KR20220061910A - Compounds, acid generators, compositions, cured products and patterns, and methods for producing cured products and patterns - Google Patents

Abstract

It is an object of the present invention to provide a compound that is excellent in acid generation sensitivity and obtains a resin composition in which coloring is suppressed. The present invention is a compound represented by the following general formula (A). (Wherein, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, etc., and R ¹³ represents an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is represented by the following general formula (1) Or a group represented by, or R ¹³ is an aryl group substituted by a group represented by the following general formula (1), R ¹ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, etc. , R ² represents a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, etc.)

Description

Compounds, acid generators, compositions, cured products and patterns, and methods for producing cured products and patterns

The present invention relates to a compound suitably used as an acid generator.

The acid generator is a substance that generates an acid by irradiation with energy rays such as light, heat treatment, or the like.

Patent Document 1 and Patent Document 2 disclose a photoacid generator or a thermal acid generator composed of a sulfonic acid derivative compound as an acid generator. In addition, Patent Document 1 and Patent Document 2 describe a negative resist in which solubility in a developer is reduced by formation of a chemical bond such as polymerization or crosslinking by an acid generated from an acid generator, an ester group or an acetal group due to the action of an acid It is described to use an acid generator together with a positive resist whose solubility in a developer is increased by cleavage of chemical bonds or the like. In addition, as specific uses, semiconductors, overcoating agents, paints, adhesives, inks, and the like are described.

Japanese Patent Laid-Open No. 2016-169173 US2020183271

However, these acid generators have low acid generation sensitivity in some cases.

Accordingly, an object of the present invention is to provide a compound excellent in acid generation sensitivity.

MEANS TO SOLVE THE PROBLEM The present inventors found that the oxime sulfonate compound which has an indole structure is excellent in acid generation sensitivity, as a result of earnestly examining in order to solve the said subject, and came to complete this invention.

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

(Wherein, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ²⁰ , -COR ²⁰ , -OCOR ²⁰ , -COOR ²⁰ , -SR ²⁰ , -SOR ²⁰ , -SO ₂ R ²⁰ , -NR ²¹ R ²² , -NR ²¹ COR ²² , -CONR ²¹ R ²² , a group represented by the following general formula (1), the number of carbon atoms 1 to An aliphatic hydrocarbon group having 20 unsubstituted or substituents, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring having 2 to 20 carbon atoms or a group in which at least one methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group is substituted with a divalent group selected from the following group I;

R ¹³ 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, and unsubstituted C 2 to 20 carbon atoms Or a heterocyclic-containing group having a substituent or an aryl group having 7 to 30 carbon atoms or an substituted group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the following general formula (1) At least one of the first aryl group or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocyclic ring-containing group, or the methylene group in the first aryl group represents a group substituted with a divalent group selected from the following group I;

R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I, and when there are a plurality of R ²⁰ , R ²¹ or R ²² , 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 combine to form a ring;

A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent, the heterocyclic ring-containing group having a substituent and the first aryl group is a halogen atom; A cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H;

At least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a group represented by the following general formula (1), or R ¹³ is the first aryl group.)

(wherein R ¹ 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 or 2 to 20 carbon atoms At least one methylene group in the unsubstituted or substituted heterocycle-containing group, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group is substituted with a divalent group selected from the following group I represents the flag,

R ² is 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, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I;

A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent and the heterocyclic ring-containing group having a substituent is a halogen atom, a cyano group, a nitro group, A hydroxyl group, a thiol group, -COOH or -SO ₂ H;

n represents 0 or 1,

When a plurality of groups represented by the general formula (1) exist in the compound represented by the general formula (A), a plurality of n, R ¹ and R ² may be the same or different, respectively,

* indicates a bonding moiety.)

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -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 ³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when two or more R ³⁰ or R ³¹ are present, they may be the same or different.

In the present invention, it is preferable that R ¹¹ is a group represented by the general formula (1).

In the present invention, n is preferably 0.

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 has the above substituents A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group and the aromatic hydrocarbon ring-containing group having a substituent is a halogen atom, and R ² is a cyano group or an unsubstituted or substituent having 1 to 20 carbon atoms. It is an aliphatic hydrocarbon group present, and it is preferable that a substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent is a halogen atom.

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.

The present invention provides an acid generator comprising a compound represented by the general formula (A) described above.

The present invention provides a composition comprising a compound represented by the above-described general formula (A) and a resin component.

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

The present invention provides a cured product of the composition comprising the above-described acid-curable resin component.

The present invention provides a method for producing a cured product having a curing step of curing a composition including the above-described acid-curable resin component.

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

The present invention provides a pattern comprising a composition comprising the above-described acid-decomposable resin component.

The present invention forms a coating film using the composition containing the acid-decomposable resin component described above, generates an acid from a compound included in the formed coating film, and develops a part of the coating film after the process of generating an acid from the compound And, to provide a method for manufacturing a pattern having a step of forming the pattern.

The present invention relates to a compound, an acid generator, a composition, a cured product and a pattern, and a method for preparing the cured product and pattern.

Hereinafter, the present invention will be described in detail.

A. Compounds

First, the compound of the present invention will be described.

The compound of the present invention is characterized in that it is represented by the following general formula (A).

(Wherein, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ²⁰ , -COR ²⁰ , -OCOR ²⁰ , -COOR ²⁰ , -SR ²⁰ , -SOR ²⁰ , -SO ₂ R ²⁰ , -NR ²¹ R ²² , -NR ²¹ COR ²² , -CONR ²¹ R ²² , a group represented by the following general formula (1), the number of carbon atoms 1 to An aliphatic hydrocarbon group having 20 unsubstituted or substituents, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring having 2 to 20 carbon atoms or a group in which at least one methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group is substituted with a divalent group selected from the following group I;

R ¹³ 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, and unsubstituted C 2 to 20 carbon atoms Or a heterocyclic-containing group having a substituent or an aryl group having 7 to 30 carbon atoms or an substituted group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the following general formula (1) At least one of the first aryl group or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocyclic ring-containing group, or the methylene group in the first aryl group represents a group substituted with a divalent group selected from the following group I;

R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I, and when there are a plurality of R ²⁰ , R ²¹ or R ²² , 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 combine to form a ring;

A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent, the heterocyclic ring-containing group having a substituent and the first aryl group is a halogen atom; A cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H;

At least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a group represented by the following general formula (1), or R ¹³ is the first aryl group.)

(wherein R ¹ 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 or 2 to 20 carbon atoms At least one methylene group in the unsubstituted or substituted heterocycle-containing group, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group is substituted with a divalent group selected from the following group I represents the flag,

R ² is 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, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I;

A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent and the heterocyclic ring-containing group having a substituent is a halogen atom, a cyano group, a nitro group, A hydroxyl group, a thiol group, -COOH or -SO ₂ H;

n represents 0 or 1,

When a plurality of groups represented by the general formula (1) exist in the compound represented by the general formula (A), a plurality of n, R ¹ and R ² may be the same or different, respectively,

* indicates a bonding moiety.)

Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -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 ³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when two or more R ³⁰ or R ³¹ are present, they may be the same or different.

According to the present invention, when compound A has an indole ring and a group represented by the general formula (1), it is excellent in acid generation sensitivity.

Here, although it is not clear about the reason which is excellent in an acid generation sensitivity, it is guessed as follows.

The compound A can generate an acid by absorbing energy during exposure by including an indole ring and a structure having a group represented by the general formula (1) (hereinafter, may be referred to as a specific structure). Here, the specific structure has absorption of light with a wavelength of visible light or less, for example, light of a wavelength region of 400 nm or less including i-line (365 nm), and the light absorption efficiency is relatively low. For example, the specific structure tends to have high light transmittance at a wavelength of visible light or less as compared with a structure having a coumarin skeleton and a group represented by the general formula (1).

For this reason, when a composition in which the compound A is added to the resin component is formed and the coating film of the composition is exposed to light, the compound A present on the opposite side to the exposed surface of the coating film can also easily absorb the exposure light. be able to That is, when the compound A is used, acid can be efficiently generated even in a portion deep in the thickness direction of the coating film.

As a result, the composition is excellent in acid generation sensitivity.

In addition, the compound A has high light transmittance in the visible region. For this reason, it can use suitably for the resin composition for member formation by which transparency is calculated|required.

As a halogen atom in the said General formula (A), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The C1-C20 aliphatic hydrocarbon group in the said General formula (A) is a hydrocarbon group which does not contain an aromatic hydrocarbon ring and a heterocyclic ring, 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. can be heard Examples of the aliphatic hydrocarbon group having a substituent include a group in which at least one hydrogen atom in the unsubstituted aliphatic hydrocarbon group is substituted with a substituent, and the substituent includes a halogen atom, a cyano group, a nitro group, A hydroxyl group, a thiol group, -COOH, or _-SO2H etc. are mentioned.

The alkyl group having 1 to 20 carbon atoms may be linear or branched. Straight chain alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl and octyl. 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, heptadecyl, octadecyl, etc. are mentioned.

