JP3052292B2 - Radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a radiation-sensitive resin composition. More specifically, ultraviolet light, far ultraviolet light, X-ray, electron beam, molecular beam, γ-ray, synchrotron radiation, proton beam obtained by adding a compound having a specific structure to an alkali-soluble resin and a 1,2-quinonediazide compound. The present invention relates to a positive-type radiation-sensitive resin composition which is sensitive to radiation such as, for example, a resist suitable for producing an integrated circuit.

[0002]

2. Description of the Related Art Conventionally, resists used for fabricating integrated circuits include a negative type resist in which a bisazide compound is blended with a cyclized rubber, and a 1,2-type resist in an alkali-soluble resin.
A positive resist containing a 2-quinonediazide compound is known. In a negative resist, the bisazide compound desorbs nitrogen by ultraviolet irradiation to become nitrene,
Since the cyclized rubber is three-dimensionally cross-linked, a difference is caused in the solubility between the UV-irradiated portion and the non-irradiated portion in a developing solution comprising a solvent of the cyclized rubber, whereby patterning is performed. However, the crosslinking does not completely cure the UV-irradiated portion, so that the resist pattern has a large swelling in the developing solution, resulting in poor resolution of the resist pattern.

On the other hand, since a positive resist contains an alkali-soluble resin and an alkali-insoluble 1,2-quinonediazide compound, it hardly dissolves in a developing solution composed of an alkaline aqueous solution and hardly swells. That is, in the positive resist, the 1,2-quinonediazide compound in the UV-irradiated portion changes to indene carboxylic acid, and even when the resist is developed with a developing solution composed of an alkaline aqueous solution, the change in the UV-irradiated portion as a resist pattern is extremely small. Therefore, a resist pattern with high resolution that is faithful to the pattern of the mask
Is obtained. For this reason, in recent years, where high integration of integrated circuits is required, positive resists having excellent resolution are often used.

However, alkali-soluble resins and 1,1,
In the case of a positive resist prepared by dissolving a 2-quinonediazide compound in a solvent, if stored for a long period of time, the deterioration of the alkali-soluble resin and the deterioration of the 1,2-quinonediazide compound will gradually progress, causing a change in sensitivity, a change in viscosity of the resist solution, and the like. There is a problem that causes.

[0005]

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a positive-type radiation-sensitive resin excellent in storage stability against a change in sensitivity and a change in viscosity of a solution. It is to provide a composition.

[0006]

According to the present invention, the object and advantages of the present invention are as follows:
A radiation-sensitive resin composition containing a 2-quinonediazide compound, and having the following structural formulas (I) to (IV):

[0007]

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[0008] At least one compound having at least one compound in the molecule is contained, and the content of the compound is 0.001 to 100 parts by weight of the alkali-soluble resin.
It is achieved by a radiation-sensitive resin composition characterized by being 10 parts by weight.

The structural formulas (I) to (I) used in the present invention
As the compound having at least one kind of V) in the molecule, the following compounds can be mentioned as preferred examples.

Compounds having the structural formula (I) include, for example, 4-amino-2,2,6,6-tetramethylpiperidine,
4-dimethylamino-2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine, N-methyl-4-amino-2,2,6,6-
Tetramethylpiperidine, N-methyl-4-dimethylamino-2,2,6,6-tetramethylpiperidine, N-methyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 2- (3, Bis (1,2,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate
2,6,6-pentamethyl-4-piperidyl), Sumi
sorb LS-2000 (manufactured by Sumitomo Chemical Co., Ltd.), TI
NUVIN 144, TINUVIN 770, TIN
UVIN 622LD, CHIMASSORB 119
FL, CHIMASSORB 944LD, CHIMA
SSORB 944FL (manufactured by Ciba Gaiki), MAR
K LA-57, MARK LA-77, MARK L
A-62, MARK LA-67, MARK LA-6
3, MARK LA-68, MARK LA-82, M
Piperidine-based compounds such as ARK LA-87 (manufactured by Adeka Gas);

The compound having the structural formula (II) includes
For example, 2,2,5,5-tetramethylpyrrolidine-3-carboxamide, 2,2,5,5-tetramethylpyrrolidine-3-carboxylic acid, 3-cyano-2,2,5,5-tetramethylpyrrolidine, 1,2,2,5,5- pentamethyl-pyrrolidin-3-mosquito Rubokisamido, 1,2,2,5,5- pentamethyl-pyrrolidine-3-carboxylic acid, 3-cyano-1,
2,2,5,5-pentamethylpyrrolidine and the like.

