JP2003267949A - Pyrenesulfonic acid onium salt compound, method for producing the same compound, photosensitive resin composition using the same compound and photosensitive material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve problems that a highly sensitive photoacid generator compound is demanded in a photosensitive resin composition exhibiting a spectral sensitivity to light at 365 nm and to provide a pyrenesulfonic acid onium salt compound. <P>SOLUTION: The pyrenesulfonic acid onium salt compound having a plurality of sulfonic acid onium salt moieties is used as the photoacid generator in a photosensitive material basically comprising a polymer increasing the solubility in an aqueous solution of an alkali by actions of an acid and the photoacid generator. Thereby, the photosensitive material exhibiting a positive type behavior with a good sensitivity can be provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pyrenesulfonic acid onium salt compound as a photoacid generator for generating an acid in an exposed area by irradiation with near-ultraviolet light, a method for producing the pyrenesulfonic acid onium salt compound, and at least the pyrene. A photosensitive resin composition containing a resin in which the solubility of an exposed portion and an unexposed portion in a developing solution is changed by an acid-catalyzed reaction of an onium sulfonate compound and a pyrenesulfonic acid onium salt compound, and this photosensitive composition The present invention relates to a photosensitive material for forming a resin layer of a resin composition on a support. For example, the present invention relates to a photosensitive resin composition and a photosensitive material that can be used for microfabrication of LSI and the like, printing, printed circuit formation, UV curable resin, and production of liquid crystal panels and the like.

[0002]

2. Description of the Related Art When a conventional resist composed of novolak and naphthoquinonediazide compound is used for pattern formation of lithography using far ultraviolet light or excimer laser light, novolak and naphthoquinonediazide are strongly absorbed in the far ultraviolet light region and light It was difficult to reach the bottom of the resist, and only a pattern with low sensitivity and a taper was obtained.

One of means for solving this problem is a chemically amplified resist composition described in US Pat. No. 4,491,628 and European Patent 29,139. A chemically amplified positive resist composition generates an acid in an exposed area by irradiation with far ultraviolet light, and a reaction catalyzed by this acid improves solubility in a developing solution in a portion irradiated with far ultraviolet light and a non-irradiated portion. It is a pattern forming material that is changed to form a pattern on a substrate.

Thus, the chemically amplified resist composition is
It was developed as a patterning material for far-ultraviolet light for microfabrication in the semiconductor industry, but there is an increasing demand for application to near-ultraviolet light because it is easy to achieve high sensitivity and thin lines. However, although there are many photoacid generator compounds having spectral sensitivity in the far-ultraviolet region, there are currently few photoacid generators exhibiting spectral sensitivity to 365 nm light.

As an example of these, Japanese Patent Laid-Open No. 22185/1998
4 is an example in which 10 to 80% of the phenolic hydroxyl group in the alkali-soluble resin having a phenolic hydroxyl group is substituted with a functional group having a specific structure and a photoacid generator shown below.

[0006]

[Chemical 7]

However, there is a problem that these compositions have low sensitivity. When the photoacid generator has low sensitivity,
The amount of exposure required for pattern formation is increased, and the exposure time is increased accordingly, resulting in low temporal efficiency.

[0008]

In recent years, there has been a demand for a photoacid generator exhibiting high spectral sensitivity to 365 nm light.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies in view of the present situation, and as a result, added pyrenesulfonic acid onium salt compounds which generate an acid upon irradiation with actinic rays or heat, and heat in the presence of an acid. In the chemically amplified positive resist composition basically having a polymer that is deprotected and becomes alkali-soluble by doing so, in order to increase the sensitivity of the pyrene sulfonic acid onium salt compound, at least the sulfonic acid onium salt moiety should be present in the pyrene ring. The present invention has been completed by using at least one compound represented by the general formula (1) characterized by having two or more.

