JP2012046435A - New compound, photoacid generator, and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound safe to heat and a nucleophilic reagent, having high compatibility with an organic medium, and having a performance as a photoacid generator.SOLUTION: This invention relates to a compound represented by formula (1). (In the formula, Rshows a substituted or unsubstituted alkyl group or the like; Rshows a hydrogen atom, or a substituted or unsubstituted alkyl group or the like; Xshows an alkyl group or an alkoxy group; Xshows each independently a hydrogen atom, an alkyl group, an alkoxy group or the like; and p shows 1-4).

Description

  The present invention relates to a novel compound having a performance as a photoacid generator, a photoacid generator and a photosensitive resin composition.

In recent years, the degree of integration of integrated circuits has been increasing. In order to achieve a high degree of integration, fine processing of the semiconductor substrate is necessary.
Such fine processing is performed by photolithography. Since the resolution at the time of processing is proportional to the wavelength of the exposure light, it is necessary to shorten the wavelength of the light used as the exposure light in order to advance the miniaturization of the processing. The g-line (438 nm) and i-line of the high-pressure mercury lamp The wavelength has been reduced from (365 nm) to KrF excimer laser (248 nm) and further to ArF excimer laser (193 nm).

  For pattern formation by photolithography, a photosensitive resin composition containing a photoacid generator that generates protonic acid by light irradiation is used. Such a photosensitive resin composition is called a chemically amplified resist, and a proton acid generated from a photoacid generator by light irradiation and a constituent resin react in a chain reaction by subsequent heat treatment and develop. It becomes soluble in the liquid.

  As the photoacid generator, sulfonium salt derivatives are widely used. For example, there are those corresponding to KrF excimer laser (Non-patent Document 1) and those corresponding to ArF excimer laser (Patent Documents 1 and 2). However, the performance of these photoacid generators is not sufficient, and development of new photoacid generators is required.

JP 2002-265436 A JP-A-7-28237

“J. Org. Chem.”, 1978, Vol. 43, p. 3055

  An object of the present invention is to provide a compound having high performance as a photoacid generator, which has high compatibility with an organic medium, is stable to heat and a nucleophilic reagent.

  As a result of intensive studies from the viewpoint of the molecular structure and reaction mechanism of the photoacid generator, the present inventors have shown that a compound having a sulfonate ester structure in an enol ester structure exhibits the performance required for the photoacid generator. The present invention was completed.

That is, the present invention includes the following matters.
[1] A compound represented by the following formula (1):

（式（１）中、Ｒ¹は置換もしくは非置換のアルキル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、フッ素原子、ニトロ基、またはシアノ基を表し；Ｒ²は水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルキニル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、アセトアミド基、アミノスルホニル基、またはハロゲン原子を表し；Ｘ¹はアルキル基またはアルコキシ基を表し；Ｘ²はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基を表し；ｐは１〜４を表す。）

(In formula (1), R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic ring, a substituted or unsubstituted heterocyclic ring, a fluorine atom, a nitro group, or a cyano group; R ² represents hydrogen; An atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle, an acetamide group, an aminosulfonyl group, or X ¹ represents an alkyl group or an alkoxy group; X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a carboxyl group, or a hydroxyl group. Represents a halogen atom or a cyano group; p represents 1-4.)

[2] The compound according to [1], wherein p is 2 to 4 in the formula (1).
[3] The compound according to [1] or [2], wherein in the formula (1), R ¹ is an alkyldifluoromethyl group, an aryldifluoromethyl group, a perfluoroalkyl group or a perfluoroaryl group .

[4] The compound according to any one of [1] to [3], wherein in the formula (1), R ² is a substituted or unsubstituted carbocyclic ring or a substituted or unsubstituted heterocyclic ring.
[5] The compound according to [4], wherein in the formula (1), R ² is a cycloalkyl group or an aryl group.

[6] In any one of [1] to [5], in the formula (1), X ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 3 to 12 carbon atoms. The described compound.
[7] The compound according to [6], wherein in the formula (1), X ¹ is a methyl group, an ethyl group or a propyl group.

[8] The compound according to any one of [1] to [7], wherein in the formula (1), X ² is a hydrogen atom, an alkyl group or a halogen atom.
[9] The compound according to any one of [1] to [8], which is a photoacid generator.

[10] A photosensitive resin composition comprising the compound according to any one of [1] to [9].
[11] A compound represented by the following formula (2) is reacted with a sulfonic acid anhydride using lithium 2,2,6,6-tetramethylpiperidide as a base: The manufacturing method of the compound represented by this.

（式（２）中、Ｒ²は水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルキニル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、アセトアミド基、アミノスルホニル基、またはハロゲン原子を表し；Ｘ¹はアルキル基またはアルコキシ基を表し；Ｘ²はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基を表し；ｐは１〜３を表す。）

(In the formula (2), R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbocycle, substituted or unsubstituted. A heterocyclic ring, an acetamido group, an aminosulfonyl group, or a halogen atom; X ¹ represents an alkyl group or an alkoxy group; X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, An alkylthio group, an arylthio group, a carboxyl group, a hydroxyl group, a halogen atom or a cyano group; p represents 1-3.)

（式（１）中、Ｒ¹は置換もしくは非置換のアルキル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、フッ素原子、ニトロ基、またはシアノ基を表し；Ｒ²は水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルキニル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、アセトアミド基、アミノスルホニル基またはハロゲン原子を表し；Ｘ¹はアルキル基またはアルコキシ基を表し；Ｘ²はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基を表し；ｐは１〜３を表す。）

(In formula (1), R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic ring, a substituted or unsubstituted heterocyclic ring, a fluorine atom, a nitro group, or a cyano group; R ² represents hydrogen; Atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted carbocycles, substituted or unsubstituted heterocycles, acetamide groups, aminosulfonyl groups, or halogens X ¹ represents an alkyl group or an alkoxy group; X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a carboxyl group, a hydroxyl group, Represents a halogen atom or a cyano group; p represents 1-3.)

  According to the present invention, it is possible to provide a novel compound that is highly compatible with an organic medium and that is used as a photoacid generator that is stable against heat and a nucleophile.

FIG. 1 shows an ultraviolet-visible absorption spectrum of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester. FIG. 2 shows a ¹⁹ F-NMR spectrum 11 hours after light irradiation after adding pyridine as a neutralizing agent to 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester of trifluoromethanesulfonic acid. .

Hereinafter, the compound of the present invention will be described in detail.
The compound of the present invention is represented by the formula (1).

式（１）中、Ｒ¹は置換もしくは非置換のアルキル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、フッ素原子、ニトロ基、またはシアノ基を表す。式（１）で表される化合物は、後述するように光照射によってスルホン酸（ＨＯＳＯ₂Ｒ¹）を発生する。このため、Ｒ¹は発生するスルホン酸の特性（酸性度など）を決める要因となるものであり、光酸発生剤の用途に応じて適宜選択する。

In the formula (1), R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocyclic ring, a fluorine atom, a nitro group, or a cyano group. The compound represented by the formula (1) generates sulfonic acid (HOSO ₂ R ¹ ) by light irradiation as described later. Thus, R ¹ is intended to be a factor in determining the characteristics of the sulfonic acid generated (such as acidity), appropriately selected depending on the use of the photoacid generator.