As the compound having the structural formula (III), for example, 2,2,4-trimethyl-1,2-dihydroquinoline, 6
-Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-methyl-2,2,4-trimethyl-1,2
-Dihydroquinoline, N-methyl-6-methoxy-2,
2,4-trimethyl-1,2-dihydroquinoline and the like.

The compound having the structural formula (IV) includes
For example, 2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 6-ethoxy-2,2,4-trimethyl-1,2,
3,4-tetrahydroquinoline, N-methyl-2,2,4
-Trimethyl-1,2,3,4-tetrahydroquinoline,
N-methyl-6-ethoxy-2,2,4-trimethyl-
1,2,3,4-tetrahydroquinoline and the like.

Among these compounds, preferred compounds include, for example, TINUVIN 144, TINUVIN 622L
D, MARK LA-57, MARK LA-63, M
ARK LA-68, 4-hydroxy-2,2,6,6-
Tetramethylpiperidine, 2,2,4-trimethyl-1,
2-dihydroquinoline, 6-methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-2,
2,4-trimethyl-1,2,3,4-tetrahydroquinoline and the like.

These compounds can be used alone or in combination of two or more. The structural formulas (I) to
The use ratio of the compound having at least one kind of (IV) in the molecule is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the use ratio is less than 0.001 part by weight, the sensitivity and the storage stability with respect to the viscosity of the solution are deteriorated. If the use ratio exceeds 10 parts by weight, the resist performance such as sensitivity, remaining film ratio, and resolution is deteriorated. It is not preferable because it deteriorates.

As the alkali-soluble resin used in the present invention, for example, an alkali-soluble novolak resin (hereinafter, referred to as an alkali-soluble novolak resin)
Simply referred to as "novolak resin"). Novolak resins are obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

The phenols used at this time include:
For example, 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, 3,4-xylenol, 3,5-xylenol,
2,3,5-trimethylphenol, p-phenylphenol, hydroxynon, catechol, resorcinol,
Examples include 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, and gallic acid ester.

Of these phenols, phenol,
o-cresol, m-cresol, p-cresol,
2,3-xylenol, 2,5-xylenol, 3,4-
Xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A are preferred. These phenols are used alone or in combination of two or more.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetoaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde,
β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-
Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-
Examples include methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and the like.

Of these aldehydes, formaldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes can be used alone or in combination of two or more. The amount of the aldehyde used is preferably 0.7 per mole of the phenol.
モ ル 3 mol.

As the acid catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid and the like are used. The amount of these acid catalysts used is usually 1 × 10 5 per mole of phenols.
^{−4 to} 5 × 10 ⁻¹ mol.

In the condensation reaction, water is usually used as a reaction medium. However, when the phenols used in the condensation reaction do not dissolve in the aqueous solution of the aldehyde and become heterogeneous from the beginning of the reaction, A hydrophilic solvent can also be used as a reaction medium. Examples of the hydrophilic solution used in this case include methanol, ethanol, and propanol.
And alcohols such as butanol and cyclic ethers such as tetrahydrofuran and dioxane.
The use of these reaction media is usually 20 to 1000 parts by weight per 100 parts by weight of the reaction raw materials.

The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials.
00 ° C.

After completion of the condensation reaction, unreacted raw materials, acid catalyst and reaction medium present in the system are removed, and a novolak resin is recovered.

In the present invention, an alkali-soluble resin other than the novolak resin is used. Examples of such a resin include polyhydroxystyrene or a derivative thereof,
Styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing methacrylic resin and the like are used.

The weight average molecular weight in terms of polystyrene of the alkali-soluble resin used in the present invention (hereinafter referred to as “Mw”)
Is preferably 2,000 to 20,000, more preferably 3,000 to 15,000. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, and there is a tendency for developability and sensitivity to decrease.

These alkali-soluble resins can be used alone or in combination of two or more.

In the present invention, a phenol compound having a low molecular weight may be used as a dissolution promoter for the purpose of promoting the alkali solubility of the novolak resin.

As the low molecular weight phenol compound, a phenol compound having a benzene ring number of about 2 to 6 is suitable, and although not particularly limited, compounds represented by the following formulas 3 and 4 are exemplified. Can be.

[0030]

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[0031]

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(Wherein, R represents a hydrogen atom or a methyl group, a, b, c and d are each an integer of 0 to 3 (except when all are 0), and k, l , M,
And n are each an integer of 0 to 3. )

The amount of the low molecular weight phenol compound to be blended is usually preferably 50 parts by weight or less per 100 parts by weight of the novolak resin.

