JP2655370B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate or a photoresist.
More specifically, the present invention relates to a negative photosensitive composition which provides a high sensitivity and high contrast image.

[0002]

2. Description of the Related Art As a negative type photosensitive composition, a diazo resin and a binder system, an azide compound and a binder system, a photopolymerization system, a photodimerization type resin system and the like are generally used.

However, recently, many patents have been filed for negative photosensitive compositions using photosensitive materials other than those described above.

[0004] For example, a photosensitive composition comprising a compound that generates an acid by the action of light and a substance whose affinity or solubility in a developer is reduced by a reaction using the acid as a catalyst is exemplified. Examples thereof include a combination of a naphthoquinonediazide compound and an acid-curable resin [Japanese Unexamined Patent Publication No.
No. 263143], a combination of a halogenated organic compound and an acid-curable resin [JP-A-62-164045], and a phenothiazine based photoacid generator which makes the photoacid generator sensitive to near ultraviolet light. A combination of a sensitizer and an acid-curable resin [Japanese Patent Laid-Open No. 3-87748], a combination of an onium salt and poly (p-butoxycarbonyloxystyrene) [Polym. Eng. Sci., 23 1012], an onium salt and a poly (p -Vinyl benzoate) [SPIE, 77
1 24], a combination of a halogenated organic compound, hexamethoxymethylmelamine and a novolak resin [Polym. Eng.
Sci., 26 1101]. However, none of the prior arts discloses a photosensitive composition which is excellent in resist pattern shape, has photosensitivity in a wide wavelength range, and has high sensitivity.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image with high sensitivity and high contrast and to be sensitive to ultraviolet rays, visible rays, electron beams or X-rays, that is, to a wide wavelength range. An object of the present invention is to provide a negative photosensitive composition having photosensitivity.

[0006]

The present invention is characterized in that it comprises an aromatic sulfonate of an onium compound and a compound having a property of decreasing affinity or solubility in a developer by a reaction catalyzed by an acid. It is a chemically amplified photosensitive composition.

That is, the present inventor has found that by combining a specific aromatic sulfonic acid as a counter anion of an onium compound, the photosensitive range of the composition can be extended to the absorption wavelength range of the aromatic sulfonic acid. Thus, the present invention has been completed. The present invention relates to a compound having a property of decreasing affinity or solubility in a developer by a reaction using an acid as a catalyst (preferably having a molecular weight of 50 to 50,000).
Combining 0) with an aromatic sulfonate of an onium compound such as diaryliodonium or triarylsulfonium to act as a negative-type image-forming material by appropriately selecting a developer;
An object of the present invention is to provide a photosensitive composition which is sensitive to visible light, electron beam or X-ray. A composition comprising the aromatic sulfonate of the onium compound and a compound (preferably having a molecular weight of 50 to 50,000) having a property of decreasing affinity or solubility in a developer by a reaction using an acid as a catalyst is used as a substrate. After being coated as a thin film, baked under controlled conditions, imagewise exposed to radiation, and optionally post-baked under controlled conditions, the unexposed areas are treated with a developing solution. An image is obtained by selective removal.

A compound (preferably having a molecular weight of 50 to 500,000) having a property of decreasing affinity or solubility in a developer by a reaction using an acid as a catalyst in the present invention.
0) is a compound having an epoxy group in the side chain [Pro
c. Microcircuit Eng., 260, (1982)), a methoxymethylated melamine derivative [Polym. Eg. Sci., 26 , 1101 (198
6)], a compound having a benzyl acetate group in the side chain [P
olym. Eng. Sci., 29 , 960 (1989)], a compound containing a silanol group such as diphenyldisilanol [Proc. SPIE.
1262 , 26 (1990)], and compounds containing a methylol group, such as 2,6-bis (hydroxymethyl) -t-butylphenol and resole resins.

