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

Abstract

The objective of the present invention is to provide a compound from which a resin composition having excellent acid-generation sensitivity and suppressed coloration can be obtained.　The present invention provides the compound represented by general formula (A). (In the formula, R11, R12, R14, R15, R16, and R17 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which is non-substituted or has a substituent, or the like, either R13 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which is non-substituted or has a substituent, or the like, and one or more among R11, R12, R14, R15, R16, and R17 is a group represented by general formula (1) or R13 represents an aryl group substituted with the group represented by general formula (1). R1 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms which is non-substituted or has a substituent, or the like, and R2 represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms which is non-substituted or has a substituent, or the like.)

Description

[Technical field]

[0001] The present invention relates to a compound that can be suitably used as an acid generator. [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. In Patent Documents 1 and 2, a photoacid generator or a thermal acid generator made of a sulfonic acid derivative compound is invented as an acid generator. In addition, Patent Documents 1 and 2 disclose the use of an acid generator together with a negative resist in which the solubility in a developer is reduced by forming chemical bonds such as polymerization or crosslinking due to the acid generated from the acid generator, and a positive resist in which the solubility in a developer is increased by the action of an acid to break chemical bonds of ester groups or acetal groups. In addition, specific applications include semiconductors, overcoats, paints, adhesives, and inks. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-169173 A [Patent Document 2] US2020183271 Summary of the Invention

[0004] However, these acid generators often have low acid generation sensitivity.

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

[0006] Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems, and as a result have found that an oxime sulfonate compound having an indole structure has excellent acid generation sensitivity, thereby completing the present invention.

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

[0008] [ka] (In the formula, R 11 , R 12 , R 14 , R 15 , R 16 and R 17 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 20 , -COR 20 , -OCOR 20 , -COOR 20 , -SR 20 , -SOR 20 , -SO2R 20 , -NR 21 R 22 , -NR 21 COR 22 , -CONR 21 R 22 a group represented by the following general formula (1), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above aliphatic hydrocarbon group, the above aromatic hydrocarbon ring-containing group, or the above heterocyclic ring-containing group are replaced by a divalent group selected from the following group I: R 13represents a first aryl group which is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or an unsubstituted or substituted aryl group having 7 to 30 carbon atoms in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the following general formula (1), or a group in which one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, the above-mentioned heterocycle-containing group, or the above-mentioned first aryl group are substituted with a divalent group selected from the following group I: R 20 , R 21 and R 22 each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced with a divalent group selected from the following group I; R 20 , R 21 or R 22 When multiple are present, they may be the same or different, R 11 and R 12 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 may be bonded to form a ring, the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, the heterocycle-containing group having the above-mentioned substituent, and the first aryl group is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SOH; R 11 , R 12 , R 14 , R 15 , R 16and R 17 At least one of the groups represented by the following general formula (1) is present, or R 13 is the first aryl group. [ka] (In the formula, R 1 represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced by a divalent group selected from the following Group I: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced by a divalent group selected from the following group I: the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SOH; n represents 0 or 1; When a plurality of groups represented by the general formula (1) are present in the compound represented by the general formula (A), a plurality of n, R 1 and R 2 may be the same or different, * indicates the site of attachment.) Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO2-, -NR 30 -, -NR 30 -CO-, -CO-NR30 -, -NR 30 -COO-, -OCO-NR 30 -, -SiR 30 R 31 -, -CO-CO-, CO-CO-O- R 30 and R 31 each independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms; R 30 or R 31 When multiple are present, they may be the same or different.

[0009] In the present invention, R 11 is preferably a group represented by the above general formula (1).

[0010] In the present invention, n is preferably 0.

[0011] In the present invention, R 1 is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, and a substituent substituting one or more hydrogen atoms in the substituted aliphatic hydrocarbon group and the substituted aromatic hydrocarbon ring-containing group is a halogen atom; R 2 is preferably a cyano group or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and the substituent substituting one or more hydrogen atoms in the substituted aliphatic hydrocarbon group is preferably a halogen atom.

[0012] In the present invention, R 13 is preferably an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms or an unsubstituted or substituted heterocyclic ring-containing group having 2 to 20 carbon atoms.

[0013] The present invention provides an acid generator comprising the compound represented by the above general formula (A).

[0014] The present invention provides a composition containing the compound represented by the above general formula (A) and a resin component.

[0015] The present invention provides a composition in which the above-mentioned resin component is an acid-curable resin component.

[0016] The present invention provides a cured product of a composition containing the above-mentioned acid-curable resin component.

[0017] The present invention provides a method for producing a cured product, comprising a curing step of curing a composition containing the above-mentioned acid-curable resin component.

[0018] The present invention provides a composition in which the above-mentioned resin component is an acid-decomposable resin component.

[0019] The present invention provides a pattern comprising a composition containing the above-mentioned acid-decomposable resin component.

[0020] The present invention provides a method for producing a pattern, comprising the steps of forming a coating film using a composition containing the above-mentioned acid-decomposable resin component, generating an acid from a compound contained in the formed coating film, and developing a part of the coating film after the step of generating an acid from the compound to form a pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The present invention relates to a compound, an acid generator, a composition, a cured product and a pattern, and a method for producing the cured product and the pattern. The present invention will be described in detail below.

[0022] A. Compound First, the compound of the present invention will be described. The compound of the present invention is characterized by being represented by the following general formula (A).

[0023] [ka] (In the formula, R 11 , R 12 , R14 , R 15 , R 16 and R 17 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR 20 , -COR 20 , -OCOR 20 , -COOR 20 , -SR 20 , -SOR 20 , -SO2R 20 , -NR 21 R 22 , -NR 21 COR 22 , -CONR 21 R 22 a group represented by the following general formula (1), an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above aliphatic hydrocarbon group, the above aromatic hydrocarbon ring-containing group, or the above heterocyclic ring-containing group are replaced by a divalent group selected from the following group I: R 13 represents a first aryl group which is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, an unsubstituted or substituted heterocycle-containing group having 2 to 20 carbon atoms, or an unsubstituted or substituted aryl group having 7 to 30 carbon atoms in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the following general formula (1), or a group in which one or more methylene groups in the above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, the above-mentioned heterocycle-containing group, or the above-mentioned first aryl group are substituted with a divalent group selected from the following group I: R 20 , R 21 and R 22each independently represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced with a divalent group selected from the following group I; R 20 , R 21 or R 22 When multiple are present, they may be the same or different, R 11 and R 12 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17 may be bonded to form a ring, the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, the heterocycle-containing group having the above-mentioned substituent, and the first aryl group is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SOH; R 11 , R 12 , R 14 , R 15 , R 16 and R 17 At least one of the groups represented by the following general formula (1) is present, or R 13 is the first aryl group.

[0024] [ka] (In the formula, R 1represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced by a divalent group selected from the following Group I: R 2 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or 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 above-mentioned aliphatic hydrocarbon group, the above-mentioned aromatic hydrocarbon ring-containing group, or the above-mentioned heterocyclic ring-containing group are replaced by a divalent group selected from the following group I: the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above-mentioned substituent, the aromatic hydrocarbon ring-containing group having the above-mentioned substituent, and the heterocycle-containing group having the above-mentioned substituent is a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SOH; n represents 0 or 1; When a plurality of groups represented by the general formula (1) are present in the compound represented by the general formula (A), a plurality of n, R 1 and R 2 may be the same or different, * indicates the site of attachment.) Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO2-, -NR 30 -, -NR 30 -CO-, -CO-NR 30 -, -NR 30 -COO-, -OCO-NR 30 -, -SiR 30 R 31 -, -CO-CO-, CO-CO-O- R 30 and R 31each independently represents a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms; R 30 or R 31 When multiple are present, they may be the same or different.

[0025] According to the present invention, compound A has an indole ring and a group represented by the above general formula (1), and thus 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 contains a structure having an indole ring and a group represented by the general formula (1) (hereinafter, may be referred to as a specific structure), and thus can absorb energy during exposure to generate an acid. Here, the specific structure absorbs light having a wavelength of visible light or less, for example, light having a wavelength of 400 nm or less including the i-line (365 nm), but its light absorption efficiency is relatively low. For example, the specific structure tends to have a higher transmittance of light having a wavelength of visible light or less than that of a structure having a coumarin skeleton and a group represented by the general formula (1). Therefore, when a composition is formed by adding the above-mentioned compound A to a resin component and a coating film of the composition is exposed to light, the compound A present on the opposite side of the exposed surface of the coating film can also easily absorb the exposure light. In other words, when the above-mentioned compound A is used, acid can be efficiently generated even at a deep position in the thickness direction of the coating film. As a result, the composition has excellent acid generation sensitivity. Moreover, the compound A has a high light transmittance in the visible light region, and can therefore be suitably used in resin compositions for forming members that require transparency.