For the same purpose as described above, a low molecular weight alkali-soluble novolak resin or an alkali-soluble resole resin (hereinafter simply referred to as “resin (A)”) may be used as a dissolution accelerator. it can.

The resin (A) is obtained by condensation of phenols and aldehydes. As phenols, phenol used in the synthesis of the novolak resin
In addition to those exemplified above, 1-naphthol, 2-naphthol and the like can be used. As the aldehydes, those used in the synthesis of the resin (A) can be used. The amount of the aldehyde used is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the phenol. In addition, in this condensation, in addition to the acid catalyst used for the condensation of the novolak resin,
Alkaline catalysts can also be used.

The Mw of the resin (A) is usually 10,000
It is preferably the following, more preferably from 200 to 2,000, and particularly preferably from 300 to 1,000. Examples of such resin (A) include phenol / formaldehyde condensed novolak resin, m-cresol / formaldehyde condensed novolak resin, p-
Cresol / formaldehyde condensed novolak resin, o
Cresol / formaldehyde condensed novolak resin,
m-cresol / p-cresol / formaldehyde condensed novolak resin. Generally, the amount of the resin (A) is 100
It is 50 parts by weight or less per part by weight.

The 1,2-quinonediazide compound used in the present invention is not particularly limited. Such compounds include, for example, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, and 1,2-naphthoquinonediazide-5.
And 1,2-quinonediazidosulfonic acid esters such as sulfonic acid esters. Examples thereof include the following.

2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone,
3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 5,5'-tetramethyl-2 ", 4,
4'-trihydroxytriphenylmethane, 1,1,1-
Tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -4- [1- (4-hydroxyphenyl) -1-methylethyl] -1-phenylethane, 2,4,4- Trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan 1,1,3-tris (4-
(Hydroxyphenyl) butane, 1,1,3-tris (2,
1,2-benzoquinonediazide-4-sulfonic acid ester such as 5-dimethyl-4-hydroxyphenyl) propane, 1,2-naphthoquinonediazide-4-sulfonic acid ester, or 1,2-naphthoquinonediazide-5-sulfonic acid ester.

The hydrogen atoms of the hydroxyl groups of the resin (A) are converted to 1,2 at a ratio of, for example, 0.2 to 1 mol per hydrogen atom.
1,2-quinonediazidesulfonic acid ester substituted with a 2-naphthoquinonediazide-5-sulfonyl group.

These 1,2-quinonediazide compounds are used alone or as a mixture of two or more.

The amount of the 1,2-quinonediazide compound is usually 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. If the amount is too small, 1,2-
Since the quinonediazide compound absorbs radiation and generates a small amount of carboxylic acid, patterning becomes difficult. On the other hand, if it is too large, 1,2 may be added in short-time irradiation.
-All of the quinonediazide compound cannot be decomposed, and development with a developing solution composed of an alkaline aqueous solution becomes difficult.

In the present invention, the above-mentioned structural formula (I)
A compound having at least one of (IV) to (IV) in a molecule may be used in combination with a phenol-based or amine-based antioxidant. Such antioxidants include, for example, p-phenylphenol, 4,4'-dihydroxyphenyl, 2,5-di-t-amylhydroquinone, 4,4'-dihydroxydiphenylcyclohexane, 2,2'- Methylene bis (4-methyl-6-t-butylphenol),
2,6-di-tert-butyl-p-cresol, 4,4′-butylidene-bis (6-tert-butyl-m-cresol),
Octadecyl-3- (3 ', 5'-di-t-butyl-4-
(Hydroxyphenyl) -propionate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5
-T-butylanilide) -1,3,5-triazine, Nocrack NS-5 (manufactured by Ouchi Shinko Co., Ltd.), Sumilizer-GM
(Manufactured by Sumitomo Chemical Co., Ltd.) and the like, and phenylenediamine, diphenylamine, aldole-
α-naphthylamine, phenyl-α-naphthylamine,
Phenyl-β-naphthylamine, p, p′-dimethoxydiphenylamine, octylated diphenylamine, N, N′-diphenyl-p-phenylenediamine,
N, N′-di-β-naphthylmethyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine, N, N′-bis (1,4-
Dimethyl-pentyl) -p-phenylenediamine, N-
Phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N, N'-bis (1-methylheptyl)-
Examples include amine antioxidants such as p-phenylenediamine and N, N'-diallyl-p-phenylenediamine.