When R ¹ is a substituted or unsubstituted alkyl group, examples of R ¹ include a linear or branched alkyl group having 1 to 20 carbon atoms, or a fluorine-substituted alkyl group having 1 to 12 carbon atoms. It is done. Here, the substituted alkyl group refers to a fluorine-substituted alkyl group having 1 to 12 carbon atoms, and the unsubstituted alkyl group refers to a linear or branched alkyl group having 1 to 20 carbon atoms. Say. Specifically, examples of the fluorine-substituted alkyl group having 1 to 12 carbon atoms include perfluoroalkyl groups such as a trifluoromethyl group, a pentafluoroethyl group, and a heptafluoropropyl group; 1,1-difluoroethyl (—CF ₂ An alkyldifluoromethyl group such as a CH ₃ ) group or a 1,1-difluoropropyl (—CF ₂ CH ₂ CH ₃ ) group; a 1,1-difluoro-1-phenylmethyl (—CF ₂ C ₆ H ₅ ) group, 1 , 1-difluoro-1-tolylmethyl (—CF ₂ C ₆ H ₄ CH ₃ ) group, 1,1-difluoro-2-phenylethyl (—CF ₂ CH ₂ C ₆ H ₅ ) group or 1,1-difluoro- Aryldifluoromethyl groups such as a 1-naphthylmethyl (—CF ₂ C ₁₀ H ₇ ) group; a fluoromethyl group or a difluoromethyl group; Examples of the branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. N-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group A linear alkyl group such as n-nonadecyl group or n-eicosyl group; a branched alkyl group such as isopropyl group, isobutyl group, s-butyl group or t-butyl group;

When R ¹ is a substituted or unsubstituted carbocyclic, cyclic alkyl group as R ^1, the aryl group having 6 to 14 carbon atoms, substituted with a fluorine-substituted aryl group or a fluoroalkyl group having 6 to 10 carbon atoms And aryl groups having 7 to 11 carbon atoms. Here, the substituted carbocycle is an atomic group containing atoms other than carbon atoms such as a fluorine-substituted aryl group having 6 to 10 carbon atoms or an aryl group having 7 to 11 carbon atoms substituted with a fluoroalkyl group. A non-substituted carbocycle is a cyclic alkyl group or an aryl group having 6 to 14 carbon atoms, and the functional group is not substituted. . Both the substituted carbocycle and the unsubstituted carbocycle are directly bonded to the sulfur atom of the sulfone group without using a linking group. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 3-methoxycyclopentyl group, 3-carboxycyclopentyl group, 3-methylcarbonylcyclopentyl group, 3-methoxycarbonylcyclopentyl group, 3-dimethyl Aminocyclopentyl group, 3-fluorocyclopentyl group, 3-trifluoromethylcyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-methoxycyclohexyl group, 4-carboxycyclohexyl group, 4-dimethylaminocyclohexyl group, 4-fluorocyclohexyl A cyclic alkyl group such as a cycloheptyl group or a cyclooctyl group; a phenyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, o Tolyl group, m-tolyl group, p-tolyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-methylcarbonylphenyl group, 4-methoxycarbonylphenyl group Dimethylaminocarbonylphenyl group, 1-naphthyl group, 4-methyl-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-carboxyl-1-naphthyl group, 2-naphthyl group, 1-anthracenyl group or 9 An aryl group such as an anthracenyl group; a perfluoroaryl group such as a pentafluorophenyl group or a heptafluoronaphthyl group; a 2-fluorophenyl group, a 3-fluorophenyl group or a 4-fluorophenyl group; a 2-trifluoromethylphenyl group 3-trifluoromethylphenyl group or An aryl group substituted with a fluoroalkyl group such as a motor fluoroethyl phenyl group.

When R ¹ is a substituted or unsubstituted heterocyclic ring, R ¹ is a heterocyclic group or a substituted heterocyclic group containing at least one hetero atom of N, O and S having 2 to 9 carbon atoms Is mentioned. Here, the substituted heterocycle refers to the above substituted heterocycle, and the unsubstituted heterocycle refers to one having no functional group. In addition, any of these heterocycles is directly bonded to the sulfur atom of the sulfone group without a linking group. Specifically, furyl group, imidazolyl group, pyridyl group, pyridiminyl group, piperidino group, piperazinyl group, morpholino group, thiomorpholino group, tetrahydrothienyl group, tetrahydrofuryl group, pyrrolyl group, thiazolyl group, pyrimidyl group, quinolyl group or Heterocyclic groups such as indolyl group; substituted heterocyclic groups such as 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group or pentafluoroethylphenyl group.

Among the above, R ¹ is preferably a fluorine-substituted alkyl group having 1 to 12 carbon atoms, more preferably an alkyldifluoromethyl group, an aryldifluoromethyl group, a perfluoroalkyl group or a perfluoroaryl group, and trifluoromethyl. A group, a pentafluoroethyl group or a heptafluoropropyl group is particularly preferable.

R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocyclic ring, an acetamide group, an amino Represents a sulfonyl group or a halogen atom. “Substituted or unsubstituted” is distinguished by whether or not it is substituted with a functional group comprising an atomic group containing an atom other than a carbon atom.

When R ² is a substituted or unsubstituted alkyl group, examples of R ² include a linear or branched alkyl group having 1 to 20 carbon atoms or a fluorine-substituted alkyl group having 1 to 12 carbon atoms. . Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group or n-eicosyl group Linear alkyl group such as isopropyl group, isobutyl group, s-butyl group or t-butyl group; branched alkyl group such as trifluoromethyl group, fluoromethyl group, difluoromethyl group, pentafluoroethyl group, 3- Fluoro-substituted alkyl groups such as fluorocyclopentyl group, 3-trifluoromethylcyclopentyl group or 4-fluorocyclohexyl group Represents.

When R ² is a substituted or unsubstituted alkenyl group, examples of R ² include linear or branched alkenyl groups having 1 to 20 carbon atoms. Specifically, ethenyl group, n-propenyl group, n-butenyl group, n-pentenyl group, n-hexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, n-decenyl group, n- Direct such as undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-octadecenyl, n-nonadecenyl or n-eicosenyl A chain alkenyl group; a branched alkenyl group such as an isopropenyl group, an isobutenyl group or an s-butenyl group.

When R ² is a substituted or unsubstituted alkynyl group, examples of R ² include a linear alkynyl group having 1 to 20 carbon atoms. Specifically, ethynyl group, n-propynyl group, n-butynyl group, n-pentynyl group, n-hexynyl group, n-heptynyl group, n-octynyl group, n-noninyl group, n-decynyl group, n- Direct such as undecynyl group, n-dodecynyl group, n-tridecynyl group, n-tetradecynyl group, n-pentadecynyl group, n-hexadecynyl group, n-heptadecynyl group, n-octadecynyl group, n-nonadecynyl group or n-eicosinyl group Examples thereof include a chain alkynyl group.

