JPS63237053A - Positive type radiation sensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having the excellent preservation stability which does not almost change the sensitivity and increase an impurity by incorporating a specified nitrogen-contg. compd. in the titled composition contg. an alkaline soluble resin and a 1,2-quinone diazide compd. CONSTITUTION:The titled composition comprises 100pts.wt. of the alkaline soluble resin, 5-100pts.wt. of the 1,2-quinone diazide compd., and 0.001-5pts.wt. of at least one kind of the nitrogen-contg. compd. selected from alkylamine, arylamine, aralkylamine and the nitrogen-contg. heterocyclic ring compd. The alkylamine of the usable nitrogen contg. compd. is exemplified by butylamine, etc. The nitrogen contg. heterocyclic ring compd. is preferably exemplified by triethanol amine, etc. The alkaline soluble resin is exemplified by an alkali soluble novolak resin, etc. Thus, the titled composition having the excellent preservation stability which does not almost change the sensitivity and increase the impurity even in case of preserving the titled composition for a long period and at a high temp. higher than a room temp. is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a positive radiation-sensitive resin composition, more specifically, a composition comprising an alkali-soluble resin, a 1,2-quinonediazide compound, and a specific nitrogen-containing compound. In particular, the present invention relates to a positive radiation-sensitive resin composition suitable as a resist for producing integrated circuits.

[Conventional technology]

Conventionally, resists used to fabricate integrated circuits include a negative resist in which a bisazide compound is blended with cyclized rubber, and a positive resist in which a 1,2-quinonediazide compound is blended in an alkali-soluble resin. ing. In a negative resist, the bisazide compound desorbs nitrogen and becomes nitrene when exposed to ultraviolet rays, and the cyclized rubber is three-dimensionally crosslinked. Therefore, the solubility of the ultraviolet irradiated areas and the non-irradiated areas in a developer consisting of a cyclized rubber solvent is There is a difference in
This results in patterning, but even though cross-linking does not mean that the UV irradiated portions are completely cured, there is a drawback that the resist pattern swells significantly in the developer and the resolution of the resist pattern is poor.

On the other hand, positive resists contain an alkali-insoluble 1,2-quinonediazide compound in an alkali-soluble resin, so they are difficult to dissolve in a developing solution consisting of an alkaline aqueous solution.
, does not swell at all. In other words, in a positive resist, the 1゜2-quinone diazide compound in the UV irradiated area changes to indene carboxylic acid, and even if it is developed with a developer consisting of an alkaline aqueous solution, there is extremely little change in the non-UV irradiated area that forms the resist pattern. , a resist pattern with high resolution can be obtained. For this reason, in recent years when integrated circuits are required to have a higher degree of integration, positive resists with excellent resolution are often used.

However, when a positive resist consisting of an alkali-soluble resin and a 1,2-quinonediazide compound is dissolved in a solvent and stored for a long period of time, the deterioration of the alkali-soluble resin and the deterioration of the 1,2-quinonediazide compound gradually progress, resulting in a change in sensitivity. , there are problems such as an increase in foreign matter. For example, even if no change in sensitivity or increase in foreign matter is observed at room temperature, a change in sensitivity or increase in foreign matter will be observed when stored at a higher temperature, and eventually a precipitate will form. Such changes in sensitivity and the generation of foreign matter have a large effect on resist performance such as resolution, sensitivity, and developability, and cause a deterioration in yield during the production of integrated circuits.

[Problems to be Solved by the Invention] An object of the present invention is to solve the problems of the prior art described above, and to provide storage with almost no change in sensitivity or increase in foreign substances even when stored for a long period of time or at a temperature higher than room temperature. An object of the present invention is to provide a positive radiation-sensitive resin composition with excellent stability.

[Means for solving problems]

The present invention includes 100 parts by weight of an alkali-soluble resin and 1.2 parts by weight of an alkali-soluble resin.
- containing 5 to 100 parts by weight of a quinonediazide compound and 0.001 to 5 parts by weight of at least one nitrogen-containing compound selected from alkylamines, arylamines, aralkylamines, and nitrogen-containing heterocyclic compounds; do.

