having the above structure.

[14] A pattern comprising the composition according to

[11] .

[15] A positive resist comprising the composition according to

[11] .

[0139] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and that provides similar effects is included within the technical scope of the present invention. [Example]

[0140] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0141] [Example 1] (Synthesis of Compound No. 1) N-Alkylation A 1-L four-neck flask was charged with 33.4 g (200 mmol) of carbazole, 3.9 g (12 mmol) of tetrabutylammonium bromide, and 167.7 g (180 mmol) of o-xylene and stirred at room temperature. 93.5 g (800 mmol) of 48% by weight aqueous potassium hydroxide solution was added dropwise. The mixture was heated and stirred at 40°C in an oil bath, and 40.6 g (210 mmol) of 1-bromo-2-ethylhexane was added dropwise. The mixture was heated and stirred at 120°C in an oil bath for 3 hours. After cooling to room temperature, ion-exchanged water was added and oil-water separation was performed. After washing once with 3% by weight hydrochloric acid and three times with ion-exchanged water, the organic layer was concentrated to obtain 52.3 g of the desired intermediate 1-A as a pale red oil in a 94% yield.

[0142] [ka]

[0143] Acylation A 1-L four-neck flask was charged with 25.2 g (90 mmol) of intermediate 1-A, 13.2 g (110 mmol) of DMAP (N,N-dimethyl-4-aminopyridine), and 337.9 g (10 times the theoretical yield) of EDC (1,2-dichloroethane), and the mixture was stirred in an ice bath at 5°C. 19.9 g (95 mmol) of trifluoroacetic anhydride was added dropwise. 36 g (270 mmol) of aluminum chloride was then added in six portions, taking care to avoid heat generation. The mixture was warmed to room temperature and stirred for 3 hours. The reaction mixture was poured into ion-exchanged water, and chloroform was added to separate the oil and water. After washing three times with ion-exchanged water, 50 g of silica gel was added to the organic layer, and the mixture was filtered. The filtrate was concentrated to obtain the desired crude intermediate 1-B as a yellow oil. This was used in the next reaction without further purification.

[0144] [ka]

[0145] Oximation reaction A 500 mL four-neck flask was charged with 18.8 g (50 mmol) of intermediate 1-B, 3.8 g (55 mmol) of hydroxylamine hydrochloride, and 97.6 g of ethanol (5 times the theoretical yield), and the mixture was heated to reflux in an oil bath at 90°C for 7 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and chloroform was added to the residue, which was then washed three times with ion-exchanged water. After concentration, intermediate 1-C was used in the next reaction without purification.

[0146] [ka]

[0147] Sulfonic acid esterification A 300 mL four-neck flask was charged with 13.5 g (40 mmol) of intermediate 1-C, 104.5 g (5 times the theoretical yield) of chloroform, and 8.1 g (80 mmol) of triethylamine, and the mixture was stirred in an ice bath at 5°C. 16.9 g (60 mmol) of trifluoromethanesulfonic anhydride was added dropwise to the mixture, ensuring the temperature did not exceed 10°C. After the addition was complete, the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into ice water, and after separation of the oil and water, the mixture was washed three times with ion-exchanged water. After concentration, HPLC analysis revealed that the starting ketone remained, but intermediate 1-D was used in the next reaction without purification.

[0148] [ka]

[0149] ·Diketone introduction A 300 mL four-neck flask was charged with 10.5 g (20 mmol) of intermediate 1-D and 62.3 g (6 times the theoretical yield) of EDC and stirred in an ice bath. 3.6 g (24 mmol) of ethyl chloroglyoxylate was added dropwise. Furthermore, 3.5 g (26 mmol) of aluminum chloride was added in four portions, taking care to avoid heat generation. After confirming the disappearance of the raw materials by HPLC, the reaction solution was poured into ion-exchanged water. After oil-water separation, the organic layer was washed three times with water and then concentrated. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane = volume ratio 1:10 to 1:5). Methanol was added to the residue for dispersion washing, and after filtration, hexane was added for further dispersion washing. 2.06 g of the target compound No. 1 was obtained in a 16% yield. 1 H-NMR and 19 The results of F-NMR measurements are shown in Tables 1 and 2.