The use ratio of these antioxidants is usually 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the alkali-soluble resin.

The composition of the present invention may contain a sensitizer in order to improve the sensitivity as a resist. Examples of these sensitizers include 2H-pyrido [3,2-b] -1,4-oxazin-3 [4H] ones and 10H-pyrido [3,2-b] [1,4] -benzothiazine , Urasols, hydantoins, barbits
Examples thereof include carboxylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The compounding amount of these sensitizers is usually 50 parts by weight or less based on 100 parts by weight of the alkali-soluble resin.

A surfactant may be added to the composition of the present invention in order to improve coatability, for example, developability of a radiation-irradiated portion after formation of a striation or a dried coating film.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate,
F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, F173 (manufactured by Dainippon Ink), Florad FC430, FC431
(Manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC1
03, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid or methacrylic acid (co) polymer polyflow No. 75, No. 95 (Kyoeisha oils and fats) Chemical Industry Co., Ltd.). The amount of these surfactants is usually 2 parts by weight or less per 100 parts by weight of the solid content in the composition.

The composition of the present invention contains a dye or a pigment for visualizing a latent image in a radiation-irradiated portion or for reducing the influence of halation upon irradiation, and for improving adhesion. And an antifoaming agent, if necessary.

When the composition of the present invention is applied to a substrate, the alkali-soluble resin, the 1,2-quinonediazide compound, a compound having at least one of the structural formulas (I) to (IV) in a molecule, and Each compounding agent is dissolved in an appropriate solvent in a predetermined amount so as to have a concentration of, for example, 5 to 50% by weight.
A composition solution is prepared by filtering with
It is applied to a silicon wafer or the like by flow coating, roll coating, or the like. As the solvent used at this time, for example, ethylene glycol monomethyl ether, ethylene glycol
Lumonoethyl ether, methyl cellosolve acetate,
Ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol methyl ether acetate
G, propylene glycol propyl ether acetate
G, toluene, xylene, methyl ethyl ketone, cyclohexanone, ethyl 2-hydroxypropionate, 2-
Ethyl hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl oxyacetate, 2-hydroxy-3-
Methyl methylbutanoate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate, butyl acetate, and the like can be used. These organic solvents are used alone or in combination of two or more. If necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonano-
High-boiling solvents such as benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

As the developer of the composition of the present invention, for example, sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanol
Lamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, or pyrrol, piperidine, 1,8-diazabicyclo (5,
An alkaline aqueous solution obtained by dissolving (4,0) -7-undenecene, 1,5-diazabicyclo (4,3,0) -5-nonane and the like is used.

The developer may be used after adding an appropriate amount of a water-soluble organic solvent, for example, alcohols such as methanol and ethanol and a surfactant.

[0050]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited by these Examples.

Example 1 A flask was charged with 324 g (3 mol) of m-cresol,
244 g (2 mol) of 5-dimethylphenol, 770 g of a 37% by weight aqueous solution of formaldehyde and 0.8 g of oxalic acid
, The flask was immersed in an oil bath,
The reaction was carried out for 1 hour while maintaining the temperature at ℃ ° C., and then 324 g (3 mol) of m-cresol and 244 g (2 mol) of 3,5-dimethylphenol were continuously charged into the flask as the reaction proceeded. Reacted. Next, the temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure inside the flask was reduced to remove water, unreacted raw materials, and the like, and the novolak resin was recovered (hereinafter, this resin is referred to as “novolak resin A”).

100 parts by weight of the obtained novolak resin A,
1,1-bis (4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) -1-methylethyl] -1
25 parts by weight of a compound (C) obtained by condensing 2.5 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride in 1.0 mol of phenylethane, and a compound having the structural formula (I) in the molecule. 0.5 parts by weight of hydroxy-2,2,6,6-tetramethylpiperidine was dissolved in 291 parts by weight of ethyl lactate to prepare a solution of the radiation-sensitive resin composition.

After the composition solution was filtered through a filter having a pore size of 0.2 μm, the viscosity and sensitivity of the solution were measured. Further, after a part of the composition solution was sealed in a bottle and stored at 25 ° C. for 3 months, the viscosity and sensitivity of the solution were measured, and the rate of change was determined by the following formula 1. The results are shown in Table 1.