In addition, the present invention can be applied to ultraviolet rays, deep ultraviolet rays, X-rays, electron beams,
It is a positive radiation-sensitive resin composition that is sensitive to radiation such as molecular beams, gamma rays, synchrotron radiation, and proton beams.

In addition, the said alkylamine, arylamine, and aralkylamine may have a substituent.

Examples of the alkylamine which is a nitrogen-containing compound used in the present invention include butylamine, amylamine, 2-aminoheptane, cetylamine, cyclohexylamine,
2-chlorocyclohexylamine, 4-aminodecalin, β-cyclohexylethylamine, monoethanolamine, 2-amino-1-hexanol, γ-methoxypropylamine, methyl β-aminopropionate, β-aminopropionitrile, methylbutylamine , ethylcyclohexylamine, diallylamine, dibenzylamine, triethylamine, tripropylamine, dimethylcyclohexylamine, dimethylfurfurylamine, triethanolamine, tributylamine, dodecyldimethylamine, ethylenediamine, tetramethylenediamine, tetramethylethylenediamine, dodecamethylenediamine, 1,4-diaminocyclohexane, triethylenediamine, diethylenetriamine, triethylenetetramine, etc.; examples of the arylamine include aniline,
N-methylaniline, dimethylaniline, toluidine,
2-naphthylamine, 2-7 minobiphenyl, 0-chloroaniline, p-bromoaniline, m-fluoroaniline, N,N-dimethyl-p-iodoaniline, 0-aminephenol, 2-anilinoethanol, 4-7 minnow 1-naphthol, aminonaphthalene, m-aminoanisole, 2-aminodiphenyl ether, m-aminopropiophenone, 2-aminobenzophenone, methyl 0-aminobenzoate, m-aminobenzonitrile, methyldiphenylamine, 1-liphenylamine , N-phenylbenzylamine, 0-phenylenediamine, m-xylylenediamine, N,N'-bistryl-p-phenylenediamine, N,N'-bis(dimethylphenyl)-p-
phenylenediamine, triaminobenzene, etc.; examples of aralkylamines include benzylamine, m-tolylbenzylamine, dibenzylamine, p-chlorobenzylamine, etc.

Furthermore, examples of nitrogen-containing heterocyclic compounds include pyrrole,
Indole, 2-phenylpyrrole, 2-bromopyrrole, pyridine, 2-ethylpyridine, 2-phenylpyridine, 2-chloropyridine, piperidine, morpholine, N-ethylmorpholine, quinoline, 2-methylquinoline, pyrimidine, pyrazine , pyridazine, pyrazole, melamine and the like.

Among these, preferable compounds include triethanolamine, triethylamine, tributylamine,
Ethylenediamine, tetramethylethylenediamine, butylamine, cetylamine, dodecyldimethylamine,
Alkylamines such as jetanolamine; aralkylamines such as hensylamine; and nitrogen-containing heterocyclic compounds such as morpholine, N-ethylmorpholine, and piperidine.

These nitrogen-containing compounds can be used alone or in combination of two or more.

The amount of the nitrogen-containing compound used is 10% of the alkali-soluble resin.
0.001 to 5 parts by weight, preferably 0.001 to 5 parts by weight.
002 to 1 part by weight, particularly preferably 0°002 to 0.5
Parts by weight. If the amount used is less than 0.001 parts by weight, there will be little effect on suppressing changes in sensitivity or increase in foreign matter, and if the amount used exceeds 5 parts by weight, sensitivity, residual film rate,
This is not preferable because it deteriorates resist performance such as resolution and developability.

Examples of the alkali-soluble resin used in the present invention include alkali-soluble novolak resin (hereinafter simply referred to as "novolak resin"). Novolac resins are obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

The phenols used in this case include, for example, phenol, O-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-cresol,
-Ethylphenol, 0-butylphenol, m-butylphenol, p-butylphenol.

Thylphenol, 2.3-xylenol, 2,4-xylenol, 2.5-xylenol, 3,4-xylenol, 3.5-xylenol, 2,3゜5-trimethylphenol, p-phenylphenol, hydroxynon,
Catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A
Examples include 1-dihydroxybenzoic acid ester and gallic acid ester. Among these phenols, phenol, 0-cresol, m-cresol, p-cresol,
2,5-xylenol, 3,5-xylenol-)'v, 2
, 3.5-) lyntylphenol, resorcinol, 2
- Methylresorcinol and bisphenol A are preferred. These phenols may be used alone or in combination of two or more.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, O-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, O-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde,
o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, 0-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p
-n-butylbenzaldehyde and the like, and among these aldehydes, formaldehyde, acetaldehyde and benzaldehyde are preferred. These aldehydes can be used alone or in combination of two or more. The amount of aldehydes used is preferably 0.7 to 3 moles per mole of phenols.