[0150] [ka]

[0151] [Example 2] (Synthesis of Compound No. 2) Compound No. 2 was synthesized in the same manner as Compound No. 1, except that ethyl iodide was used instead of 1-bromo-2-ethylhexane and methyl chloroglyoxylate was used instead of ethyl chloroglyoxylate. The solid obtained is the target product. 1 H-NMR and 19 The results were confirmed by F-NMR, and are shown in Tables 1 and 2.

[0152] [ka]

[0153] [Example 3] (Synthesis of Compound No. 3) Compound No. 3 was synthesized in the same manner as Compound No. 1 after the acylation reaction, except that fluorene was used instead of carbazole as the main raw material. 1 H-NMR and 19 The results were confirmed by F-NMR, and are shown in Tables 1 and 2.

[0154] [ka]

[0155] [Example 4] (Synthesis of Compound No. 4) A 100 mL four-neck flask was charged with 2.0 g (32 mmol) of Compound No. 1 and 21.5 g (10 times the theoretical yield) of EDC, and the mixture was stirred in an ice bath. To this mixture, 1.5 g (110 mmol) of aluminum chloride was added in four portions, taking care to avoid heat generation. After confirming the disappearance of the raw materials by HPLC, the reaction mixture was poured into ion-exchanged water. After oil-water separation, the organic layer was washed three times with water and then concentrated. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate:hexane = volume ratio 1:10 to 1:5). 1.27 g of the target compound No. 4 was obtained in a yield of 59%. 。

[0156] [ka]

[0157] [Table 1]

[0158] [Table 2]

[0159] [Examples 5 to 7 and Comparative Examples 1 to 2] According to the formulations shown in Table 3 below, the resin component, acid generator, and surfactant were added to propylene glycol monomethyl ether acetate (PGMEA) and stirred at 25°C for 1 hour to obtain a composition (PGMEA solution with a solid content of 25% by mass). The following materials were used for each component. The amounts in Table 3 are expressed in parts by mass.

[0160] Resin component: MARUKA LYNKER TST (Maruzen Petrochemicals, p-hydroxystyrene-styrene-t-butyl acrylate copolymer, acid-decomposable component) Surfactant: FZ2122 (manufactured by Toray Dow Corning) Acid generator: Compounds prepared in Examples 1 to 3 (acid generators consisting of Compounds Nos. 1 to 3) Acid generator: Comparative compounds No. 1 and No. 2 below

[0161] [ka]

[0162] 1.Sensitivity evaluation The composition prepared above was filtered through a 5 μm microfilter and spin-coated (1300 rpm, 7 s) onto a glass substrate so that the film thickness after pre-baking was 3 μm. The resist was then pre-baked at 110°C for 120 seconds using a hot plate to obtain a positive resist film. After exposure using a high-pressure mercury lamp, PEB (Post Exposure Bake) was performed at 120°C for 120 seconds, and the resist was developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 10 seconds to obtain a positive resist pattern. Mask opening 20 μm, exposure dose 20 mJ / cm 2 and 40 mJ / cm 2 The line width of the pattern obtained in step 1 (the width of the developed and removed portion) was measured using a microscope. The wider the developed width, the higher the sensitivity was evaluated. The results are shown in Table 3.

[0163] 2. Solubility The solubility of each acid generator in PGMEA at 25° C. was evaluated. The results are shown in Table 3. The values ​​shown in Table 3 are soluble concentrations (% by mass).

[0164] 3. Molar absorption coefficient (ε) and transmittance The positive resist film obtained in the same manner as described in "1. Sensitivity evaluation" was measured for absorption spectrum using a UV-visible spectrophotometer (U-3010 manufactured by Hitachi High-Tech Science) and the molar absorption coefficient at 365 nm and the transmittance at 400 nm were calculated. The results are shown in Table 3.

[0165] [Table 3]

[0166] The absorption coefficients of Compounds Nos. 1 to 3 used in Examples 5 to 7 at i-line (365 nm) were able to maintain high values. The compositions of the examples using Compounds Nos. 1 to 3 of the present invention produced patterns with line widths that were larger than the developed widths of patterns produced from the comparative compositions using other compounds, demonstrating superior acid generation sensitivity. Furthermore, the transmittance of the positive resist film at 400 nm was the highest in each example, and highly transparent resist films with suppressed coloration were obtained. Furthermore, Compounds Nos. 1 to 3 of the present invention had high solubility in solvents. As described above, the compound of the present invention has high sensitivity, excellent transparency, and sufficient solvent solubility, and is therefore suitable as a photoacid generator for use in a photoresist.