[0010]

[Chemical 8] [In the above formula, each R ₁ is independently a hydrogen atom, an alkyl group, an unsubstituted or substituted aryl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, an alkenyl group, an acyl group, an acyloxy group, a nitro group, a carboxyl group, or a cyano group. Group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, aralkyl group, haloalkyl group,
Unsubstituted or substituted cycloalkyl group, alkoxycarbonyl group, mercapto group, or halogen (fluorine, chlorine,
Bromine, iodine) atom, R ₁ may be attached to any position of the four rings of the condensed ring, and a represents an integer of 0 to 8,
The sulfonic acid group may be attached at any position of the four rings of the condensed ring, e represents an integer of 2 to 10, and d represents an integer of 0 to 8. X represents a sulfur atom or an iodine atom and may have an oxoiodonium or oxosulfonium structure. Y represents lithium, sodium, potassium, magnesium, calcium or quaternary ammonium.
R ₂ , R ₃ and R ₄ represent an alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, an unsubstituted or substituted cycloalkyl group or a heterocyclic group. . R ₂ , R ₃ and R ₄ may be linked to form a ring. b, c and f represent the integer of 0-3. Incidentally, the alkyl group, the aromatic hydrocarbon ring and the heterocyclic ring are further an alkyl group, an alkoxy group, a hydroxyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, Acyloxy group, alkenyl group,
It may have a substituent such as a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aromatic sulfonic acid group, a substituted amino group or a heterocyclic group. m represents 1, 2 or 3. ]

The pyrenesulfonic acid onium salt compound represented by the general formula (1) is almost quantitatively determined by adding a solution of the onium salt (7) to the solution of the sulfonate (6) according to the following reaction formula and reacting the solution. Can be manufactured with high purity.

[0012]

[Chemical 9] [In the above formula, each R ₁ is independently a hydrogen atom, an alkyl group, an unsubstituted or substituted aryl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, an alkenyl group, an acyl group, an acyloxy group, a nitro group, a carboxyl group, or a cyano group. Group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, aralkyl group, haloalkyl group,
Unsubstituted or substituted cycloalkyl group, alkoxycarbonyl group, mercapto group, or halogen (fluorine, chlorine,
Bromine, iodine) atom, R ₁ may be attached to any position of the four rings of the condensed ring, and a represents an integer of 0 to 8,
The sulfonic acid group may be attached at any position of the four rings of the condensed ring, e represents an integer of 2 to 10, and d represents an integer of 0 to 8. X represents a sulfur atom or an iodine atom and may have an oxoiodonium or oxosulfonium structure. Y represents lithium, sodium, potassium, magnesium, calcium or quaternary ammonium.
R ₂ , R ₃ and R ₄ represent an alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, an unsubstituted or substituted cycloalkyl group or a heterocyclic group. . R ₂ , R ₃ and R ₄ may be linked to form a ring. b, c and f represent the integer of 0-3. Incidentally, the alkyl group, the aromatic hydrocarbon ring and the heterocyclic ring are further an alkyl group, an alkoxy group, a hydroxyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, Acyloxy group, alkenyl group,
It may have a substituent such as a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aromatic sulfonic acid group, a substituted amino group or a heterocyclic group. m represents 1, 2 or 3. Z represents a chlorine atom, a bromine atom, an iodine atom or a hydroxyl group. In the above formula, the solvent used in the reaction is preferably water or an alcohol solvent such as methanol or ethanol. The reaction temperature may be in the range of 0 to 90 ° C, preferably 10 to 40 ° C.

Specific examples of the sulfonate (6) are shown in Tables 1 to 1.
4, but not limited thereto. The following structural formula is shown without Y.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

[0017]

[Table 4]

Specific examples of the onium salt (7) are shown in Tables 5 to 7, but are not limited thereto.

[Table 5]

[0019]

[Table 6]

[0020]

[Table 7] Specific examples of the pyrenesulfonic acid onium salt compound (hereinafter referred to as a photoacid generator) which can be produced by the reaction of the sulfonate (6) and the onium salt (7) are shown below, but the invention is not limited thereto. Absent.