As the acid catalyst, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid are used. The amount of these acid catalysts used is usually 1X10-4 to 5X10-1 mole per mole of phenol.

In condensation reactions, water is usually used as the reaction medium, but if the phenols used in the condensation reaction do not dissolve in the aqueous solution of aldehydes and the reaction becomes a heterogeneous system from the beginning, a hydrophilic solvent may be used as the reaction medium. You can also use Examples of the hydrophilic solvent used in this case include alcohols such as methanol, ethanol, propatool, and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 parts by weight per 100 parts by weight of the reaction raw materials.
~1000ii 1 part.

The reaction temperature of the condensation reaction can be adjusted as appropriate depending on the reactivity of the reaction raw materials, but is usually 10 to 200°C.

After the condensation reaction is completed, the unreacted raw materials, acid catalyst, and reaction medium present in the system are removed, and the novolac resin is recovered.

Examples of alkali-soluble resins other than novolak resins used in the present invention include polyhydroxystyrene or derivatives thereof, styrene-maleic anhydride copolymers, polyvinylhydroxybenzoate, carboxyl group-containing methacrylic resins, and the like.

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

Examples of the 1,2-quinonediazide compound used in the present invention include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-
Sulfonic acid ester, 1゜2-naphthoquinone diazide
Examples include 5-sulfonic acid ester. Specifically, p
-Cresol-1,2-benzoquinonediazide-4-sulfonic acid ester, resorcinol-1,2-naphthoquinonediazide-4-sulfonic acid ester, pyrogallol-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. ) 1,2-quinonediazide sulfonic acid esters of hydroxybenzene, 2,4-dihydroxyphenyl-propyl ketone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,4-dihydroxyphenyl-n-hexyl ketone-1 , 2-naphthoquinonediazide-4-sulfonic acid ester, 2.4-dihydroxybenzophenone-1,2-naphthoquinonediazide-5-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, 2.3.4-)dihydroxybenzophenone-1,2-naphthoquinonediazide- 5-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,z--j phthoquinonediazide-5-sulfonic acid ester, 2,3,4.4'-tetrahydroxybenzophenone-1,2- Naphthoquinone diazide-5-sulfonic acid ester, 2.2'.

4.41-tetrahydroxybenzophenone-1゜2-
naphthoquinonediazide-4-sulfonic acid ester, 2,
3.4.4'-tetrahydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
2,2°,3,4.6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2.2',3,4.6'-pentahydroxybenzophenone-1,2-naphtho Quinonediazide-5-
Sulfonic acid ester, 2.3.3', 4.4'.