When the molecular weight of the above compound is lower than 50, the film-forming property is deteriorated, and when the molecular weight is higher than 50,000, the developability (removability of an unexposed area by a developer) tends to be deteriorated.
The above compound is used in an amount of 5 to 98% by weight, preferably 20 to 98% by weight, based on the weight of the entire photosensitive composition (not including the coating solvent).
It is used in an amount of 95% by weight. The effects of the present invention become more remarkable when these exemplified compounds are used in combination with an alkali-soluble resin.

[0010] Examples of the alkali-soluble resin that can be used in the present invention include a novolak resin, an acetone-pigalol resin, polyhydroxystyrene and derivatives thereof.

Among these, a novolak resin is particularly preferable, and is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst. Examples of the predetermined monomer include phenols, m-cresol, p-cresol, cresols such as o-cresol, 2,5-xylenol, 3,5-xylenol,
Xylenols such as 3,4-xylenol and 2,3-xylenol; alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol and pt-butylphenol; p-methoxyphenol and m-methoxyphenol Alkoxyphenols such as 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol , Bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenol, bisphenol A, phenylphenol, Rucinol, although the hydroxyaromatic compounds of naphthol or the like can be used alone or two or more, but is not limited thereto.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, for example, chloroacetaldehyde ethyl acetal, can be used, and among these, formaldehyde is preferably used.

These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 2,000 to 30,000. If it is less than 2,000, the film loss of the exposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred is a range of 6,000 to 20,000.

Here, the weight average molecular weight is defined as the value in terms of polystyrene by gel permeation chromatography. Further, the aromatic sulfonate of the onium compound used as the photosensitive material in the present invention has the following general formula:
(1) Also shown in (2).

[0016]

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In the formula, Ar ¹ and Ar ² may be the same or different, and represent a substituted or unsubstituted aromatic group. Preferred substituents are alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carbonyl, alkoxycarbonyl, hydroxy, mercapto groups and halogen atoms, more preferably 1 to 8 carbon atoms.
Alkyl, an alkoxy having 1 to 8 carbon atoms, a nitro group and a chlorine atom. R ¹ , R ² and R ³ may be the same or different and represent a substituted or unsubstituted alkyl group or aromatic group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are alkoxy having 1 to 8 carbon atoms, alkyl having 1 to 8 carbon atoms, nitro, carbonyl, hydroxy group and halogen atom for the aryl group, and 1 carbon atom for the alkyl group. ~ 8 alkoxy, carbonyl and alkoxycarbonyl groups. Further, ^{two of} R ¹ , R ² and R ³ and Ar ¹ and A
r ² may be bonded through a single bond or a substituent. And X ^- represents an aromatic sulfonate anion. More preferably, a condensed polynuclear aromatic sulfonic acid or a sulfonic acid having two or more aromatic rings is used. Specifically, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, anthracene-1-sulfonic acid, 9-nitroanthracene-1-sulfonic acid, 9,10-dichloroanthracene-2-sulfonic acid, 9,10 -Dimethoxyanthracene-2-sulfonic acid, 9,10-dimethoxyanthracene-2-sulfonic acid, anthracene-2-sulfonic acid, phenanthrene-2-sulfonic acid, 9-bromophenanthrene-3-sulfonic acid, 1-methyl -7-isopropylphenanthrene-3-sulfonic acid, pyrene-
2-sulfonic acid, benz [a] anthracene-4-sulfonic acid, triphenylene-2-sulfonic acid, chrysene-
6-sulfonic acid, 5,6-dichloroanthracene-3-
Condensed polynuclear aromatic sulfonic acid anions such as sulfonic acid, 6-nitroacenaphthene-5-sulfonic acid, 2-t-butylnaphthalene-7-sulfonic acid, 9,10-dioxo-9,10-dihydroanthracene-2- Sulfonic acid,
1-bromo-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid, 2-chloro-9,10
Anthraquinonesulfonic acid such as -dioxo-9,10-dihydroanthracene-2-sulfonic acid, 9,10-dioxo-9,10-dihydrophenanthrene-3-sulfonic acid, phenanthraquinonesulfonic acid anion; 2
Naphthoquinone sulfonic acid anions such as naphthoquinone-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, and 1,2-naphthoquinonediazide-5-sulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfone Examples include, but are not limited to, acids, phenol red, methyl orange, alizarin S, indigo carmine, patent blue, chlorophenol red, and sulfonic acid group-containing dyes such as chrysofenin.

