JPH063818A - Radiation sensitive resin compositi0n for dry development - Google Patents

Abstract

PURPOSE:To form a superior resist pattern by low-temperature silylation treatment by incorporating a resin having phenolic hydroxyl groups, a specified compound, and a 1,2-quinonediazido-sulfonate component. CONSTITUTION:This radiation sensitive resin composition contains the resin having phenolic hydroxyl groups, the quinonediazido-sulfonate component, and one of the compounds represented mainly by formulae I-IV in which R<1> is halogen, alkyl, etc., X<1> is a heterocylic group having as a ring-forming atom N atom combined with S; D is a 1,2-naphthoquinonediazido group; X<2> is the same as X<1>; R<6> is halogen, alkyl, etc., X<3> is C ring or a hetero ring group; R<7> is halogen, aryl, etc., Y is halogen, hydroxy, etc., and Z is a single bond or oxy group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
A radiation-sensitive resin composition sensitive to rays, electron rays, etc.,
More specifically, it relates to a radiation-sensitive resin composition for dry development using plasma etching.

[0002]

2. Description of the Related Art Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, a negative photoresist in which a cyclized product of polyisoprene is mixed with bisazide or a novolac resin is mixed with a quinonediazide compound on a substrate to be processed. Type radiation sensitive resin composition such as photoresist,
Mercury lamp g-line (wavelength 436nm) and i-line (wavelength 365n)
m) is used, and a photolithography method of forming a pattern by developing with a developing solution is adopted.
However, in recent years, LSIs have been further miniaturized, and the minimum dimension of a pattern to be formed on a substrate is entering a region of 1 μm or less. In such a fine dimension region, conventional development using a developing solution is performed. Even if the photolithography method is adopted, particularly when a substrate having a step structure is used, there is a problem that the pattern is not sufficiently resolved due to the influence of light reflection during exposure and the shallow depth of focus in the exposure system. there were. As a method to solve such problems,
A method of forming a resist pattern by performing dry development by etching using gas plasma such as oxygen plasma having anisotropy instead of developing using a developing solution has been proposed. That is, JP-A-61-107346
In the publication, a photosensitive resin layer containing a polymer mixed or combined with a photoactive compound is applied to a substrate and exposed to ultraviolet rays or visible light through a mask which exposes only selected portions of the photosensitive resin layer. By treating the photosensitive resin layer after exposure with a silylating agent, the silylating agent is selectively diffused and absorbed in the exposed portion of the photosensitive resin layer to cause a reaction, and then treated in this manner. By plasma-etching the dry photosensitive resin layer and performing dry development,
It describes a method of selectively removing the unexposed portion to form a desired negative pattern. According to this method,
Since the silylating agent selectively absorbed in the portion exposed to visible light or ultraviolet light has very high resistance to plasma, a resist having steep sidewalls can be obtained by etching with highly anisotropic oxygen plasma. It is known that a pattern can be obtained and thus a fine pattern can be resolved. In addition, the 52nd year of the fall of 1991
Proceedings No. 2,536
In (1991), it is clarified that a pattern is formed by using a gelmylating agent such as bis (triethylgermyl) amine in place of the silylating agent. Although there are many kinds of these silylating agents or germylating agents, hexamethyldisilazane (hereinafter referred to as "HMDS") is the most easy-to-use substance in terms of physical properties and price. However, when HMDS is used as a silylating agent, in the conventional resist, an appropriate sensitivity cannot be obtained unless the silylation temperature is as high as 160 to 200 ° C. That is, at lower temperatures,
Since the progress of silylation is extremely slow and the resistance of the silylation layer to oxygen plasma is insufficient, the entire area of the resist layer is etched by dry development, and a good pattern cannot be formed. However, as the silylation temperature becomes higher, precise temperature control becomes difficult, and the resist layer is softened and deformed, which makes it difficult to control the size and shape of the pattern. Therefore, there has been a strong demand for a dry developing resist capable of forming a good pattern even when silylation is performed at a lower temperature than conventional ones using HMDS.

[0003]

Therefore, it is an object of the present invention to form a resist pattern having a good shape with high sensitivity by a silylation treatment at a temperature lower than that of a conventional resist even when using HMDS. It is an object of the present invention to provide a radiation-sensitive resin composition for dry development, which is capable of

[0004]

According to the present invention, the aforementioned problems are (a) a phenolic hydroxyl group-containing resin and (b)
The composition contains at least one compound selected from the group consisting of compounds represented by the following general formulas (I), (II), (III), (IV) and (V), and (c) 1 , 2-quinonediazide sulfonic acid ester component is contained in the radiation-sensitive resin composition for dry development.

[In the general formula (I), R ¹ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group, or the following general formula: (VI), (VII) or (VII
I) {in the general formulas (VI), (VII) and (VIII), R ² , R
³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, a nitro group or a cyano group. } Represents a group formed by decomposition of a 1,2-naphthoquinonediazide group by the action of light or heat, and X ¹ is a non-ring group containing a nitrogen atom bonded to a sulfur atom of the general formula (I) as a ring-constituting atom. It represents a condensed ring or a condensed ring heterocyclic group.

[Chemical 6]

[Chemical 7]

[Chemical formula 8]

[In the general formula (II), D is the general formula (VI),
Represents a 1,2-naphthoquinonediazide group represented by (VII) or (VIII), X ² is a non-condensed ring or a condensed ring heterocycle containing a nitrogen atom bonded to a sulfur atom of the general formula (II) as a ring-constituting atom. A cyclic group, which is a heterocyclic group consisting of one nitrogen atom, 4 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, and two nitrogen atoms adjacent to each other. A heterocyclic group consisting of an atom and 3 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, 2 separated by one or more carbon atoms, oxygen atoms or sulfur atoms
Heterocyclic groups consisting of 3 nitrogen atoms and 3 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, and may or may not be adjacent to each other. 3-
Represents a group selected from a heterocyclic group consisting of 6 nitrogen atoms, 2 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms]

[In the general formula (III), R ⁶ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group; VI), (VII) or (VIII) represents a 1,2-naphthoquinonediazide group or a group formed by decomposing the 1,2-naphthoquinonediazide group by the action of light or heat, and X ³ is a non- It represents a condensed ring or a condensed ring carbocyclic or heterocyclic group. ]

[In the general formula (IV), R ⁷ represents an aryl group or an alkyl group which may be substituted with one or more halogen atoms or a hydroxyl group, -SR ⁸ (wherein R ⁸ represents an aryl group) ) Or --SO ₂ --R ⁹ (wherein R ⁹ is an aryl group optionally substituted with a nitro group or a cyano group, 1, represented by the general formula (VI), (VII) or (VIII) It represents a 2-naphthoquinonediazide group or a group formed by decomposing a 1,2-naphthoquinonediazide group by the action of light or heat. }, Y is one or more halogen atoms,
It represents an arylene group which may be substituted with a hydroxyl group, an alkyl group, a nitro group or a cyano group, an alkylene group or an alkenylene group, and Z represents a single bond or an oxy group. ]

[In the general formula (V), R ¹⁰ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group; VI), (VII) or (VIII) represents a 1,2-naphthoquinonediazide group or a group formed by decomposing the 1,2-naphthoquinonediazide group by the action of light or heat, R ¹¹ and R ¹² independently represents a hydrogen atom, an alkyl group or an aryl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group, and at least one of R ¹¹ and R ¹² Is a group other than a hydrogen atom. ]

The present invention will be specifically described below, but the purpose, constitution and effect of the present invention will be clarified by this. First, the (a) phenolic hydroxyl group-containing resin used in the present invention is a resin having a hydroxyl group directly bonded to a carbocyclic or heterocyclic aromatic ring such as a non-condensed ring or a condensed ring. Is a novolac resin, a styrene-based resin having a phenolic hydroxyl group (hereinafter referred to as "phenolic styrene-based resin"), and a resin obtained by converting a part of the phenolic hydroxyl group in these resins into 1,2-quinonediazide sulfonic acid ester. Etc. can be mentioned.

Of these (a) phenolic hydroxyl group-containing resins, the novolak resin is produced by polycondensing a phenolic compound and an aldehyde in the presence of an acidic catalyst. Examples of the phenolic compound include 1-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-.
Hydroxynaphthalenes such as 1-naphthol, 5-methyl-1-naphthol, 2-ethyl-1-naphthol, 2-propyl-1-naphthol, 2-butyl-1-naphthol, such as phenol, o-cresol, m-. Cresol, p-cresol, o-ethylphenol, m-
Ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol,
2,5-xylenol, 2,6-xylenol, 3,4
-Xylenol, 3,5-xylenol, 3,6-xylenol, 2,3,5-trimethylphenol, 3,
Phenols such as 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, bisphenol C, bisphenol S, gallic acid, gallic acid ester be able to. These phenolic compounds may be used alone or in admixture of two or more.

Examples of the aldehyde 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,
Examples thereof include o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and the like. Of these aldehydes, formaldehyde, acetaldehyde, benzaldehyde and the like are preferable. These aldehydes are used alone or in admixture of two or more.