When R ² is a substituted or unsubstituted carbocycle, examples of R ² include aryl groups having 6 to 14 carbon atoms, cyclic alkyl groups having 1 to 20 carbon atoms, cyclic alkenyl groups, and cyclic alkynyl groups. . Specifically, phenyl group, 2,4-xylyl group, 2,5-xylyl group, 3,4-xylyl group, 3,5-xylyl group, o-tolyl group, m-tolyl group, p-tolyl group 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 4-carboxyphenyl group, 4-methylcarbonylphenyl group, 4-methoxycarbonylphenyl group, dimethylaminocarbonylphenyl group, 1-naphthyl group, Aryl groups such as 4-methyl-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-carboxyl-1-naphthyl group, 2-naphthyl group, 1-anthracenyl group or 9-anthracenyl group; cyclopropyl group, Cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 3-methoxycyclopentyl group, 3-carboxycyclope Tyl group, 3-methylcarbonylcyclopentyl group, 3-methoxycarbonylcyclopentyl group, 3-dimethylaminocyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-methoxycyclohexyl group, 4-carboxycyclohexyl group, 4-dimethylaminocyclohexyl Group, cyclic alkyl group such as cycloheptyl group or cyclooctyl group; cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, 3-methylcyclopentenyl group, 3-methoxycyclopentenyl group, 3-carboxycyclopentenyl group, 3-methyl Carbonylcyclopentenyl group, 3-methoxycarbonylcyclopentenyl group, 3-dimethylaminocyclopetenyl group, cyclohexenyl group, 4-methylcyclohexenyl group, 4-methoxycyclyl Cyclic alkenyl groups such as hexenyl, 4-carboxycyclohexenyl, 4-dimethylaminocyclohexenyl, cycloheptenyl or cyclooctenyl; cyclopropynyl, cyclobutynyl, cyclopentynyl, 2-methyl-3-cyclopentenyl 2-methoxy-3-cyclopentenyl group, 2-carboxy-3-cyclopentenyl group, 2-methylcarbonyl-3-cyclopentenyl group, cyclohexynyl group, 2-methyl-3-cyclohexynyl group, 2-methoxy- Examples thereof include cyclic alkynyl groups such as a 3-cyclohexynyl group, 2-carboxy-3-cyclohexynyl group, 2-dimethylamino-3-cyclohexynyl group, cycloheptynyl group, and cyclooctynyl group.

When R ² is a substituted or unsubstituted heterocyclic ring, R ² is a heterocyclic group or substituted heterocyclic group containing at least one hetero atom among N, O and S having 2 to 9 carbon atoms. Can be mentioned. Specifically, furyl group, imidazolyl group, pyridyl group, pyridiminyl group, piperidino group, piperazinyl group, morpholino group, thiomorpholino group, tetrahydrothienyl group, tetrahydrofuryl group, pyrrolyl group, thiazolyl group, pyrimidyl group, quinolyl group or And indolyl group.

As for R ² , “substituted or unsubstituted” in “substituted or unsubstituted alkyl group”, “substituted or unsubstituted alkenyl group” and “substituted or unsubstituted alkynyl group” is the same as R ^1. Are substituted with a functional group comprising an atomic group containing an atom other than a carbon atom, for example, those substituted with the functional group are “substituted alkyl groups”; A substituted alkyl group. “Carbocycle” and “heterocycle” refer to those directly bonded to the sulfur atom of the sulfone group without a linking group.

When R ² is an acetamide group, examples of R ² include an acetamide group having 2 to 10 carbon atoms. Specific examples include an acetylamide group, a propionylamide group, a butyrylamide group, an isobutyrylamide group, a pivaloylamide group, or a benzoylamide group.

When R ² is an aminosulfonyl group, examples of R ² include an aminosulfonyl group having 2 to 10 carbon atoms. Specific examples include mesylamide group, n-propanesulfonylamide group, n-butanesulfonylamide group, isobutanesulfonylamide group, t-butanesulfonylamide group, and benzenesulfonylamide group.

When R ² is a halogen atom, examples of R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among the above, R ² is preferably a branched alkyl group, a substituted or unsubstituted carbocyclic ring or a substituted or unsubstituted heterocyclic ring, more preferably a t-butyl group, a cycloalkyl group or an aryl group, and a t-butyl group. A naphthyl group or a phenyl group is particularly preferable.

X ¹ represents an alkyl group or an aryl group. Specifically, it represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 3 to 12 carbon atoms. Among the above, X ¹ is preferably a methyl group, an ethyl group or a propyl group, and a methyl group is particularly preferable.

X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a carboxyl group, a hydroxyl group, a halogen atom or a cyano group.

When X ² is an alkyl group, examples of X ² include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group Or a linear alkyl group such as benzyl group; a branched alkyl group such as isopropyl group, isobutyl group, s-butyl group or t-butyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 3 -Methoxycyclopentyl group, 3-carboxycyclopentyl group, 3-methylcarbonylcyclopentyl group, 3-methoxycarbonyl Cycloalkyl group, 3-dimethylaminocyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-methoxycyclohexyl group, 4-carboxycyclohexyl group, 4-dimethylaminocyclohexyl group, cycloheptyl group or cyclooctyl group Etc.

When X ² is an alkoxy group, examples of X ² include an alkoxy group having 1 to 20 carbon atoms. Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an isopropoxy group, an isobutoxy group, Examples thereof include s-butyroxy group and t-butyroxy group.

When X ² is an alkoxycarbonyl group, examples of X ² include an alkoxycarbonyl group having ^{2 to} 13 carbon atoms. Specifically, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group, pentoxycarbonyl group, neopentoxycarbonyl group , Amyloxycarbonyl group, hexoxycarbonyl group, heptoxycarbonyl group, octoxycarbonyl group, 2-ethylhexoxycarbonyl group, heptoxycarbonyl group or octoxycarbonyl group.

When X ² is an acyl group, examples of X ² include an acyl group having 2 to 10 carbon atoms. Specific examples include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

When X ² is an alkylthio group, examples of X ² include an alkylthio group having 1 to 20 carbon atoms. Specifically, methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, n-nonylthio group, n- Decylthio group, n-undecylthio group, n-dodecylthio group, n-tridecylthio group, n-tetradecylthio group, n-pentadecylthio group, n-hexadecylthio group, n-heptadecylthio group, n-octadecylthio group, n -Linear alkylthio group such as nonadecylthio group, n-eicosylthio group or benzylthio group; branched alkylthio group such as isopropylthio group, isobutylthio group, s-butylthio group or t-butylthio group; cyclopropylthio group, cyclobutyl Thio group, cyclopentylthio group, 3-methylcyclopentylthio group 3-methoxycyclopentylthio group, 3-carboxycyclopentylthio group, 3-methylcarbonylcyclopentylthio group, 3-methoxycarbonylcyclopentylthio group, 3-dimethylaminocyclopentylthio group, cyclohexylthio group, 4-methylcyclohexylthio group, 4 Examples thereof include cyclic alkylthio groups such as -methoxycyclohexylthio group, 4-carboxycyclohexylthio group, 4-dimethylaminocyclohexylthio group, cycloheptylthio group, and cyclooctylthio group.

When X ² is an arylthio group, examples of X ² include an arylthio group having 6 to 14 carbon atoms. Specifically, phenylthio group, 2,4-xylylthio group, 2,5-xylylthio group, 3,4-xylylthio group, 3,5-xylylthio group, o-tolylthio group, m-tolylthio group, p-tolylthio group 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-methoxyphenylthio group, 4-carboxyphenylthio group, 4-methylcarbonylphenylthio group, 4-methoxycarbonylphenylthio group, dimethylaminocarbonylphenylthio Group, 1-naphthylthio group, 4-methyl-1-naphthylthio group, 4-methoxy-1-mononaphthylthio group, 4-carboxyl-1-naphthylthio group, 2-naphthylthio group, 1-anthracenylthio group or 9-anthracenyl group And a ruthio group.

When X ² is a halogen atom, examples of X ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among the above, X ² is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom, a methyl group or a halogen atom, and particularly preferably a hydrogen atom.

p represents 1-4. Among the above, p is preferably 2 to 4, and 2 is particularly preferable.
The compound represented by the above formula (1) may have the above substituents alone or in combination of two or more.