Photoacid generator-1

[Chemical 10]

Photoacid generator-2

[Chemical 11]

Photoacid generator-3

[Chemical 12]

Photoacid generator-4

[Chemical 13]

Photoacid generator-5

[Chemical 14]

Photoacid generator-6

[Chemical 15]

Photoacid generator-7

[Chemical 16]

Photoacid generator-8

[Chemical 17]

Photoacid generator-9

[Chemical 18]

Photoacid generator-10

[Chemical 19]

Photoacid generator-11

[Chemical 20]

Photoacid generator-12

[Chemical 21]

Photoacid generator-13

[Chemical formula 22]

Photoacid generator-14

[Chemical formula 23]

Photoacid generator-15

[Chemical formula 24]

Photoacid generator-16

[Chemical 25]

Photoacid generator-17

[Chemical formula 26]

These photoacid generators may be used alone or in combination of two or more. The amount thereof used is in the range of 1 to 45% by weight, preferably 3 to 30% by weight, based on the polymer component.

The polymer used in the present invention is one that is deprotected and becomes alkali-soluble by applying heat in the presence of an acid. Examples of the polymer system having a phenolic hydroxyl group include a copolymer of p-hydroxystyrene and p-hydroxystyrene having a hydroxyl group protected by an ethoxyethyl group, a t-butoxycarbonyl group or a pyranyl group. As the polymer system having a carboxyl group, for example, a two-component or three-component copolymer such as acrylic acid or methacrylic acid, acrylate or methacrylate protected with acetal or ketal, and acrylate or methacrylate esterified with alcohol. Is mentioned. The average molecular weight of the copolymer is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the unexposed portion is greatly reduced in film thickness due to development, and if it exceeds 200,000, the alkali dissolution rate of the alkali-soluble resin itself becomes slow and the sensitivity is lowered. More preferably 6,000-150,
The range of 000 is good, and more preferably 10,000 to
The range of 140,000 is preferable. The amount of the polymer used in the present invention is 10 to 99% by weight, preferably 15 to 40% by weight, based on the total solid content. Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto.

[0040]

[Chemical 27]

[0041]

[Chemical 28]

The present invention further comprises, if necessary, a compound having two or more phenolic hydroxyl groups which promotes solubility in a surfactant and a developing solution, stability of a photoresist film during storage and line width by heating after exposure. You may add the organic basic compound etc. which reduce a change.

Specific examples of suitable surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, and polyoxyethylene alkyl ethers. Polyoxyethylene alkyl allyl ethers such as oxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monostearate, sorbitan monooleate and sorbitan fatty acid esters such as tristearate And the like.

These surfactants may be used alone or in admixture of two or more.

Specific examples of the compound having two or more phenolic hydroxyl groups which promote solubility in a developing solution include resorcin, phloroglucin, phlorogluside,
2,3,4-trihydroxybenzophenone, 2,3
Examples include polyhydroxy compounds such as 4,4′-tetrahydroxybenzophenone.

Specific examples of the organic basic compound include guanidine, 1,1'-dimethylguanidine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 2-diethylaminopyridine and 2-amino-3-
Methylpyridine, 2-amino-4-methylpyridine, 2-
Amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-ethylaminopyridine, 4-ethylaminopyridine, 3-aminopyrrolidine, piperazine, 4-piperidinopiperidine, 2-iminopiperidine, 3-amino -5-methylpyrazole, pyrazine, 2,4-diaminopyrimidine, 2-pyrazoline, 3-pyrazoline and N
—Aminomorpholine and the like.

The photosensitive resin composition containing the photo-acid generator of the present invention is used as a photosensitive material for manufacturing a semiconductor material by drawing a resist pattern on a metal substrate and processing such as etching and plating. You can Further, the photosensitive material of the present invention can be prepared by applying a solution of a photosensitive resin composition onto a silicon wafer as a liquid resist and drying it to form a photosensitive layer.

In order to prepare a solution that is easy to apply, the photosensitive resin composition is ethylene dichloride, cyclopentanone, 2-heptanone, methyl ethyl ketone, 2-methoxyethyl acetate, toluene, ethyl acetate, methyl lactate, acetone, ethyl lactate. , Methyl methoxypropionate, ethyl ethoxypropionate, ethyl pyruvate,
Solvents such as methyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran methyl cellosolve, methanol, propylene glycol monoethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, or these solvents. It can be diluted with a mixed solvent to give a solution that is easy to apply.