The amount of aldehyde used is preferably 0.7 to 3 mol, and particularly preferably 0.7 to 2 mol, per mol of the phenolic compound.

As the acidic catalyst, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as formic acid, oxalic acid and acetic acid are used. The amount of the acidic catalyst used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of the phenolic compound.

In the condensation reaction of a phenolic compound and an aldehyde, water is usually used as a reaction medium. However, when the phenolic compound used does not dissolve in the aldehyde and becomes a heterogeneous system from the initial stage of the reaction, hydrophilicity is obtained. It is also possible to use a protic solvent as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is preferably 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material.

The temperature of the condensation reaction between the phenolic compound and the aldehyde varies depending on the reactivity of the reaction raw material, but is usually 10 to 200 ° C, preferably 70 to 150 ° C.

After completion of the condensation reaction, in order to remove unreacted raw materials, acidic catalyst, reaction medium and the like existing in the system, the temperature of the reaction solution is usually raised to 130 to 230 ° C. and volatile matter is removed under reduced pressure. The resulting novolak resin is recovered by distillation.

The polystyrene reduced weight average molecular weight of the novolak resin in the present invention (hereinafter referred to as "Mw").
Is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and particularly preferably 2,000 to 30,000.

Examples of the phenolic styrene resin include hydroxystyrene and α-methyl-m-
Homopolymers of monomers selected from hydroxystyrenes such as hydroxystyrene and α-methyl-p-hydroxystyrene or derivatives thereof, copolymers of these monomers with each other, the above-mentioned hydroxystyrenes or derivatives thereof And at least one monomer selected from the group consisting of other vinyl-based monomers such as styrene, α-methylstyrene, vinyl ether, acrylonitrile, methacrylonitrile, vinyl chloride, acrylic acid ester, methacrylic acid ester, maleic anhydride, Examples thereof include halogenated phenolic styrene resins and the like, which are halogenated with a copolymer with an organic acid vinyl ester or the like, or a homopolymer or copolymer thereof with chlorine, bromine, iodine, or the like. .

Among these phenolic styrene resins, poly (hydroxystyrene) and poly (α-methyl-
m-hydroxystyrene), poly (α-methyl-p-hydroxystyrene), and the like are preferable.

The Mw of the phenolic styrenic resin is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and particularly preferably 3,0.
It is from 00 to 50,000.

In the present invention, the novolac resin,
The phenolic hydroxyl group-containing resin such as the phenolic styrene resin may be used alone or in combination of two or more.

Further, in the present invention, a part of the phenolic hydroxyl group in the resin is converted to 1,2-quinonediazide sulfonic acid ester instead of or together with the novolac resin, the phenolic styrene resin and the like. One or more resins (hereinafter referred to as "esterified resin") can be used. In the composition of the present invention, the esterified resin may be used in combination with (c) the 1,2-quinonediazide sulfonic acid ester compound described below.
It constitutes the 1,2-quinonediazide sulfonic acid ester component.

As the esterified resin, a phenolic hydroxyl group-containing resin such as the novolac resin or phenolic styrene resin is used, for example, 1,2-quinonediazide sulfonyl halide, in a suitable reaction solvent using a basic condensation catalyst. It can be produced by esterification. As the (a) phenolic hydroxyl group-containing resin in the present invention, the above esterified resin is particularly preferable.

Examples of the 1,2-quinonediazide sulfonyl halide include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphthoquinonediazide-6-sulfonyl chloride. 1,2-naphthoquinonediazide-4-sulfonylbromide, 1,2-naphthoquinonediazide-5-sulfonylbromide, 1,2-
1,2-naphthoquinone diazide sulfonyl halides such as naphthoquinone diazide-6-sulfonyl bromide,
1,2-benzoquinonediazide-4-sulfonyl chloride, 1,2-benzoquinonediazide-5-sulfonyl chloride, 1,2-benzoquinonediazide-6-sulfonyl chloride, 1,2-benzoquinonediazide-4-sulfonylbromide, 1, 2-benzoquinonediazide-5-
Sulfonyl bromide, 1,2-benzoquinonediazide-
Examples thereof include 1,2-benzoquinonediazide sulfonyl halides such as 6-sulfonyl bromide.
These 1,2-quinonediazide sulfonyl halides can be used alone or in admixture of two or more.

Of these 1,2-quinonediazide sulfonyl halides, 1,2-naphthoquinonediazide-4
-Sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride and the like are preferable.

The esterification ratio of the 1,2-quinonediazide sulfonyl halide in the esterified resin is usually 50 mol% or less, preferably 30 mol% or less, of the phenolic hydroxyl group in the phenolic hydroxyl group-containing resin before esterification. Is. If the esterification rate exceeds 50 mol%, the solubility of the esterified resin in the solvent will decrease,
It may be difficult to prepare a resist solution.

The reaction solvent for the esterification reaction of the phenolic hydroxyl group-containing resin with 1,2-quinonediazidesulfonyl halide is, for example, acetone, dioxane, ethyl lactate, ethyl acetate, methyl 3-methoxypropionate or ethyl 3-methoxypropionate. , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,
Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, methyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, acetonitrile, methyl ethyl ketone,
Examples thereof include diisobutyl ketone and methyl isobutyl ketone. These reaction solvents are usually 100 to 10
000 parts by weight, preferably 200 to 3,000 parts by weight are used. In the esterification reaction, water may be added, if necessary, in order to dissolve the salt of the by-product base and the halogen. The amount of water added is the reaction solvent 1
It is about 1 to 10 parts by weight per 00 parts by weight.

Examples of the basic condensation catalyst include alkali metal salts such as sodium hydrogencarbonate, sodium carbonate, sodium hydroxide, potassium hydrogencarbonate, potassium carbonate, potassium hydroxide, triethylamine, triethanolamine, tributylamine, and monometal. Ethanolamine,
Examples thereof include amines such as pyridine, ammonium salts such as ammonium hydroxide and trimethylammonium, and ammonia. The amount of these condensation catalysts used is 1, 2
-Per mole of quinone diazide sulfonyl halide,
0.1 to 10 mol is preferable, and 0.5 to 2.0 mol is more preferable.

The esterification reaction is preferably 5 to 5
At a temperature of 0 ° C, more preferably 10 to 40 ° C, preferably 15 minutes to 10 hours, more preferably 30 minutes to
It takes about 5 hours.

When the radiation-sensitive resin composition for dry development of the present invention does not contain at least another 1,2-quinonediazide sulfonic acid ester component, the following 1,2:
-A quinonediazide sulfonate compound has to be added. However, 1,2-
When the quinonediazide sulfonic acid ester component is already contained, this 1,2-quinonediazide sulfonic acid ester compound may or may not be added.

Examples of the 1,2-quinonediazide sulfonic acid ester compound include 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-group. Examples thereof include compounds having a sulfonyl group, a 1,2-naphthoquinonediazide-6-sulfonyl group, or a 1,2-naphthoquinonediazide-8-sulfonyl group.

Specific examples of the 1,2-quinonediazide sulfonic acid ester compound include p-cresol-1,2.
-Benzoquinone diazide-4-sulfonic acid ester, resorcinol-1,2-naphthoquinone diazide-4-sulfonic acid ester, pyrogallol-1,2-naphthoquinone diazide-5-sulfonic acid ester such as 1,2 of (poly) hydroxybenzene -Quinone diazide sulfonic acid esters; 2,4-dihydroxyphenyl-propyl ketone-1,2-benzoquinone diazide-4-sulfonic acid ester, 2,4-dihydroxyphenyl-n-hexyl ketone-1,2-naphthoquinone diazide-4 -Sulfonic acid ester, 2,4-dihydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4-dihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4
-Dihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4-trihydroxyphenyl-n-hexylketone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3
4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-
Trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone- 1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5
-Sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2- Naphthoquinonediazide-6-sulfonate, 2,2 ', 4,
4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3
4,4'-Tetrahydroxybenzophenone-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4,4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
2,3,4,4'-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxy Benzophenone-1,2-benzoquinonediazide-5-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5
-Sulfonates, 2,4,6,3 ', 4', 5 '
-(Hydroxy) alkylphenylketones such as hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester or 1,2-quinonediazidesulfonic acid esters of (poly) hydroxyphenylarylketone; bis (p-hydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-tri) Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5
Sulfonic acid ester, 2,2-bis (p-hydroxyphenyl) propane-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, 2,2-bis (2,4-dihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,2
3,4-trihydroxyphenyl) propane-1,2-
1,2-bis [(poly) hydroxyphenyl] alkanes such as naphthoquinonediazide-5-sulfonate
Quinonediazide sulfonates; 3,5-dihydroxybenzoic acid lauryl-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5-sulfone Acid ester, propyl 3,4,5-trihydroxybenzoate-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 3,4,5-trihydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5
-1,2-quinonediazide sulfonic acid esters of (poly) hydroxybenzoic acid alkyl ester such as sulfonic acid ester or (poly) hydroxybenzoic acid aryl ester; bis (2,5-dihydroxybenzoyl) methane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxybenzoyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4,6-trihydroxybenzoyl) methane-1 , 2-naphthoquinonediazide-5
-Sulfonic acid ester, p-bis (2,5-dihydroxybenzoyl) benzene-1,2-naphthoquinonediazide-4-sulfonic acid ester, p-bis (2,3,4-)
Trihydroxybenzoyl) benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-bis (2,4,6-trihydroxybenzoyl) benzene-
1,2-naphthoquinonediazide-5-sulfonic acid ester and other bis [(poly) hydroxybenzoyl] alkanes or bis [(poly) hydroxybenzoyl] benzene 1,2-quinonediazidesulfonic acid esters; ethylene glycol-di (3 , 5-Dihydroxybenzoate) -1,2-naphthoquindiazide-5-sulfonic acid ester, polyethylene glycol-di (3,4,5-trihydroxybenzoate) -1,2-naphthoquindiazide-5-sulfonic acid ester 1,2-quinonediazidesulfonic acid esters of (poly) ethylene glycol-di-[(poly) hydroxybenzoate]; 1,2-quinonediazidesulfonic acid esters of hydroxy group-containing α-pyrone natural dyes; hydroxy Γ-pyrone based natural color 1,2-quinonediazide sulfonic acid esters of elementary compounds; 1,2-quinonediazide sulfonic acid esters of diazine natural dyes having a hydroxy group. Furthermore, in addition to these exemplified compounds, J. Kosar "Light-Sensiti"
ve Systems ”pp. 339-352 (1965).
(John Wiley and Sons, New
York) and W. S. De Forest “Phot”
orestist ”, p. 50 (1975) (McGraw-
1, 2, published in Hill, New York)
-Naphthoquinonediazide sulfonic acid ester compounds can also be used. These 1,2-quinonediazide sulfonic acid ester compounds can be used alone or in admixture of two or more.