Next, specific examples of the compound represented by formula (1) used in the present invention will be shown, but it should not be construed that the invention is limited thereto.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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Specific examples of the compound represented by the general formula (2) used in the present invention are shown below, but are not limited thereto.

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The amount of the aromatic sulfonate of the onium compound used in the present invention is about 2 to 60% by weight based on the total weight of the photosensitive composition (not including the coating solvent).
More preferably, it is 5 to 40% by weight. General formula (1) or
The compound represented by (2) is, for example, JW Knapczyk
Authors, J. Am. Chem. Soc., Vol. 91, pp. 145 (1969
), AL Maycock et al., J. Org. Chem., Volume 35,
2532 (1970), by E. Goethals et al., Bull
l. Soc. Chem. Belg., 73, 546, 1964
HM Leicester, J. Am. Chem. Soc., No. 51
3587 (1929), JV Crivello et al., J. Polym. Soc. Polym. Chem. Ed., Volume 18, No. 2
677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, FM Beringer et al., L. Am.
Chem. Soc., 75, 2705 (1953),
An aromatic sulfonic acid or a sodium salt aqueous solution or an alcoholic solution thereof is added to an aqueous solution or an alcoholic solution of a halogen, bisulfate or perchlorate of an onium compound produced by a procedure disclosed in JP-A-53-101331 or the like. It is obtained by adding and filtering the precipitate formed.

The photosensitive composition of the present invention may optionally contain
Further, a dye, a pigment, a plasticizer, a surfactant, a sensitizer, and the like can be contained. Suitable dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 1
01, oil yellow # 103, oil pink # 31
2. Oil green BG, oil proof BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI4
2555), methyl violet (CI42535),
Rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI1520)
15) and the like.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. Examples of the solvent used here include ethylene dichloride, cyclohexanone, cyclopentanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, toluene, and acetic acid. Ethyl, methyl lactate, ethyl lactate, N, N-dimethylformamide, dimethylsulfoxide and the like are preferable, and these solvents are used alone or in combination.

Further, a surfactant may be added to the above solvent. The photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) such as used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then exposed through a predetermined mask, By developing, a good resist can be obtained.

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Aqueous solutions of alkalis such as triamines, alcohols such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, etc. Can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the aqueous solution of the above alkalis for use.

[0042]

The photosensitive composition of the present invention has high sensitivity,
In addition, a negative resist composition having photosensitivity in a wide wavelength range and having excellent resolution is provided.

[0043]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

[0044]

Synthesis Example 1 Synthesis of Exemplified Compound (1-3) 36 parts by weight of diphenyliodonium perchlorate was added to water 50
An aqueous solution in which 34 parts by weight of sodium 9,10-dimethoxyanthracene-2-sulfonate is dissolved in 500 parts by weight of water is gradually added dropwise to the aqueous solution dissolved in 0 part by weight with stirring. The mixture was then stirred for 2 hours, causing precipitation of the product. The product was filtered and washed with 200 parts of water.
The salt was then dried at 40 ° C. under reduced pressure. Thus 51.3
Part, the target product diphenyliodonium.
9,10-Dimethoxyanthracene-2-sulfonate was obtained.