The alkenyl group having 2 to 20 carbon atoms may be linear or branched. Moreover, the terminal alkenyl group which has an unsaturated bond at the terminal may be sufficient, and the internal alkenyl group which has an unsaturated bond inside may be sufficient. Examples of the terminal alkenyl group include vinyl, allyl, 2-methyl-2-propenyl, 3-butenyl, 4-pentenyl and 5-hexenyl. Internal alkenyl groups include, for example, 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, and the like.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include a saturated monocyclic alkyl group having 3 to 20 carbon atoms, a saturated polycyclic alkyl group having 3 to 20 carbon atoms, and at least one hydrogen atom in the ring of these groups is an alkyl group. and a group having 4 to 20 carbon atoms substituted with . Examples of the saturated monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of the saturated polycyclic alkyl group include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]fentanyl. Examples of the alkyl group for substituting a hydrogen atom in the ring of the saturated monocyclic or saturated polycyclic alkyl group include the groups exemplified as the aforementioned alkyl group having 1 to 20 carbon atoms. Examples of the group in which at least one hydrogen atom in the ring of the saturated polycyclic alkyl group is substituted with an alkyl group include a bornyl group.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the 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 in which the cycloalkyl group is a monocyclic group include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, and cyclooctylmethyl. , 2-cyclononylethyl, 2-cyclodecylethyl, and the like. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms in which the cycloalkyl group is a polycyclic group include 3-3-adamantylpropyl and decahydronaphthylpropyl.

At least one hydrogen atom in the unsubstituted aliphatic hydrocarbon group is substituted by a substituent, and the group in which the substituent is a halogen atom includes 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, 7H-dodeca Alkyl halide such as fluorohexyl, norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2-tetrafluoropropyl, bicyclo[2.2 and .1] a halogenated cycloalkyl or halogenated cycloalkylalkyl such as heptane-tetrafluoromethyl.

In the present invention, the number of carbon atoms in a group defines the number of carbon atoms in the group after the substitution when a hydrogen atom in the group is substituted with a substituent. For example, when the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms are substituted, the number of carbon atoms refers to the number of carbon atoms after the hydrogen atoms are substituted, and refers to the number of carbon atoms before the hydrogen atoms are substituted. not.

In the present invention, the number of carbon atoms in the group in which the methylene group in the group having a predetermined number of carbon atoms is substituted with a divalent group defines the number of carbon atoms in the group before the substitution. For example, in the present specification, a group in which a methylene group in an alkyl group having 1 to 20 carbon atoms is substituted with a divalent group has 1 to 20 carbon atoms.

The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms in the general formula (A) is a hydrocarbon group containing an aromatic hydrocarbon ring and not containing a heterocycle, and may have an aliphatic hydrocarbon group or 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 aromatic hydrocarbon ring-containing group having a substituent include a group in which at least one hydrogen atom in the unsubstituted aromatic hydrocarbon ring-containing group is substituted with a substituent, and the substituent includes a halogen atom and a cyano group , a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H, and the like.

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 connected thereto.

As the aryl group in which two aromatic hydrocarbon rings are connected, two aromatic hydrocarbon rings having a monocyclic structure may be connected, or an aromatic hydrocarbon ring having a monocyclic structure and an aromatic hydrocarbon ring having a condensed ring structure may be connected. of aromatic hydrocarbon rings may be linked.

A single bond, a carbonyl group, etc. are mentioned as a coupling group which connects two aromatic hydrocarbon rings. Examples of the monocyclic aryl group include phenyl, tolyl, xylyl, ethylphenyl, and 2,4,6-trimethylphenyl. Examples of the aryl group of the condensed ring structure include naphthyl, anthracenyl, phenanthryl and pyrenyl. As an aryl group to which the aromatic hydrocarbon ring of two monocyclic structures was connected, biphenyl, benzoylphenyl, etc. are mentioned, for example.

In addition, the aromatic hydrocarbon ring having a monocyclic structure or a condensed ring structure is not limited to those in which a hydrogen atom in the ring is not substituted with an alkyl group, such as phenyl and naphthyl, and a hydrogen atom in the ring is substituted with an alkyl group, such as tolyl and trimethylphenyl, as described above. (Hereinafter, it may call an alkyl-substituted aromatic hydrocarbon ring), and it also includes. In particular, those in which a hydrogen atom in a phenyl group such as tolyl or trimethylphenyl is substituted with an alkyl group is sometimes referred to as an alkyl-substituted phenyl group.

The arylalkyl group having 7 to 20 carbon atoms means a group in which at least one hydrogen atom in the alkyl group is 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. and the like.

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

The unsubstituted heterocyclic-containing group includes a pyridyl group, a quinolyl group, a thiazolyl group, a tetrahydrofuran group, a dioxolanyl group, a tetrahydropyranyl group, a morpholylfuran group, a thiophene group, a methylthiophene group, and a hexylthiophene group. group, benzothiophene group, pyrrole group, pyrrolidine group, imidazole group, imidazolidine group, imidazoline group, pyrazole group, pyrazolidine group, piperidine group, piperazine group, pyrimidyl group, furyl group, Heterocyclic groups such as thienyl group, benzoxazol-2-yl group, thiazole group, isothiazole group, oxazole group, isoxazole group, morphonyl group, and groups in which one or more hydrogen atoms of the alkyl group are substituted with heterocycles, etc. can be heard Examples of the heterocyclic-containing group having a substituent include a group in which at least one hydrogen atom in the unsubstituted heterocyclic-containing group is substituted with a substituent, and the substituent includes a halogen atom, a cyano group, A nitro group, a hydroxyl group, a thiol group, -COOH, or -SO ₂ H, etc. are mentioned.

Moreover, as the unsubstituted heterocyclic-containing group, one in which a heterocyclic ring and an aromatic hydrocarbon ring are connected can be preferably used, and more specifically, one in which a heterocyclic ring and an aromatic hydrocarbon ring having a monocyclic structure are connected. Rings may be connected. A single bond, a carbonyl group, etc. are mentioned as a coupling group which connects two aromatic hydrocarbon rings. Examples of the heterocyclic-containing group in which a heterocyclic ring and an aromatic hydrocarbon ring having a monocyclic structure are connected include benzoylthiophene in which a phenyl group and a thiophene ring are connected to a carbonyl group, and a group in which a phenyl group and a heterocyclic benzofuran ring are connected to a carbonyl group as in Compound A4 to be described later. there is.

The first aryl group in the general formula (A) has an unsubstituted or substituted group having 7 to 30 carbon atoms in which at least one hydrogen atom in the aromatic hydrocarbon ring is substituted with a group represented by the general formula (1) It is an aryl group.

Here, the aryl group having a substituent in which at least one hydrogen atom in the aromatic hydrocarbon ring is substituted with a group represented by the general formula (1) is at least one hydrogen atom in the aromatic hydrocarbon ring of the aryl group having a substituent Those substituted with the group represented by the general formula (1), that is, at least one hydrogen atom in the aromatic hydrocarbon ring is substituted with the group represented by the general formula (1), and further, at least one other hydrogen atom as described above It is a group substituted with a substituent other than the group represented by General formula (1).

As a substituent other than the group represented by the said General formula (1) in the said 1st aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H, etc. are mentioned.

More specifically, examples of the first aryl group include a group in which one hydrogen atom in an aryl group having a monocyclic structure such as phenyl and tolyl is substituted with a group represented by the general formula (1).

At least one methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocycle-containing group or the first aryl group in the general formula (A) is substituted with a divalent group selected from the group I The group does not have a structure in which a plurality of divalent groups are adjacent to each other. A plurality of divalent groups may be the same or different.

Examples of the group in which at least one methylene group of the aliphatic hydrocarbon group is substituted with a divalent group selected from Group I include a 10-camphoryl group in which the methylene group in the aliphatic hydrocarbon group bornyl group is substituted with -CO- can

In the general formula (A), the ring formed by combining R ¹¹ and R ¹² , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , and R ¹⁶ and R ¹⁷ may be a monocyclic ring or a condensed ring. Examples of monocyclic rings include monocyclic cycloalkanes such as cyclopentane, cyclohexane and cyclopentene, monocyclic aromatic rings such as benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, Monocyclic heterocycles, such as a lactone ring and a lactam ring, are mentioned. Examples of the condensed ring include naphthalene and anthracene.

In the present invention, at least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a group represented by the general formula (1), or R ¹³ is the first aryl group. That is, in the compound A, at least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ has a group represented by the general formula (1).

The compound A is (a1) at least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a group represented by the general formula (1), and R ¹³ is 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 are other than the group represented by the general formula (1). group, (a3) R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are groups represented by the general formula (1), and R ¹³ may be the first aryl group. In the present invention, the compound A preferably satisfies (a1). It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

In the present invention, at least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is preferably a group represented by the general formula (1), and among them, at least one of R ¹¹ and R ¹⁶ is It is preferable that the group is a group represented by the general formula (1), and in particular, it is preferable that R ¹¹ in the general formula (A) is a group represented by the general formula (1). It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

The number of groups represented by the general formula (1) in compound A, that is, the number of groups represented by the general formula (1) in R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ ; And it is preferable that the sum total of the number of groups represented by the said General formula (1) which the 1st aryl group in said R ¹³ has is 1 or more and 3 or less, Among these, it is preferable that it is 1 or 2, and it is especially preferable that it is 1. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by the said number. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy.

In the present invention, R ¹¹ in the general formula (A) is a group represented by the general formula (1), and the number of groups represented by the general formula (1) in the compound A is one, that is, the compound A It is preferable that is a structure represented by the following general formula (A1). It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

When a plurality of groups represented by the general formula (1) exist 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. It is because compound A becomes easy to synthesize|combine.

(Wherein, R ¹ , R ² , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and n have the same meaning as in the general formula (A).)