The coating is performed by a roll coater or an air knife coater.
It can be carried out with a counter, a bar coater or a spin coater. Drying is good in the range of 40-160 ℃,
It is preferably in the range of 60 to 130 ° C. The thickness of the photosensitive layer after drying is preferably 1 to 2 μm.

The exposure of the photosensitive layer can be carried out by selecting a wavelength of 365 nm with a cut filter (manufactured by Toshiba) using a light source such as an ultra-high pressure mercury lamp. Examples of the developing solution for the photosensitive layer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate and sodium metasilicate, aqueous ammonia, ethylamine and n-propylamine. Primary amines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine,
Amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzyl The fourth such as methyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Aqueous solutions of primary ammonium hydroxides and cyclic amines such as pyrrole and piperidine are used.

Etching and plating are performed by known methods. A strong alkaline aqueous solution or the like can be used for peeling the photosensitive layer.

[0052]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Synthesis Examples and Examples, but the present invention is not limited to these Examples.

[0053]

EXAMPLES (Synthesis Example 1) Synthesis of Photoacid Generator-7 Aqueous solution containing 1.51 g of diphenyliodonium chloride (reagent) in a four-necked flask equipped with a thermometer, a cooling tube, a dropping funnel and a stirrer. After adding 200 g and stirring, 20 g of 0.5 g pyranine (reagent) aqueous solution was added dropwise at room temperature. When the dropping was completed, a white solid gradually precipitated. After continuing stirring for 2 hours, filtration, washing with water, and drying under reduced pressure at room temperature gave 1.23 g of a white solid. As a result of NMR analysis, the obtained white solid could be identified as photoacid generator-7. 1H-NMR (ppm) 7.52, 7.64, 8.15, 8.24, 8.28,
8.86, 8.98, 9.01, 10.63 Melting point 181.3-184.9 ° C

A 4.96 × 10 −6 mol / L methanol solution of photo-acid generator-7 was measured with a Hitachi U-3000 spectrophotometer. The maximum absorption wavelength of the absorption spectrum is 41
It was 2 nm. The absorption spectrum is shown in FIG.

Example 1 p-Hydroxystyrene and t-
The molecular weight of 6 was obtained by copolymerizing p-hydroxystyrene in which the phenolic hydroxyl group was protected with a butoxycarbonyl group.
A copolymer having 20,000 phenolic hydroxyl groups was prepared. A solvent was added to 100 g of this copolymer as shown in Table 8 to obtain a resin solution.

[0056]

[Table 8]

A solution of 9.3 g of the photo-acid generator-7 obtained in Synthesis Example 1 dissolved in 125 g of methanol was added to the above resin solution in the dark to obtain a photosensitive resin composition.

A solution of this photosensitive resin composition was applied onto a silicon wafer (Sumitomo Bakelite Co., Ltd.) with a spin coater and dried on a hot plate at 120 ° C. for 10 minutes to form a photosensitive resist film having a photosensitive resist film with a thickness of 1 μm. A flexible material was prepared.

An exposure pattern is placed on this photosensitive material,
The ultrahigh-pressure mercury lamp light source was irradiated with 365 nm light obtained through a cut filter (made by Toshiba) and a neutral density filter (made by Toshiba) to expose it. Next, post-exposure heating (PE
B: post exposure bake) was performed, and for development, the exposed portion was removed by immersing in a 1.5 wt% tetramethylammonium hydroxide aqueous solution at 20 ° C. for 1.5 minutes and shaking. The minimum exposure amount at which the photosensitive film did not remain on the silicon wafer was defined as the sensitivity.

Example 2 Sensitivity was measured in the same manner as in Example 1 except that photoacid generator-17 in place of photoacid generator-7 in Example 1 was used.

Example 3 Sensitivity was measured in the same manner as in Example 1 except that photoacid generator-14 was used instead of photoacid generator-7 in Example 1.