[Method for producing compound]
The method for producing a compound of the present invention comprises reacting a sulfonic acid anhydride with a compound represented by the following formula (2) using lithium 2,2,6,6-tetramethylpiperidide as a base. And

Various bases can be used to extract α hydrogen in the cyclic part of the compound represented by the formula (2), but many of these bases are free from sulfonic acid (HOSO ₂ R) and side reaction. Is generated, and a by-product is generated, so that it is difficult to isolate and purify the compound represented by the above formula (1). However, if 2,2,6,6-tetramethylpiperidide is used, the four methyl groups become steric barriers, so side reactions with sulfonic acid (HOSO ₂ R) are suppressed, and after the reaction Isolation and purification of the compound represented by the formula (1) can be easily performed.

式（２）中、Ｒ²は水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアルキニル基、置換もしくは非置換の炭素環、置換もしくは非置換の複素環、アセトアミド基、アミノスルホニル基、またはハロゲン原子を表し、Ｘ¹はアルキル基またはアルコキシ基を表し、Ｘ²はそれぞれ独立に、水素原子、アルキル基、アルコキシ基、アルコキシカルボニル基、アシル基、アルキルチオ基、アリールチオ基、カルボキシル基、ヒドロキシル基、ハロゲン原子またはシアノ基を表し、ｐは１〜３を表す。ここで、Ｒ²、Ｘ¹、Ｘ²およびｐは、上記式（１）中のＲ²、Ｘ¹、Ｘ²およびｐについて定義したのと同じである。
上記式（１）で表される化合物の製造方法の具体例を以下に示す。

In the formula (2), R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbocycle, a substituted or unsubstituted heterocycle. A ring, an acetamido group, an aminosulfonyl group, or a halogen atom, X ¹ represents an alkyl group or an alkoxy group, and each X ² independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group Represents a group, an arylthio group, a carboxyl group, a hydroxyl group, a halogen atom or a cyano group, and p represents 1-3. Here, R ^2, X ^1, X ² and p are the same as defined for R ^2, X ^1, X ² and p in the formula (1).
Specific examples of the method for producing the compound represented by the above formula (1) are shown below.

まず、Ｓｃｈｅｍｅ（Ｉ）について説明すると、シクロペンタノンおよびピロリジンを反応させて得られた１−ピロリジノ−１−シクロペンテンと、１−ナフトイルクロリドとを１，４−ジオキサン中で撹拌後、加熱還流し、塩酸を加えた後さらに加熱還流して２−（ナフタレン−１−カルボニル）シクロペンタノンを得る。

First, Scheme (I) will be described. 1-Pyrrolidino-1-cyclopentene obtained by reacting cyclopentanone and pyrrolidine and 1-naphthoyl chloride are stirred in 1,4-dioxane and then heated to reflux. After adding hydrochloric acid, the mixture is further heated to reflux to give 2- (naphthalene-1-carbonyl) cyclopentanone.

  Subsequently, as shown in Scheme (II), the obtained 2- (naphthalene-1-carbonyl) cyclopentanone was stirred in acetone with potassium carbonate and methyl iodide added thereto. (Naphthalene-1-carbonyl) cyclopentanone is obtained.

  Next, as shown in Scheme (III), n-butyllithium was added to a solution of 2,2,6,6-tetramethylpiperidine dissolved in tetrahydrofuran (THF) and stirred, and then 2-methyl-2- ( Add naphthalene-1-carbonyl) cyclopentanone. Next, trifluoromethanesulfonic anhydride is added and stirred to obtain trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester. Here, 2,2,6,6-tetramethylpiperidine is used as a base and abstracts α hydrogen in the cyclic part of 2-methyl-2- (naphthalene-1-carbonyl) cyclopentanone. By reacting the enolate anion thus formed with sulfonic anhydride, trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester is obtained.

  In addition, the said synthesis example shows an example of the manufacturing method of the compound of this invention, It can synthesize | combine using not only the said manufacturing method but a various well-known method.

[Evaluation of compound properties]
The compound represented by the above formula (1) has the following characteristics (i) to (iii).
(i) Since the compound represented by the formula (1) is composed of neutral organic molecules rather than ionic, it is highly compatible with an organic medium. Therefore, for example, when used as a component of a photosensitive resin composition, it can be dispersed extremely uniformly in an arbitrary ratio with respect to an organic medium such as a resin. If such a photosensitive resin composition is used for photolithography, the edge of the formation pattern is not roughened and fine processing with extremely high accuracy is possible.

(ii) Various R ² can be introduced into the compound by appropriately selecting an acid halide which is a raw material of R ^{2 in} the compound represented by the formula (1). That is, the absorption wavelength for light irradiation can be flexibly changed by R ² . For example, if R ² is a conjugated substituent such as naphthalene, longer wavelength light can be absorbed, and if R ² is a methyl group or t-butyl group, shorter wavelength light can be absorbed. Compounds can be designed.
Further, if the molecular weight of the substituent of R ² is increased, no gas is generated after sulfonic acid (R ¹ SO ₃ H) is eliminated.

(Iii) In the structure of formula (1), the α-position carbon of —OSO ₂ R ¹ has a double bond. That is, in this state, since -OSO ₂ R ¹ is present on the SP ² orbit, it is stable under a dark reaction. When light is irradiated here, a Norrish type I reaction occurs and homolytic cleavage occurs between the carbonyl carbon and the α carbon. The radical on the carbonyl carbon side that has been homolytically cleaved pulls out hydrogen at the β-position to form an aldehyde and a cyclic diene. Thereafter, when heat such as post-baking after exposure is applied to the cyclic diene, the cyclic diene causes dislocation, and a structure in which -OSO ₂ R ¹ is on the SP ³ orbit is formed. In this structure, since a nucleophilic substitution reaction easily occurs, an acid (R ¹ SO ₃ H) is effectively generated.

  Scheme (IV) shows the reaction mechanism of acid generation by light irradiation for an example of the compound represented by formula (1).

〔光酸発生剤および感光性樹脂組成物〕
本発明の式（１）で表される化合物は光酸発生剤として用いられる。

[Photoacid generator and photosensitive resin composition]
The compound represented by the formula (1) of the present invention is used as a photoacid generator.

The light to be irradiated to generate a sulfonic acid photoacid generator of the present invention, is determined by the structure of R ^2, if for example R ² is a conjugated system substituents as naphthalene, longer Light of wavelength can be absorbed, and further, selection of the structure of R ² enables use on the shorter wavelength side. For example, 313 nm, 254 nm resonance lines of an isobaric mercury lamp, KrF excimer laser light (248 nm) and ArF excimer Laser light (193 nm) can be used. Of these, ArF excimer laser light is preferably used.

  The photosensitive resin composition of this invention is characterized by including the said photo-acid generator. Although the said photo-acid generator is used individually, you may mix and use 2 or more types. The content of the photoacid generator in the photosensitive resin composition of the present invention is usually 0.1 to 40 parts by weight, preferably 1 to 25 parts by weight with respect to 100 parts by weight of the total solid content of the photosensitive resin composition. It is. If the content is less than 0.1 part by weight, the sensitivity is remarkably lowered and it is difficult to form a pattern. On the other hand, when the amount exceeds 40 parts by weight, it becomes difficult to form a uniform coating film, and further problems such as residue (scum) are likely to occur after development.

  As the resin constituting the photosensitive resin composition of the present invention, a resin having a high transparency to the light used and having a group unstable to an acid is used. For example, a resin represented by the following formula (V) is used.