It is preferable that n in the said general formula (A) is 0. This is because, when n is 0, the compound A becomes a compound having more excellent acid generation sensitivity. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

At least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having the substituent, and the heterocyclic ring-containing group having the substituent represented by R ¹ in the general formula (A) It is preferable that it is a halogen atom, and, as for the substituent to be substituted, it is more preferable that it is a fluorine atom. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

R ¹ in the general formula (A) is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsubstituted or substituted group, or an aromatic hydrocarbon-containing group having 6 to 20 carbon atoms, unsubstituted or substituted, Among them, 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 is preferable, and in particular, an aliphatic hydrocarbon having a substituent having 1 to 20 carbon atoms. a group or an aromatic hydrocarbon-containing group having a substituent having 6 to 20 carbon atoms, wherein a substituent is It is preferably a halogen atom, and among them, it is an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms, and a substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent is a halogen atom desirable. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

The aliphatic hydrocarbon group represented by R ¹ in the general formula (A) is preferably an alkyl group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

It is preferable that the number of carbon atoms of the group represented by R< ¹ > of the said general formula (A) is 1-10, and it is especially preferable that it is 1-5. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

Among them, in the present invention, it is preferable that R ¹ in the general formula (A) is a halogenated alkyl having 1 to 20 carbon atoms, a group in which at least one hydrogen atom in an alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, Among them, it is preferable that a halogenated alkyl group having 1 to 10 carbon atoms is a group in which at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom, and all hydrogens in the alkyl group having 1 to 5 carbon atoms are preferred. It is more preferable that it is a perhaloalkyl group having 1 to 5 carbon atoms, a group in which the atoms are substituted with halogen atoms, and a perfluoroalkyl group having 1 to 5 carbon atoms in which all hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. It is most preferable that

This is because, when R ¹ has such a structure, the compound A becomes a compound having a higher sensitivity to acid generation.

At least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent, and the heterocyclic ring-containing group having a substituent, which is represented by R ² in the general formula (A) It is preferable that it is a halogen atom, and, as for the substituent to be substituted, it is more preferable that it is a fluorine atom. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

R ² in the general formula (A) is 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 Preferably, it is a cyano group or an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, more preferably a cyano group or an aliphatic hydrocarbon group having an unsubstituted or substituent having 1 to 20 carbon atoms, It is more preferable that a substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent is a halogen atom, and among them, it is an aliphatic hydrocarbon group having a substituent having 1 to 20 carbon atoms, and has the above substituent It is preferable that the substituent for substituting at least one hydrogen atom in the present aliphatic hydrocarbon group is a halogen atom.

The aliphatic hydrocarbon group represented by R ² in the general formula (A) is preferably an alkyl group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

It is preferable that the number of carbon atoms of the group represented by R< ² > of the said General formula (A) is 1-10, Especially, it is preferable that it is 1-5. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

Among them, in the present invention, R ² in the general formula (A) is preferably a halogenated alkyl having 1 to 20 carbon atoms, a group in which at least one hydrogen atom in the alkyl group having 1 to 20 carbon atoms is substituted with a halogen atom, Among them, it is particularly preferable that a halogenated alkyl group having 1 to 10 carbon atoms is a group in which at least one hydrogen atom in the alkyl group having 1 to 10 carbon atoms is substituted with a halogen atom, and all hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are The group substituted with a halogen atom is more preferably a perhaloalkyl group having 1 to 5 carbon atoms, and a perfluoroalkyl group having 1 to 5 carbon atoms in which all hydrogen atoms in the alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. it is most preferable It is because compound A becomes a compound which is more excellent in acid generation sensitivity because R< ² > has such a structure. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

R ¹³ in the general formula (A) 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 Do. In particular, it is preferably an aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms or an unsubstituted or substituted group, more preferably an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, and 12 carbon atoms It is more preferable that it is an aryl group in which two aromatic hydrocarbon rings are connected, which has an unsubstituted or substituted group of ~20, and an aryl group in which two aromatic hydrocarbon rings of a monocyclic structure having an unsubstituted or substituted group having 12 to 20 carbon atoms are connected. more preferably, an aryl group in which two monocyclic aromatic hydrocarbon rings having an unsubstituted or substituent having 13 to 20 carbon atoms are connected with a carbonyl group, and an unsubstituted or substituted phenyl group having an unsubstituted or More preferably, a group in which an alkyl-substituted phenyl group having a substituent is connected with a carbonyl group, or a group in which an unsubstituted or substituted phenyl group and an unsubstituted or substituted phenyl group are connected with a carbonyl group, and an unsubstituted phenyl group and unsubstituted Most preferably, a group in which an alkyl-substituted phenyl group of It is preferable that it is a linked group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy. Moreover, the said compound A becomes a thing with favorable solubility with a resin component. It is because the sensitivity becomes more excellent also from such a result.

On the other hand, the compound A1 to be described later shows an example in which R ¹³ is an aryl group in which two aromatic hydrocarbon rings are connected, and more specifically, an example of a group in which an unsubstituted phenyl group and an unsubstituted phenyl group are connected by a carbonyl group.

In addition, compound A2 to be described later shows an example in which R ¹³ is an aryl group in which two aromatic hydrocarbon rings are connected, and more specifically, an example of a group in which an unsubstituted phenyl group and an unsubstituted alkyl-substituted phenyl group are connected with a carbonyl group.

When R ¹³ is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, the substituent for substituting a hydrogen atom in the aromatic hydrocarbon ring-containing group is preferably a halogen atom. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy. On the other hand, compounds (8), (10), and (11) to be described later show examples in which a hydrogen atom is substituted with a halogen atom, and among them, an example in which a hydrogen atom in an alkyl group of an alkyl-substituted aromatic hydrocarbon ring is substituted with a halogen atom is shown. (10) (11) shows an example in which all hydrogen atoms in the above alkyl group are substituted with halogen atoms.

In addition, the compound A7 to be described later represents an example in which R ¹³ is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, and represents an example in which a hydrogen atom in an aryl group in which two aromatic hydrocarbon rings are connected is substituted with a halogen atom , more specifically, shows an example of a group 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 is connected by a carbonyl group.

Further, the compound A8 to be described later shows an example in which R ¹³ is 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 the alkyl group is an alkyl-substituted phenyl group in which a halogen atom is substituted.

When R ¹³ is an aromatic hydrocarbon ring-containing group having a substituent having 6 to 20 carbon atoms, the substituent for substituting a hydrogen atom in the aromatic hydrocarbon ring-containing group is preferably a nitro group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy. On the other hand, compounds (9) (or compounds A6) and (25), which will be described later, show examples in which a hydrogen atom is substituted with a nitro group, and among them, an example in which a hydrogen atom in the ring of an aromatic hydrocarbon ring is substituted with a nitro group is shown.

On the other hand, compound (9) shows an example in which R ¹³ is a group in which a hydrogen atom in a ring of one aromatic hydrocarbon ring is substituted with a nitro group.

When R ¹³ 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 preferably 1 or more and 2 or less. Do. This is because, when R ¹³ has such a structure, the compound A becomes a compound having a higher sensitivity to acid generation. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

In addition, the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R ¹³ is preferably a group having 6 to 20 carbon atoms in which a heterocyclic group and an aromatic hydrocarbon ring are connected, among them, carbon atoms It is preferably a group in which a heterocyclic group having a number of 10 to 18 and an aromatic hydrocarbon ring having a monocyclic structure are connected, and particularly preferably a group having 12 to 16 carbon atoms in which a heterocyclic group and an aromatic hydrocarbon ring having a monocyclic structure are connected by a carbonyl group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

When R ¹³ is a group in which a heterocyclic group and an aromatic hydrocarbon ring are connected, the heterocyclic group may not contain an aromatic hydrocarbon ring structure, but it is preferably a structure in which a heterocyclic ring and an aromatic hydrocarbon ring are condensed. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

On the other hand, the compound A4 to be described later is a heterocycle-containing group in which a heterocyclic group and an aromatic hydrocarbon ring are connected with a carbonyl group, and more specifically, a phenyl group, a heterocyclic group as a condensed ring of a heterocyclic ring such as a benzofuran ring, and an aromatic hydrocarbon ring is a group in which a heterocyclic group is connected with a carbonyl group. to indicate an example.

When the group represented by R ¹³ is a group in which at least one methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocycle-containing group or the first aryl group is substituted with a divalent group selected from Group I , the divalent group substituting the methylene group is preferably a divalent group selected from -O-, -CO-, -CO-CO-, -CO-CO-O-, -SO-, -SO ₂ -, -O It is more preferably a divalent group selected from -, -CO-CO-O-, -SO ₂ -, and more preferably a divalent group selected from -O-, -SO ₂ -, especially -SO ₂ - it is preferable It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

Moreover, when one or more of the methylene groups in an aromatic hydrocarbon ring containing group are substituted by the above-mentioned divalent group, it is preferable that the methylene group to be substituted is a methylene group in the alkyl group of an alkyl-substituted aromatic hydrocarbon ring. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

For example, in the compound A11 to be described later, an example is shown in which R ¹³ is a group in which the methylene group in the alkyl group of the alkyl-substituted aromatic hydrocarbon ring is substituted with -SO ₂ -.

In addition, compounds A3, A5, and A9 which will be described later show examples of groups 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, in compounds A3 and A5, each of R ¹³ is a group in which two aromatic hydrocarbon rings are connected, and the methylene group in the alkyl group of the alkyl-substituted aromatic hydrocarbon ring, which is one aromatic hydrocarbon ring, is a group in which -O- or -CO-CO-O- is substituted. Examples will indicate

In addition, compound A9 shows the example in which R< ¹³ > is the group in which the methylene group in the alkyl group of one alkyl group-substituted aromatic hydrocarbon ring was substituted with -O-.