The addition amount of the 1,2-quinonediazide sulfonic acid ester compound is such that the total amount of 1,2-quinonediazidesulfonyl groups in the composition is usually 0.1 to 2 per 1 kg of the total solid components in the composition. 5 mol%, preferably 0.
It is adjusted to be 2 to 2.0 mol%. Here, the solid component means a solid substance at 25 ° C. and 1 atm.

Next, among the components (b) in the present invention,
In the compound represented by the general formula (I), the aryl group and alkyl group in R ¹ are one or more halogen atoms,
It may be substituted with an alkyl group, an alkoxy group, a nitro group or a cyano group, and these substituents and
Two or more kinds of substituents in R ² , R ³ , R ⁴ or R ⁵ can be present together. Examples of the compound represented by the general formula (I) include 1- (4'-methylbenzenesulfonyl) pyrrole, 1- (4'-nitrobenzenesulfonyl) pyrrole, 1- (4'-cyanobenzenesulfonyl) pyrrole, 1- Arylsulfonylpyrroles such as (3'-nitrobenzenesulfonyl) pyrrole and 1- (naphthalene-2'-sulfonyl) pyrrole; 1- (1 ', 2'-
Photoreaction product of naphthoquinonediazide-4'-sulfonyl) pyrrole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) pyrrole photoreaction product, 1-
(1 ', 2'-naphthoquinonediazide-6'-sulfonyl) pyrrole photoreaction product such as 1', 2'-naphthoquinonediazidesulfonylpyrrole photoreaction product; 1
-(4'-methylbenzenesulfonyl) piperidine, 1
-(4'-nitrobenzenesulfonyl) piperidine, 1
-(4'-cyanobenzenesulfonyl) piperidine, 1
-(3'-nitrobenzenesulfonyl) piperidine, 1
Arylsulfonyl piperidines such as-(naphthalene-2'-sulfonyl) piperidine; a photoreaction product of 1- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) piperidine, 1- (1', 2'- Photoreaction product of naphthoquinonediazide-5'-sulfonyl) piperidine, 1
-(1 ', 2'-naphthoquinonediazide-6'-sulfonyl) photoreaction product of 1', 2'-naphthoquinonediazidesulfonyl piperidines such as photoreaction product; 1- (4'-methylbenzenesulfonyl ) Pyrrolidine, 1- (4'-nitrobenzenesulfonyl) pyrrolidine, 1- (4'-cyanobenzenesulfonyl) pyrrolidine, 1- (3'-nitrobenzenesulfonyl) pyrrolidine, 1- (naphthalene-2'-sulfonyl) pyrrolidine, etc. Arylsulfonylpyrrolidines; 1- (1 ',
Photoreaction product of 2'-naphthoquinonediazide-4'-sulfonyl) pyrrolidine, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) pyrrolidine photoreaction product, 1- (1', 2 ' -Naphthoquinone diazide-6 '
-Sulfonyl) pyrrolidine photoreaction products such as 1 ',
Photoreaction products of 2'-naphthoquinonediazidesulfonylpyrrolidines; 1- (4'-methylbenzenesulfonyl) indole, 1- (4'-nitrobenzenesulfonyl) indole, 1- (4'-cyanobenzenesulfonyl) indole, 1 Arylsulfonylindoles such as-(3'-nitrobenzenesulfonyl) indole and 1- (naphthalene-2'-sulfonyl) indole;
Photoreaction product of 1- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) indole, 1- (1', 2 '
-Naphthoquinonediazide-5'-sulfonyl) indole photoreaction product, 1- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) indole photoreaction product, etc. 1', 2'-naphthoquinonediazidesulfonyl Photoreaction products of indoles; 1- (4'-methylbenzenesulfonyl) pyrazole, 1- (4'-nitrobenzenesulfonyl) pyrazole, 1- (4'-cyanobenzenesulfonyl) pyrazole, 1- (3'-nitrobenzene Arylsulfonylpyrazoles such as sulfonyl) pyrazole, 1- (naphthalene-1′-sulfonyl) pyrazole, 1- (naphthalene-2′-sulfonyl) pyrazole; 1- (1 ′, 2′-naphthoquinonediazide-4′-
Photo-reaction product of sulfonyl) pyrazole, 1- (1 ',
Photoreaction product of 2'-naphthoquinonediazide-5'-sulfonyl) pyrazole, 1- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) pyrazole, 1- (1', 2 ' -Naphthoquinone diazide-4 '
-Sulfonyl) -3,5-dimethylpyrazole photoreaction product, 1- (1 ', 2'-naphthoquinonediazide-
1'of photoreaction product of 5'-sulfonyl) -3,5-dimethylpyrazole, 1- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) -3,5-dimethylpyrazole Photoreaction product of ', 2'-naphthoquinonediazidesulfonylpyrazoles; 1- (4'-methylbenzenesulfonyl) imidazole, 1- (4'-
Nitrobenzenesulfonyl) imidazole, 1- (4 '
-Cyanobenzenesulfonyl) imidazole, 1-
(3'-nitrobenzenesulfonyl) imidazole, 1
-(Naphthalene-1'-sulfonyl) imidazole, 1
Arylsulfonylimidazoles such as-(naphthalene-2'-sulfonyl) imidazole; 1- (1 ', 2'
-Naphthoquinonediazide-4'-sulfonyl) imidazole photoreaction product, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) imidazole photoreaction product, 1- (1', 2'-naphtho Quinone diazide-6 '
-Sulfonyl) imidazole photoreaction product or the like 1 ′,
Photoreaction product of 2'-naphthoquinone diazide sulfonyl imidazoles; 1- (4'-methylbenzenesulfonyl) -1,2,4-triazole, 1- (4'-nitrobenzenesulfonyl) -1,2,4-triazole 1
-(4'-Cyanobenzenesulfonyl) -1,2,4-
Triazole, 1- (3'-nitrobenzenesulfonyl) -1,2,4-triazole, 1- (naphthalene-
1'-sulfonyl) -1,2,4-triazole, 1-
(Naphthalene-2'-sulfonyl) -1,2,4-triazole, 1- (4'-methylbenzenesulfonyl)-
3-nitro-1,2,4-triazole, 1- (4'-
Nitrobenzenesulfonyl) -3-nitro-1,2,4
-Triazole, 1- (4'-cyanobenzenesulfonyl) -3-nitro-1,2,4-triazole, 1-
(3'-Nitrobenzenesulfonyl) -3-nitro-
1,2,4-triazole, 1- (naphthalene-1'-
Arylsulfonyltriazoles such as sulfonyl) -3-nitro-1,2,4-triazole and 1- (naphthalene-2'-sulfonyl) -3-nitro-1,2,4-triazole; 1- (1 ', Photoreaction product of 2'-naphthoquinonediazide-4'-sulfonyl) -1,2,4-triazole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -1,2,4-triazole Photoreaction product of 1- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) -1,2,4-triazole photoreaction product, 1- (1', 2'-naphthoquinonediazide-4) ′ -Sulfonyl) -3-nitro-1,2,4-
Photoreaction product of triazole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -3-nitro-
Photoreaction product of 1,2,4-triazole, 1-
Photoreaction products of 1 ', 2'-naphthoquinonediazide sulfonyltriazoles such as photoreaction products of (1', 2'-naphthoquinonediazide-6'-sulfonyl) -3-nitro-1,2,4-triazole 1- (4'-methylbenzenesulfonyl) benzimidazole, 1- (4 '
-Nitrobenzenesulfonyl) benzimidazole, 1
-(4'-cyanobenzenesulfonyl) benzimidazole, 1- (3'-nitrobenzenesulfonyl) benzimidazole, 1- (naphthalene-1'-sulfonyl)
Benzimidazole, 1- (naphthalene-2'-sulfonyl) benzimidazole, 1- (4'-nitrobenzenesulfonyl) -5-nitrobenzimidazole, 1-
Arylsulfonylbenzimidazoles such as (4′-nitrobenzenesulfonyl) -2-methylbenzimidazole and 1- (4′-nitrobenzenesulfonyl) -2-phenylbenzimidazole; 1- (1 ′, 2′-naphthoquinonediazide-4) Photo-reaction product of'-sulfonyl) benzimidazole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) benzimidazole photo-reaction product, 1- (1', 2'-naphthoquinonediazide-6 Photoreaction products of 1 ', 2'-naphthoquinonediazide sulfonylbenzimidazoles such as photoreaction products of'-sulfonyl) benzimidazole; 1- (4'-methylbenzenesulfonyl) indazole, 1- (4'-
Arylsulfonylindazoles such as nitrobenzenesulfonyl) indazole; a photoreaction product of 1- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) indazole, 1- (1', 2'-naphthoquinonediazide-5'- Photoreaction products of 1 ', 2'-naphthoquinonediazide sulfonylindazoles such as sulfonyl) indazole photoreaction products; 1-methyl-3- (4'-methylbenzenesulfonyl) hydantoin, 1-methyl-3
Arylsulfonylhydantoins such as-(4'-nitrobenzenesulfonyl) hydantoin; 1-methyl-3
Photo-reaction product of-(1 ', 2'-naphthoquinonediazide-4'-sulfonyl) hydantoin, 1-methyl-3-
Photoreaction product of 1 ', 2'-naphthoquinonediazidesulfonylhydantoins such as photoreaction product of (1', 2'-naphthoquinonediazide-5'-sulfonyl) hydantoin; 1-methyl-4- (4'- Arylsulfonyl piperazines such as nitrobenzenesulfonyl) piperazine and 1-phenyl-4- (4'-nitrobenzenesulfonyl) piperazine; 1-methyl-4- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) piperazine light Photoreaction products of 1 ', 2'-naphthoquinonediazide sulfonylpiperazines such as reaction products and photoreaction products of 1-methyl-4- (1', 2'-naphthoquinonediazide-5'-sulfonyl) piperazine; 2- (4'-nitrobenzenesulfonyl) phthalimide, 2- (4'-nitrobenzenesulfonyl chloride ) -4-arylsulfonyl phthalimide such as nitro phthalimide; 2- (1 ', 2'-
Photoreaction products of naphthoquinonediazide-4'-sulfonyl) phthalimide, photoreaction products of 2- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) phthalimide, and 1', 2'-naphthoquinonediazidesulfonylphthalimide 2- (4′-nitrobenzenesulfonyl) -1-phthalazinone, 2- (4′-methylbenzenesulfonyl) -1-phthalazinone and other arylsulfonylphthalazinones; 2- (1 ′, 1'of the photoreaction product of 2'-naphthoquinonediazide-4'-sulfonyl) -1-phthalazinone, the photoreaction product of 2- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -1-phthalazinone, and the like. Photoreaction product of ', 2'-naphthoquinone diazide sulfonylphthalazinones; 2-methyl-
Arylsulfonylquinazolinones such as 3- (4'-nitrobenzenesulfonyl) -4-quinazolinone and 2-methyl-3- (4'-methylbenzenesulfonyl) -4-quinazolinone; 2-methyl-3- (1 ', 2 Photo-reaction product of'-naphthoquinonediazide-4'-sulfonyl) -4-quinazolinone, 2-methyl-3- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -4-quinazolinone Photoreaction products of 1 ', 2'-naphthoquinonediazide sulfonylquinazolinones such as; 2-
(4'-Nitrobenzenesulfonyl) -1-phenyl-
Arylsulfonylpyrazolidinones such as 3-pyrazolidinone and 2- (4'-methylbenzenesulfonyl) -1-phenyl-3-pyrazolidinone; 2- (1 ', 2'-
Naphthoquinonediazide-4'-sulfonyl) -1-phenyl-3-pyrazolidinone photoreaction product, 2-
(1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -1-phenyl-3-pyrazolidinone photoreaction product such as 1', 2'-naphthoquinonediazidosulfonylpyrazolidinone photoreaction product; N -(4'-Nitrobenzenesulfonyl) naphthosultam, N- (4'-methylbenzenesulfonyl) naphthosultam, and other arylsulfonyl naphthosultams; N- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) naphthosultam light Photoreaction products of 1 ', 2'-naphthoquinonediazidesulfonylnaphthosultams such as reaction products and photoreaction products of N- (1', 2'-naphthoquinonediazide-5'-sulfonyl) naphthosultam; 4- (4'-Nitrobenzenesulfonyl) morpholine, 4- (4'-methylbenzenesulfonyl) Arylsulfonyl morpholines such Ruhorin; 4- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) photoreaction product of morpholine, 4-
(1 ', 2'-naphthoquinonediazide-5'-sulfonyl) morpholine photoreaction products such as 1', 2'-naphthoquinonediazidesulfonylmorpholine photoreaction products. Incidentally, these general formula (I)
In the photoreaction product of the compound represented by, a carboxyl group is formed at the position of the quinonediazide group, and this is the same in the compounds represented by the following general formulas (III), (IV) and (V). Is.