式（Ｖ）中、ｎは５〜１０００、好ましくは１０〜２００の正の整数、Ｒ³は表１に示すようなトリシクロデカニル基、ジシクロペンテニル基、ジシクロペンテニルオキシエチル基、シクロヘキシル基、ノルボニル基またはアダマンチル基、Ｒ⁴はｔ−ブチル基、メチル基、エチル基、プロピル基、テトラヒドロピラニル基または３−オキソシクロヘキシル基、ｘは０．１〜１、好ましくは０．２〜０．７を表す。

In the formula (V), n is a positive integer of 5 to 1000, preferably 10 to 200, R ³ is a tricyclodecanyl group, dicyclopentenyl group, dicyclopentenyloxyethyl group or cyclohexyl as shown in Table 1. Group, norbornyl group or adamantyl group, R ⁴ is t-butyl group, methyl group, ethyl group, propyl group, tetrahydropyranyl group or 3-oxocyclohexyl group, x is 0.1 to 1, preferably 0.2 to It represents 0.7.

また、本発明の感光性樹脂組成物には、必要に応じて界面活性剤、色素、安定剤、塗布性改良剤、染料および架橋剤などの他の成分を添加してもよい。

Moreover, you may add other components, such as surfactant, a pigment | dye, a stabilizer, a coating property improving agent, dye, and a crosslinking agent, to the photosensitive resin composition of this invention as needed.

  The solvent used when applying the photosensitive resin composition of the present invention is preferably an organic solvent that sufficiently dissolves the photosensitive resin composition and that can form a uniform coating film by spin coating. . Examples of the organic solvent include n-propanol, isopropanol, n-butanol, t-butanol, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 2-methoxybutyl acetate, and acetic acid 2 -Ethoxyethyl, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, N-methyl-2-pyrrolidinone, cyclohexanone, cyclopentanone, cyclohexanol, methyl ethyl ketone, 1,4-dioxane , Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, di Examples include ethylene glycol monomethyl ether and diethylene glycol dimethyl ether. These may be used alone or in combination of two or more.

  As a developer for forming a fine pattern using the photosensitive resin composition of the present invention, an appropriate organic solvent or a mixed solvent thereof or an appropriate concentration depending on the solubility of the photosensitive resin composition. An alkaline solution or an alkaline aqueous solution may be selected. Examples of the organic solvent used include acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, tetrahydrofuran and dioxane. Examples of the alkaline solution used include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate and ammonia; organic amines such as ethylamine, propylamine, diethylamine, dipropylamine, trimethylamine and triethylamine. A solution or an aqueous solution containing an organic ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxymethylammonium hydroxide, triethylhydroxymethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. It is not limited to.

  Photolithography using the photosensitive resin composition of the present invention will be described. First, the photosensitive resin composition of the present invention is applied to form a resist film, and when exposed to irradiation light such as an ArF excimer laser, the photoacid generator contained in the exposed portion of the resist film generates sulfonic acid. .

For example, when a resin represented by the formula (V) (R ⁴ is a t-butyl group, k represents a positive integer) is used, the sulfonic acid generated by light irradiation is the resin t according to Scheme (VI). Acts on the butoxy group to produce carboxylic acid and 2-methylpropene, thereby inducing a change in the solubility of the resist film.

露光に引き続く加熱処理（ポストエクスポージャベイク）を所定温度で行うと、この脱保護反応が触媒反応的に進行し、感度の増幅が起こる。この反応により官能基が水酸基に変化した樹脂はアルカリ可溶性となるため、アルカリ性の現像液を使用することにより樹脂が溶け出し、結果として露光部が溶けてポジ型のパターンを形成する。

When the heat treatment (post-exposure bake) subsequent to exposure is performed at a predetermined temperature, this deprotection reaction proceeds catalytically, and sensitivity is amplified. Since the resin in which the functional group is changed to a hydroxyl group by this reaction becomes alkali-soluble, the resin is dissolved by using an alkaline developer, and as a result, the exposed portion is melted to form a positive pattern.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this.
The identification method of the reaction product and the evaluation method of the photoacid generation function are as follows.

(1) Melting point (mp)
Apparatus: DSC-60 (manufactured by Shimadzu Corporation)
Measuring method: DSC
(2) Nuclear magnetic resonance method ( ¹ H-NMR and ¹⁹ F-NMR)
Apparatus: BRUKER AC-300 (manufactured by Bruker)
Measurement conditions Internal standard: TMS
¹ H resonance frequency: 300 MHz
(3) Ultraviolet / visible (UV-VIS) spectroscopy apparatus: U-3410 spectrophotometer (manufactured by Hitachi)
Measurement method: Double beam measurement method Measurement conditions Solvent: Benzene

[Example 1] Preparation of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester (1) Synthesis of 1-pyrrolidino-1-cyclopentene -An eggplant-shaped flask (containing a Claisen type connecting tube, a Liebig condenser tube, a distillation connecting tube, and a distillate containing 1.2 g (6.2 × 10 ⁻³ mol) of toluenesulfonic acid monohydrate and a stirring bar One was two-necked and had an appropriate amount of potassium hydroxide in it). After Ar substitution, 200 ml of benzene, 27 ml (0.30 mol) of cyclopentanone and 50 ml (0.60 mol) of pyrrolidine were added to the system, heated in a hot water bath, and stirred at 70 ° C. for 2 hours.

The temperature was raised to 90 ° C. and azeotropy was started. Stirring was continued for 4 hours, but the benzene layer distilled twice was extracted with a syringe and returned to the 300 ml two-necked eggplant type flask.
The temperature was further raised to blow benzene. Then, another distillation apparatus was assembled next to this reaction apparatus, and the reaction solution from which benzene had been removed was transferred to the other distillation apparatus by cannulation. Then, 1-pyrrolidino-1-cyclopentene was obtained by distillation under reduced pressure.
The results are shown below.
Yield: 35 ml (0.24 mol)
Yield: 80%
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.82-1.88 (m, cyclopentene & pyrrolidino, —CH ₂ CH ₂ CH ₂ —, 6H), 2.35 (m, cyclopentene,> C═CHCH ₂ CH ₂ —, 2H), 2 .41-2.44 (m, cyclopentene,> CCH 2 CH 2 -, 2H), 3.07 (m, pyrrolidino, -NCH 2 CH 2 -, 4H), 4.05 (s, cyclopentene,> C = CHCH _2- , 1H)

（２）１−ナフトイルクロリドの合成
５０ｍｌ二口ナス型フラスコに撹拌子を入れ、三方コックを付けた還流管を、もう一方にセプタムラバーを付け、真空乾燥した。

(2) Synthesis of 1-naphthoyl chloride A 50 ml two-necked eggplant-shaped flask was charged with a stirrer, and a reflux tube with a three-way cock was attached to the other with a septum rubber and vacuum dried.

After Ar substitution, the Sepra rubber was removed and Ar gas was introduced, and 5.0 g (2.9 × 10 ⁻² mol) of 1-naphthoic acid was introduced into the system, the septum rubber was returned, and 6.6 ml of thionyl chloride (9. 0 × 10 ⁻² mol) and 10 μl (1.3 × 10 ⁻⁴ mol) of dimethylformamide (DMF) were injected, and the septum rubber was changed to a ball plug and stirred.

Heating was started after 2 hours, and refluxing was performed for 1.5 hours. After allowing to cool, the pressure was reduced with a vacuum pump for 2 hours to remove thionyl chloride.
Since the obtained 1-naphthoyl chloride was unstable, the whole amount was used as it was in the next reaction.