Example 4 The sensitivity was measured in the same manner as in Example 1 except that the photo-acid generator-11 in place of the photo-acid generator-7 in Example 1 was used.

Comparative Example The sensitivity was measured in the same manner as in Example 1 except that the compound 29 was used in place of the photoacid generator-7 of Example 1.

[Chemical 29]

Table 2 shows the results of sensitivity evaluation of Examples 1, 2 and 3. The sensitivity is represented by the minimum exposure amount when the exposed area is completely dissolved within the developing time, and the lower the number, the higher the sensitivity.

[0065]

[Table 9]

From the results shown in Table 2, it was demonstrated that the photosensitive resin composition of the present invention was more sensitive when the pyrene ring contained more onium salt of pyrenesulfonic acid.

[0067]

The photosensitive resin composition of the present invention and the photosensitive material using the same can be easily prepared and have high sensitivity.

[0068]

[Brief description of drawings]

FIG. 1 is an absorption spectrum of photoacid generator-7.

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C07C 309/43 C07C 309/43 C07D 333/46 C07D 333/46 C08K 5/42 C08K 5/42 C08L 101/00 C08L 101 / 00 G03F 7/004 503 G03F 7/004 503A H01L 21/027 H01L 21/30 502R (72) Gen Yamazaki 45 Miyukigaoka, Tsukuba City, Ibaraki Prefecture Hodogaya Chemical Co., Ltd. Reference) 2H025 AA01 AB16 AC01 AD03 BE07 BG00 FA03 FA12 FA17 4H006 AA01 AA02 AB76 AC61 4J002 CC011 CC031 EV296 FD206 GP03

Claims (8)