Examples of the compound represented by the general formula (II) include 1- (1 ', 2'-naphthoquinonediazide-
4'-sulfonyl) pyrrole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) pyrrole, 1-
1 ', 2'-naphthoquinonediazidesulfonylpyrroles such as (1', 2'-naphthoquinonediazide-6'-sulfonyl) pyrrole; 1- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) piperidine, 1 −
1 ', 2'- such as (1', 2'-naphthoquinonediazide-5'-sulfonyl) piperidine and 1- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) piperidine
Naphthoquinonediazide sulfonylpiperidines; 1-
(1 ', 2'-naphthoquinonediazide-4'-sulfonyl) pyrrolidine, 1- (1', 2'-naphthoquinonediazide-5'-sulfonyl) pyrrolidine, 1- (1 ',
1 ', 2'-naphthoquinonediazidesulfonylpyrrolidines such as 2'-naphthoquinonediazide-6'-sulfonyl) pyrrolidine; 1- (1', 2'-naphthoquinonediazide-4'-sulfonyl) indole, 1- (1 ' ，
2'-naphthoquinonediazide-5'-sulfonyl) indole, 1- (1 ', 2'-naphthoquinonediazide-
1 ', 2'-naphthoquinonediazidesulfonylindoles such as 6'-sulfonyl) indole; 1- (1',
2'-naphthoquinonediazide-4'-sulfonyl) pyrazole, 1- (1 ', 2'-naphthoquinonediazide-
1 ', 2'-naphthoquinonediazidesulfonylpyrazoles such as 5'-sulfonyl) pyrazole and 1- (1', 2'-naphthoquinonediazide-6'-sulfonyl) pyrazole; 1- (1 ', 2'-naphthoquinonediazide −
4'-sulfonyl) imidazole, 1- (1 ', 2'-
Naphthoquinonediazide-5'-sulfonyl) imidazole, 1- (1 ', 2'-naphthoquinonediazide-6'-
1 ', 2'-naphthoquinonediazide sulfonylimidazoles such as sulfonyl) imidazole; 1- (1',
2'-naphthoquinonediazide-4'-sulfonyl)-
1,2,4-triazole, 1- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -1,2,4-triazole, 1- (1', 2'-naphthoquinonediazide-6'-sulfonyl) ) -1,2,4-triazole, 1
-(1 ', 2'-naphthoquinonediazide-4'-sulfonyl) -3-nitro-1,2,4-triazole, 1-
(1 ′, 2′-naphthoquinonediazide-5′-sulfonyl) -3-nitro-1,2,4-triazole, 1-
1 ', 2'-naphthoquinonediazidesulfonyltriazoles such as (1', 2'-naphthoquinonediazide-6'-sulfonyl) -3-nitro-1,2,4-triazole; 1- (1 ', 2'- Naphthoquinone diazide-
4'-sulfonyl) benzimidazole, 1- (1 ',
1 ', 2'-naphthoquinonediazidesulfonylbenzimidazoles such as 2'-naphthoquinonediazide-5'-sulfonyl) benzimidazole and 1- (1', 2'-naphthoquinonediazide-6'-sulfonyl) benzimidazole; 1- (1 ′, 2′-naphthoquinonediazide-4′-sulfonyl) indazole, 1- (1 ′,
2'-naphthoquinonediazide-5'-sulfonyl) indazole, 1- (1 ', 2'-naphthoquinonediazide-
1 ', 2'-naphthoquinonediazide sulfonylindazoles such as 6'-sulfonyl) indazole; 1-methyl-3- (1', 2'-naphthoquinonediazide-4'-
Sulfonyl) hydantoin, 1-methyl-3- (1 ',
1 ', 2'-naphthoquinonediazidesulfonylhydantoins such as 2'-naphthoquinonediazide-5'-sulfonyl) hydantoin and 1-methyl-3- (1', 2'-naphthoquinonediazide-6'-sulfonyl) hydantoin; 1 -Methyl-4- (1 ', 2'-naphthoquinonediazide-4'-sulfonyl) piperazine, 1-methyl-4- (1', 2'-naphthoquinonediazide-5'-sulfonyl) piperazine, 1-methyl-4 -(1 ', 2'
-Naphthoquinonediazide-6'-sulfonyl) piperazine and other 1 ', 2'-naphthoquinonediazidesulfonylpiperazines; 2- (1', 2'-naphthoquinonediazide-4'-sulfonyl) phthalimide, 2- (1 ', 2) ′
-Naphthoquinonediazide-5'-sulfonyl) phthalimide, 2- (1 ', 2'-naphthoquinonediazide-6'
-Sulfonyl) phthalimide and the like 1 ', 2'-naphthoquinonediazide sulfonylphthalimides; 2- (1',
2'-naphthoquinonediazide-4'-sulfonyl) -1
-Phthalazinone, 2- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -1-phthalazinone, 2-
(1 ′, 2′-naphthoquinonediazide-6′-sulfonyl) -1-phthalazinone and other 1 ′, 2′-naphthoquinonediazidesulfonylphthalazinones; 2-methyl-3-
(1 ', 2'-naphthoquinonediazide-4'-sulfonyl) -4-quinazolinone, 2-methyl-3- (1',
2'-naphthoquinonediazide-5'-sulfonyl) -4
-Quinazolinone, 2-methyl-3- (1 ', 2'-naphthoquinonediazide-6'-sulfonyl) -4-quinazolinone and other 1', 2'-naphthoquinonediazidesulfonylquinazolinones; 2- (1 ', 2'-Naphthoquinonediazide-4'-sulfonyl) -1-phenyl-3-pyrazolidinone, 2- (1 ', 2'-naphthoquinonediazide-
5'-sulfonyl) -1-phenyl-3-pyrazolidinone, 2- (1 ', 2'-naphthoquinonediazide-6'-
Sulfonyl) -1-phenyl-3-pyrazolidinone and other 1 ', 2'-naphthoquinonediazide sulfonylpyrazolidinones; N- (1', 2'-naphthoquinonediazide-
4'-sulfonyl) naphthosultam, N- (1 ', 2'
-Naphthoquinonediazide-5'-sulfonyl) naphthoultam, N- (1 ', 2'-naphthoquinonediazide-
6'-sulfonyl) naphthosultam and other 1 ', 2'-naphthoquinonediazidesulfonylnaphthoultams; 4-
(1 ', 2'-naphthoquinonediazide-4'-sulfonyl) morpholine, 4- (1', 2'-naphthoquinonediazide-5'-sulfonyl) morpholine, 4- (1 ',
2'-naphthoquinonediazide-6'-sulfonyl) morpholine and other 1 ', 2'-naphthoquinonediazidesulfonylmorpholines.