[0026] Examples of the halogen atom in the above general formula (A) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0027] The aliphatic hydrocarbon group having 1 to 20 carbon atoms in the above general formula (A) is a hydrocarbon group that does not contain an aromatic hydrocarbon ring or a heterocycle and may have a substituent. The aliphatic hydrocarbon group having a substituent is a group having a structure in which one or more hydrogen atoms in the aliphatic hydrocarbon group are substituted with a substituent. Examples of the unsubstituted aliphatic hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms. Examples of the aliphatic hydrocarbon group having a substituent include the unsubstituted aliphatic hydrocarbon group in which one or more hydrogen atoms have been substituted with a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SOH.

[0028] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.

[0029] The alkenyl group having 2 to 20 carbon atoms may be linear or branched. It may also be a terminal alkenyl group having an unsaturated bond at the end, or an internal alkenyl group having an unsaturated bond inside. Examples of the terminal alkenyl group include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl, and 5-hexenyl. Examples of the internal alkenyl group 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.

[0030] 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 an alkyl group. Examples of the saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of the saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of the alkyl groups substituting hydrogen atoms in the ring of a saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified above as the alkyl groups having 1 to 20 carbon atoms. Examples of the groups 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.

[0031] 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 the cycloalkylalkyl group 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 the cycloalkylalkyl group having 4 to 20 carbon atoms and a polycyclic cycloalkyl group include 3-3-adamantylpropyl, decahydronaphthylpropyl, and the like.

[0032] Examples of the unsubstituted aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a substituent and the substituent is a halogen atom include halogenated alkyl 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; halogenated cycloalkyl such as norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2-tetrafluoropropyl, and bicyclo[2.2.1]heptane-tetrafluoromethyl; and halogenated cycloalkylalkyl.

[0033] In the present invention, the number of carbon atoms of a group specifies the number of carbon atoms of the group after the substitution when a hydrogen atom in the group is substituted with a substituent. For example, when a hydrogen atom of 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. In the present invention, the number of carbon atoms in a group in which a methylene group in a group having a predetermined number of carbon atoms is replaced with a divalent group defines the number of carbon atoms in the group before the replacement. 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 1 to 20.

[0034] The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms in the above general formula (A) is a hydrocarbon group that contains an aromatic hydrocarbon ring and does not contain a heterocycle, and may have an aliphatic hydrocarbon group or may have a substituent. The aromatic hydrocarbon ring-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the aromatic hydrocarbon ring-containing group are substituted with a substituent. Examples of the unsubstituted aromatic hydrocarbon ring-containing group include an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, and a group in which an unsaturated aliphatic hydrocarbon group is substituted with an aryl group. Examples of the substituted aromatic hydrocarbon ring-containing group include groups in which one or more hydrogen atoms in the unsubstituted aromatic hydrocarbon ring-containing group are substituted with a substituent, and examples of the substituent include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SO2H.

[0035] The aryl group having 6 to 20 carbon atoms may have a monocyclic structure or a condensed ring structure, or may have two aromatic hydrocarbon rings linked together. The aryl group in which two aromatic hydrocarbon rings are linked may be an aryl group in which two aromatic hydrocarbon rings of a monocyclic structure are linked, an aromatic hydrocarbon ring of a monocyclic structure and an aromatic hydrocarbon ring of a fused ring structure are linked, or an aromatic hydrocarbon ring of a fused ring structure and an aromatic hydrocarbon ring of a fused ring structure are linked. Examples of the linking group linking two aromatic hydrocarbon rings include a single bond and a carbonyl group. Examples of the aryl group having a single ring structure include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl. Examples of the aryl group having a condensed ring structure include naphthyl, anthracenyl, phenanthryl, and pyrenyl. Examples of the aryl group having two aromatic hydrocarbon rings linked to each other having a single ring structure include biphenyl and benzoylphenyl. Furthermore, the aromatic hydrocarbon rings of the monocyclic structure and the condensed ring structure are not limited to those in which the hydrogen atoms in the ring are not substituted with alkyl groups, such as phenyl and naphthyl, but also include those in which the hydrogen atoms in the ring are substituted with alkyl groups, such as the above-mentioned tolyl and trimethylphenyl (hereinafter, these may be referred to as alkyl-substituted aromatic hydrocarbon rings). In particular, those in which the hydrogen atoms in the phenyl group, such as tolyl and trimethylphenyl, are substituted with alkyl groups may be referred to as alkyl-substituted phenyl groups.

[0036] The arylalkyl group having 7 to 20 carbon atoms means a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl groups.

[0037] The heterocyclic ring-containing group having 2 to 20 carbon atoms in the above general formula (A) is a group containing a heterocycle, and specifically means a group consisting of a heterocyclic ring group and a group combining a heterocyclic ring group with a hydrocarbon group. The heterocyclic ring-containing group may have an aromatic hydrocarbon ring-containing group, an aliphatic hydrocarbon group, or a substituent. The heterocyclic ring-containing group having a substituent is a group having a structure in which one or more hydrogen atoms in the heterocyclic ring-containing group are substituted with a substituent.

[0038] Examples of unsubstituted heterocycle-containing groups include heterocycle groups such as pyridyl, quinolyl, thiazolyl, tetrahydrofuran, dioxolanyl, tetrahydropyranyl, morpholylfuran, thiophene, methylthiophene, hexylthiophene, benzothiophene, pyrrole, pyrrolidine, imidazole, imidazolidine, imidazoline, pyrazole, pyrazolidine, piperidine, piperazine, pyrimidyl, furyl, thienyl, benzoxazol-2-yl, thiazole, isothiazole, oxazole, isoxazole, and morpholinyl groups, as well as groups in which one or more hydrogen atoms of an alkyl group are substituted with a heterocycle. In addition, 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, a hydroxyl group, a thiol group, -COOH, or -SOH.

[0039] Furthermore, the unsubstituted heterocyclic ring-containing group may preferably be one in which a heterocyclic ring is linked to an aromatic hydrocarbon ring, more specifically, one in which a heterocyclic ring is linked to an aromatic hydrocarbon ring of a monocyclic structure, or one in which a heterocyclic ring is linked to an aromatic hydrocarbon ring of a condensed ring structure. Examples of the linking group linking two aromatic hydrocarbon rings include a single bond and a carbonyl group. Examples of the heterocyclic ring-containing group in which a heterocyclic ring is linked to an aromatic hydrocarbon ring of a monocyclic structure include benzoylthiophene in which a phenyl group is linked to a thiophene ring via a carbonyl group, and a group in which a phenyl group is linked to a benzofuran ring, which is a heterocyclic ring, via a carbonyl group, as in the compound A4 described later.

[0040] The first aryl group in the above general formula (A) is an unsubstituted or substituted aryl group having 7 to 30 carbon atoms in which one or more hydrogen atoms in an aromatic hydrocarbon ring are substituted with a group represented by the above general formula (1). Here, the substituted aryl group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the above general formula (1) refers to an aryl group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the above general formula (1), i.e., a group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the above general formula (1) and further one or more other hydrogen atoms are substituted with a substituent other than the group represented by the above general formula (1). Examples of the substituent in the first aryl group other than the group represented by general formula (1) include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH, or -SO2H. More specifically, such a first aryl group includes a group in which one hydrogen atom in a monocyclic aryl group such as phenyl or tolyl is substituted with a group represented by the above general formula (1).

[0041] The aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocycle-containing group, or the group in which one or more methylene groups in the first aryl group are replaced with a divalent group selected from Group I in the general formula (A) does not have a structure in which multiple divalent groups are adjacent to each other. The multiple divalent groups may be the same or different.

[0042] Examples of the aliphatic hydrocarbon group in which one or more methylene groups have been replaced with a divalent group selected from Group I include a 10-camphoryl group, which is a bornyl aliphatic hydrocarbon group in which a methylene group has been replaced with -CO-.