[0054]

(Equation 1)

The viscosity of the above solution was measured by E
It measured using the LD type viscometer. The sensitivity was measured by spin coating on a silicon wafer by a spinner in the usual manner, pre-baking at 90 ° C. for 2 minutes on a hot plate to form a 1.2 μm thick resist film, and then reducing the thickness. Exposure was performed using a projection exposure machine (Nikon Corporation, NSR-1505i6A, lens aperture coefficient: 0.45), a 2.4 wt% aqueous solution of tetramethylammonium hydroxide was used as a developing solution at 25 ° C. for 60 seconds, and then water was applied. After rinsing and drying, the obtained resist pattern was observed with a scanning electron microscope,
The measurement was performed by obtaining an exposure amount at which the line of the 2 μm pattern and the space became one-to-one.

Example 2 A flask was charged with 162 g (1.5 mol) of m-cresol.
468 g (6 mol) of p-cresol, 770 g of a 37% by weight aqueous solution of formaldehyde and 0.45 g of oxalic acid were charged, the flask was immersed in an oil bath, and the reaction was carried out for 1 hour while maintaining the internal temperature at 100 ° C. Cresol 27
0 g (2.5 mol) was continuously charged into the flask as the reaction proceeded, and reacted for 2 hours. Then set the oil bath temperature to 1
Raise to 80 ° C, and at the same time reduce the pressure inside the flask,
Water, unreacted raw materials and the like were removed, and the novolak resin was recovered (hereinafter, this resin is referred to as “novolak resin B”).

The resulting novolak resin B and TINUVIN 622LD having the structural formula (I) in the molecule
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that 0.1 part by weight (manufactured by Ciba Geigy Co., Ltd.) was used, and stored immediately after preparation and at 25 ° C. for 3 months as in Example 1. After this, the viscosity and the rate of change in sensitivity of the solution were determined. Table 1 shows the results
It was shown to.

Comparative Example 1 In Example 1, a compound having the structural formula (I) in the molecule
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that hydroxy-2,2,6,6-tetramethylpiperidine was not used.
The rate of change in viscosity and sensitivity of the solution after storage at 3 ° C. for 3 months was determined. The results are shown in Table 1.

Comparative Example 2 In Example 2, the TI having the structural formula (I) in the molecule was used.
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 2 except that NOVIN 622LD was not used, and the viscosity and sensitivity of the solution immediately after preparation and after storage at 25 ° C. for 3 months as in Example 1. Was determined. The results are shown in Table 1.

Examples 3 to 6 Novolak resins shown in Table 1, 1,2-quinonediazide compounds, structural formulas (I), (II), (III) and (I)
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the compound containing V) in the molecule and a solvent were used, and stored immediately after preparation and at 25 ° C. for 3 months as in Example 1. The rate of change in viscosity and sensitivity of the solution afterwards was determined.
The results are shown in Table 1.

Comparative Example 3 In Example 1, a compound having the structural formula (I) in the molecule
Instead of hydroxy-2,2,6,6-tetramethylpiperidine, a phenolic antioxidant, Sumilizer-
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that 2 parts by weight of GM (manufactured by Sumitomo Chemical Co., Ltd.) was used, and immediately after preparation and after storage at 25 ° C. for 3 months as in Example 1. Of the solution and the rate of change in sensitivity. The results are shown in Table 1.

Comparative Example 4 In Example 2, the TI having the structural formula (I) in the molecule was used.
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that 2 parts by weight of Nocrack NS-5 (manufactured by Ouchi Shinko Co., Ltd.), which is a phenolic antioxidant, was used instead of NEVIN 622LD. Immediately after preparation and 25 as in Example 1.
The rate of change in viscosity and sensitivity of the solution after storage at 3 ° C. for 3 months was determined. The results are shown in Table 1.

[0063]

[Table 1]

[0064]

According to the present invention, by adding a compound having a specific structure to a positive-type radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound, the sensitivity change and the solution Storage stability against a change in viscosity can be improved.

Continuation of the front page (72) Inventor Koji Yumoto 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-63-237053 (JP, A) JP-A-1 JP-A-154145 (JP, A) JP-A-63-218946 (JP, A) JP-A-62-121443 (JP, A) JP-A-53-102025 (JP, A) (58) Fields investigated (Int. .7, DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] 1. A radiation-sensitive resin composition comprising an alkali-soluble resin and a 1,2-quinonediazide compound, wherein the radiation-sensitive resin composition has the following structural formulas (I) to (IV): Wherein at least one compound having at least one type of structure in the molecule is contained, and the content of the compound is 0.001 to 10 parts by weight based on 100 parts by weight of the alkali-soluble resin. Radiation-sensitive resin composition.