In the compound represented by the general formula (III), the aryl group and alkyl group of R ⁶ are substituted with one or more halogen atom, alkyl group, alkoxy group, nitro group or cyano group. Maybe,
Two or more kinds of these substituents can coexist. Examples of the compound represented by the general formula (III) include 7-hydroxycoumarin and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl. Condensates with chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, etc .; 4-hydroxycoumarin and 4- Methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide- - sulfonyl chloride, 1,2
-Naphthoquinonediazide-5-sulfonyl chloride,
Condensation product of 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; N-hydroxysuccinimide and 4-
Methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide Condensation product with -5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; 3-hydroxy-2-methyl-4-pyrone and 4-
Methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide Condensation product with -5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; 4-hydroxy-6-methyl-2-pyrone and 4-
Methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide Condensation product with -5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; α-pyrone natural dye having a hydroxyl group and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzene Sulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5 Condensation products with lufonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, etc .; γ-pyrone natural dye having a hydroxyl group and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene -1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, etc. A condensate of
2-Hydroxybenzimidazole and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-
Sulfonyl chloride, 1,2-naphthoquinonediazide-
Condensation product with 4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, etc .; 3-hydroxy-1,2,3-benzotriazine-4 (3H )
-One and 4-methylbenzenesulfonyl chloride, 4-
Nitrobenzenesulfonyl chloride, 4-cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2
-Naphthoquinonediazide-4-sulfonyl chloride,
Condensation product of 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; 1-hydroxybenzotriazole and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4- Cyanobenzenesulfonyl chloride, naphthalene-1-sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2
-Naphthoquinonediazide-5-sulfonyl chloride,
Condensation product with 1,2-naphthoquinonediazide-6-sulfonyl chloride and the like; 6-hydroxy-1,3-benzooxathiol-2-one and 4-methylbenzenesulfonyl chloride, 4-nitrobenzenesulfonyl chloride, 4
-Cyanobenzenesulfonyl chloride, naphthalene-1
-Sulfonyl chloride, naphthalene-2-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-
Examples thereof include condensates with sulfonyl chlorides and the like.

In the compound represented by the general formula (IV), the aryl group and alkyl group of R ⁷ may be substituted with one or more halogen atoms or hydroxyl groups, and the arylene group of Y, The alkylene group and alkenylene group may be substituted with one or more halogen atoms, hydroxyl groups, alkyl groups, nitro groups or cyano groups. Two or more kinds of the above-mentioned substituents in R ⁷ and Y can coexist. Examples of the compound represented by the general formula (IV) include N-methylolsaccharin, the following formula (IX),
Examples thereof include compounds represented by (X), (XI) or (XII), or photoreaction products of compounds represented by the formulas (IX) to (XII).

[Chemical 9] ,

[Chemical 10] ,

[Chemical 11] ,

[Chemical 12]

In the compound represented by the general formula (V), the aryl group and alkyl group of R ¹⁰ are substituted with one or more halogen atom, alkyl group, alkoxy group, nitro group or cyano group. Good. Also, R
Two or more kinds of the substituents for R ¹⁰ , R ¹¹ and R ¹² may coexist. Examples of the compound represented by the general formula (V) include 2-methylbenzenesulfonanilide and 3-
Methylbenzenesulfonanilide, 4-methylbenzenesulfonanilide, N- (4'-methylbenzenesulfonyl) -2-nitroaniline, N- (4'-methylbenzenesulfonyl) -3-nitroaniline, N- (4'-
Methylbenzenesulfonyl) -4-nitroaniline, N
-(4'-Methylbenzenesulfonyl) -3-cyanoaniline, N- (4'-methylbenzenesulfonyl) -4
-Cyanoaniline, N- (4'-methylbenzenesulfonyl) -3-methylaniline, N- (4'-methylbenzenesulfonyl) -4-methylaniline, N- (4'-
Methylbenzenesulfonyl) -3-chloroaniline, N
-(4'-methylbenzenesulfonyl) -4-fluoroaniline, N- (3'-nitrobenzenesulfonyl)-
3-nitroaniline, N- (3'-nitrobenzenesulfonyl) -4-nitroaniline, N- (4'-nitrobenzenesulfonyl) -3-nitroaniline, N- (4 '
-Nitrobenzenesulfonyl) -4-nitroaniline,
N- (3'-nitrobenzenesulfonyl) -3-cyanoaniline, N- (3'-nitrobenzenesulfonyl)-
4-cyanoaniline, N- (4'-nitrobenzenesulfonyl) -3-cyanoaniline, N- (4'-nitrobenzenesulfonyl) -4-cyanoaniline, N- (4 '
-Methylbenzenesulfonyl) -2-methoxyaniline, N- (4'-methylbenzenesulfonyl) -3-methoxyaniline, N- (4'-methylbenzenesulfonyl) -4-methoxyaniline, N- (4'-methyl Benzenesulfonyl) -N-methylaniline, N- (1 ',
2'-naphthoquinonediazide-4'-sulfonyl) aniline and its photoreaction product, N- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) aniline and its photoreaction product, N- (1', 2'-naphthoquinonediazide-4'-sulfonyl) -4-nitroaniline and its photoreaction product, N- (1 ', 2'-naphthoquinonediazide-5'-sulfonyl) -4-nitroaniline and its photoreaction product Compounds, aniline derivatives such as N- (4-methylbenzenesulfonyl) -2,4-dinitroaniline; N, N-dimethyl-4-methylbenzenesulfonamide, N, N-diethyl-4-methylbenzenesulfonamide, N, N-dimethyl-4-nitrobenzenesulfonamide, N, N-diethyl-4-nitrobenzenesulfonamide, N Hexyl -N- methyl-4-methylbenzenesulfonamide, N- hexyl -N- methyl -
4-Nitrobenzenesulfonamide, N, N-diethyl-1,2-naphthoquinonediazide-4-sulfonamide and its photoreaction product, N, N-diethyl-1,2-
N, N-dialkyl sulfonamides such as naphthoquinone diazide-5-sulfonamide and a photoreaction product thereof can be mentioned.