More specifically, in compound A3, R ¹³ is an aryl group in which a phenyl group and an alkyl-substituted naphthyl group are connected by a carbonyl group, and a methylene group in the alkyl group of the alkyl-substituted naphthyl group is substituted with -O-.

Compound A5 is a group in which the methylene group in the alkyl group of the alkyl-substituted phenyl group is substituted with -CO-CO-O-.

Compound A9, which will be described later, is a group in which R ¹³ is a methylene group in an alkyl group of an alkyl-substituted phenyl group in which -O- is substituted.

When R ¹³ 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, particularly, in particular, an aliphatic hydrocarbon group having 1 to 5 carbon atoms It is preferable that it is an aliphatic hydrocarbon group of 3. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

Moreover, when R< ¹³ > is a C1-C20 aliphatic hydrocarbon group, it is preferable that it is an alkyl group as a kind of aliphatic hydrocarbon group, and it is more preferable that it is a linear alkyl group. It is because compound A becomes a compound which is more excellent in acid generation sensitivity. Moreover, it is because it is easy to synthesize|combine and formation of the acid generator excellent in acid generation sensitivity becomes easy. Moreover, it is because formation of the composition etc. in which the coloring was suppressed is easy.

In the present invention, when R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ in the general formula (A) are groups other than those represented by the general formula (1), it is preferably a hydrogen atom. It is because compound A becomes a compound which is more excellent in acid generation sensitivity by such a structure. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

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

The method for producing the compound A may be any method in which a compound having a desired structure can be obtained, and it can be synthesized by applying a known chemical reaction. For example, the method represented by the following scheme is mentioned. Specifically, a ketone compound is obtained by reacting a known and commercially available indole compound with an acid anhydride, and an oxime compound is obtained by reacting the obtained ketone compound with hydroxylamine hydrochloride. Then, the method of obtaining the compound A by making an oxime compound react with a sulfonic acid anhydride is mentioned. There is no restriction|limiting in particular in reaction conditions, such as reaction temperature in a manufacturing method, reaction time, and the usage-amount of a raw material, Well-known conditions may be employ|adopted.

(Each symbol in the formula has the same meaning as in the general formula (A).)

The compound A has a function of generating an acid.

As a method of generating an acid from the compound A, a method generally used for acid generators can be used. Specific examples include a method of irradiating an energy ray, a method of heat treatment, and a method of performing these methods simultaneously or sequentially.

Examples of the energy rays include g-rays (436 nm), h-rays (405 nm), i-rays (365 nm), visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. In the present invention, it is preferable that the energy ray has a maximum spectrum in a wavelength range of 200 nm or more and 450 nm or less and a wavelength of 300 nm or more and 400 nm or less. It is preferable to have. This is because an acid can be effectively generated from the compound A.

In addition, as light sources, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halide lamp, electron beam irradiation device, X-ray irradiation device, laser (argon laser, dye laser, nitrogen laser, light emitting diode (LED), helium cadmium laser, etc.).

There is no restriction|limiting in particular about the exposure amount of an energy-beam, as long as a desired amount of acid can be generated, According to the use of the said compound A, etc., it can determine suitably. The exposure amount is preferably 5 mJ/cm 2 or more and 2000 mJ/cm 2 or less.

As a heating temperature in the said heat processing, it is preferable that they are 70 degreeC or more and 450 degrees C or less, for example, and it is especially preferable that they are 150 degrees C or more and 300 degrees C or less. Moreover, as a heating time in heat processing, it is preferable that they are 1 minute or more and 100 minutes or less, for example. It is because the effect that the composition by which coloring was suppressed is obtained can be exhibited effectively by the said heat processing conditions.

An acid generator is mentioned as a use of the said compound A, More specifically, the photo-acid generator which generate|occur|produces an acid by energy-beam irradiation, the thermal acid generator which generate|occur|produces an acid by heat treatment, etc. are mentioned. In this invention, it is preferable that the use of the said compound A is a photo-acid generator. This is because the effect of excellent acid generation sensitivity can be effectively exhibited.

Moreover, as a use of an acid generator, the use with respect to the composition containing a resin component is mentioned.

Uses of the composition include, for example, optical filters, paints, coatings, linings, adhesives, printing plates, insulating varnishes, insulating sheets, laminates, printed circuit boards, semiconductor devices, LED packages, liquid crystal injection ports, organic EL · For optical devices, for electrical insulation, for electronic parts, for separation films, etc., sealing materials, molding materials, putty, glass fiber impregnating agents, filling agents, passivation layers for semiconductors and solar cells, etc.; An interlayer insulating film, a surface protection film, a printed circuit board, or a color filter for a color TV, PC monitor, portable information terminal, CCD image sensor, plasma display panel used for thin transistor (TFT), liquid crystal display, organic EL display, printed circuit board, etc. Electrode material, printing ink, dental composition, stereolithography resin, both liquid and dry film, micro mechanical parts, glass fiber cable coating, holographic recording material, magnetic recording material, optical switch, plating mask, etching Masks, stencils for screen printing, touch panels such as transparent conductive films, MEMS devices, nanoimprint materials, photofabrication such as 2D and 3D high-density mounting of semiconductor packages, decorative sheets, artificial nails, glass replacement optics Microlens arrays used for film, electronic paper, optical disks, lasers for projectors and optical communication, etc., prism lens sheets used for backlights of liquid crystal display devices, Fresnel lens sheets used for screens such as projection TVs, lenticular ( lenticular) lens part of a lens sheet, such as a lens, or a backlight using such a sheet, optical lenses such as microlenses and imaging lenses, optical elements, optical connectors, optical waveguides, insulating packings, heat-shrinkable rubber tubes, O- Ring, sealing agent for display devices, protective material, optical fiber protective material, adhesive, die bonding agent, high heat dissipation material, high heat resistance sealing material, solar cell/fuel cell/secondary cell member, solid electrolyte for battery, insulating coating material, photosensitive drum for copier, gas Civil engineering and construction such as separation membrane, concrete protective material, lining, soil injection, sealing agent, heat storage material, glass coating, foam, etc. It can be used in various applications such as materials, tube sealing materials, coating materials, sealing materials for sterilization devices, contact lenses, oxygen-enriched membranes, medical materials such as biochips, automobile parts, and various mechanical parts, and there is no particular limitation on the use. .

From the viewpoint of more effectively exhibiting the effect of excellent acid generation sensitivity of the present invention, it is preferable that the above use is for a pattern forming composition, for example, for a negative composition used together with an acid curable component, use with an acid decomposable component It is preferable that it is for a positive type composition that is used, and more specifically, an optical lens, an optical element, an optical connector, an optical waveguide, an interlayer insulating film used for a liquid crystal display device requiring high acid generation sensitivity, an organic EL display device, a printed circuit board, etc. It is preferable that it is for a composition used for the formation of

From the viewpoint of more effectively exhibiting the effect that the composition with suppressed coloring of the present invention is obtained, it is preferable that the above use is for forming a member requiring transparency, specifically, an optical filter, a coating agent for an optical filter, an optical lens, an optical element It is preferable that it is for formation of a transparent insulating layer used for , an optical connector, an optical waveguide, and the electronic circuit which transparency is requested|required.

B. Acid Generator

The acid generator of the present invention is characterized in that it contains the aforementioned compound A.

When the acid generator contains the compound A, an acid generator excellent in acid generation sensitivity can be easily obtained.

1. Compound A

As the kind of compound A used in the acid generator of the present invention, an acid generator excellent in acid generation sensitivity can be easily obtained, and only one type or two or more types of acid generators may be used.

The content of the compound A in the acid generator of the present invention should just be an amount capable of easily obtaining an acid generator excellent in acid generation sensitivity, and is appropriately set according to the type of the acid generator. As the content of the compound A in the acid generator of the present invention, for example, 100 parts by mass per 100 parts by mass of the solid content of the acid generator, that is, only the compound A in the solid content of the acid generator. . The content of the compound A in the acid generator of the present invention is less than 100 parts by mass per 100 parts by mass of the solid content of the acid generator, that is, the acid generator may be a composition comprising the compound A and other components, for example, It can be set as more than 20 mass parts and 99.99 mass parts or less. It is because the acid generator excellent in the acid generation sensitivity can be obtained easily when content of the compound A is the above-mentioned range.

When the acid generator of the present invention contains other components other than the above compound A, the lower limit of the content of Compound A in the acid generator of the present invention is from the viewpoint that an acid generator excellent in acid generation sensitivity can be obtained more easily. It is preferable that it is 50 mass parts or more in 100 mass parts of solid content of a preparation, It is more preferable that it is 70 mass parts or more, It is more preferable that it is 90 mass parts or more. It is because the acid generator excellent in acid generation sensitivity can be obtained easily when the upper limit of content of the said compound A is the above-mentioned range. In addition, from the viewpoint of facilitating particle size control of the acid generator, etc., the upper limit of the content of Compound A in the acid generator of the present invention is preferably 99 parts by mass or less per 100 parts by mass of the solid content of the acid generator, 95 It is more preferable that it is mass parts or less, and it is still more preferable that it is 90 mass parts or less. It is because the acid generator excellent in the acid generation sensitivity can be obtained easily when content of the compound A is the above-mentioned range.