[0043] In the above general formula (A), R 11 and R 12 , R 14 and R 15 , R 15 and R 16 , R 16 and R 17The ring formed by bonding may be a monocyclic ring or a condensed 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 ring, and lactam ring. Examples of the condensed ring include naphthalene and anthracene.

[0044] In the present invention, R 11 , R 12 , R 14 , R 15 , R 16 and R 17 At least one of the above is a group represented by the general formula (1), or 13 is the first aryl group. That is, the compound A is 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 At least one of them has a group represented by the above general formula (1). The compound A is represented by the formula (a1) R 11 , R 12 , R 14 , R 15 , R 16 and R 17 At least one of the groups represented by the general formula (1) is a group represented by R 13 may be a group other than the first aryl group, (a2) R 13 is the first aryl group, and R 11 , R 12 , R 14 , R 15 , R 16 and R 17 may be a group other than the group represented by the general formula (1), (a3) ​​R 11 , R 12 , R 14 , R 15 , R 16 and R 17 is a group represented by the above general formula (1), and R13 may be the first aryl group. In the present invention, it is preferable that the compound A satisfies (a1). With such a structure, the 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. Furthermore, it is easy to form a composition with suppressed coloration. In the present invention, R 11 , R 12 , R 14 , R 15 , R 16 and R 17 It is preferable that at least one of the groups represented by the above general formula (1) is a group represented by R 11 and R 16 It is preferable that at least one of the groups is a group represented by the above general formula (1), and in particular, R 11 is preferably a group represented by the above general formula (1). With such a structure, 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. Furthermore, it is easy to form a composition with suppressed coloration. The number of groups represented by the above general formula (1) contained in compound A, that is, R 11 , R 12 , R 14 , R 15 , R 16 and R 17 the number of groups represented by the above general formula (1) in 13 The total number of groups represented by the above general formula (1) possessed by the first aryl in the is preferably 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 1. This is because the above number makes compound A a compound with superior acid generation sensitivity. In addition, this is because the compound is easily synthesized, and an acid generator with superior acid generation sensitivity can be easily formed. In the present invention, R in the above general formula (A) 11is a group represented by the above general formula (1), and the number of groups represented by the above general formula (1) in compound A is one, that is, compound A has a structure represented by the following general formula (A1). With such a structure, 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. Furthermore, it is easy to form a composition with suppressed coloration. When a plurality of groups represented by the general formula (1) are present in the compound represented by the general formula (A), a plurality of n, R 1 and R 2 may be the same or different, but are usually the same, because compound A is easy to synthesize.

[0045] [ka] (In the formula, R 1 , R 2 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 and n has the same meaning as in general formula (A) above.

[0046] In the above general formula (A), n is preferably 0. When n is 0, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to form a composition with suppressed coloration.

[0047] R in the above general formula (A) 1The substituents replacing one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent, the aromatic hydrocarbon ring-containing group having the above substituent, and the heterocyclic ring-containing group having the above substituent, which are represented by the above formula, are preferably halogen atoms, more preferably fluorine atoms. This is because compound A has such a structure, and is 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. Furthermore, it is easy to form a composition with suppressed coloration. R in the above general formula (A) 1 is preferably an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon-containing group having 6 to 20 carbon atoms, and among these, it is preferably an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms or an aromatic hydrocarbon-containing group having a substituent having 6 to 20 carbon atoms, and in particular, it is preferably an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms or an aromatic hydrocarbon-containing group having a substituent having 6 to 20 carbon atoms, and the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent and the aromatic hydrocarbon ring-containing group having the above substituent is preferably a halogen atom, and among these, it is particularly preferably an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms and the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent is preferably a halogen atom. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. R in the above general formula (A) 1 The aliphatic hydrocarbon group represented by is preferably an alkyl group. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. R in the above general formula (A) 1The number of carbon atoms in the group represented by is preferably 1 to 10, and more preferably 1 to 5. 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. Furthermore, it is easy to form a composition with suppressed coloration. In particular, in the present invention, R 1 However, it is preferably a halogenated alkyl group having 1 to 20 carbon atoms, which is a group in which one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms are substituted with a halogen atom, and among these, it is particularly preferably a halogenated alkyl group having 1 to 10 carbon atoms, which is a group in which one or more hydrogen atoms in an alkyl group having 1 to 10 carbon atoms are substituted with a halogen atom, it is more preferably a perhaloalkyl group having 1 to 5 carbon atoms, which is a group in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms, and it is most preferably a perfluoroalkyl group having 1 to 5 carbon atoms, which is a group in which all hydrogen atoms in an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. R 1 This is because compound A has such a structure and is a compound with superior acid generation sensitivity.

[0048] R in the above general formula (A) 2 The substituents replacing one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent, the aromatic hydrocarbon ring-containing group having the above substituent, and the heterocyclic ring-containing group having the above substituent, which are represented by the above formula, are preferably halogen atoms, more preferably fluorine atoms. This is because compound A has such a structure, and is 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. Furthermore, it is easy to form a composition with suppressed coloration. R in the above general formula (A) 2is preferably a cyano group, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon-containing group having 6 to 20 carbon atoms, more preferably a cyano group or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a cyano group or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably a cyano group or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, in which the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent is a halogen atom, and particularly preferably an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms, in which the substituent substituting one or more hydrogen atoms in the aliphatic hydrocarbon group having the above substituent is a halogen atom. R in the above general formula (A) 2 The aliphatic hydrocarbon group represented by is preferably an alkyl group. With such a structure, 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. Furthermore, it is easy to form a composition with suppressed coloration. R in the above general formula (A) 2 The number of carbon atoms in the group represented by is preferably 1 to 10, and more preferably 1 to 5. With such a structure, 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. Furthermore, it is easy to form a composition with suppressed coloration. 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 are substituted with a halogen atom, 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 are 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 are 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 are substituted with a fluorine atom. 2 This is because compound A has excellent acid generation sensitivity due to the structure, and also because it is easy to form a composition or the like with reduced coloration.

[0049] R in the above general formula (A) 13is preferably an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms and unsubstituted or substituted, or a heterocyclic ring-containing group having 2 to 20 carbon atoms and unsubstituted or substituted. In particular, it is preferably an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms and unsubstituted or substituted, more preferably an aryl group having 6 to 20 carbon atoms and unsubstituted or substituted, more preferably an aryl group having two aromatic hydrocarbon rings linked together and having 12 to 20 carbon atoms and unsubstituted or substituted, more preferably an aryl group having two monocyclic aromatic hydrocarbon rings linked together and having 12 to 20 carbon atoms and unsubstituted or substituted, and more preferably an aryl group having two monocyclic aromatic hydrocarbon rings linked together and having 13 to 20 carbon atoms and unsubstituted or substituted, via a carbonyl group. Preferably, it is a group in which an unsubstituted or substituted phenyl group and an unsubstituted or substituted alkyl-substituted phenyl group are linked by a carbonyl group, or a group in which an unsubstituted or substituted phenyl group and an unsubstituted or substituted phenyl group are linked by a carbonyl group, and it is most preferably a group in which an unsubstituted phenyl group and an unsubstituted alkyl-substituted phenyl group are linked by a carbonyl group, or a group in which an unsubstituted phenyl group and an unsubstituted or substituted phenyl group are linked by a carbonyl group, and it is preferable that it is a group in which an unsubstituted phenyl group and an unsubstituted alkyl-substituted phenyl group are linked by a carbonyl group. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. In addition, the above compound A has good solubility with the resin component. This result also shows that it is more excellent in sensitivity. In addition, the compound A1 described later is R 13 shows an example of an aryl group in which two aromatic hydrocarbon rings are linked, more specifically, shows an example of a group in which an unsubstituted phenyl group and an unsubstituted phenyl group are linked via a carbonyl group. In addition, the compound A2 described later is R 13shows an example of an aryl group in which two aromatic hydrocarbon rings are linked together, more specifically, shows an example of a group in which an unsubstituted phenyl group and an unsubstituted alkyl-substituted phenyl group are linked together via a carbonyl group. R 13 is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, the substituent substituting the hydrogen atom in the aromatic hydrocarbon ring-containing group is preferably a halogen atom. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. Note that compounds (8), (10), and (11) described later show examples in which hydrogen atoms are substituted with halogen atoms, and among them, they show examples in which hydrogen atoms in the alkyl group of the alkyl-substituted aromatic hydrocarbon ring are substituted with halogen atoms, and in particular, compounds (10) and (11) show examples in which all hydrogen atoms in the alkyl group are substituted with halogen atoms. In addition, compound A7 described later is R 13 is an example of an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, and shows an example in which a hydrogen atom in an aryl group in which two aromatic hydrocarbon rings are linked is substituted with a halogen atom, and more specifically, shows an example in which an unsubstituted alkyl-substituted phenyl group and an alkyl-substituted phenyl group in which a hydrogen atom in the alkyl group is substituted with a halogen atom are linked via a carbonyl group. Furthermore, the compound A8 described below is R 13 is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, and is an alkyl-substituted phenyl group in which a hydrogen atom in the alkyl group is substituted with a halogen atom.