5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2.3.
3',4.4',5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2.3',4°4',5',6-hexahydroxybenzophenone -1,2-naphthoquinonediazide-
4-sulfonic acid ester, 2.3", 4.4', 5',
(Poly) such as 6-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester
1,2-quinonediazide sulfonic acid esters of hydroxyphenylalkyl ketone or (poly)hydroxyphenylaryl ketone, bis(p-hydroxyphenyl)methane-1,2-nafdoquinonediazide-4-sulfonic acid ester, bis(2, 4-dihydroxyphenyl)methane 1,2-naphthoquinonediazide-5-sulfonic acid ester, bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2- Bis(p-hydroxyphenyl)propane-1,2--1-phthoquinonediazide 4-sulfonic acid ester, 2,2-bis(2,4-dihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfone acid ester, 2,2-bis(2,
3,4-trihydroxyphenyl)propane-1,2-
1,2- of bis[(poly)hydroxyphenyl coalkanes such as naphthoquinonediazide-5-sulfonic acid ester
Quinonediazide sulfonic acid esters, 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-naphthoquinone diazide
5-sulfonic acid ester, 3,4.5-1-lyhydroxybenzoic acid phenyl-1,2-naphthoquinone diazide
1゜2-quinonediazide sulfonic acid esters of (poly)hydroxybenzoic acid alkyl esters or (poly)hydroxybenzoic acid child esters such as 5-sulfonic acid esters, bis(2,5-dihydroxybenzoyl)
Methane-1゜2-naphthoquinonediazide-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
-)dihydroxybenzoyl)benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-bis(2,4,6-)dihydroxybenzoyl)benzene-
1,2-quinonediazide sulfonic acid esters of bis[(poly)hydroxybenzoyl coalkane or bis[(poly)hydroxybenzoyl]benzene such as 1,2-naphthoquinonediazide-5-sulfonic acid ester, ethylene glycol di(3, 5-dihydroxybenzoate)-1,2-naphthoquinonediazide-5-sulfonic acid ester, polyethylene glycol di(3°4.5-
Examples include 1,2-quinonediazide sulfonic acid esters of (poly)ethylene glycol [(poly)hydroxybenzoate] such as 1-dihydroxybenzoate)-1,2-naphthoquinonediazide-5-sulfonic acid ester. In addition to these compounds, "Light-3-enhancing Systems" by J. Kosar,
"339-352 (1965), John Wi
fey & 5ons (New York) and W.

“Photoresist” 5 by S. DeForest
0. (1975), McGraw-Hi 11, In
1 and 2 published in c, (New York)
-Quinonediazide compounds can also be used.

These 1,2-quinonediazide compounds may be used alone or in combination of two or more.

The blending amount of these 1,2-quinonediazide compounds is 100! 5 to 1 for it part
00 parts by weight, preferably 10 to 50 parts by weight.

If this amount is too small, the amount of carboxylic acid generated by the 1,2-quinonediazide compound after absorbing radiation is small, making patterning difficult; on the other hand, if it is too large,
A short period of radiation irradiation cannot completely decompose the added 1,2-quinonediazide compound, making development with a developer consisting of an alkaline aqueous solution difficult.

The composition of the present invention can also be used in combination with a storage stability improver for ordinary positive radiation-sensitive resin compositions. Examples of these storage stability improvers include p-phenylphenol, 4,4'-dihydroxydiphenyl, 2,5-
Di-t-amylhydroquinone, 4,4'-dihydroxydiphenylcyclohexane, 2,2'-methylenebis(
4-methyl-6-t-butylphenol), 2.6-di-L-butyl-p-cresol, 4.4'-butylidene-bis(6-t-butyl-m-cresol), 2.6-
t-Butyl-4-octadecanylpropionittaphenol, 2,4-bis(n-octylthio')-6-(4
-hydroxy-3,5-t-butylanilide)-1,3
, 5-triazine, and other known sulfur-containing anti-aging agents.

The usage ratio of these storage stability improvers is usually 10 parts by weight or less, preferably 0.01 to 5 parts by weight, based on 100 M parts of the alkali-soluble resin.

A sensitizer can also be added to the composition of the present invention in order to improve the sensitivity as a resist. Examples of these sensitizers include 2H-pyridoC3,2-b]-1
, 4-oxazin-3[4H]ones, 10H-pyrido(3,2-b) (1゜4)-benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazole kind,
Alloxanes, maleimides, and also
Examples thereof include sensitizers described in Japanese Patent Publication No. 242, Japanese Patent Publication No. 48-35402, Japanese Patent Application Laid-open No. 58-37641, and Japanese Patent Application Publication No. 149042-1984. The blending amount of these sensitizers is as follows: 1,2-quinonediazide compound 1
The amount is usually 100 parts by weight or less, preferably 4 to 60 parts by weight.

The composition of the present invention may also contain a surfactant in order to improve the coating properties, for example, the striations and the developability of the radiation irradiated area after forming a dry coating film. Examples of surfactants include polyoxyethylene lauryl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkyl phenol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate, etc. Nonionic surfactants of polyethylene glycol dialkyl ethers, FTOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Mega Fasoku F171, F173 (manufactured by Dainippon Ink Co., Ltd.), as exemplified in JP-A-57-178242. Linear fluorosurfactants having a fluorinated alkyl group or perfluoroalkyl group, Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, 5C10
1,5C102,5CIO3,5C104,5C105
, 5C106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants,
Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid type or methacrylic acid type (both)
Polymer Polyflow No. 75, No. 95 (
(manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), etc. The blending amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the total amount of the alkali-soluble resin and 1,2-quinonediazide compound in the composition.