[Claims] 1. A pyrenesulfonic acid onium salt compound represented by the following general formula (1). [Chemical 1] [In the above formula, each R ₁ is independently a hydrogen atom, an alkyl group, an unsubstituted or substituted aryl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, an alkenyl group, an acyl group, an acyloxy group, a nitro group, a carboxyl group, or a cyano group. Group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, aralkyl group, haloalkyl group,
Unsubstituted or substituted cycloalkyl group, alkoxycarbonyl group, mercapto group, or halogen (fluorine, chlorine,
Bromine, iodine) atom, R ₁ may be attached to any position of the four rings of the condensed ring, and a represents an integer of 0 to 8,
The sulfonic acid group may be attached at any position of the four rings of the condensed ring, e represents an integer of 2 to 10, and d represents an integer of 0 to 8. X represents a sulfur atom or an iodine atom and may have an oxoiodonium or oxosulfonium structure. Y represents lithium, sodium, potassium, magnesium, calcium or quaternary ammonium.
R ₂ , R ₃ and R ₄ represent an alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, an unsubstituted or substituted cycloalkyl group or a heterocyclic group. . R ₂ , R ₃ and R ₄ may be linked to form a ring. b, c and f
Represents an integer of 0 to 3. Incidentally, the alkyl group, the aromatic hydrocarbon ring and the heterocyclic ring are further an alkyl group, an alkoxy group, a hydroxyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, It may have a substituent such as an acyloxy group, an alkenyl group, a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aromatic sulfonic acid group, a substituted amino group or a heterocyclic group. m represents 1, 2 or 3. ] 2. A pyrenesulfonic acid iodonium salt compound represented by the following general formula (2), wherein the pyrenesulfonic acid onium salt compound according to claim 1 is represented. [Chemical 2] [In the above formula, each R ₇ independently represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a halogen (fluorine, chlorine, bromine, iodine) atom, and R ₇ is a condensed ring 4
It may be attached at any position of one ring, and h represents an integer of 0 to 4. The sulfonic acid group may be attached to any position of the four rings of the condensed ring, and g represents an integer of 2 to 4. Also, R ₅
And R ₆ represent an unsubstituted or substituted aryl group. R ₅ and R ₆
May combine to form a ring. The aromatic hydrocarbon ring may further have a substituent such as an alkyl group, an alkoxy group, a hydroxyl group and a halogen atom. ] 3. A pyrenesulfonic acid sulfonium salt compound represented by the following general formula (3), wherein the pyrenesulfonic acid onium salt compound according to claim 1 is represented by the following general formula (3). [Chemical 3] [In the above formula, R ₈ , R ₉ and R ₁₀ represent an alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group or a heterocyclic group. R ₈ , R ₉ and R ₁₀ may combine to form a ring. The alkyl group, aromatic hydrocarbon ring, aryloxy group, arylthio group or heterocyclic group may further have a substituent such as an alkyl group, an alkoxy group, a hydroxyl group and a halogen atom. The sulfonic acid group may be attached at any position of the four rings of the condensed ring, and g represents an integer of 2 to 4. R ₇ and h are the same as defined in the general formula (2). ] 4. A pyrenesulfonic acid iodonium salt compound in which the pyrenesulfonic acid onium salt compound according to claim 1 or the pyrenesulfonic acid iodonium salt compound according to claim 2 is represented by the following general formula (4). [Chemical 4] [In the formula, R ₁₁ each independently represent a hydrogen atom or a hydroxyl group, R _{1 1} may be attached to any position of the four condensed rings, j represents an integer of 0 to 2. The sulfonic acid group may be attached to any position of the four rings of the condensed ring,
i represents an integer of 2 to 4. ] 5. A pyrenesulfonic acid sulfonium salt compound represented by the following general formula (5), wherein the pyrenesulfonic acid onium salt compound according to claim 1 or the pyrenesulfonic acid sulfonium salt compound according to claim 3 is represented by the following general formula (5). [Chemical 5] [In the above formula, R ₁₁ and j are the same as defined in the general formula (4). The sulfonic acid group may be attached to any position of the four rings of the condensed ring, and i represents an integer of 2 to 4. ] 6. A sulfonate (6) represented by the following reaction formula:
A method for producing a compound represented by the general formula (1) according to claim 1, wherein an onium salt (7) is reacted with [In the above formula, each R ₁ is independently a hydrogen atom, an alkyl group, an unsubstituted or substituted aryl group, an alkoxy group, an alkoxyalkyl group, a hydroxyl group, an alkenyl group, an acyl group, an acyloxy group, a nitro group, a carboxyl group, or a cyano group. Group, unsubstituted or substituted aryloxy group, unsubstituted or substituted arylthio group, aralkyl group, haloalkyl group,
Unsubstituted or substituted cycloalkyl group, alkoxycarbonyl group, mercapto group, or halogen (fluorine, chlorine,
Bromine, iodine) atom, R ₁ may be attached to any position of the four rings of the condensed ring, and a represents an integer of 0 to 8,
The sulfonic acid group may be attached at any position of the four rings of the condensed ring, e represents an integer of 2 to 10, and d represents an integer of 0 to 8. X represents a sulfur atom or an iodine atom and may have an oxoiodonium or oxosulfonium structure. Y represents lithium, sodium, potassium, magnesium, calcium or quaternary ammonium.
R ₂ , R ₃ and R ₄ represent an alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, an unsubstituted or substituted cycloalkyl group or a heterocyclic group. . R ₂ , R ₃ and R ₄ may be linked to form a ring. b, c and f represent the integer of 0-3. Incidentally, the alkyl group, the aromatic hydrocarbon ring and the heterocyclic ring are further an alkyl group, an alkoxy group, a hydroxyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aryloxy group, an unsubstituted or substituted arylthio group, an acyl group, Acyloxy group, alkenyl group,
It may have a substituent such as a halogen atom, a nitro group, a cyano group, an unsubstituted or substituted aromatic sulfonic acid group, a substituted amino group or a heterocyclic group. m represents 1, 2 or 3. Z represents a chlorine atom, a bromine atom, an iodine atom or a hydroxyl group. ] 7. A photosensitive resin composition comprising at least one pyrene sulfonic acid onium salt compound according to any one of claims 1 to 5. 8. A photosensitive material comprising the photosensitive resin composition according to claim 7.