[0050] R 13is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, the substituent substituting the hydrogen atom in the aromatic hydrocarbon ring-containing group is preferably a nitro group. This is because compound A is 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. Furthermore, it is easy to form a composition or the like with suppressed coloration. Note that compounds (9) (or compounds A6) and (25) described later show examples in which a hydrogen atom is substituted with a nitro group, and in particular, show examples in which a hydrogen atom in the ring of an aromatic hydrocarbon ring is substituted with a nitro group. In addition, compound (9) is R 13 This shows an example in which one hydrogen atom in the aromatic hydrocarbon ring is replaced with a nitro group. R 13 When R is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, the number of substituents substituting hydrogen atoms in the aromatic hydrocarbon ring-containing group is preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. 13 This is because compound A has excellent acid generation sensitivity due to the structure, and also because it is easy to form a composition or the like with reduced coloration.

[0051] Also, R 13 The heterocyclic ring-containing group having 2 to 20 carbon atoms and no substituent, represented by the formula (I), is preferably a group in which a heterocyclic group having 6 to 20 carbon atoms is linked to an aromatic hydrocarbon ring, and more preferably a group in which a heterocyclic group having 10 to 18 carbon atoms is linked to an aromatic hydrocarbon ring having a monocyclic structure, and particularly preferably a group in which a heterocyclic group having 12 to 16 carbon atoms is linked to an aromatic hydrocarbon ring having a monocyclic structure via a carbonyl group. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. R 13In the case where the heterocyclic group is a group in which an aromatic hydrocarbon ring is linked to the heterocyclic group, the heterocyclic group may not include an aromatic hydrocarbon ring structure, but is preferably a structure in which a heterocycle and an aromatic hydrocarbon ring are condensed. This is because compound A is 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. Furthermore, it is easy to form a composition with suppressed coloration. Compound A4 described later is a heterocycle-containing group in which a heterocycle group and an aromatic hydrocarbon ring are linked via a carbonyl group, more specifically, it is an example of a group in which a phenyl group and a heterocycle such as a benzofuran ring and a heterocycle group as a condensed ring of an aromatic hydrocarbon ring are linked via a carbonyl group.

[0052] R 13 In the case where the group represented by is a group in which one or more methylene groups in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocyclic ring-containing group, or the first aryl group are replaced with a divalent group selected from Group I, the divalent group replacing the methylene group is preferably a divalent group selected from -O-, -CO-, -CO-CO-, -CO-CO-O-, -SO-, and -SO2-, more preferably a divalent group selected from -O-, -CO-CO-O-, and -SO2-, even more preferably a divalent group selected from -O- and -SO2-, and particularly preferably -SO2-. This is because compound A is 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. In addition, it is easy to form a composition with suppressed coloration. In addition, when one or more methylene groups in the aromatic hydrocarbon ring-containing group are replaced with the above-mentioned divalent group, the replaced methylene group is preferably a methylene group in the alkyl group of the alkyl-substituted aromatic hydrocarbon ring. This is because compound A becomes a compound with better acid generation sensitivity. In addition, it is easy to synthesize, and it is easy to form an acid generator with excellent acid generation sensitivity. Furthermore, it is easy to form a composition with suppressed coloration. For example, in compound A11 described below, R 13The above shows an example in which a methylene group in the alkyl group of an alkyl-substituted aromatic hydrocarbon ring is replaced with -SO2-. Compounds A3, A5, and A9 described below are examples in which the methylene group in the alkyl group of the alkyl-substituted aromatic hydrocarbon ring is substituted with -O-, -CO-CO-O-, and -O-, respectively. In particular, compounds A3 and A5 are each R 13 is a group in which two aromatic hydrocarbon rings are linked, and one of the aromatic hydrocarbon rings, an alkyl-substituted aromatic hydrocarbon ring, has a methylene group replaced with -O- or -CO-CO-O-. Compound A9 is also R 13 The above-mentioned alkyl group-substituted aromatic hydrocarbon ring has a methylene group in the alkyl group replaced with -O-. More specifically, compound A3 is R 13 is an aryl group in which a phenyl group and an alkyl-substituted naphthyl group are linked via a carbonyl group, and a methylene group in the alkyl group of the alkyl-substituted naphthyl group is replaced with -O-. Compound A5 is an alkyl-substituted phenyl group in which a methylene group in the alkyl group is replaced with --CO--CO--O--. Compound A9 described below is R 13 is an alkyl-substituted phenyl group in which the methylene group in the alkyl group is replaced with -O-.

[0053] R 13 When is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, it is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably an aliphatic 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. Furthermore, it is easy to form a composition with suppressed coloration. Also, R 13When is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, the type of the aliphatic hydrocarbon group is preferably an alkyl group, more preferably a linear alkyl group. 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. Furthermore, it is easy to form a composition with suppressed coloration.

[0054] In the present invention, R in the above general formula (A) 12 , R 14 , R 15 , R 16 and R 17 When is a group other than the group represented by the above general formula (1), it is preferably a hydrogen atom. With such a structure, compound A becomes a compound with superior acid generation sensitivity. In addition, it is easy to form a composition with suppressed coloration.

[0055] Specific examples of the compound A include compounds represented by the following formulas (1) to (113).

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] The method for producing the compound A may be any method that can obtain a compound of a desired structure, and can be synthesized by applying a known chemical reaction. For example, the method shown in the following scheme can be mentioned. Specifically, a known and commercially available indole compound is reacted with an acid anhydride to obtain a ketone compound, and the obtained ketone compound is reacted with hydroxylamine hydrochloride to obtain an oxime compound. Subsequently, the oxime compound is reacted with a sulfonic acid anhydride to obtain the compound A. There is no particular limitation on the reaction conditions such as the reaction temperature, reaction time, and amount of raw material used in the production method, and known conditions may be adopted.

[0068] [ka] (The symbols in the formula are the same as those in the general formula (A) above.)

[0069] The compound A has the function of generating an acid. The method for generating an acid from the compound A may be a method generally used for an acid generator, specifically, a method of irradiating with energy rays, a method of heat treatment, a method of carrying out these methods simultaneously or sequentially, etc. 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. In the present invention, the energy rays preferably have a maximum spectrum in the wavelength range of 200 nm to 450 nm and more preferably have a maximum spectrum in the wavelength range of 300 nm to 400 nm, and more preferably have a maximum spectrum in the wavelength range of 340 nm to 380 nm. This is because the acid can be effectively generated from the compound A. 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, light-emitting diodes (LEDs), helium cadmium lasers, etc.). The amount of exposure to the energy ray is not particularly limited as long as it can generate a desired amount of acid, and can be appropriately determined depending on the application of the compound A. The amount of exposure is 5 mJ / cm 2 More than 2000mJ / cm 2 The following is preferred: The heating temperature in the heat treatment is preferably, for example, 70° C. or more and 450° C. or less, and more preferably, 150° C. or more and 300° C. or less. The heating time in the heat treatment is preferably, for example, 1 minute or more and 100 minutes or less. This is because the above heat treatment conditions can effectively exert the effect of obtaining a composition with suppressed coloration.