（３）２−（ナフタレン−１−カルボニル）シクロペンタノン
３００ｍｌ二口ナス型フラスコに撹拌子を入れ、三方コックの付いた還流管を、もう一方にはセプタムラバーを付け、真空乾燥した後、Ａｒ置換した。乾燥ジオキサン３０ｍｌおよび実施例１の（１）で合成した１−ピロリジノ−１−シクロペンタン８．８ｍｌ（６．０×１０^-2ｍｏｌ）を系内に入れ、常に系内が１０℃弱になるような氷浴に浸け、撹拌した。

(3) 2- (Naphthalene-1-carbonyl) cyclopentanone A stirrer was placed in a 300 ml two-necked eggplant-shaped flask, a reflux tube with a three-way cock was attached, a septum rubber was attached to the other, and vacuum dried. Ar substituted. 30 ml of dry dioxane and 8.8 ml (6.0 × 10 ⁻² mol) of 1-pyrrolidino-1-cyclopentane synthesized in (1) of Example 1 were put into the system, and the inside of the system was always less than 10 ° C. Soaked in an ice bath and stirred.

1-Naphthoyl chloride dissolved in 30 ml of dry dioxane was added dropwise over 2 hours, and the ice bath was removed and the mixture was stirred at room temperature for 68 hours.
The mixture was heated to reflux for 1 hour, 30 ml of 1N hydrochloric acid was added, and the mixture was further heated to reflux for 1 hour.

The mixture was extracted with diethyl ether, washed with a saturated aqueous sodium hydrogen carbonate solution and distilled water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. It was isolated and purified by silica gel column chromatography (developing solvent; methylene chloride) to obtain 2- (naphthalene-1-carbonyl) cyclopentanone.
The results are shown below.
Yield: 1.7 g (7.1 × 10 ⁻³ mol)
Yield: 24%
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.86-1.96 (m, —CH ₂ CH ₂ CH ₂ —, 2H), 2.44-2.49 (t,> CHCH ₂ CH ₂ —, 2H), 2.53 _{-2.58 (t, -COCH 2 CH 2} -, 2H), 7.45-7.64 (m, naphthyl, 4H), 7.88-7.95 (m, naphthyl, 2H), 8.06 -8.17 (m, naphthyl, 1H), 14.05-14.25 (s, enol, 1H)

（４）２−メチル−２−（ナフタレン−１−カルボニル）シクロペンタノンの合成
１００ｍｌナス型フラスコに２−（ナフタレン−１−カルボニル）シクロペンタノン１．７ｇ（７．１×１０^-3ｍｏｌ）および撹拌子を入れ、三方コックおよびセプタムラバーを付け、真空乾燥した後Ａｒ置換した。モレキュラーシーブスで乾燥させたアセトン２０ｍｌを系内に加え、撹拌して完全に溶解させた。氷浴にした後、炭酸カリウム４．０ｇ（２．９×１０^-2ｍｏｌ）を系内に入れ、さらにヨウ化メチル１．５ｍｌ（２．４×１０^-2ｍｏｌ）を加えた。１０分後に氷浴を除き、９時間撹拌した。

(4) Synthesis of 2-methyl-2- (naphthalene-1-carbonyl) cyclopentanone In a 100 ml eggplant type flask, 1.7 g (7.1 × 10 ⁻³ mol) of 2- (naphthalene-1-carbonyl) cyclopentanone was added. ) And a stirring bar were added, a three-way cock and a septum rubber were attached, and after vacuum drying, Ar was substituted. 20 ml of acetone dried with molecular sieves was added to the system and stirred until completely dissolved. After putting into an ice bath, 4.0 g (2.9 × 10 ⁻² mol) of potassium carbonate was put into the system, and 1.5 ml (2.4 × 10 ⁻² mol) of methyl iodide was further added. After 10 minutes, the ice bath was removed and the mixture was stirred for 9 hours.

The reaction solution was filtered, ethyl acetate was added, and acetone was removed by a rotary evaporator. The mixture was poured into distilled water, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. It was isolated and purified by silica gel column chromatography (developing solvent; methylene chloride) to obtain 2-methyl-2- (naphthalene-1-carbonyl) cyclopentanone.
The results are shown below.
Yield: 1.5 g (5.9 × 10 ⁻³ mol)
Yield: 84%
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.41 (s, —CH ₃ , 3H), 1.90 to 2.07 (m,> C (CH ₃ ) CH (H) CH ₂ —, —COCH ₂ CH ₂ —, 3H _{), 2.37-2.45 (m, -CH 2} CH 2 CH 2 -, 2H), 2.61-2.72 (m,> C (CH 3) CH (H) CH 2 -, 1H) 7.42-7.49 (m, naphthyl, 2H), 7.50-7.55 (m, naphthyl, 2H), 7.74-7.78 (m, naphthyl, 1H), 7.84- 7.93 (m, naphthyl, 2H)

（５）トリフルオロメタンスルホン酸５−メチル−５−（ナフタレン−１−カルボニル）シクロペント−１−エニルエステルの合成
５０ｍｌ二口ナス型フラスコに撹拌子を入れ、三方コックおよびセプタムラバーを付け、真空乾燥した後Ａｒ置換した。乾燥ＴＨＦ８ｍｌおよび２，２，６，６−テトラメチルピペリジン０．７ｍｌ（４．１×１０^-3ｍｏｌ）を入れ、撹拌し、メタノールバスで−７０℃付近まで冷やした。

(5) Synthesis of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester A stirrer was placed in a 50 ml two-necked eggplant type flask, and a three-way cock and septum rubber were attached, followed by vacuum drying. And then substituted with Ar. 8 ml of dry THF and 0.7 ml (4.1 × 10 ⁻³ mol) of 2,2,6,6-tetramethylpiperidine were added, stirred, and cooled to around −70 ° C. with a methanol bath.

After 30 minutes, 2.6 ml (4.2 × 10 ⁻³ mol) of n-butyllithium (1.6 M hexane solution) was added dropwise. 25 minutes later, 0.87 g (3.5 × 10 ⁻³ mol) of 2-methyl-2- (naphthalene-1-carbonyl) cyclopentanone previously dissolved in 5 ml of dry THF was added. Further 20 minutes later, 0.7 ml (4.3 × 10 ⁻³ mol) of trifluoromethanesulfonic anhydride was added.

After stirring for 40 minutes, the mixture was extracted with diethyl ether, washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. Isolation and purification by silica gel column chromatography (developing solvent; diethyl ether: hexane = 1: 8) gave trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester. .
The results are shown below.
Yield: 380 mg (9.9 × 10 ⁻⁴ mol)
Yield: 29%
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.54 (s, —CH ₃ , 3H), 2.01-2.11 (m,> C (CH ₃ ) CH (H) CH ₂ —, 1H), 2.33-2 _{.50 (m, = CHCH 2 CH} 2 -, 2H), 2.58-2.65 (m,> CCH 3 CH (H) CH 2 -, 1H), 5.82-5.84 (t,> _{CCHCH 2 -, 1H), 7.45-7.48} (m, naphthyl, 2H), 7.51-7.55 (m, naphthyl, 2H), 7.74-7.77 (m, naphthyl, 1H ), 7.86-7.94 (m, naphthyl, 2H)
¹⁹ F-NMR (300 MHz, CDCl ₃ )
δ (ppm): 2.10 (s, -CF ₃ , 3F)

［実施例２］トリフルオロメタンスルホン酸５−メチル−５−（ナフタレン−２−カルボニル）シクロペント−１−エニルエステルの製造
（１）２−ナフトイルクロリドの合成
５０ｍｌ二口ナス型フラスコに撹拌子を入れ、三方コックを付けた還流管を、もう一方にセプタムラバーを付け、真空乾燥した。

[Example 2] Preparation of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester (1) Synthesis of 2-naphthoyl chloride A stirrer was placed in a 50 ml two-necked eggplant type flask. Then, a reflux tube equipped with a three-way cock was attached to the other end with a septum rubber and vacuum dried.