Claims

1. A compound having a structure represented by the following general formula (A): 【Chemistry 1】 (wherein Ar is a group represented by the following general formula (Ara) or (Arb) or a benzene ring, R 31 represents a group represented by the following general formula (1): R 32 is a group represented by the following general formula (IVf): R 33 represents a halogen atom, a nitro group, a cyano group, -OR 34 , -COR 34 , -OCOR 34 , -COOR 34 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group are replaced by a divalent group selected from the following group Ia: R 31 , R 32 or R 33 When there are multiple, they may be the same or different, R 34 each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 34 s are present, they may be the same or different; The substituent substituting one or more hydrogen atoms in the substituted hydrocarbon group is an atom or group selected from the following Group IIa: a represents an integer of 1 or 2; b represents an integer of 1 or 2; c represents an integer of 0 to 3. 【Chemistry 2】 (wherein X 1 is a single bond or no bond; X 2 is a sulfur atom, CR 41 R 42 or NR 43 ; when X 1 is a single bond, X 2 is CR 41 R 42 or NR 43 ; When X 1 is no bond, X 2 is a sulfur atom; X3 is NR53; R 41 , R 42 and R 43 each independently represent a hydrogen atom, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced with a divalent group selected from the following group Ib; when a plurality of R 41 , R 42 and R 43 are present, they may be the same or different; R 53 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, —OR 111 , —COR 111 , —OCOR 111 , —COOR 111 , an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group have been replaced by a divalent group selected from the following group Ib: R 111 each independently represents a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R 111 are present, they may be the same or different; The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocyclic ring-containing group are atoms or groups selected from the following Group IIb: 【Transformation 3】 (In the formula, R 1 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or a group in which one or more methylene groups in the hydrocarbon group or the heterocycle-containing group are substituted with a divalent group selected from the following group Ia: The substituents substituting one or more hydrogen atoms in the substituted hydrocarbon group and the substituted heterocycle-containing group are atoms or groups selected from the following Group IIa: * indicates the bonding site.) 【Chemistry 4】 (wherein R 67 represents a single bond; R 68 represents an unsubstituted or substituted hydrocarbon group having 1 to 20 carbon atoms, * indicates the bonding site.) (Group Ia: -O-, -COO-, -OCO-, -CO-, -CO-CO- or -CO-CO-O-. Group IIa: halogen atoms, cyano groups, nitro groups, —CO—H, —OH, —SH, —NH 2 , —COOH or —SO 3 H. Group Ib: -O-, -COO-, -OCO-, -CO-, -CO-CO- or -CO-CO-O-. Group IIb: a halogen atom, a cyano group, a nitro group, —CO—H, —OH, —SH, —NH 2 , —COOH, or —SO 3 H.

2. R 1 is a hydrocarbon group having 1 to 20 carbon atoms and having a halogen atom as a substituent, R 2 a cyano group, a carbon atom having 1 to 20 carbon atoms and a halogen atom as a substituent The compound according to claim 1, which is a hydrogen group or a hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted with a halogen atom, in which one or more methylene groups are replaced with -COO-.

3. An acid generator comprising the compound according to claim 1 or 2.

4. A compound according to claim 1 or 2; A resin component, A composition comprising:

5. The composition of claim 4 , wherein the resin component is an acid-hardening resin component.

6. A cured product of the composition according to claim 5.

7. A method for producing a cured product, comprising a curing step of curing the composition according to claim 5.

8. The composition according to claim 4 , wherein the resin component is an acid-decomposable resin component.

9. A pattern made from the composition of claim 8.

10. A step of forming a coating film using the composition according to claim 8 and generating an acid from the compound contained in the formed coating film; a step of developing the coating film after the step of generating an acid from the compound to remove a portion of the coating film and form a pattern; A method for manufacturing a pattern having the above structure.

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