[0070] The use of the compound A can be an acid generator, more specifically, a photoacid generator that generates an acid by irradiation with energy rays, a thermal acid generator that generates an acid by heat treatment, etc. In the present invention, the use of the compound A is preferably a photoacid generator, because it can effectively exhibit the effect of excellent acid generation sensitivity. Furthermore, the acid generator can be used for purposes such as being added to a composition containing a resin component. The applications of the above composition include, for example, optical filters, paints, coating agents, lining agents, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic electroluminescence (EL) devices, optical elements, electrical insulation, electronic components, separation membranes, and the like, molding materials, putties, glass fiber impregnation agents, fillers, passivation films for semiconductors, solar cells, and the like, interlayer insulating films, surface protective films, printed circuit boards, and color televisions used in thin film transistors (TFTs), liquid crystal displays, organic electroluminescence (EL) displays, printed circuit boards, and the like, PC monitors, mobile information terminals, color filters for CCD image sensors, electrode materials for plasma display panels, printing inks, dental compositions, resins for stereolithography, both liquid and dry films, micromachine parts, glass fiber cable coatings, holographic recording materials, magnetic recording materials, optical switches, plating masks, etching masks, stencils for screen printing, transparent conductive films and other touch panels, MEMS elements, nanoimprint materials, photofabrication such as two-dimensional and three-dimensional high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass-substitute optical filters Microlens arrays used in films, electronic paper, optical disks, projectors, lasers for optical communication, etc., prism lens sheets used in backlights of liquid crystal display devices, Fresnel lens sheets used in screens of projection televisions, etc., lens portions 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, protective materials, optical fiber protective materials, adhesives, die bonding agents, high heat dissipation materials, high heat resistant sealants, solar cell, fuel cell, 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, foams, tubes, sealants, coating materials, sealants for sterilization treatment equipment, contact lenses, oxygen enrichment membranes, medical materials such as biochips, automobile parts, various machine parts, and the like, and there are no particular limitations on the uses. From the viewpoint of more effectively exerting the effect of 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-curable component, or for a positive composition used together with an acid-decomposable component, and more specifically, for a composition used in the formation of an optical lens, an optical element, an optical connector, an optical waveguide, or an interlayer insulating film used in liquid crystal display devices, organic EL display devices, printed circuit boards, etc., which require high acid generation sensitivity. From the viewpoint of more effectively exerting the effect of obtaining a composition with suppressed coloration of the present invention, the above-mentioned use is preferably for forming a component that requires transparency, and specifically, it is preferable for the use to form an optical filter, a coating agent for an optical filter, an optical lens, an optical element, an optical connector, an optical waveguide, a transparent insulating layer used in an electronic circuit that requires transparency, and the like.

[0071] B. Acid generator The acid generator of the present invention is characterized by containing the above-mentioned compound A. By including compound A in the acid generator, an acid generator having excellent acid generation sensitivity can be easily obtained.

[0072] 1. Compound A The type of the compound A used in the acid generator of the present invention may be any type that can easily provide an acid generator having excellent acid generation sensitivity, and the acid generator may contain only one type or two or more types.

[0073] The content of the compound A in the acid generator of the present invention may be an amount that can easily obtain an acid generator with excellent acid generation sensitivity, and is appropriately set according to the type of acid generator. The content of the compound A in the acid generator of the present invention may be, for example, 100 parts by mass in 100 parts by mass of the solid content of the acid generator, that is, the solid content of the acid generator may be only 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 in 100 parts by mass of the solid content of the acid generator, that is, 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 and 99.99 parts by mass or less. This is because the content of the compound A in the above-mentioned range makes it easy to obtain an acid generator with excellent acid generation sensitivity. When the acid generator of the present invention contains other components than the compound A, from the viewpoint of easily obtaining an acid generator having excellent acid generation sensitivity, the lower limit of the content of the 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 in 100 parts by mass of the solid content of the acid generator. This is because an acid generator having excellent acid generation sensitivity can be easily obtained by setting the upper limit of the content of the compound A in the above-mentioned range. In addition, from the viewpoint of easily controlling the particle size of the acid generator, etc., the upper limit of the content of the 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 in 100 parts by mass of the solid content of the acid generator. This is because an acid generator having excellent acid generation sensitivity can be easily obtained by setting the content of the compound A in the above-mentioned range. The solid content includes all components other than the solvent. Moreover, when two or more kinds of compound A are contained, the content of compound A indicates the total amount of compound A.

[0074] The compound A can be the same as described in the section "A. Compound" above, and therefore the description here is omitted.

[0075] 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 above-mentioned solvent is capable of dispersing or dissolving each component in the acid generator. Therefore, even if the solvent is liquid at room temperature (25°C) and atmospheric pressure, the above-mentioned compound A is not included in the solvent. As the above-mentioned solvent, either water or an organic solvent can be used. In the present invention, the above-mentioned solvent is preferably an organic solvent, because it is easy to dissolve or disperse the above-mentioned compound A.

[0076] 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 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.

[0077] 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.

[0078] Examples of components other than the solvent include those described in the sections "2. Resin component" and "3. Other components" in "C. Composition" below. Examples of 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, 50 parts by mass or less, and preferably 10 parts by mass or less, per 100 parts by mass 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.

[0079] 3.Other The acid generator may be produced by any method as long as it is capable of containing the compound A in a desired amount. When the acid generator contains compound A and other components, a method using a known mixing means can be used.

[0080] The acid generator may be used in the form of an additive to a composition containing a resin component, and specifically, may be used in the same manner as described in the section "A. Compound" above.

[0081] C. Composition The composition of the present invention is characterized by containing the above-mentioned compound A and a resin component. By including the compound A, the resulting composition etc. will have excellent acid generation sensitivity.

[0082] 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.

[0083] The content of the compound A in the composition of the present invention may be any content 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, 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. In addition, it is easy to form a composition with suppressed coloration. The content of compound A in the composition of the present invention is preferably, for example, 0.001 parts by mass or more and 20 parts by mass or less in 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. In addition, it is easy to form a composition with suppressed coloration. The content of the compound A in the composition of the present invention is preferably, for example, 0.001 parts by mass or more and 20 parts by mass or less in 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. In addition, it is easy to form a composition with suppressed coloration. The content of compound A above indicates the total amount of compound A when two or more kinds of compound A are contained.

[0084] In addition, the compound A can be the same as described in the above section "A. Compound", so the description here is omitted.

[0085] 2. Resin component As the resin component, a polymer compound or a component capable of becoming a polymer compound can be used. The resin component may be an acid-reactive component having a structure capable of reacting with the acid generated from compound A, or may be a non-acid-reactive component that does not react with the acid generated from compound A, but it is preferable that the resin component is an acid-reactive component. By using an acid-reactive component as the resin component, the composition can easily obtain the effect of excellent acid generation sensitivity that compound A has. In addition, it is easy to form a composition with suppressed coloration.

[0086] 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 is increased by 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. Also, 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. Also, a composition in which coloring is suppressed in non-developed areas that do not cause solubility changes in the developer can be obtained.

[0087] The acid-curable component may include a cationic polymerizable compound. Examples of the cationic 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, aryldialdehydes, and the like, as well as polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in their side chains. These may be used alone or in a mixture of two or more kinds. Specific examples of such cationic polymerizable compounds that can be used include the acid-reactive organic substances described in WO 2017 / 130896 and the compounds described as cationic polymerizable compounds in WO 2014 / 084269 and WO 2016 / 132413.

[0088] The acid-curable 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 polymers selected from the group consisting of metathesis ring-opening polymers; polymers having an alkoxysilyl group; and polymers in which these polymers are partially substituted with acid labile groups having alkali solubility control ability. Examples of polymers containing structural units derived from hydroxystyrene such as the above-mentioned 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 International Publication No. 2017 / 130896, the resin whose solubility in an alkaline developer changes due to the action of the acid of component (A) described in JP-A-2003-192665, claim 3 of JP-A-2004-323704, and the alkali-soluble resin described in JP-A-10-10733. 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.

[0089] The crosslinking agent may be any agent capable of crosslinking the crosslinkable resins together in the presence of an acid. Examples of such crosslinking agents include compounds capable of reacting with acidic groups, such as phenolic hydroxyl groups and carboxyl groups, contained in the resins in the presence of an acid, such as epoxy group-containing compounds, hydroxyl group-containing compounds, alkoxy group-containing compounds, methylol group-containing compounds, and carboxymethyl group-containing compounds. More specifically, examples of the crosslinking agent include the crosslinking agents described in JP-A-2016-169173 and JP-A-2018-112670.

[0090] The acid-decomposable component may be any component whose solubility in a developer is increased by the acid generated from compound A, and examples of such components 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 such resins having 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-A-2018-112670 can also be used. The protecting group may be any group capable of protecting the acidic group, and examples thereof include the protecting group described in JP 2016-169173 A, the acid labile group described in WO 2017 / 130896 A, and the acid dissociable group described in JP 2018-112670 A. Examples of the silanol group protected by a protecting group include an alkoxysilyl group. As a polymer having an alkoxysilyl group used as an acid decomposable component, for example, a 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, as described in JP 2019-66828 A can be used. Moreover, examples of the developer include the developers described in the section "G. Pattern manufacturing method" below.