[0045]

Synthesis Example 2 Synthesis of Exemplified Compound (2-5) 30 parts by weight of triphenylsulfonium chloride was added to water 1
An aqueous solution in which 31 parts by weight of 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid is dissolved in 500 parts by weight of water is gradually added dropwise to an aqueous solution dissolved in 00 parts by weight with stirring. After the addition was complete, the mixture was stirred for 2 hours, causing precipitation of the product. The product was filtered and washed with 200 parts of water. The salt was then dried at 40 ° C. under reduced pressure. Thus 4
5.8 parts, triphenylsulfonium 2-hydroxy-4-methoxybenzophenone-in a yield of 80.4%
The 5-sulfonate was obtained.

[0046]

Examples 1 to 3 By changing the type of the compound of the present invention,
Three types of photosensitive solutions [A] -1 to [A] -3 shown in No. 1 were prepared.

Table-1 ─────────────────────────────────── [A] -1 [A]- 2 [A] -3} Compound of the present invention (1-3) 0.5g (1-9) 0.5g (2-7) 0.5g ──────────────────────────────────ヘ キ サ Hexamethoxymethyl 0.75g ─ 0.5g Melamine ─────────────────────────────────── 2,6 -Bis (hydroxy) {1.0 g 0.5 g methyl) -t-butyl phenol ─── m, p-cresol novolak resin 2 g ─ 1.75 g (m / p = 40/60 molar ratio) (weight average molecular weight 8,000) ──────────────── ─ポ リ Poly (p-hydroxystyrene) ─ 1.75 g ─ (weight average molecular weight 10,000) ──────────────溶 剤 Solvent (diglyme) 10g 10g 10g ────────────────────── ─────────────

[0048]

Comparative Examples 1 to 3 Next, as comparative examples, photosensitive solutions [B] -1 to [B] -3 shown in Table 2 below were prepared.

Table-2 ─────────────────────────────────── [B] -1 [B]- 2 [B] -3 @ diphenyliodonium 0.5 g 0.5 g ─ Hexafluorophosphate salt ─────────────────────────────────── 2,4-bis (trichloromethyl ) -6- (p-methoxyphenyl) ─ ─ 0.5 g -s-triazineヘ キ サ Hexamethoxymethyl 0.75 g ─ 0.75 g melamine ─────────────────────────────────── 2,6-bis (hydroxymethyl) ─0.75 g ─-t-butylphenol ─────────────────────────────────── m, p-cresol novolak resin (m / p = 40 2g 2g 2g (weight average molecular weight 8,000) 溶 剤 Solvent (Diglyme) 10g 10g 10g ───────────────────────────────────

[0050]

[Preparation and evaluation of photosensitive composition] The photosensitive solutions shown in Tables 1 and 2 were applied to a silicon wafer using a spinner,
The resist film was dried in a convection oven under a nitrogen atmosphere at 90 ° C. for 30 minutes to obtain a resist film having a thickness of 1.2 μm.

After exposing the film through a test chart mask using a reduced projection exposure apparatus (i-line stepper manufactured by Canon Inc.), the film was post-baked on a hot plate at 90 ° C. for 1 minute, and then 2.38% The film was developed with an aqueous solution of tetramethylammonium hydroxide for 1 minute, washed with water for 30 seconds and dried. The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. Table 3 shows the results.

The sensitivity was defined as the reciprocal of the exposure amount for reproducing a 0.70 μm mask pattern, and was shown as a relative value of the sensitivity of Comparative Example 3.

The residual film ratio was expressed as a percentage of the ratio of the film thickness of the exposed portion before and after development. The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.70 μm mask pattern.

Table 3 ─────────────────────────────────── Photosensitivity Relative sensitivity Resolution Power Remaining film ratio Resist Pattern (μm) (%) Profile ─────────────────────────────────── Example 1 [A] -1 32.5 0.37 100 good 2 [A] -2 21.0 0.37 98 good 3 [A] -3 28.5 0.37 99 good ─────────比較 Comparative Example 1 [B] -1 image not obtained ０ 0 ─ 2 [B] -2 image obtained ─ 0 ─ 3 [B] -3 1.0.45 82 Rounded ───────────────────────────────る よ う As can be seen, the aromatic sulfonate of the onium compound of the present invention was used. The photosensitive composition was sensitive,
Excellent performance in residual film ratio and resist pattern profile.