Of these components (b), preferred compounds are N-methylolsaccharin, N- (4'-nitrobenzenesulfonyl) -4-nitroaniline and N-.
(3'-nitrobenzenesulfonyl) -4-cyanoaniline, 1- (1 ', 2'-naphthoquinonediazide-5'
-Sulfonyl) -1,2,4-triazole, 1-
(1 ′, 2′-naphthoquinonediazide-5′-sulfonyl) pyrazole, N- (4′-nitrobenzenesulfonyl) imidazole, N- (4′-methylbenzenesulfonyl) imidazole, N- (naphthalene-2-sulfonyl) imidazole Etc.

The component (b) in the present invention has the general formula [I]
Each of the compounds represented by the formulas [V] to [V] can be used alone or in combination of two or more, and two or more compounds represented by the formulas can be used in combination. .

The amount of component (b) used in the present invention is
(A) It is usually 0.001 to 50 parts by weight, preferably 0.01 to 30 parts by weight, and more preferably 0.1 to 20 parts by weight per 100 parts by weight of the phenolic hydroxyl group-containing resin.
Parts by weight. If the amount of the component (b) used is less than 0.001 part by weight, the effect of the present invention is not sufficiently achieved, and if it exceeds 50 parts by weight, a residue remains in the unexposed portion after dry development, and the developability deteriorates. To do.

If desired, various additives may be added to the positive-type radiation-sensitive resin composition of the present invention. Examples of such an additive include a surfactant. The surfactant exhibits an action of improving the coating property of the composition of the present invention, striation, and the developability of the exposed area after the formation of a dry coating film. Examples of such a surfactant include polyoxyethylene lauryl ether,
Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic Polyflow No. which is an acid-based or methacrylic acid-based (co) polymer. 75, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), F-top E as a fluorine-based surfactant
F301, EF303, EF352 (above, manufactured by Shin-Akita Kasei), Megafac F171, F172, F173 (above, manufactured by Dainippon Ink), Florard FC430, FC4
31 (above, Sumitomo 3M), Asahi Guard AG7
10, Surflon S-382, SC-101, SC-1
02, SC-103, SC-104, SC-105, S
C-106 (above, manufactured by Asahi Glass) and the like can be mentioned. The blending amount of these surfactants is preferably 2 parts by weight or less, and more preferably 0.005 to 1 part by weight, per 100 parts by weight of the (a) phenolic hydroxyl group-containing resin.

Other additives include dyes and pigments, ultraviolet absorbers, etc., which have the effect of visualizing the latent image in the exposed area and reducing the effect of halation during exposure. Preferred dyes and pigments are trade names, for example, Neopengelb 075 (manufactured by Basuf), Neozavongelb 073.
(Same), Solvent Yellow 162, SOT Yellow 3
(Hodogaya Chemical Industry), Macrolex Yellow (Bayer), Hydroxyazobenzene, Kayalite B
(Manufactured by Nippon Kayaku), hydroxymethyl chalcone, oxaloyloxy chalcone and the like.

Further, a preferable ultraviolet absorber is, for example, 2
-(2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t-
Butylphenyl) -benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-t-butylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-amylphenyl) -5-benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -benzotriazole, 2-
(2'-Hydroxy-5'-t-butylphenyl) -benzotriazole, 2- (2'-hydroxy-5'-t
-Octylphenyl) -benzotriazole and the like.

Further, the composition of the present invention may optionally contain an adhesion aid, a storage stabilizer, an antifoaming agent and the like.

In use, the radiation-sensitive resin composition for dry development of the present invention is dissolved in a solvent so that the solid content concentration is usually 5 to 50% by weight, and then, for example, the pore size is 0.2.
It is prepared as a solution by filtering with a filter of about μm.

Examples of the solvent used for preparing the solution include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate,
Methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, acetonyl acetone, acetophenone, isophorone, benzyl ethyl ether, 1,2-dibutoxyethane, dihexyl ether, Caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, 1-decanol, benzyl alcohol, ethyl acetate, butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, benzyl acetate, benzyl benzoate,
Diethyl oxalate, dibutyl oxalate, diethyl malonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate,
Examples thereof include ethyl 3-ethoxypropionate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl phthalate, dibutyl phthalate, ethylene carbonate, propylene carbonate, γ-butyrolactone, and dimethylimidazolidinone. These solvents are used alone or in admixture of two or more.

When forming a resist film from the composition of the present invention, the solution prepared as described above is coated with, for example, a silicon wafer or aluminum by means such as spin coating, cast coating, or roll coating. It is applied on the substrate such as the wafer thus formed. Then, in order to remove the solvent, it is preheated to a temperature of, for example, 70 to 130 ° C. afterwards,
To form the pattern, the resist layer on the substrate is exposed to radiation through the mask only in selected areas. The radiation used is not particularly limited, and examples thereof include visible light, ultraviolet rays, far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Irradiation conditions such as radiation dose are appropriately selected according to the composition of the composition, the type of each additive, and the like.

In the radiation-sensitive resin composition for dry development of the present invention, 1,2-in the (c) 1,2-quinonediazidesulfonic acid ester component such as esterified resin and 1,2-quinonediazidesulfonic acid ester compound. The 1,2-quinonediazidesulfonyl group in the quinonediazidesulfonic acid ester bond is decomposed by exposure. After exposure, the resist film is preferably heated to about 120 to 200 ° C., so that 1,2-
The quinonediazidesulfonyl group and the phenolic hydroxyl group-containing resin react with each other, and the 1,2-quinonediazidesulfonyl groups react with each other to form a crosslinked structure in the molecular chain. On the other hand, in the exposed portion, most of the 1,2-quinonediazidesulfonyl group is decomposed, so that the formation of the crosslinked structure is extremely small as compared with the unexposed portion.

The resist layer which has undergone the treatment steps such as exposure and heating after exposure as described above is treated with a silylating agent such as HMDS or a gelmylating agent to selectively expose the exposed portion to the silylating agent. Alternatively, it reacts by absorbing a gel-milting agent, but the unexposed portion hardly absorbs the silylating agent or the gel-milting agent due to the formed cross-linking structure, and the reaction is strongly suppressed. ,
A negative latent image for dry etching is formed. As a result, the exposed area and the unexposed area differ in resistance to dry development, and a pattern is formed by dry development described later.

Examples of the silylating agent include tetrachlorosilane, trimethylylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, trimethylbromosilane, trimethyliodosilane, triphenylchlorosilane, hexamethyldisilazane, 1,1,3,3. -Tetramethyldisilazane, heptamethyldisilazane, hexaphenyldisilazane, 1,3-bis (chloromethyl)
-1,1,3,3-tetramethyldisilazane, N-trimethylsilylimidazole, N-trimethylsilylacetamide, N-trimethylsilyldimethylamine, N-
Trimethylsilyldiethylamine, hexamethylsilanediamine, N, O-bis (triethylsilyl) acetimide, N, N'-bis (trimethylsilyl) urea, N,
Examples thereof include N'-diphenyl-N- (trimethylsilyl) urea. These silylating agents may be used alone or in admixture of two or more.

Examples of the gel-milling agent include bis- (trimethylgermyl) -amine, bis- (dimethylgermyl) -amine, bis- (triethylgermyl) -amine, bis- (diethylgermyl). -Amine,
Trimethylchlorogermane, triethylchlorogermane, dimethyldichlorogermane, methyltrichlorogermane, tetrachlorogermane, N- (dimethylphenylgermyl) -dimethylamine, N- (trimethylgermyl) -dimethylamine, N- (trimethylgermyl) −
Diethylamine, N- (diethylphenylgermyl)-
Dimethylamine, N- (trimethylgermyl) -imidazole, N- (trimethylgermyl) -acetamide,
Trimethylcyanogermane, dimethylcyanogermane,
Examples thereof include triethyl cyanogermane and diethyl cyanogermane. These gelmylating agents can be used alone or in admixture of two or more.

The temperature of the treatment with the silylating agent or the gelmylating agent is selected according to the composition of the composition, the type of treating agent used, the treating time, etc., but the preferable treating temperature is 0 to 250 ° C. And more preferably 100 to
It is 200 ° C.

The resist film treated with the silylating agent or the gelmylating agent as described above is dry-developed by etching with, for example, anisotropic oxygen plasma to form a desired negative pattern.

The radiation-sensitive resin composition for dry development of the present invention can be used not only for pattern formation of ICs, LSIs and the like using a silicon wafer as a substrate, but also for silicon wafers, gallium / arsenic wafers, metal,
It can also be used for processing thin film heads using glass, cerax, etc. as substrates, liquid crystal display elements, image pickup elements, surface acoustic wave elements, etc., as well as parts such as minute coils and capacitors, parts for micromechanics and the like.