[0091] The acid-reactive component may be a component that reacts with an acid, other than the acid-hardening component and the acid-decomposable component, and may be, for example, a resin having an alkali-soluble group that is insolubilized by an acid.Specific examples of the acid-insolubilized resin include an acid-insolubilized resin that undergoes an intramolecular or intermolecular crosslinking reaction due to acid-catalyzed dehydration condensation between a hydroxyl group and a carboxyl group, or between carboxyl groups as exemplified below.An example of an acid-insolubilized resin that undergoes acid-catalyzed dehydration condensation between carboxyl groups includes, for example, a resin having a phthalic acid structure in which carboxyl groups undergo dehydration condensation with each other by an acid, as shown below.

[0092] [ka]

[0093] 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.

[0094] 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 per 100 parts by mass of the solid content of the composition, 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 99.9 parts by mass or less, because the effect of obtaining a composition having excellent acid generation sensitivity can be effectively obtained. The content of the resin component in the composition of the present invention can be, for example, 10 parts by mass or more in 100 parts by mass of the composition, 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 99.9 parts by mass or less, because the effect of obtaining a composition having excellent acid generation sensitivity can be effectively obtained.

[0095] 3. Solvent The composition may include a solvent. The above-mentioned solvent is capable of dispersing or dissolving each component in the composition. Therefore, even if the solvent is in a liquid state at room temperature (25° C.) and atmospheric pressure, the above-mentioned compound A and resin component are not included in the solvent. As the solvent, either water or an organic solvent can be used. In the present invention, the solvent is preferably an organic solvent, since the compound A can be easily dissolved or dispersed in the organic solvent. The organic solvent may be the same as that described in the section "B. Acid generator" above. The content of the solvent in the composition of the present invention is appropriately set depending on the 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.

[0096] 4. Other Ingredients The composition may contain other ingredients as needed. Such other components can be selected depending on the application 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 consisting of 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, carbon black and the like; 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, silica and the like; fillers such as glass fiber, calcium carbonate and the like; crystallization agents such as nucleating agents, crystallization accelerators and the like, agents imparting rubber elasticity such as silane coupling agents, flexible polymers and the like, sensitizers and the like. 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 the compounds described as "[D] Acid Diffusion Controller" in JP2019-8300A. The content of these other components in the composition of the present invention may be 50 parts by mass or less per 100 parts by mass of the composition.

[0097] 5.Other The composition can be produced by any known method as long as it is capable of mixing the above 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.

[0098] D. Cured product The cured product of the present invention is a cured product of the above-mentioned composition. The resin component contained in the composition is an acid-curable component.

[0099] According to the present invention, by using the above-mentioned composition, a cured product is obtained in which the curing of the acid-curable component has progressed sufficiently.

[0100] The cured product of the present invention uses the above-mentioned composition. The resin component is an acid-curable component. The cured product is a product of the curing of the acid-curable component, and includes a polymer in which the acid-curable components are polymerized together or a crosslinked product in which the acid-curable components are crosslinked together. The contents of such compositions can be similar to those described in the above section "C. Composition," and therefore, description thereof will be omitted here.

[0101] The shape of the cured product in a 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.

[0102] The uses of the cured product may be similar to those described in the section "A. Compound" above.

[0103] The method for producing the cured product is not particularly limited as long as it is a method that can form a 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 the cured product" below can be used.

[0104] E. Manufacturing method of the cured product Next, the method for producing the cured product of the present invention will be described. The method for producing a cured product of the present invention is characterized by having a curing step of curing the above-mentioned composition. The resin component contained in the composition is an acid-curable component.

[0105] According to the present invention, by using the above-mentioned composition, the effect of excellent acid generation sensitivity can be effectively exhibited, and a cured product in which the curing of the acid-curable component has progressed sufficiently can be easily formed.

[0106] 1.Curing process The curing step in the present invention is a step of curing the above-mentioned composition. The method for curing the above composition may be any method capable of curing the acid-curing 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 capable of generating a desired amount of acid from compound A, and examples of such methods include a method of irradiating with energy rays, a method of heat treatment, and a method of carrying out 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 above section "A. Compound." In this step, it is particularly preferable that the method for generating the acid includes a method of irradiating energy rays, since this effectively exerts the effect of excellent acid generation sensitivity and effectively cures the acid-curable component. The composition contains an acid-curable component as a resin component. The content of the composition can be the same as that described in the above section "C. Composition," so a description thereof will be omitted here.

[0107] 2.Other processes The method for producing a cured product of the present invention may include other steps, if necessary, in addition to the curing step. Examples of the other steps include a developing step of removing unpolymerized portions in the coating film of the composition after the curing step to obtain a patterned cured product, a post-bake step of heat-treating the cured product after the curing step, a pre-bake step of heat-treating the composition to remove the solvent in the composition before the curing step, and a step of forming a coating film of the composition before the curing step. In the present invention, the other steps preferably include a post-baking step, because the acid generated from compound A can be effectively diffused, and as a result, it becomes easy to form a cured product in which the curing of the acid-curable component has progressed sufficiently.

[0108] As a method for removing the unpolymerized portion in the above-mentioned developing step, for example, a method of applying a developer such as an alkaline developer to the unpolymerized portion can be mentioned. As the alkaline developer, there can be used those that are generally used as alkaline developers, such as an aqueous solution of tetramethylammonium hydroxide (TMAH), an aqueous solution of potassium hydroxide, and an aqueous solution of potassium carbonate. 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 above-mentioned developer may be any method capable of bringing 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-bake step may be any conditions that can improve the strength of the cured product obtained in the curing step, and may be, for example, at 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 printing methods, immersion, or the like. The coating film can be formed on a substrate. The substrate can be appropriately selected depending on the application of the cured product, and examples thereof include soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like. In addition, after the cured product is formed on the substrate, it may be peeled off from the substrate and used, or it may be transferred from the substrate to another adherend and used.

[0109] F. Pattern The pattern of the present invention comprises the composition described above. The resin component contained in the composition is an acid-decomposable component.

[0110] According to the present invention, by using the above-mentioned composition, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-decomposable component can be easily decomposed, which makes it easy to form a pattern having excellent dimensional accuracy.

[0111] The pattern of the present invention uses the above-mentioned composition. The resin component is an acid-decomposable component. The above-mentioned pattern is formed by forming a coating film using the above-mentioned composition and removing unnecessary portions. The contents of such compositions can be similar to those described in the above section "C. Composition," and therefore, description thereof will be omitted here.

[0112] The planar shape of the pattern can be appropriately set depending on the application of the pattern, and can be, for example, a dot-like, line-like, or other pattern.

[0113] The uses of the above pattern may be similar to those described in the above section "A. Compounds."

[0114] 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. Manufacturing method of a pattern" below can be used.

[0115] 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 a part of the coating film after the step of generating an acid from the compound to form a pattern. The resin component contained in the composition is an acid-decomposable component.

[0116] According to the present invention, by using the above-mentioned composition, a pattern excellent in dimensional accuracy and the like can be obtained.

[0117] 1. Acid generation process The step of generating an acid in the present invention is a step of generating an acid from the above-mentioned 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 capable of generating a desired amount of acid from the compound A, and examples of such methods include a method of irradiating with energy rays, a method of heat treatment, and a method of carrying out 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 above section "A. Compound." In this step, it is particularly preferable that the method for generating the acid includes a method of irradiating energy rays, since this can effectively exert the effect of obtaining a pattern having excellent dimensional accuracy and the like. In this step, the portion in the coating film where 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, description thereof will be omitted here.

[0118] 2. Pattern formation process The step of forming a pattern in the present invention is a step of developing a part of the coating film 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 may be the same as those described in the above section "E. Method for producing a cured product."

[0119] 3.Other processes The method for producing a pattern of the present invention comprises the above-mentioned step of generating an acid and the step of forming a pattern, but may also comprise 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, and as a result, the decomposition of the acid-decomposable component can proceed more effectively. The step of forming the coating film and the step of pre-baking can be the same as those described in the above 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.

[0120] 4.Other The pattern produced by the above-mentioned production method and its uses can be the same as those described in the above section "A. Composition."