[0055]

Examples 4 to 6 Table 4 by changing the kind of the compound of the present invention.
The following three types of photosensitive solutions [A] -4 to [A] -6 were prepared.

Table-4 ─────────────────────────────────── [A] -4 [A]- 5 [A] -6} Compound of the Present Invention (1-1) 0.5g (1-1) 0.5g (1-3) 0.5g ──────────────────────────────────ヘ キ サ Hexamethoxymethyl 0.8g 0.8g ─ Melamine ─────────────────────────────────── 2,6 -Bis (hydroxy) {0.8 g methyl) -t-butyl phenol ─ m, p-cresol novolak resin 2 g ─ 2 g (m / p = 50/50 molar ratio) (weight average molecular weight 8,000) ──────────────────── ─ポ リ Poly (p-hydroxystyrene) ─ 2 g ─ (weight average molecular weight 20,000) ─────────────────────溶 剤 Solvent (diglyme) 10g 10g 10g ───────────────────────────── ──────

[0057]

[Comparative Examples 4 and 5]

Next, as comparative examples, photosensitive solutions [B] -4 and [B] -5 shown in Table 5 below were prepared.

Table-5 ─────────────────────────────────── [B] -4 [B]- 5 ─────────────────────────────────── diphenyliodonium hexafluorophosphate 0.5 g ─ salt ─ ────────────────────────────────── Triphenylsulfonium ・ ─ 0.5g Tetrafluoroborate salt ────ヘ キ サ Hexamethoxymethyl 0.8g 0.8g Melamine ─────────ポ リ 2 g of poly (p-hydroxystyrene) 2 g (weight average molecular weight: 20,000) ─────── ──────────────── ─────────── Solvent (diglyme) 10g 10g ───────────────────────────────── ──

The photosensitive solutions shown in Tables 4 and 5 were applied to a silicon wafer using a spinner and dried on a hot plate at 90 ° C. for 60 seconds to obtain a resist film having a thickness of 1.0 μm. A low-pressure mercury lamp was used for the exposure, and an interference filter was attached to the exposure, and light having a single wavelength of 254 nm was used as exposure light. The light intensity on the exposed surface was about 1.5 mW / cm ² on average. The desired pattern was exposed through a quartz chrome test mask having a minimum line width of 0.5 μm. Immediately after exposure, heat on a hot plate at 100 ° C for 60 seconds, and then
The film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 1 minute, washed with water for 30 seconds and dried.

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. The evaluation was performed in the same manner as in Examples 1 to 3, and the results shown in Table 6 were obtained. The relative sensitivity was shown as a relative value to the sensitivity of Example-4.

Table 6 ─────────────────────────────────── Photosensitive Liquid Relative Sensitivity Resolution Power Remaining Film Ratio ( μm) (%) ──────────────────────────────────── Example 4 [A] -41 0.0 0.50 995 [A] -5 1.8 0.52 100 6 [A] -6 1.1 0.50 99 Comparative Example 4 [B] -4 0.4 0.57 925 [B ] -5 0.5 0.60 93 本 As you can see from this book The photosensitive composition using the aromatic sulfonate of the onium compound of the present invention exhibits excellent performance in sensitivity, resolution and remaining film ratio.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-179355 (JP, A) JP-A-2-150848 (JP, A) JP-A-2-170165 (JP, A) JP-A-3-179 107162 (JP, A) JP-A-3-154059 (JP, A)

Claims (1)

(57) [Claims] 1. A condensed polynuclear aromatic sulfonic acid salt of a compound having a property of decreasing affinity or solubility in a developer by an acid-catalyzed reaction and an onium compound,
A chemically amplified photosensitive composition comprising a sulfonate having two or more aromatic rings .