The composition of the present invention also contains a coloring agent to visualize the latent image of the radiation irradiated area and to reduce the effect of halation during radiation irradiation, and an adhesion aid to improve adhesiveness. Furthermore, an antifoaming agent or the like can be added as necessary.

When applying the composition of the present invention to a substrate, the alkali-soluble resin, the 1,2-quinonediazide compound,
The nitrogen-containing compound and various compounding agents may be added at a concentration of, for example, 5.
A composition solution is prepared by dissolving a predetermined amount in an appropriate solvent so that the concentration is ~50% by weight, and filtering it through a filter with a pore size of about 0.2 μm, for example, and spin coating, flow coating,
Coat onto a silicon wafer, etc. by roll coating or the like. Examples of the solvent used in this case include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate, methyl 2-oxypropionate, 2-
Examples include monooxymonocarboxylic acid esters such as ethyl oxypropionate, aromatic hydrocarbons such as 1-toluene and xylene, ketones such as methyl ethyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate. These solvents may be used alone or in combination of two or more. Also, as necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol 7-methyl ether, diethylene glycol 7-methyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octatool, 1-nonanol, benzyl alcohol, benzyl acetate, benzoic acid. High boiling point solvents such as ethyl acid, diethyl oxalate, diethyl maleate, T-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

Examples of the developer for the composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide , tetraethylammonium hydroxide, quaternary ammonium salts such as choline, or pyrrole, piperidine, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4,3,0)- An alkaline aqueous solution prepared by dissolving a cyclic amine such as 5-nonane is used.

Further, a water-soluble organic solvent, such as alcohols such as methanol and ethanol, or a surfactant may be added to the developer in an appropriate amount.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way.

(A) In a synthetic flask of novolac resin A, 324 g (3 mol) of m-cresol was added, 3.
244 g (2 mol) of 5-dimethylphenol, 770 g of a 37% by weight formaldehyde aqueous solution, and 0.5 g of oxalic acid.
After charging 8g, immerse the flask in an oil bath and lower the internal temperature to 1.
React for 1 hour while maintaining at 00°C, then further m
As the reaction progressed, 324 g (3 moles) of -cresol and 244 g (2 moles) of 3,5-dimethylphenol were continuously charged into the flask and allowed to react for 2 hours. Next, the oil bath temperature was raised to 180°C, and at the same time the pressure inside the flask was reduced to remove water, unreacted formaldehyde, m-cresol, 3,5-dimethylphenol, oxalic acid, etc., and recover Novolanc resin (hereinafter referred to as , this resin is referred to as "novolak resin A").

(B) In a synthetic flask of novolac resin B, 162 g (1.5 mol) of m-cresol,
468 g (6 mol) of p-cresol, 770 g of 37% by weight formaldehyde aqueous solution and 0.45 g of oxalic acid
was charged, the flask was immersed in an oil bath, and reacted for 1 hour while maintaining the internal temperature at 100°C. After that, 270 g (2.5 mol) of m-cresol was continuously added to the flask as the reaction progressed, and the reaction took place for 42 hours. I let it happen. Next, the oil bath temperature was raised to 180°C, and at the same time the pressure inside the flask was reduced to remove water, unreacted formaldehyde, m-cresol and p-cresol, oxalic acid, etc., and recover the novolac resin. (referred to as "Novolac Resin B").

Example 1 100 parts by weight of novolak resin A in a flask, 2°3.4
．． 4'-tetrahydroxybenzophenone (TEH
29 parts by weight of a compound prepared by condensing 1.2-naphthoquinonediazide-5-sulfonyl chloride (NQD) with an average of 2.5 moles in B), 0.005 [1 part of triethylamine] and 320 parts by weight of ethyl cellosolve acetate were added, and the mixture was stirred. and dissolved. The solution was then filtered through a membrane filter with a pore size of 0.2 μm to obtain a positive radiation-sensitive resin composition solution.

Regarding the composition solution immediately after preparation, the particle size in the solution is 0.
．． The number of fine particles of 5 μm or more and the sensitivity when used as a positive resist were measured.