In addition, solid content contains all components other than a solvent.

In addition, content of the said compound A shows the total amount of compound A, when two or more types are included as compound A.

Since the compound A can be the same as the contents described in the "A. compound" section, a description thereof will be omitted.

2. Other Ingredients

The said acid generator may contain other components other than the said compound A. As such other components, a solvent is mentioned, for example.

The solvent is one capable of dispersing or dissolving each component in the acid generator. Therefore, even if it is liquid under atmospheric pressure at room temperature (25°C), the compound A is not contained in the solvent. As the solvent, either water or an organic solvent can be used. In this invention, it is preferable that the said solvent is an organic solvent. This is because dissolution or dispersion of the compound A is easy.

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 monomethyl ether or monophenyl ether of ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol and 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.

Content of the said solvent in the said acid generator can be made into 1 mass part or more and 99 mass parts or less in 100 mass parts of acid generators.

Other components other than the solvent include those described in "2. Resin component" and "3. Other components" of "C. Composition" to be described later.

Moreover, as said other component, the well-known compound used as an acid generator, etc. are mentioned.

Content of the said other component can be set suitably according to the use of the said acid generator etc., For example, it can be set as 50 mass parts or less in 100 mass parts of acid generators, and it is preferable that it is 10 mass parts or less. It is because the said acid generator makes it easy to make the content rate of the compound A a large thing, and it becomes a thing which can obtain the acid generator excellent in the acid generation sensitivity more easily.

3. Other

As a manufacturing method of the said acid generator, what is necessary is just a method which can be made into what contains the said compound A in a desired compounding quantity.

When the said acid generator contains compound A and other components, the method of using a well-known mixing means is mentioned.

Examples of the use of the acid generator include an addition use to a composition containing a resin component, and specifically, it may be the same as described in the section "A. Compound".

C. Composition

The composition of the present invention is characterized in that it contains the aforementioned compound A and a resin component.

By including the said compound A, the composition etc. obtained become a thing excellent in acid generation sensitivity.

1. Compound A

The compound A used in the composition of the present invention may be one that can exhibit the effect of being excellent in acid generation sensitivity, and may be of one type or two or more types in the composition.

The content of the compound A in the composition of the present invention should just be one that can exhibit the effect of being excellent in acid generation sensitivity, and is appropriately set according to the kind of resin component to be used.

The content of the compound A in the composition of the present invention is, for example, preferably 0.05 parts by mass or more and 100 parts by mass or less, and more preferably 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component. This is because a composition capable of exhibiting the effect of being excellent in acid generation sensitivity can be easily obtained. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

It is preferable that content of the compound A in the composition of this invention is 0.001 mass part or more and 20 mass parts or less in 100 mass parts of solid content of the said composition, for example. This is because a composition capable of exhibiting the effect of being excellent in acid generation sensitivity can be easily obtained. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

As content of the said compound A in the composition of this invention, it is preferable that they are 0.001 mass parts or more and 20 mass parts or less in 100 mass parts of said compositions, for example. This is because a composition capable of exhibiting the effect of being excellent in acid generation sensitivity can be easily obtained. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

When two or more types are included as compound A, content of the said compound A shows the total amount of compound A.

On the other hand, since the compound A can be the same as the contents described in the "A. compound" section, a description thereof will be omitted.

2. Resin component

As the resin component, a high molecular compound or a component capable of being a high molecular compound may be used.

In addition, the resin component may be an acid-reactive component having a structure capable of reacting with the acid generated from the compound A, or may be a non-acid-reactive component that does not react with the acid generated from the compound A, wherein the resin component is an acid-reactive component it is preferable This is because, when the resin component is an acid-reactive component, the composition can easily obtain the effect of being excellent in the acid generation sensitivity of the compound A. Moreover, it is because formation of the composition etc. in which coloring was suppressed is easy.

As such an acid-reactive component, it is preferable to use an acid-curable component that is cured by polymerization or crosslinking with an acid generated from the compound A, or an acid-decomposable component whose solubility in a developer is increased by the acid generated from the compound A.

In the present invention, when the resin component is an acid-curable component, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-curable component can be easily cured. Moreover, when the resin component is an acid-decomposable component, the effect of being excellent in acid generation sensitivity can be effectively exhibited, and decomposition|disassembly of an acid-decomposable component becomes easy. Also, a composition in which discoloration is suppressed in a non-developed portion that does not cause a change in solubility in a developer is obtained.

A cationically polymerizable compound is mentioned as said acid-curable component.

Examples of the cationically polymerizable compound include cyclic ether compounds such as epoxy compounds and oxetane compounds, vinyl ether compounds, vinyl compounds, styrenes, spiroorthoesters, bicycloorthoesters, spiroorthocarbonates, lactones, and oxazoline. Polymerizable or crosslinkable polymers and oligomers having these polymerizable groups in the side chain, in addition to compounds, adylidines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams, aryldialdehydes, and the like are exemplified. These may be used individually or in mixture of 2 or more types.

Specific examples of such a cationically polymerizable compound include, for example, an acid-reactive organic substance described in International Publication WO2017/130896, WO2014/084269, a compound described as a cationically polymerizable compound described in International Publication WO2016/132413, etc. can be used

A mixture of a crosslinking resin and a crosslinking agent may also be used as the acid curable component.

Examples of the crosslinkable resin include polyhydroxystyrene and derivatives thereof; polyacrylic acid and its derivatives; polymethacrylic acid and its derivatives; two or more copolymers selected from hydroxystyrene, acrylic acid, methacrylic acid, and derivatives thereof; two or more copolymers selected from hydroxystyrene, styrene, and derivatives thereof; a copolymer of three or more selected from cycloolefin and its derivatives, maleic anhydride, and acrylic acid and its derivatives; three or more copolymers selected from cycloolefin and its derivatives, maleimide, and acrylic acid and its derivatives; polynorbornene; one or more polymers selected from the group consisting of metathesis ring-opening polymers; a polymer having an alkoxysilyl group; and high molecular weight polymers in which these high molecular polymers are partially substituted with acid labile groups having alkali dissolution control ability.

Examples of the polymer containing a structural unit derived from hydroxystyrene such as polyhydroxystyrene include phenolic hydroxyl group-containing resin (QN) described in Japanese Patent Application Laid-Open No. 2018-112670.

The crosslinkable resin is, for example, a resist base resin described in International Publication WO2017/130896, and a resin whose solubility in an alkali developer is changed due to the acid action of component (A) described in Japanese Patent Application Laid-Open No. 2003-192665. , and resins described as alkali-soluble resins as described in claim 3 of Japanese Unexamined Patent Application, First Publication No. 2004-323704, and Japanese Patent Application Laid-Open No. Hei 10-10733 can also be used.

As the polymer having an alkoxysilyl group, for example, a compound in which an alkoxysilyl group is not directly bonded to an aromatic ring may be used.

The crosslinking agent may be one that can crosslink the crosslinkable resins in the presence of an acid. Examples of such a crosslinking agent include an epoxy group-containing compound, a hydroxyl group-containing compound, an alkoxy group-containing compound, a methylol group-containing compound, and a carboxymethyl group-containing compound. Acidic groups such as phenolic hydroxyl groups and carboxyl groups contained in the resin react in the presence of an acid Possible compounds may be used.

More specifically, the crosslinking agent described in Japanese Patent Application Laid-Open No. 2016-169173 and Japanese Patent Application Laid-Open No. 2018-112670 may be mentioned.

As said acid-decomposable component, the solubility with respect to a developing solution may be increased by the acid generated from compound A, For example, the hydrogen atom of the acidic group in the resin which has acidic groups, such as a phenolic hydroxyl group, a carboxyl group, a sulfonyl group, a silanol group. and resins in which part or all of is protected by a protecting group.

Examples of the resin having such an acidic group include a crosslinkable resin used together with a crosslinking agent as the acid-curable component described above. The positive chemical amplification resin described in JP-A-2018-112670 can also be used.

The protecting group may be any one capable of protecting the acidic group, for example, a protecting group described in Japanese Patent Application Laid-Open No. 2016-169173, an acid labile group described in International Publication WO2017/130896, and Japanese Unexamined Patent Application Publication No. 2018- The acid dissociable group of 112670, etc. are mentioned. In addition, 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, "Structural unit (I) comprising an aromatic ring and an alkoxysilyl group directly bonded to the aromatic ring, and polymer component (A)" having structural unit (II) containing an acidic group.

In addition, examples of the developer include the developer described in the section “G. Method for producing a pattern” to be described later.

As the acid-reactive component, in addition to the acid-curable component and the acid-decomposable component, a component that reacts with an acid may be used, for example, a resin in which a resin having an alkali-soluble group is insolubilized by an acid may also be used. Specific examples include acid insolubilizing resins that cause intramolecular or intermolecular crosslinking reaction by acid-catalyzed dehydration condensation of a hydroxyl group and a carboxyl group and a carboxyl group and a carboxyl group as exemplified below. Examples of the acid-insoluble resin that causes acid-catalyzed dehydration condensation of a carboxyl group and a carboxyl group include a resin having a phthalic acid structure in which carboxyl groups are dehydrated and condensed with an acid, as shown below.

As the non-acid-reactive component, one that does not react with the acid generated from compound A, more specifically, one that does not cause curing, decomposition, or change in solubility in an alkali developer by the acid generated from compound A can be used, for example, For example, thermoplastic resins, such as polyolefin resin, polybutadiene resin, polystyrene resin, polystyrene butadiene resin, and polystyrene olefin resin, etc. are mentioned.