After Ar substitution, the Sepura rubber was removed, and while flowing Ar gas, 4.6 g (2.7 × 10 ⁻² mol) of ² -naphthoic acid was put into the system, the septum rubber was returned, and 6.0 ml of thionyl chloride (8. 2 × 10 ⁻² mol) and 10 μl of DMF (1.3 × 10 ⁻⁴ mol) were injected, and the septum rubber was replaced with a ball plug and stirred.

  The reaction was promoted by heating a little, and the mixture was stirred at room temperature for 1 hour and then heated to reflux for 1.5 hours. After allowing to cool, the pressure was reduced with a vacuum pump for 2 hours to remove thionyl chloride. Since the obtained 1-naphthoyl chloride was unstable, the whole amount was used as it was in the next reaction.

（２）２−（ナフタレン−２−カルボニル）シクロペンタノンの合成
３００ｍｌ二口ナス型フラスコに撹伴子を入れ、三方コックの付いた還流管を、もう一方にはセプタムラバーを付け、真空乾燥した後、Ａｒ置換した。乾燥ジオキサン３０ｍｌおよび１−ピロリジノ−１−シクロペンテン７．９ｍｌ（５．４×１０^-2ｍｏｌ）を系内に入れ、常に系内が１０℃弱になるような氷浴に浸け、撹拌した。

(2) Synthesis of 2- (naphthalene-2-carbonyl) cyclopentanone A stirrer was placed in a 300 ml two-necked eggplant type flask, a reflux tube with a three-way cock was attached, and a septum rubber was attached to the other, followed by vacuum drying. After that, Ar substitution was performed. 30 ml of dry dioxane and 7.9 ml (5.4 × 10 ⁻² mol) of 1-pyrrolidino-1-cyclopentene were put into the system, and immersed in an ice bath so that the inside of the system always became less than 10 ° C. and stirred.

2-Naphthoyl chloride dissolved in 30 ml of dry dioxane was added dropwise over 3.5 hours, and the ice bath was removed and the mixture was stirred at room temperature for 22 hours.
The mixture was heated to reflux for 1 hour, 27 ml of 1N hydrochloric acid was added, and the mixture was further heated to reflux for 1 hour.

The mixture was extracted with diethyl ether, washed with a saturated aqueous sodium hydrogen carbonate solution and distilled water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. Recrystallization from diisopropyl ether gave 2- (naphthalene-2-carbonyl) cyclopentanone.
The results are shown below.

収量：５．８ｇ（２．４×１０^-2ｍｏｌ）
収率：９０％
融点：７１〜８２℃
¹Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ₃）
ｋｅｔｏ体
δ（ｐｐｍ）：１．９５−２．０５（ｍ，＞ＣＨＣＨ（Ｈ）ＣＨ₂−，１Ｈ），２．２２−２．３７（ｍ，−ＣＨ₂ＣＨ₂ＣＨ₂−，２Ｈ），２．３８−２．４３（ｔ，−ＣＯＣＨ₂ＣＨ₂−，２Ｈ），２．６１−２．６８（ｍ，＞ＣＨＣＨ（Ｈ）ＣＨ₂−，１Ｈ），４．４０−４．４５（ｔ，＞ＣＨＣＨ₂−，１Ｈ），７．５０−７．６１（ｍ，ｎａｐｈｔｈｙｌ，２Ｈ），７．８３−７．９３（ｍ，ｎａｐｈｔｈｙｌ，２Ｈ），７．９８−８．００（ｄ，ｎａｐｈｔｈｙｌ，１Ｈ），８．０４−８．０７（ｄｄ，ｎａｐｈｔｈｙｌ，１Ｈ），８．５４（ｓ，ｎａｐｈｔｈｙｌ，１Ｈ）
ｅｎｏｌ体
δ（ｐｐｍ）：１．９５−２．０５（ｍ，−ＣＨ₂ＣＨ₂ＣＨ₂−，２Ｈ），２．５０−２．５５（ｔ，＞ＣＨＣＨ₂ＣＨ₂−，２Ｈ），２．９５−３．００（ｔ，−ＣＯＣＨ₂ＣＨ₂−，２Ｈ），７．５０−７．６１（ｍ，ｎａｐｈｔｈｙｌ，２Ｈ），７．８３−７．９３（ｍ，ｎａｐｈｔｈｙｌ，４Ｈ），８．２７（ｓ，ｎａｐｈｔｈｙｌ，１Ｈ），１４．６３（ｓ，−ＯＨ，１Ｈ）

Yield: 5.8 g (2.4 × 10 ⁻² mol)
Yield: 90%
Melting point: 71-82 ° C
¹ H-NMR (300 MHz, CDCl ₃ )
keto body δ (ppm): 1.95-2.05 (m ,> CHCH (H) CH 2 -, 1H), 2.22-2.37 (m, -CH 2 CH 2 CH 2 -, 2H) _{, 2.38-2.43 (t, -COCH 2 CH} 2 -, 2H), 2.61-2.68 (m,> CHCH (H) CH 2 -, 1H), 4.40-4.45 _{(t,> CHCH 2 -,} 1H), 7.50-7.61 (m, naphthyl, 2H), 7.83-7.93 (m, naphthyl, 2H), 7.98-8.00 (d , Naphthyl, 1H), 8.04-8.07 (dd, naphthyl, 1H), 8.54 (s, naphthyl, 1H)
enol body δ (ppm): 1.95 to 2.05 (m, —CH ₂ CH ₂ CH ₂ —, 2H), 2.50 to 2.55 (t,> CHCH ₂ CH ₂ —, 2H), 2 _{.95-3.00 (t, -COCH 2 CH 2} -, 2H), 7.50-7.61 (m, naphthyl, 2H), 7.83-7.93 (m, naphthyl, 4H), 8 .27 (s, naphthyl, 1H), 14.63 (s, -OH, 1H)

(3) Synthesis of 2-methyl-2- (naphthalene-2-carbonyl) cyclopentanone In a 200 ml two-necked eggplant type flask was added 4.0 g (1.7 × 10 ⁻ ) of 2- (naphthalene-2-carbonyl) cyclopentanone. ² mol) and a stirring element were added, a three-way cock and a septum rubber were attached, vacuum-dried, and then replaced with Ar. 50 ml of acetone dried with molecular sieves was added to the system and stirred until completely dissolved. After putting into an ice bath, 9.3 g (6.7 × 10 ⁻² mol) of potassium carbonate was put into the system, and 3.7 ml (5.9 × 10 ⁻² mol) of methyl iodide was further added. After 10 minutes, the ice bath was removed and the mixture was stirred for 24 hours.