[0121] The present invention is not limited to the above-mentioned embodiment. The above-mentioned embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. EXAMPLES

[0122] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0123] [Example 1] (Synthesis of Compound A1) <Step 1> In a flask, indole (1.0 eq.), 4-fluorobenzophenone (1.2 eq.), potassium carbonate (3.0 eq.) and dimethyl sulfoxide (5 times the theoretical yield) were placed and heated and stirred at 130°C for 3 hours under a nitrogen atmosphere. After cooling to room temperature, ion-exchanged water was added and the precipitated solid was filtered. The obtained solid was washed with ion-exchanged water and dried to obtain intermediate 1.

[0124] [ka]

[0125] <Step 2> Into a flask, 5.00g (16.82mmol) of intermediate 1, 53g (8 times the theoretical yield) of EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide), and 2.26g (18.50mmol) of DMAP (N,N-dimethyl-4-aminopyridine) were added and stirred under a nitrogen stream to obtain a homogeneous solution. The flask was placed in an ice bath, and when the temperature inside the system reached 0°C, 3.89g (18.50mmol) of trifluoroacetic anhydride was added dropwise over 30 minutes. Then, 36.73g (50.44mmol) of AlCl was added in four portions, and the temperature was raised to 40°C to carry out the reaction. After reacting at 40°C for 3 hours, the reaction solution was poured into ice water to quench. The oil layer was extracted with chloroform, washed with water three times, dehydrated with sodium sulfate, and the solvent was distilled off to obtain 5.99g of crude product. Column chromatography was carried out using toluene to obtain 1.92 g (yield 29.0%) of a white solid (Intermediate 2).

[0126] [ka]

[0127] <Step 3> 1.90g (4.83mmol) of intermediate 2, 10g of ethanol, and 0.34g (4.8mmol) of hydroxylamine hydrochloride were added to a flask, and the reaction was carried out under heating and refluxing conditions for 10 hours, after which water was added to quench the reaction. The oil layer was extracted with ethyl acetate, washed with water three times, and dehydrated with sodium sulfate. The solvent was then distilled off to obtain 1.14g of crude product (intermediate 3).

[0128] [ka]

[0129] <Step 4> To a flask containing 1.06 g (2.50 mmol) of intermediate 3, 5.0 g of chloroform (5 times the theoretical yield) was added under a nitrogen atmosphere. After cooling the solution to 0°C, 0.79 g (7.76 mmol) of triethylamine and 2.12 g (7.51 mmol) of trifluoromethanesulfonic anhydride were added dropwise at 10°C or less, and the mixture was stirred for 1 hour under ice cooling. The mixture was quenched by adding 4 mL of water and extracted with chloroform. The mixture was washed three times with water, dehydrated with sodium sulfate, and the solvent was distilled off. The obtained crude product was subjected to column chromatography with hexane:ethyl acetate = 5:1, and then crystallized from methanol to obtain 0.10 g (yield 9.8%) of a white solid (compound A1). 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0130] [ka]

[0131] [Example 2] (Synthesis of Compound A2) <Step 1> Fluorobenzene (60.0g, 624.3mmol) and 2,4,6-trimethylbenzoyl chloride (15.0g, 82.1mmol) were placed in a flask and cooled to below 5℃, after which aluminum chloride (12.0g, 90.3mmol) was added in three portions and stirred. The reaction was then carried out at 80℃ for 16 hours, the reaction liquid was cooled to room temperature and poured into ice water. 20g of EDC was added and stirred, after which the oil and water were separated. The oil layer was washed three times with water, dehydrated with sodium sulfate, and the solvent was distilled off. Purification was carried out by column chromatography to obtain 13.8g of intermediate 4 as a yellow liquid.

[0132] [ka]

[0133] <Step 2-1> Indole (5.0g, 42.7mmol), DMSO (3 times the theoretical yield), intermediate 4 (12.4g, 51.2mmol), and potassium carbonate (17.7g, 128.0mmol) were added to a flask, stirred at 120°C for 5 hours, and the cooled reaction solution was added to 100g of water. After filtering the solid matter, the filtered matter was dissolved in 200mL of ethyl acetate and water was added to separate the oil and water. After that, the mixture was washed with water three times, washed with saturated saline, and dehydrated using sodium sulfate, and the solvent was distilled off. In addition, 100g of methanol was added and stirred for 30 minutes, and the filtered solid was dried under reduced pressure to obtain 13.6g of intermediate 5 as a white solid.

[0134] [ka]

[0135] <Step 2-2> Intermediate 5 (10.0 g, 29.5 mmol) and DMF (three times the theoretical yield) were added to a flask and stirred, and then trifluoroacetic anhydride (7.4 g, 35.4 mmol) was added dropwise at room temperature. After stirring for 3 hours, water was added and the precipitated solid was filtered. After washing with water and drying under reduced pressure, crystallization was performed with ethanol / ethyl acetate to obtain 8.6 g of intermediate 6 as a white powder.

[0136] [ka]

[0137] In the same manner as in Step 3 and Step 4 of Example 1, intermediate 6 was oximed and sulfonated to give compound A2. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0138] [ka]

[0139] [Example 3] (Synthesis of Compound A3) <Step 1> Methoxynaphthalene (10.0 g, 63.2 mmol), fluorobenzoyl chloride (10.0 g, 63.2 mmol), and EDC (5 times the theoretical yield) were placed in a flask and cooled to below 5°C. Aluminum chloride (9.27 g, 69.5 mmol) was then added in three portions and reacted at 50°C for 3 hours. The reaction solution was then cooled to room temperature and poured into ice water to separate the oil and water. The oil layer was washed three times with water, dehydrated with sodium sulfate, and the solvent was distilled off to obtain intermediate 7.

[0140] Using intermediate 7 instead of intermediate 4, a reaction was carried out in the same manner as in step 2-1 of Example 2 to obtain intermediate 8. Also, using intermediate 8 instead of intermediate 5, a reaction was carried out in the same manner as in step 2-2 of Example 2 to obtain intermediate 9.

[0141] [ka]

[0142] In the same manner as in Step 3 and Step 4 of Example 1, intermediate 9 was oximed and sulfonated to give compound A3. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0143] [ka]

[0144] [Example 4] (Synthesis of Compound A4) <Step 1> Benzofuran-2-carboxylic acid (15.0 g, 92.5 mmol), toluene (4.5 times the theoretical yield), and DMF (0.3 g, 4.6 mmol) were added to the flask and heated to 40 ° C., then thionyl chloride (15.4 g, 129.5 mmol) was added dropwise and stirred under heating and reflux for 2 hours. The flask containing the reaction solution was concentrated, EDC (4.5 times the theoretical yield) and fluorobenzene (8.9 g, 92.5 mmol) were added, and the mixture was cooled to 0 ° C., after which aluminum chloride (18.5 g, 138.8 mmol) was added in four portions and stirred at room temperature. After the reaction, the reaction solution was poured into ice water, ethyl acetate was added to separate the oil and water, washed with saturated saline, dehydrated with sodium thiosulfate, and the solvent was distilled off. Crystallization was performed with hexane to obtain 7.74 g of intermediate 10.

[0145] Using intermediate 10 instead of intermediate 4, a reaction was carried out in the same manner as in step 2-1 of Example 2 to obtain intermediate 11. Also, using intermediate 11 instead of intermediate 5, a reaction was carried out in the same manner as in step 2-2 of Example 2 to obtain intermediate 12.

[0146] [ka]

[0147] In the same manner as in Step 3 and Step 4 of Example 1, intermediate 12 was oximed and sulfonated to give compound A4. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0148] [ka]

[0149] [Example 5] (Synthesis of Compound A5) <Step 1> 2-Bromo-p-xylene (25.0g, 135.1mmol) and EDC (3 times the theoretical yield) were added to the flask and stirred. After cooling to 0°C, methyl chloroglyoxylate (18.2g, 148.6mmol) was added, and aluminum chloride (19.8g, 148.6mmol) was added in 4 portions. After reacting at room temperature for 4 hours, the reaction was allowed to proceed at 40°C for 1 hour. A beaker was prepared in which a mixture of 150g of 1N hydrochloric acid and 300g of ethyl acetate was added with ice, and the reaction solution was poured into it to separate the oil and water, washed with water six times, washed with saturated saline, dehydrated with sodium thiosulfate, and the solvent was removed and dried. The mixture was further crystallized from hexane to obtain 28.2g of intermediate 13.