Content of the said resin component in the composition of this invention should just be what can acquire the effect of being excellent in acid generation sensitivity, and it will set suitably according to the kind etc. of the resin component to be used.

Content of the said resin component in the composition of this invention can be 10 mass parts or more in 100 mass parts of solid content of the said composition, for example, It is preferable that it is 30 mass parts or more and 99.9 mass parts or less, 50 mass parts or more and 99.9 mass parts It is more preferable that it is less than a mass part. It is because the effect that a thing excellent in acid generation sensitivity is obtained can be acquired effectively.

Content of the said resin component in the composition of this invention can be 10 mass parts or more in 100 mass parts of said composition, for example, It is preferable that it is 30 mass parts or more and 99.9 mass parts or less, 50 mass parts or more and 99.9 mass parts It is more preferable that it is the following. It is because the effect that a thing excellent in acid generation sensitivity is obtained can be acquired effectively.

3. Solvent

The composition may contain a solvent.

The solvent is one capable of dispersing or dissolving each component in the composition. Therefore, even if it is liquid under normal temperature (25 degreeC) atmospheric pressure, the said compound A and the resin component are not contained in a solvent.

As the solvent, either water or an organic solvent can be used.

In this invention, it is preferable that the said solvent is an organic solvent. This is because dissolution or dispersion of the compound A is easy.

The organic solvent may be the same as described in the section "B. Acid generator".

In addition, content of the said solvent in the composition of this invention is suitably set according to the use of the said composition, etc., For example, it can be 1 mass part or more and 99 mass parts or less in 100 mass parts of said compositions.

4. Other Ingredients

The composition may include other components as needed.

Such other components may be selected according to the use of the composition, for example, benzotriazole-based, triazine-based, benzoate-based ultraviolet absorbers; phenolic, phosphorus-based and sulfur-based antioxidants; Antistatic agent which consists of a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, etc.; flame retardants such as halogen compounds, phosphate ester compounds, phosphoric acid amide compounds, melamine compounds, fluororesins or metal oxides, (poly) melamine phosphate, and (poly) piperazine phosphate; hydrocarbon-based, fatty acid-based, aliphatic alcohol-based, aliphatic ester-based, aliphatic amide-based or metal soap-based lubricants; colorants such as dyes, pigments and carbon black; Fumed silica, particulate silica, silicate, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, vermiculite, attapulgite, talc, mica, minnesoite , silicic acid-based inorganic additives such as pyrophyllite and silica; fillers such as glass fiber and calcium carbonate; and crystallizing agents such as nucleating agents and crystal accelerators, silane coupling agents, rubber elasticity-imparting agents such as flexible polymers, and sensitizers.

In addition, the other components may include an acid diffusion control agent such as an amine compound, an amide group-containing compound, a urea compound, and a nitrogen-containing heterocyclic compound.

As said sensitizer, the compound described as a spectral sensitizer in Unexamined-Japanese-Patent No. 2008-506749 is mentioned, for example.

As said acid diffusion controlling agent, the compound described as "[D] acid diffusion controlling body" in Unexamined-Japanese-Patent No. 2019-8300 is mentioned, for example.

Content of these other components in the composition of this invention can be 50 mass parts or less in 100 mass parts of said compositions.

5. Others

As a manufacturing method of the said composition, what is necessary is just a method which can mix the said each component in a desired compounding quantity, and a well-known method can be used.

For example, after dissolving or dispersing the said compound A in a solvent, the method of adding a resin component to the said solvent, etc. are mentioned.

D. Cured product

The cured product of the present invention is a cured product of the above-described composition.

In addition, the resin component contained in the said composition is an acid-curable component.

According to the present invention, by using the above-described composition, a cured product in which curing of the acid-curable component has been sufficiently advanced is obtained.

The cured product of the present invention uses the composition described above. In addition, the resin component is an acid-curable component. The cured product is one in which an acid-curable component is cured, and includes a polymer in which the acid-curable components are polymerized or a cross-linked product.

Since the content of such a composition can be the same as that described in the "C. Composition" section, a description thereof will be omitted.

About the planar view shape of the said hardened|cured material, it can set suitably according to the use of the said hardened|cured material, For example, it can set it as pattern shape, such as a dot shape and a line shape.

The use of the cured product may be the same as described in the section “A. Compound”.

The method for producing the cured product is not particularly limited as long as it is a method capable of forming the cured product of the composition into a desired shape.

As such a manufacturing method, for example, the manufacturing method described in the section of "Method for manufacturing a cured product E." which will be described later can be used.

E. Manufacturing method of cured product

Next, the manufacturing method of the hardened|cured material of this invention is demonstrated.

The method for producing a cured product of the present invention is characterized by having a curing step of curing the composition described above.

In addition, the resin component contained in the said composition is an acid-curable component.

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

1. Curing process

The curing step in the present invention is a step of curing the above-described composition.

As a method of curing the composition, any method capable of curing the acid-curable component may be used, and a method of generating an acid from the compound A may 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, for example, a method of irradiating an energy ray, a method of heat treatment, and a method of performing these simultaneously or sequentially can be heard As for the method of irradiating such an energy ray, the method of heat processing, etc., the method similar to the method described in the said "A. compound" section is mentioned.

In this process, it is preferable that the method of generating the said acid especially includes the method of irradiating an energy ray. It is because the effect of being excellent in acid generation sensitivity can be exhibited effectively and an acid-curable component can be effectively hardened|cured.

Meanwhile, the composition includes an acid curable component as a resin component. Since the content of such a composition can be the same as that described in the "C. Composition" section, a description thereof will be omitted.

2. Other processes

The manufacturing method of the hardened|cured material of this invention may include other processes as needed other than the said hardening process.

The other steps include a developing step of removing the unpolymerized portion in the coating film of the composition after the curing step to obtain a pattern-shaped cured product, a post-baking step of heat-treating the cured product after the curing step, and heat treatment of the composition before the curing step and a pre-baking step of removing the solvent in the composition, a step of forming a coating film of the composition before the curing step, and the like.

In the present invention, it is preferable that the other process has a post-baking process. The acid generated from the compound A can be effectively diffused. As a result, it is because formation of the hardened|cured material which hardening of an acid-curable component fully advanced is easy.

As a method of removing the unpolymerized part in the said image development process, the method of apply|coating developing solutions, such as an alkali developer, to an unpolymerized part is mentioned, for example.

As said alkaline developing solution, what is generally used as an alkali developing solution, such as a tetramethylammonium hydroxide (TMAH) aqueous solution, potassium hydroxide aqueous solution, potassium carbonate aqueous solution, can be used.

Moreover, as a developing solution, what is generally used as a solvent developing solution, such as propylene glycol monomethyl ether acetate (PEGMEA) and cyclohexanone, can be used.

The developing method using the developer may be any method capable of bringing the developer into contact with the site to be developed, and a known method such as a shower method, a spray method, or an immersion method may be used.

As an implementation timing of the said image development process, what is necessary is just after the said hardening process.

As the heating conditions in the post-baking step, the strength and the like of the cured product obtained by the curing step can be improved, for example, at 200°C or higher and 250°C or lower for 20 minutes to 90 minutes.

As heating conditions in the said prebaking process, what is necessary is just to be able to remove the solvent in a composition, For example, it can be set as 30 second - 300 second at 70 degreeC or more and 150 degrees C or less.

As a method of applying the composition in the step of forming the coating film, a known method such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various kinds of printing and immersion can be used.

The coating film can be formed on a substrate.

The substrate can be appropriately set depending on the use of the cured product, and examples include those containing soda glass, quartz glass, semiconductor substrates, wiring substrates, metals, paper, plastics, and the like.

In addition, after the said hardened|cured material is formed on a base material, it may peel and use from a base material, and may use it by transferring it to another to-be-complexed body from a base material.

F. Pattern

The pattern of the present invention comprises the composition described above.

In addition, the resin component contained in the said composition is an acid-decomposable component.

According to the present invention, by using the composition described above, the effect of excellent acid generation sensitivity can be effectively exhibited, and the acid-decomposable component can be easily decomposed. As a result, the formation of a pattern excellent in dimensional accuracy and the like becomes easy.

The pattern of the present invention is to use the composition described above. In addition, the resin component is an acid-decomposable component. The pattern is formed by forming a coating film using the above-described composition and removing unnecessary portions.

Since the content of such a composition can be the same as that described in the "C. Composition" section, a description thereof will be omitted.

About the planar shape of the said pattern, it can set suitably according to the use of the said pattern, For example, it can be set as pattern shape, such as a dot shape and a line shape.

The use of the pattern may be the same as described in the "A. Compound" section above.

The method for producing the pattern is not particularly limited as long as it is a method capable of forming the composition into a desired shape.

As such a manufacturing method, for example, the manufacturing method described in the "G. Pattern manufacturing method" section to be described later can be used.

G. Method of making the pattern

Next, the manufacturing method of the pattern of this invention is demonstrated.

In the method for producing a pattern of the present invention, a coating film is formed using the composition described above, an acid is generated from a compound included in the formed coating film, and a part of the coating film is developed after the step of generating an acid from the compound, It is to have a process of forming a pattern. The resin component included in the composition is an acid-decomposable component.

According to the present invention, a pattern having excellent dimensional accuracy and the like can be obtained by using the composition described above.

1. Process for generating acid

The step of generating an acid in the present invention is a step of generating an acid from the compound A contained in a coating film formed using the above-described composition.