EXAMPLES The present invention will be described with reference to Examples and Comparative Examples below.
The present invention will be described in more detail with reference to these examples.
It is not limited to. Where the sensitivity of each resist
And Mw of each resin was measured as follows. Resist sensitivity Spinner dry resist on silicon wafer
After applying, hot at 120 ° C for 90 seconds
Preheated on the plate to form a resist with a film thickness of 1.5 μm
A film layer was formed. Then this resist film
Stepper (manufactured by Nikon Corporation, NSR1755i)
7A) and through the line pattern mask
Exposure is performed by changing the exposure amount depending on the location on the silicon wafer.
After that, the silylation device (UCB-JSR Electronic
Using PLASMASTER-Si manufactured by Susu Co., Ltd.
Firing in vacuum for 3 minutes at temperature (hereinafter referred to as "pre-silylation firing"
It's called "Naru". )did. Then, using the silylation device
The silicon wafer at the same temperature as the pre-silylation baking.
While performing the silylation treatment with HMDS vapor for 2 minutes
It was. Then, the silicon wafer after the silylation treatment is
Magnetron enhanced reactive ion etching system (UC
B-JSR Electronics, PLAMASTER
R-De) for 2 minutes and 30 seconds,
Zuma etching, dry development, resist pattern
Formed. The etching conditions at this time are as follows.
RF power: 1000 W, oxygen flow rate: 70 SCCM, pressure
Force: 4 mTorr After that, it is the same with a scanning electron microscope.
Design by measuring the width of the line pattern on the conwafer
A line pattern with a width of 0.5 μm is formed
The exposure amount for the exposed portion was defined as the sensitivity. Exposure dose
If it is less than this, the dimension of the resist pattern is smaller than the design width.
If it becomes thin and conversely there are many, the dimension of the resist pattern is designed.
It becomes thicker than the width.

Shape of resist pattern Using a scanning electron microscope, the lower side A and the upper side B of a rectangular section of a 0.5 μm resist pattern after development were measured, and 0.85 ≦ B / A ≦ 1. In this case, the pattern shape was judged to be good. However, even if B / A was within the above range, if the pattern had a hem, was overhanged, or had irregularities on the pattern surface, it was not considered as good. ..

Mw Mw is gel permeation chromatography (G
PC) method. The measurement conditions are as follows. Device: High-speed GPC device HLC-8 manufactured by Tosoh Corporation
02A, detector: RI, column: TSK-GEL, G400 manufactured by Tosoh Corporation
0H8, G3000H8, G2000H8 x 2, elution solvent: tetrahydrofuran (THF), flow rate: 1.2 ml / min, column temperature: 40 ° C, sample concentration: 0.02 g / 10 ml (THF
During).

Example 1 Production of Novolac Resin A flask equipped with a stirrer, a condenser and a thermometer was charged with m-
Cresol 303 g, p-cresol 130 g, 37 wt% formaldehyde aqueous solution 276 g and oxalic acid dihydrate 0.756 g were charged. Next, the flask was immersed in an oil bath with stirring, the liquid temperature was kept at 100 ° C., and the reaction was carried out for 2 hours. After the reaction, 500 g of water was added, and the mixture was stirred, allowed to stand for 2 minutes, and the treatment of removing the upper layer (water, unreacted cresol, unreacted formaldehyde, and oxalic acid) was repeated twice. Then, the oil bath temperature was raised to 180 ° C. and the mixture was stirred for 2 hours, and then the pressure in the flask was reduced to remove residual water, unreacted cresol, unreacted formaldehyde and oxalic acid. Next, the molten novolak resin was cooled to room temperature, and the solidified resin was recovered. The Mw of this novolak resin was 3,000.

Production of esterified novolac resin 100 g of the novolak resin obtained above, 36.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 77.6 g of water were added to 2300 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMA"). 8% by weight of triethylamine P.
A GMA solution (188.6 g) was added, and the mixture was reacted for 90 minutes while stirring. Thereafter, 14.92 ml of 1N hydrochloric acid was added and stirred for 20 minutes. Next, after adding 1000 g of water and stirring, the mixture was left to stand, separated into an aqueous layer and an organic layer, and subjected to a water washing treatment for discarding the water layer, and then the same water washing treatment was performed twice to leave the reaction solution in the reaction solution. Triethylamine and its hydrochloride and hydrochloric acid were removed. Then, PGMA and water were removed from the reaction solution under reduced pressure to partially 1,2-naphthoquinonediazide-5-sulfonate esterified resin (hereinafter referred to as "esterified novolak resin A") 1.
28 g was obtained.

Evaluation of resist sensitivity 20 g of esterified novolac resin A, 0.2 g of N-methylol saccharin, 0.6 g of neopengelp 075 (dye), 1 g of Kayalite B (dye), and 0.004 g of Megafac F172 (surfactant) were added. The solution dissolved in 58 g of PGMA was filtered with a membrane filter having a pore size of 0.2 μm to prepare a resist solution. With respect to this resist solution, the sensitivity of the resist was measured by the above-mentioned measurement method.
In C, it was 500 mJ / cm ² . The shape of the resist pattern was good.

Example 2 N-Methylolsaccharin was replaced with N- instead of 0.2 g.
A resist solution was prepared in the same manner as in Example 1 except that 1 g of (4′-nitrobenzenesulfonyl) -3-nitroaniline was used. The sensitivity of the resist measured on this resist solution is 140 ° C. at the silylation temperature.
In C, it was 400 mJ / cm ² , and the shape of the resist pattern was also good.

Example 3 N-Methylolsaccharin was replaced by N-in place of 0.2 g.
A resist solution was prepared in the same manner as in Example 1 except that 1 g of (3′-nitrobenzenesulfonyl) -3-nitroaniline was used. The sensitivity of the resist measured on this resist solution is 140 ° C. at the silylation temperature.
C was 300 mJ / cm ² , and the shape of the resist pattern was also good.

Example 4 N-Methylolsaccharin was replaced with N- instead of 0.2 g.
A resist solution was prepared in the same manner as in Example 1 except that 1 g of (3′-nitrobenzenesulfonyl) -3-cyanoaniline was used. The sensitivity of the resist measured on this resist solution is 140 ° C. at the silylation temperature.
In C, it was 450 mJ / cm ² , and the shape of the resist pattern was also good.

Example 5 N-methylol saccharin was replaced by N- instead of 0.2 g.
A resist solution was prepared in the same manner as in Example 1 except that 1 g of (1 ′, 2′-naphthoquinonediazide-5′-sulfonyl) aniline was used. The resist sensitivity measured for this resist solution was 600 mJ / cm ² at a silylation temperature of 140 ° C., and the shape of the resist pattern was also good.

Example 6 N-methylolsaccharin was replaced by N-in place of 0.2 g.
A resist solution was prepared in the same manner as in Example 1, except that 1 g of (1 ′, 2′-naphthoquinonediazide-4′-sulfonyl) -4-methylaniline was used.
The resist sensitivity measured for this resist solution is
It was 600 mJ / cm ² at the silylation temperature of 140 ° C., and the shape of the resist pattern was also good.

Example 7 20 g of esterified novolak resin A, 2 g of N- (4'-methylbenzenesulfonyl) -2-nitroaniline, 0.6 g of neopengelp 075 (dye), 0.004 g of Megafac F172 (surfactant) Was dissolved in 58 g of PGMA, and the solution was filtered through a membrane filter having a pore size of 0.2 μm to prepare a resist solution. The resist sensitivity measured for this resist solution was 500 mJ / c at a silylation temperature of 140 ° C.
m ² and the shape of the resist pattern was also good.

Example 8 2 g of N- (4'-methylbenzenesulfonyl) -3-nitroaniline was used instead of 2 g of N- (4'-methylbenzenesulfonyl) -2-nitroaniline.
A resist solution was prepared with the same components and method as in Example 7. The resist sensitivity measured for this resist solution was 400 mJ / c at a silylation temperature of 140 ° C.
m ² and the shape of the resist pattern was also good.

Example 9 N- (4'-methylbenzenesulfonyl) -2-nitroaniline was replaced with 2g of N- (4'-methylbenzenesulfonyl) -4-nitroaniline, except that 2g of N- (4'-methylbenzenesulfonyl) -4-nitroaniline was used.
A resist solution was prepared with the same components and method as in Example 7. The resist sensitivity measured for this resist solution was 300 mJ / c at a silylation temperature of 140 ° C.
m ² and the shape of the resist pattern was also good.

Example 10 N- (4'-methylbenzenesulfonyl) -2-nitroaniline was replaced with 2 g of N- (4'-methylbenzenesulfonyl) -3-chloroaniline, except that 2 g was used.
A resist solution was prepared with the same components and method as in Example 7. The resist sensitivity measured for this resist solution was 350 mJ / c at a silylation temperature of 140 ° C.
m ² and the shape of the resist pattern was also good.