The reaction solution was filtered, ethyl acetate was added, and acetone was removed by a rotary evaporator. The mixture was poured into distilled water, extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. Isolation and purification were performed by silica gel column chromatography (developing solvent; methylene chloride: ethyl acetate = 40: 1) to obtain 2-methyl-2- (naphthalene-2-carbonyl) cyclopentanone.
Yield: 2.6 g (1.0 × 10 ⁻² mol)
Yield: 61%
Melting point: 57-59 ° C
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.56 (s, —CH ₃ , 3H), 1.92 to 2.02 (m,> C (CH ₃ ) CH (H) CH ₂ —, 1H), 2.03-2 .11 (m, —CH ₂ CH (H) CH ₂ —, —COCH (H) CH ₂ —, 2H), 2.40-2.50 (m, —CH ₂ CH (H) CH ₂ —, 1H ), 2.53-2.63 (m, —COCH (H) CH ₂ —, 1H), 2.85-2.93 (m,> C (CH ₃ ) CH (H) CH ₂ —, 1H) 7.52-7.62 (m, naphthyl, 2H), 7.84-7.91 (m, naphthyl, 3H), 7.93-7.96 (dd, naphthyl, 1H), 8.41 ( s, naphthyl, 1H)

（４）トリフルオロメタンスルホン酸５−メチル−５−（ナフタレン−２−カルボニル）シクロペント−１−エニルエステルの合成
５０ｍｌ二口ナス型フラスコに撹拌子を入れ、三方コックおよびセプタムラバーを付け、真空乾燥した後Ａｒ置換した。乾燥ＴＨＦ１０ｍｌおよび２，２，６，６−テトラメチルピペリジン０．８ｍｌ（４．８×１０^-3ｍｏｌ）を入れ、撹拌し、メタノールバスで−７０℃付近まで冷やした。

(4) Synthesis of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester A 50 ml two-necked eggplant-shaped flask was charged with a stirring bar, fitted with a three-way cock and a septum rubber, and vacuum dried. And then substituted with Ar. 10 ml of dry THF and 0.8 ml (4.8 × 10 ⁻³ mol) of 2,2,6,6-tetramethylpiperidine were added, stirred, and cooled to around −70 ° C. with a methanol bath.

After 20 minutes, 3.0 ml (4.8 × 10 ⁻³ mol) of n-butyllithium (1.6 M hexane solution) was added dropwise. One hour later, 1.0 g (4.0 × 10 ⁻³ mol) of 2-methyl-2- (naphthalene-2-carbonyl) cyclopentanone previously dissolved in 5 ml of dry THF was added. Further 25 minutes later, 0.8 ml (4.8 × 10 ⁻³ mol) of trifluoromethanesulfonic anhydride was added.

After stirring for 1 hour, the mixture was extracted with diethyl ether, washed with a saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. Isolation and purification by silica gel column chromatography (developing solvent; diethyl ether: hexane = 1: 5) gave trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-2-carbonyl) cyclopent-1-enyl ester. .
The results are shown below.
Yield: 680 mg (1.8 × 10 ⁻³ mol)
Yield: 45%
¹ H-NMR (300 MHz, CDCl ₃ )
δ (ppm): 1.66 (s, —CH ₃ , 3H), 2.22-2.31 (m,> C (CH ₃ ) CH (H) CH ₂ —, 1H), 2.57-2 _{.64 (m, = CHCH 2 CH} 2 -, 2H), 2.74-2.81 (m,> CCH 3 CH (H) CH 2 -, 1H), 5.87-5.89 (t,> _{CCHCH 2 -, 1H), 7.53-7.63} (m, naphthyl, 2H), 7.87-7.96 (m, naphthyl, 4H), 8.44 (s, naphthyl, 1H)
¹⁹ F-NMR (300 MHz, CDCl ₃ )
δ (ppm): 2.02 (s, -CF ₃ , 3F)

［実施例３］トリフルオロメタンスルホン酸５−メチル−５−（ナフタレン−１−カルボニル）シクロペント−１−エニルエステルの光酸発生機能の評価
実施例１で製造したトリフルオロメタンスルホン酸５−メチル−５−（ナフタレン−１−カルボニル）シクロペント−１−エニルエステルの紫外・可視（ＵＶ−ＶＩＳ）吸収スペクトルを測定したところ、波長３１３ｎｍにおけるモル吸光係数は２３００であった。ＵＶ−ＶＩＳ吸収スペクトルを図１に示す。

[Example 3] Evaluation of photoacid generation function of 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester of trifluoromethanesulfonic acid 5-methyl-5 trifluoromethanesulfonate prepared in Example 1 When the ultraviolet-visible (UV-VIS) absorption spectrum of-(naphthalene-1-carbonyl) cyclopent-1-enyl ester was measured, the molar extinction coefficient at a wavelength of 313 nm was 2300. The UV-VIS absorption spectrum is shown in FIG.

Subsequently, 4.2 mg (1.1 × 10 ⁻⁵ mol) of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester was dissolved in 4.0 ml of benzene for spectrum measurement. To the solution, 0.1 μl of pyridine was added as a neutralizing agent, and after freeze degassing, light irradiation was performed. For light irradiation, light having a center wavelength of 313 nm (bandwidth: 15 nm) selected from a xenon lamp light by a diffraction grating was used. The generation efficiency of the amine salt of trifluoromethanesulfonic acid was determined from ¹⁹ F-NMR measurement. The ¹⁹ F-NMR spectrum after 11 hours of light irradiation is shown in FIG.

In the ¹⁹ F-NMR spectrum after the reaction, a signal of the trifluoromethyl group of trifluoromethanesulfonic acid 5-methyl-5- (naphthalene-1-carbonyl) cyclopent-1-enyl ester was observed at 1.64 ppm, and pyridine triflate Was observed at -1.99 ppm. From these integrated values, it was found that the quantum yield of acid generation was 0.013 when the conversion rate was 7.4%.

Claims (11)

A compound represented by the following formula (1);

(In formula (1), R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic ring, a substituted or unsubstituted heterocyclic ring, a fluorine atom, a nitro group, or a cyano group; R ² represents hydrogen. Atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted carbocycles, substituted or unsubstituted heterocycles, acetamide groups, aminosulfonyl groups, or halogens X ¹ represents an alkyl group or an aryl group; X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a carboxyl group, a hydroxyl group, Represents a halogen atom or a cyano group; p represents 1 to 4)   The compound according to claim 1, wherein p is 2 to 4 in the formula (1). The compound according to claim 1 or 2, wherein in the formula (1), R ¹ is an alkyldifluoromethyl group, an aryldifluoromethyl group, a perfluoroalkyl group, or a perfluoroaryl group. The compound according to any one of claims 1 to 3, wherein in the formula (1), R ² is a substituted or unsubstituted carbocyclic ring or a substituted or unsubstituted heterocyclic ring. The compound according to claim 4, wherein in the formula (1), R ² is a cycloalkyl group or an aryl group. The compound according to any one of claims 1 to 5, wherein in the formula (1), X ¹ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 3 to 12 carbon atoms. The compound according to claim 6, wherein X ¹ in the formula (1) is a methyl group, an ethyl group or a propyl group. The compound according to any one of claims 1 to 7, wherein in the formula (1), X ² is a hydrogen atom, an alkyl group or a halogen atom.   The compound according to any one of claims 1 to 8, which is a photoacid generator.   The photosensitive resin composition containing the compound in any one of Claims 1-9. A compound represented by the following formula (2) is reacted with a compound represented by the following formula (2) using lithium 2,2,6,6-tetramethylpiperidide as a base. The manufacturing method of the compound made.

(In the formula (2), R ² is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted carbocycle, substituted or unsubstituted. X ¹ represents an alkyl group or an alkoxy group; X ² independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio; A group, an arylthio group, a carboxyl group, a hydroxyl group, a halogen atom or a cyano group; p represents 1-3.)

(In formula (1), R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbocyclic ring, a substituted or unsubstituted heterocyclic ring, a fluorine atom, a nitro group, or a cyano group; R ² represents hydrogen. Atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted carbocycles, substituted or unsubstituted heterocycles, acetamide groups, aminosulfonyl groups, or halogens X ¹ represents an alkyl group or an alkoxy group; X ² each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an alkylthio group, an arylthio group, a carboxyl group, a hydroxyl group, Represents a halogen atom or a cyano group; p represents 1-3.)

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