The method for generating an acid from compound A in this step may be any method capable of generating a desired amount of acid from compound A, for example, a method of irradiating an energy ray, a method of heat treatment, and these simultaneously or sequentially Here are some ways to do it. As for the method of irradiating such an energy ray, the method of heat processing, etc., the method similar to the method described in the said "A. compound" section is mentioned.

In this process, it is preferable that the method of generating the said acid especially includes the method of irradiating an energy ray. It is because the effect that the pattern excellent in dimensional accuracy etc. is obtained can be exhibited effectively.

In addition, in this process, it is preferable that it is a part of the coating film in planar view about the part which generate|occur|produces the acid in a coating film. This is because the process of forming a pattern to be described later can be easily performed.

About the planar view shape and thickness of the said coating film, it sets suitably according to the use etc. of a pattern coating film.

Meanwhile, the composition includes an acid-decomposable component as a resin component. Since the content of such a composition can be the same as that described in the "C. Composition" section, a description thereof will be omitted.

2. The process of forming a pattern

The step of forming a pattern in the present invention is a step of developing a part of the coating film after the step of generating an acid from the compound to form a pattern.

As a method of developing in this process, the method of developing using a developing solution is mentioned.

Such a developing solution and a developing method may be the same as described in the section "E. Method for producing a cured product".

3. Other processes

The pattern manufacturing method of the present invention includes the step of generating the acid and the step of forming the pattern, but may include other steps if necessary.

Such other steps include a step of forming a coating film of the composition before the step of generating the acid, and a prebaking step of removing a solvent in the coating film by heat treatment after the step of forming the coating film.

In the present invention, it is preferable that the above other processes include a post-exposure baking process. The acid generated from the compound A can be effectively diffused. As a result, it is because decomposition|disassembly of an acid-decomposable component can advance more effectively.

About the process of forming the said coating film, and the process of prebaking, it can carry out similarly to the content described in the said "E. Manufacturing method of a hardened|cured material".

Moreover, as conditions of a baking process after exposure, it can be set as 30 second - 300 second at 70 degreeC or more and 150 degrees C or less, for example.

4. Others

The pattern prepared by the above manufacturing method and its use may be the same as described in the “A. Composition” section.

This invention is not limited to the said embodiment. The above-mentioned embodiment is an illustration, and any thing which has substantially the same structure as the technical idea described in the claim of this invention, and exhibits the same operation and effect is included in the technical scope of this invention.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Example 1] (Synthesis of Compound A1)

<Step 1>

Indole (1.0eq.), 4-fluorobenzophenone (1.2eq.), potassium carbonate (3.0eq.) and dimethyl sulfoxide (5 times the theoretical amount) were put in a flask, and 3 at 130°C under a nitrogen atmosphere. It was heated and stirred for an hour. After cooling to room temperature, ion-exchanged water was added, and the precipitated solid was filtered out. The obtained solid was washed with ion-exchanged water and dried to obtain an intermediate 1.

<Step 2>

5.00 g (16.82 mmol) of Intermediate 1 in a flask, 53 g of EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide) (8 times the theoretical amount), DMAP (N,N-dimethyl-4) -aminopyridine) 2.26 g (18.50 mmol) was added and stirred under a nitrogen stream to obtain a uniform solution. The flask was placed in an ice bath, and when the system internal temperature reached 0°C, 3.89 g (18.50 mmol) of trifluoroacetic anhydride was added dropwise over 30 minutes. Then, 6.73 g (50.44 mmol) of AlCl ₃ was dividedly added in 4 times, the temperature was raised and reaction was performed at 40 degreeC. After reaction at 40°C for 3 hours, the reaction solution was poured into ice water and quenched. The oil layer was extracted with chloroform, washed with water 3 times, dehydrated with sodium sulfate, and then the solvent was distilled off to obtain 5.99 g of a crude product. Column chromatography was performed with toluene to obtain 1.92 g (yield 29.0%) of a white solid (Intermediate 2).

<Step 3>

1.90 g (4.83 mmol) of Intermediate 2, 10 g of ethanol, and 0.34 g (4.8 mmol) of hydroxylamine hydrochloride were added to the flask, and after reacting for 10 hours under heating and reflux conditions, water was added and quenched. The oil layer was extracted with ethyl acetate, washed with water 3 times, dehydrated with sodium sulfate, and the solvent was distilled off to obtain 1.14 g of a crude product (Intermediate 3).

<Step 4>

To a flask containing 1.06 g (2.50 mmol) of Intermediate 3, 5.0 g (5 times the theoretical amount) of chloroform 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 1 under ice-cooling time was stirred. 4 ml of water was added, quenched, and extracted with chloroform. After washing with water 3 times and dehydrating with sodium sulfate, the solvent was distilled off. The obtained crude product was subjected to column chromatography in hexane:ethyl acetate = 5:1, and then crystallized with methanol to obtain 0.10 g (yield 9.8%) of a white solid (Compound A1). ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Example 2] (Synthesis of Compound A2)

<Step 1>

Fluorobenzene (60.0 g, 624.3 mmol) and 2,4,6-trimethylbenzoyl chloride (15.0 g, 82.1 mmol) were put in a flask, and after cooling at 5 ° C. or less, aluminum chloride (12.0 g, 90.3 m) mol) was added in 3 portions and stirred. After that, the reaction was performed at 80° C. for 16 hours, and the reaction solution was cooled to room temperature and poured into ice water. After adding 20 g of EDC and stirring, oil-water separation was carried out. The oil layer was washed with water 3 times, then dehydrated with sodium sulfate, and the solvent was distilled off. Purification by column chromatography was carried out to obtain Intermediate 4 as 13.8 g of a yellow liquid.

<Step 2-1>

Indole (5.0 g, 42.7 mmol), DMSO (3 times the theoretical amount), Intermediate 4 (12.4 g, 51.2 mmol), potassium carbonate (17.7 g, 128.0 mmol) were added to a flask, and 5 at 120 ° C. After stirring for an hour, the cooled reaction solution was added to 100 g of water. After the solid was filtered and extracted, the filtrate was dissolved in 200 ml of ethyl acetate, and water was added thereto, followed by oil-water separation. Thereafter, washing with water 3 times, washing with saturated brine, and dehydration using sodium sulfate were performed, and the solvent was distilled off. Furthermore, 100 g of methanol was added, and after stirring for 30 minutes, the filtered-extracted solid was dried under reduced pressure to obtain 13.6 g of an intermediate 5 as a white solid.

<Step 2-2>

Intermediate 5 (10.0 g, 29.5 mmol) and DMF (3 times the theoretical amount) were added to the flask, and after stirring, 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 out. After washing with water, drying under reduced pressure, and crystallization with ethanol/ethyl acetate, 8.6 g of an intermediate 6 was obtained as a white powder.

Oximation and sulfonation of Intermediate 6 were carried out in the same manner as in Step 3 and Step 4 of Example 1 to obtain Compound A2. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[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 amount) were put in a flask, cooled to 5 ° C or less, and aluminum chloride (9.27 g, 69.5 mmol) was added in 3 portions, and reacted at 50°C for 3 hours. Then, the reaction solution was cooled to room temperature, poured into ice water, and oil-water separation was performed. The oil layer was washed with water 3 times, dehydrated with sodium sulfate, and the solvent was distilled off to obtain Intermediate 7.

The reaction was carried out in the same manner as in Step 2-1 of Example 2 using Intermediate 7 instead of Intermediate 4 to obtain Intermediate 8. In addition, the reaction was carried out in the same manner as in Step 2-2 of Example 2 using Intermediate 8 instead of Intermediate 5 to obtain Intermediate 9.

Oximation and sulfonation of Intermediate 9 were carried out in the same manner as in Step 3 and Step 4 of Example 1 to obtain Compound A3. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Example 4] (Synthesis of Compound A4)

<Step 1>

Benzofuran-2-carboxylic acid (15.0 g, 92.5 mmol), toluene (4.5 times the theoretical amount), and DMF (0.3 g, 4.6 mmol) were added to the flask and the temperature was raised to 40 ° C. O'Neil (15.4 g, 129.5 mmol) was added dropwise, followed by stirring under heating and refluxing for 2 hours. After concentrating the flask containing the reaction solution, EDC (4.5 times the theoretical amount) and fluorobenzene (8.9 g, 92.5 mmol) were added and cooled to 0 ° C., aluminum chloride (18.5 g, 138.8 mmol) was added. It added in 4 portions, and stirred at room temperature. After the reaction, the reaction solution was poured into ice water, ethyl acetate was added to separate oil and water, washed with saturated brine, dehydrated with sodium thiosulfate, and the solvent was distilled off. Crystallization was carried out with hexane to obtain 7.74 g of Intermediate 10.

The reaction was carried out in the same manner as in step 2-1 of Example 2 using Intermediate 10 instead of Intermediate 4 to obtain Intermediate 11. In addition, the reaction was carried out in the same manner as in Step 2-2 of Example 2 using Intermediate 11 instead of Intermediate 5 to obtain Intermediate 12.