Example 11 N- (4'-methylbenzenesulfonyl) -2-nitroaniline was replaced with 2 g of N- (4'-methylbenzenesulfonyl) -3-methylaniline, except that 2 g was used.
A resist solution was prepared with the same components and method as in Example 7. The resist sensitivity measured for this resist solution was 400 mJ / c at a silylation temperature of 140 ° C.
m ² and the shape of the resist pattern was also good.

Example 12 1-instead of 0.2 g of N-methylol saccharin
(4'-Methylbenzenesulfonyl) imidazole 1g
A resist solution was prepared by using the same components and method as in Example 1 except that was used. The resist sensitivity measured for this resist solution was 250 mJ / cm ² at a silylation temperature of 140 ° C., and the shape of the resist pattern was also good.

Example 13 1-instead of 0.2 g of N-methylolsaccharin
(3′-Nitrobenzenesulfonyl) imidazole 1 g
A resist solution was prepared by using the same components and method as in Example 1 except that was used. The resist sensitivity measured for this resist solution was 300 mJ / cm ² at a silylation temperature of 140 ° C., and the shape of the resist pattern was also good.

Example 14 Preparation of esterified styrene resin Poly (hydroxystyrene) resin 1 with Mw = 2,600
00g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 44g and water 77.6g, 2,300g
PGMA solution of 8% by weight of triethylamine was added, and the mixture was reacted for 90 minutes with stirring. Thereafter, 18 g of 1N hydrochloric acid was added, and the mixture was stirred for 20 minutes. Then, after adding 1,000 g of water and stirring, the mixture was left to stand to separate into an aqueous layer and an organic layer, and the water layer was discarded. The residual triethylamine and its hydrochloride and hydrochloric acid were removed. Thereafter, PGMA and water were removed from the reaction solution under reduced pressure, and the resin was partially esterified with 1,2-naphthoquinonediazide-5-sulfonate (hereinafter, referred to as “esterified styrene resin B”) 12.
5 g was obtained.

Evaluation of resist sensitivity Esterified styrene resin B 20 g, 1- (1,2-naphthoquinonediazide-4-sulfonyl) -1,2,4-triazole
A resist solution was prepared by filtering 0.6 g, Neopengelp 075 0.6 g, Kayalite B 1 g, and Megafac F172 0.004 g dissolved in PGMA 58 g through a membrane filter having a pore size of 0.2 μm. With respect to this resist solution, the sensitivity of the resist was measured by the above-mentioned measurement method.
In C, it was 430 mJ / cm ² . The shape of the resist pattern was also good.

Comparative Example 1 Example 1 except that N-methylol saccharin was not used.
A resist solution was prepared by using the same components and method as described above. With respect to this resist solution, no resist pattern was formed at an exposure dose of 1000 mJ / cm ² or less at a silylation temperature of 140 ° C.

Comparative Example 2 Using the resist solution of Comparative Example 1, a silylation temperature of 160
Silylation was performed at ° C, but no resist pattern was formed at an exposure dose of 1000 mJ / cm ² or less.

Comparative Example 3 N-methylol saccharin was replaced by 1,2-, instead of 0.2 g.
Naphthoquinonediazide-5-sulfonic acid (NQDS)
Treatment with the same components and method as in Example 1 was attempted except that 0.2 g was used, but 1,2-naphthoquinonediazide-5-sulfonic acid was not completely dissolved, and a resist solution was prepared. I couldn't.

Comparative Example 4 Esterified novolak resin A 20
g, 1,2-naphthoquinonediazide-5-sulfonic acid 0.
2 g 1,3-dimethyl-2-imidazolidone 0.
8 g Neopengelp 075 (dye) 0.
6g, Kayalite B (dye) 1
g, Megafac F172 (surfactant) 0.
A solution prepared by dissolving 004 g in 57 g of PGMA was filtered through a membrane filter having a pore size of 0.2 μm to prepare a resist solution. Using this resist solution, a silylation temperature of 140
Silylation was performed at ° C, but no resist pattern was formed at an exposure dose of 1000 mJ / cm ² or less.

Comparative Example 5 Using the resist solution of Comparative Example 4, a silylation temperature of 160 was used.
Silylation at ° C showed a sensitivity of 300 mJ / cm ²
Met.

Comparative Example 6 Using the resist solution of Comparative Example 4, a silylation temperature of 150 was used.
Silylation at ° C showed a sensitivity of 800 mJ / cm ²
And the surface of the resist pattern had irregularities.

As shown above, the radiation-sensitive resin composition of the present invention has a silylation temperature of 150 ° C. or lower.
By dry development, a resist pattern can be formed with high sensitivity, and the shape of the resist pattern is also good. On the other hand, the conventional resist has low sensitivity, requires silylation at a high temperature of 160 ° C. or higher in order to form a resist pattern, and the shape of the resist pattern is insufficient. The evaluation results for each example and comparative example are shown in Table 1-1 (Example 1) together with the main composition.
-10), Table 1-2 (Examples 11-14) and Table 2
(Comparative Examples 1 to 6) are collectively shown.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

The radiation-sensitive resin composition for dry development of the present invention has higher sensitivity and lower silylation temperature than conventional resists. Therefore, there is no risk of softening deformation of the resist layer during the silylation treatment, and a precise negative resist pattern having a good shape can be formed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Yanagihara 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A resin containing (a) a phenolic hydroxyl group and (b) the following general formulas (I), (II), (III), (IV) and
(C) 1,2 in a composition containing at least one compound selected from the group consisting of compounds represented by (V)
A radiation-sensitive resin composition for dry development, which comprises a quinonediazide sulfonic acid ester component. [Chemical 1] [In the general formula (I), R ¹ is one or more halogen atoms,
An alkyl group, an alkoxy group, an aryl group or an alkyl group which may be substituted with a nitro group or a cyano group, or the following general formula (VI), (VII) or (VIII) {general formula (VI), (VII) and In (VIII), R ² , R ³ , R
⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group, an amino group, a nitro group or a cyano group. } Represents a group formed by decomposition of a 1,2-naphthoquinonediazide group by the action of light or heat, and X ¹ is a non-ring group containing a nitrogen atom bonded to a sulfur atom of the general formula (I) as a ring-constituting atom. It represents a condensed ring or a condensed ring heterocyclic group. [Chemical 6] [Chemical 7] [Chemical 8] ] [Chemical 2] [In the general formula (II), D represents a 1,2-naphthoquinonediazide group represented by the general formula (VI), (VII) or (VIII), and X ² is bonded to a sulfur atom of the general formula (II). A heterocyclic group of a non-condensed ring or a condensed ring containing a nitrogen atom as a ring-constituting atom, wherein one nitrogen atom, 4 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 Heterocyclic group consisting of sulfur atom, two nitrogen atoms adjacent to each other and 3 to
A heterocyclic group consisting of 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, 1 or more carbon atoms,
A heterocyclic group consisting of two nitrogen atoms separated by an oxygen atom or a sulfur atom and 3 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms, and adjacent to each other. Selected from heterocyclic groups consisting of 3 to 6 nitrogen atoms, which may or may not be adjacent to each other, 2 to 10 carbon atoms, 0 to 3 oxygen atoms and 0 to 3 sulfur atoms. Represents a group. ] [Chemical 3] [In the general formula (III), R ⁶ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group, the general formula (VI), ( VII) or (VIII), a 1,2-naphthoquinonediazide group represented by
2 A naphthoquinonediazide group represents a group formed by decomposition by the action of light or heat, and X ³ represents a non-condensed ring or a condensed ring carbocyclic group or a heterocyclic group. ] [Chemical 4] [In the general formula (IV), R ⁷ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms or a hydroxyl group, -SR ⁸ (wherein R ⁸ represents an aryl group) or- SO ₂ -R ⁹ {wherein R ⁹ is an aryl group optionally substituted with a nitro group or a cyano group, 1,2naphthoquinonediazide represented by the above general formula (VI), (VII) or (VIII) Represents a group or a group formed by decomposing the 1,2-naphthoquinonediazide group by the action of light or heat. }, Y represents an arylene group which may be substituted with one or more halogen atoms, a hydroxyl group, an alkyl group, a nitro group or a cyano group, an alkylene group or an alkenylene group, and Z represents a single bond or an oxy group. ] [Chemical 5] [In the general formula (V), R ¹⁰ is an aryl group or an alkyl group which may be substituted with one or more halogen atoms, an alkyl group, an alkoxy group, a nitro group or a cyano group, the general formula (VI), ( VII) or (VIII), a 1,2-naphthoquinonediazide group represented by
2 Naphthoquinonediazide group represents a group formed by decomposition by the action of light or heat, R ¹¹ and R ¹² are independently of each other a hydrogen atom, an alkyl group or one or more halogen atoms, an alkyl group, an alkoxy group, Represents an aryl group which may be substituted with a nitro group or a cyano group, R ¹¹
At least one of R ¹² and R ¹² is a group other than a hydrogen atom. ]