[0150] After carrying out a reaction in the same manner as in step 2-1 of Example 2 using intermediate 13 instead of intermediate 4, the resulting compound was dissolved in toluene (3 times the theoretical yield), DMF (0.4 g, 5.3 mmol) was added, and the mixture was heated to 40° C., after which thionyl chloride (13.9 g, 116.9 mmol) was added dropwise and stirred for 1 hour. After that, the mixture was cooled, methanol (1.5 times the theoretical yield) was added, and the precipitated solid was filtered to obtain intermediate 14. In addition, a reaction was carried out in the same manner as in step 2-2 of Example 2 using intermediate 14 instead of intermediate 5, to obtain intermediate 15.

[0151] [ka]

[0152] Intermediate 15 was used for oxime conversion and sulfonation conversion in the same manner as in Step 3 and Step 4 of Example 1 to obtain compound A5. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0153] [ka]

[0154] [Example 6] (Synthesis of Compound A6) Except for using 1-fluoro-4-nitrobenzene instead of 4-fluorobenzophenone, an indole intermediate was synthesized in the same manner as in step 1 of Example 1. Then, acylation was carried out in the same manner as in step 2-2 of Example 2, and oxime formation and sulfonation were carried out in the same manner as in steps 3 and 4 of Example 1 to obtain compound A6. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0155] [ka]

[0156] [Example 7] (Synthesis of Compound A7) Compound A7 was obtained in the same manner as in Example 6, except that Intermediate 16 was used instead of 1-fluoro-4-nitrobenzene. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0157] [ka]

[0158] [ka]

[0159] [Example 8] (Synthesis of Compound A8) Compound A8 was obtained in the same manner as in Example 6, except that 4-fluorobenzotrifluoride was used instead of 1-fluoro-4-nitrobenzene. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0160] [ka]

[0161] [Example 9] (Synthesis of Compound A9) Trifluoroacetylindole (8.5 g, 40.0 mmol), p-bromoanisole (11.2 g, 60.0 mmol), metaformin hydrochloride (1.3 g, 8.0 mmol), copper(I) iodide (0.8 g, 4.0 mmol), and DMF (three times the theoretical yield) were added to a flask and stirred at 120°C for 24 hours. The mixture was then cooled to room temperature, and ion-exchanged water was poured in to precipitate crystals, which were then filtered out. The obtained crystals were used to carry out oxime conversion and sulfonation in the same manner as in Step 3 and Step 4 of Example 1, to obtain Compound A9. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0162] [ka]

[0163] [Example 10] (Synthesis of Compound A10) Trifluoroacetylindole (4.3 g, 20.0 mmol), ethyl iodide (3.4 g, 22.0 mmol), potassium carbonate (4.15 g, 3.0 mmol), and acetone (three times the theoretical yield) were added to a flask and stirred at 60° C. for 3 hours. The mixture was then cooled to room temperature, and ion-exchanged water was poured in to precipitate crystals, which were then filtered out. The obtained crystals were used to carry out oxime conversion and sulfonation conversion in the same manner as in Step 3 and Step 4 of Example 1, to obtain compound A10. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0164] [ka]

[0165] [Example 11] (Synthesis of Compound A11) Compound A11 was obtained in the same manner as in Example 10, except that methyl p-bromobenzenesulfonate was used instead of ethyl iodide. 1 H-NMR, 19 The measurement results of F-NMR and FT-IR are shown in Tables 1 to 3.

[0166] [ka]

[0167] [Table 1]

[0168] [Table 2]

[0169] [Table 3]

[0170] [Examples 101 to 111, Comparative Examples 1 to 3] According to the formulation shown in Table 4 below, a resin component, an acid generator, and a surfactant were added to propylene glycol monomethyl ether acetate (PGMEA), and the mixture was 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 the table are in parts by weight.

[0171] Resin component: p-hydroxystyrene-styrene-t-butyl acrylate copolymer (p-hydroxystyrene / styrene / t-butyl acrylate = 60 / 20 / 20 (mass ratio), weight average molecular weight 12,000 (polystyrene equivalent), acid decomposable component) Surfactant: FZ2122 (manufactured by Toray Dow Corning) Acid generator: Compounds A1 to A11 prepared in Examples 1 to 11 (acid generators consisting of compound A) Acid generator: Compounds represented by the following formulas (B1) to (B3) (Compound B1, Compound B2, and Compound B3; acid generators other than Compound A)

[0172] [ka]

[0173] 1.Sensitivity evaluation The composition prepared above was filtered through a 5 μm microfilter and spin-coated (1300 rpm, 7 s) on a glass substrate so that the film thickness after pre-baking was 3 μm. Then, the resist was pre-baked at 110° C. for 120 seconds using a hot plate to obtain a positive resist film. After exposure through an i-line bandpass filter using a high-pressure mercury lamp, PEB (Post Exposure Bake) was performed at 120° C. for 120 seconds, and development was performed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 10 seconds to obtain a positive pattern. Mask opening 20μm, exposure dose 20mJ / cm 2 and 40 mJ / cm 2 The line width of the pattern obtained in step 2 (the line width of the portion removed by development) was measured using a microscope. The wider the line width, the higher the sensitivity was evaluated to be. The results are shown in Table 3.

[0174] 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 the table are soluble concentrations (% by mass).

[0175] 3. Molar absorption coefficient (ε) and transmittance The positive resist film obtained in the same manner as described in "1. Sensitivity evaluation" was subjected to absorption spectrum measurement using a UV-Vis 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.

[0176] [Table 4]

[0177] The absorption coefficient of compound A1 used in the examples, which corresponds to compound A of the present invention, at i-line (365 nm) was lower than that of acid generators (compounds B1 and B2) having other structures. The composition of the examples using compound A of the present invention was confirmed to have a thicker line width of the pattern obtained than the line width of the pattern obtained from the compositions using other compounds, and thus to have excellent acid generation sensitivity. Furthermore, the transmittance of the positive resist film at 400 nm was the highest in the Example, and a highly transparent resist film with suppressed coloring was obtained. Furthermore, the compounds of the present invention are highly soluble in solvents. [Industrial Applicability]

[0178] According to the present invention, a compound having excellent acid generation sensitivity can be provided.

Claims

1. A compound represented by the following general formula (A): 【Chemistry 1】 (In the formula, R １１ is a group represented by the following general formula (1), R １２ , R １４ , R １５ , R １６ and R １７ represents a hydrogen atom, R １３ is a group in which an unsubstituted phenyl group is linked to an unsubstituted phenyl group via a carbonyl group; a group in which an unsubstituted phenyl group is linked to an unsubstituted alkyl-substituted phenyl group via a carbonyl group; a group in which an unsubstituted alkyl-substituted phenyl group is linked to an alkyl-substituted phenyl group in which a hydrogen atom in the alkyl group is substituted with a halogen atom via a carbonyl group; an alkyl-substituted phenyl group in which a hydrogen atom in the alkyl group is substituted with a halogen atom; a group in which a hydrogen atom in an aromatic hydrocarbon ring is substituted with a nitro group; a group in which a phenyl group is linked to a heterocyclic ring such as a benzofuran ring or a heterocyclic ring as a condensed ring of an aromatic hydrocarbon ring via a carbonyl group; a group in which a methylene group in the alkyl group of the alkyl-substituted naphthyl group is replaced by -; an aryl group in which a phenyl group and an alkyl-substituted naphthyl group are linked by a carbonyl group, and in which a methylene group in the alkyl group of the alkyl-substituted naphthyl group is replaced by -O-; a group in which a methylene group in the alkyl group of an alkyl-substituted phenyl group is replaced by -CO-CO-O-; a group in which a methylene group in the alkyl group of an alkyl-substituted phenyl group is replaced by -O-; or a linear alkyl group having 1 to 10 carbon atoms. 【Chemistry 2】 (In the formula, R １ and R2 represents a perfluoroalkyl group having 1 to 5 carbon atoms; n represents 0.)

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

3. A compound according to claim 1; A resin component, A composition comprising:

4. The composition of claim 3 , wherein the resin component is an acid-curable resin component.

5. A cured product of the composition according to claim 4.

6. A method for producing a cured product, comprising a curing step of curing the composition according to claim 4.

7. The composition according to claim 3 , wherein the resin component is an acid-decomposable resin component.

8. A pattern comprising the composition of claim 7.

9. A step of forming a coating film using the composition according to claim 7 and generating an acid from a compound contained in the formed coating film; developing a portion of the coating film to form a pattern after the step of generating an acid from the compound; A method for manufacturing a pattern having the above structure.

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