Oximation and sulfonation of Intermediate 12 were carried out in the same manner as in Step 3 and Step 4 of Example 1 to obtain Compound A4. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Example 5] (Synthesis of Compound A5)

<Step 1>

2-bromo-p-xylene (25.0 g, 135.1 mmol) and EDC (3 times the theoretical amount) were added to the flask, stirred, and after cooling to 0° C., methyl chloroglyoxylate (18.2 g, 148.6 m) mol), and aluminum chloride (19.8 g, 148.6 mmol) was added in 4 portions. After the reaction at room temperature for 4 hours, the reaction was carried out at 40°C for 1 hour. Prepare a beaker with ice added to a mixture of 150 g of 1N hydrochloric acid and 300 g of ethyl acetate, pour the reaction solution into it, separate oil and water, wash with water 6 times, wash with saturated saline, and dehydrate with sodium thiosulfate, and evaporate the solvent to dry made it Further, it was crystallized with hexane to obtain 28.2 g of Intermediate 13.

After carrying out the reaction in the same manner as in step 2-1 of Example 2 using Intermediate 13 instead of Intermediate 4, the obtained compound was dissolved in toluene (3 times the theoretical amount), and DMF (0.4 g, 5.3 mmol) After adding and raising the temperature to 40°C, thionyl chloride (13.9 g, 116.9 mmol) was added dropwise, followed by stirring for 1 hour. Then, it cooled, methanol (1.5 times the theoretical amount) was added, and the precipitated solid was filtered and extracted, and the intermediate body 14 was obtained. In addition, the 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.

Using Intermediate 15, oximation and sulfonation were carried out in the same manner as in Step 3 and Step 4 of Example 1 to obtain Compound A5. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Example 6] (Synthesis of Compound A6)

An indole intermediate was synthesized in the same manner as in Step 1 of Example 1 except that 1-fluoro-4-nitrobenzene was used instead of 4-fluorobenzophenone. Subsequently, acylation was carried out in the same manner as in Step 2-2 of Example 2, followed by oximation and sulfonation in the same manner as in Steps 3 and 4 of Example 1 to obtain Compound A6. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[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 F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[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 F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Example 9] (Synthesis of Compound A9)

In a flask, 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 (I) ( 0.8 g, 4.0 mmol) and DMF (3 times the theoretical amount) were added, and it stirred at 120 degreeC for 24 hours. After that, it was cooled to room temperature, ion-exchanged water was poured, and the precipitated crystals were extracted by filtration. Using the obtained crystals, compound A9 was obtained by oximation and sulfonation in the same manner as in steps 3 and 4 of Example 1. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[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 (3 times the theoretical amount) were added to the flask, It stirred at 60 degreeC for 3 hours. After that, it was cooled to room temperature, ion-exchanged water was poured, and the precipitated crystals were extracted by filtration. The obtained crystals were subjected to oximation and sulfonation in the same manner as in Steps 3 and 4 of Example 1 to obtain Compound A10. ¹ H-NMR, ¹⁹ F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[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 F-NMR, and FT-IR measurement results are shown in Tables 1-3.

[Examples 101 to 111, Comparative Examples 1-3]

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 stirred at 25° C. for 1 hour to obtain a composition (PGMEA solution having a solid content of 25% by mass). .

Each component used the following materials. In addition, the compounding quantity in a table|surface represents a mass part.

Resin component: p-hydroxystyrene-styrene-t-butyl acrylate copolymer (p-hydroxystyrene/styrene/t-butylacrylate = 60/20/20 (mass ratio), weight average molecular weight 12,000 (polystyrene conversion) , acid-degradable ingredients)

Surfactant: FZ2122 (manufactured by Toray Dow Corning)

Acid generator: Compounds A1 to A11 prepared in Examples 1 to 11 (acid generator comprising compound A)

Acid generator: a compound represented by the following formulas (B1) to (B3) (compound B1, compound B2 and compound B3; acid generator other than compound A)

1. Sensitivity evaluation

The composition prepared above was filtered with a microfilter of 5 µm, and spin-coated (1300 rpm, 7 s) on a glass substrate so that the film thickness after prebaking was set to 3 µm. Then, it prebaked at 110 degreeC for 120 second using a hotplate, and obtained the 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 developed for 10 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide to form a positive type. got a pattern.

The line width of the pattern obtained with a mask opening of 20 µm, an exposure amount of 20 mJ/cm 2 , and 40 mJ/cm 2 (line width of a portion where development was removed) was measured using a microscope. The thicker the line width, the higher the sensitivity was evaluated. A result is shown in Table 3.

2. Solubility

Solubility evaluation with respect to PGMEA in 25 degreeC was performed about each acid generator. A result is shown in Table 3. The values shown in the table are concentrations (% by mass) that can be dissolved.

3. Molar extinction coefficient (ε) and transmittance

For the positive resist film obtained in the same manner as described in "1. Sensitivity evaluation", the absorption spectrum was measured using an ultraviolet-visible spectrophotometer (U-3010, manufactured by Hitachi High-Tech Sciences), and a molar extinction coefficient of 365 nm and The transmittance of 400 nm was computed. A result is shown in Table 3.

The absorption coefficient at i-line (365 nm) of Compound A1 used in Examples corresponding to Compound A of the present invention was lower than that of acid generators (Compounds B1 to B2) having other structures.

The composition of the Example using the compound A of the present invention had a line width of the obtained pattern thicker than that of the pattern obtained from the composition using other compounds, and it was confirmed that the acid generation sensitivity was excellent.

Moreover, the transmittance|permeability at 400 nm of a positive resist film was the highest in Example, and the high transparency resist film in which coloring was suppressed was obtained.

Moreover, the compound of the present invention was highly soluble in solvents.

ADVANTAGE OF THE INVENTION According to this invention, the compound excellent in acid generation sensitivity can be provided.

Claims (13)

A compound represented by the following general formula (A).

(Wherein, R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, -OR ²⁰ , -COR ²⁰ , -OCOR ²⁰ , -COOR ²⁰ , -SR ²⁰ , -SOR ²⁰ , -SO ₂ R ²⁰ , -NR ²¹ R ²² , -NR ²¹ COR ²² , -CONR ²¹ R ²² , a group represented by the following general formula (1), the number of carbon atoms 1 to An aliphatic hydrocarbon group having 20 unsubstituted or substituents, an unsubstituted or substituted aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms, or an unsubstituted or substituted heterocyclic ring having 2 to 20 carbon atoms or a group in which at least one methylene group in the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group or the heterocyclic ring-containing group is substituted with a divalent group selected from the following group I;
R ¹³ 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, and unsubstituted C 2 to 20 carbon atoms Or a heterocyclic-containing group having a substituent or an aryl group having 7 to 30 carbon atoms or an substituted group in which one or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with a group represented by the following general formula (1) At least one of the first aryl group or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, the heterocyclic ring-containing group, or the methylene group in the first aryl group represents a group substituted with a divalent group selected from the following group I;
R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I, and when there are a plurality of R ²⁰ , R ²¹ or R ²² , 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 combine to form a ring;
A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent, the heterocyclic ring-containing group having a substituent and the first aryl group is a halogen atom; A cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H;
At least one of R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is a group represented by the following general formula (1), or R ¹³ is the first aryl group.)

(wherein R ¹ 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 or 2 to 20 carbon atoms At least one methylene group in the unsubstituted or substituted heterocycle-containing group, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocycle-containing group is substituted with a divalent group selected from the following group I represents the flag,
R ² is 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, or an unsubstituted or substituted aromatic hydrocarbon ring having 6 to 20 carbon atoms At least one methylene group in the containing group or the heterocyclic ring-containing group having an unsubstituted or substituted group having 2 to 20 carbon atoms, or the aliphatic hydrocarbon group, the aromatic hydrocarbon ring-containing group, or the heterocyclic ring-containing group represents a group substituted with a divalent group selected from I;
A substituent for substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent, the aromatic hydrocarbon ring-containing group having a substituent and the heterocyclic ring-containing group having a substituent is a halogen atom, a cyano group, a nitro group, A hydroxyl group, a thiol group, -COOH or -SO ₂ H;
n represents 0 or 1,
When a plurality of groups represented by the general formula (1) exist in the compound represented by the general formula (A), a plurality of n, R ¹ and R ² may be the same or different, respectively,
* indicates a bonding moiety.)
Group I: -O-, -COO-, -OCO-, -CO-, -CS-, -S-, -SO-, -SO ₂ -, -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 ³¹ each independently represent a hydrogen atom or an unsubstituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when two or more R ³⁰ or R ³¹ are present, they may be the same or different. According to claim 1,
A compound wherein R ¹¹ is a group represented by the general formula (1). 3. The method of claim 1 or 2,
n is 0; 4. The method according to any one of claims 1 to 3,
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 the aliphatic hydrocarbon having the above substituent A substituent for substituting at least one hydrogen atom in the group and the aromatic hydrocarbon ring-containing group having a substituent is a halogen atom,
A compound in which R ² is a cyano group or an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a substituent substituting at least one hydrogen atom in the aliphatic hydrocarbon group having a substituent is a halogen atom. 5. The method according to any one of claims 1 to 4,
A compound in which R ¹³ is 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. An acid generator comprising the compound according to any one of claims 1 to 5. The compound according to any one of claims 1 to 5, and
A composition comprising a resin component. 8. The method of claim 7,
The composition, wherein the resin component is an acid curable resin component. A cured product of the composition according to claim 8. The manufacturing method of the hardened|cured material which has a hardening process of hardening the composition of Claim 8. 8. The method of claim 7,
The composition, wherein the resin component is an acid-decomposable resin component. A pattern comprising the composition according to claim 11 . A step of forming a coating film using the composition according to claim 11, and generating an acid from a compound contained in the formed coating film;
A method for producing a pattern, comprising: after the step of generating an acid from the compound, a step of developing a part of the coating film to form a pattern.