Moreover, after storing this composition solution at 30°C for 2 months,
The number of fine particles with a particle size of 0.5 μm or more in the solution and the sensitivity when used as a positive resist were measured, and the rate of change in sensitivity was determined.

The number of particles mentioned above was measured using an automatic particle counter manufactured by HI AC/ROYCO.

In addition, the sensitivity was determined by applying the composition solution onto a silicon wafer using a spinner, and then using a real plate at 90°C for 2 hours.
A resist layer with a thickness of 1.2 μm was formed by bre-baking for 1 minute, then exposed using a stepper, developed for 60 seconds using a 2.4% by weight aqueous solution of tetramethylammonium hydroxide as a developer, rinsed with water, dried, and then exposed to light using a stepper. , the obtained resist pattern was observed with a scanning electron microscope,
The measurement was carried out by determining the exposure amount at which the lines and spaces of the 2 μm pattern were 1:1.

Comparative Example 1 In Example 1, triethylamine o, o o s
A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that no part by weight was added, and measurements were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 2 A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 1 except that novolac resin B was used instead of novolac resin in Example 1, and the solution was prepared in the same manner as in Example 1. Measurements were made. The results are shown in Table 1.

Comparative Example 2 A positive radiation-sensitive resin composition solution was prepared in the same manner as in Example 2, except that 0.005 parts by weight of triethylamine was not added, and measurements were performed in the same manner as in Example 1. . The results are shown in Table 1.

Examples 3 to 10 In Examples 1 and 2, positive type was used in the same manner as in Examples 1 and 2, except that triethylamine was replaced with the nitrogen-containing compound shown in Table 1, and the amount used was changed to the amount shown in Table 1. A radiation-sensitive resin composition solution was prepared and measured in the same manner as in Examples 1 and 2. The results are shown in Table 1.

Examples 11 to 15 In Example 2, the 1,2-quinonediazide compound Cb:2' shown in Table 1 was used as the 1,2-quinonediazide compound.
3.4-) Condensate of 1 mol of lyhydroxybenzophenone (THB) and 2.2 mol of 1,2°-naphthoquinonediazide-5-sulfonyl chloride (NQD), c: THB
Condensate of 1 mol and 3 mol of NQD, d: TEHB
A positive type was prepared in the same manner as in Example 2, except that the amount used was changed to the amount shown in Table 1, and the nitrogen-containing compound was replaced with tripropylamine. A radiation-sensitive resin composition solution was prepared, and measurements were performed in the same manner as in Example 2. The results are shown in Table 1.

Comparative Example 3 A positive test was carried out in the same manner as in Example 1 except that 2,6-di-t-butyl-p-cresol o, o o s parts by weight was used instead of 0.0 parts by weight of triethylamine. A radiation-sensitive resin composition solution was prepared, and measurements were carried out in the same manner as in Example 1. The results are shown in Table 1.

Margin below (Effects of the Invention) According to the present invention, by adding a specific nitrogen compound to a positive radiation-sensitive resin composition containing an alkali-soluble resin and a 1,2-quinonediazide compound, changes in sensitivity and foreign substances can be prevented. It is possible to obtain a composition having excellent storage stability with almost no increase in .

Agent Patent Attorney Takeshi Kawakita Long Procedural Amendment Commissioner of the Patent Office Black 1) Mr. Akio 1. Indication of the Case 1988 Patent Application No. 72665 2. Title of Invention Positive Radiation Sensitive Resin Composition 3. Amendment Relationship with the case of a person who does
(417) Yoshimitsu, Representative of Japan Synthetic Rubber Co., Ltd.
Ku4, Agent 103 Address: 11-8, Kayabacho, Nihonbashi, Chuo-ku, Tokyo.

5. Date of amendment order Voluntary 6. Subject of amendment Column 7, Detailed explanation of the invention in the specification, Contents of amendment (1) After "pyrazine," in the second line of page 7 of the specification.
Add piperazine.

(2) “Jetanolamine” on page 7, line 8 of the specification
After that add ", tripropylamine, monoethanolamine".

(3) On page 11, line 12 of the specification, add "1,2-quinonediazide novolac resin" after "for example, as a potash-soluble resin."

(4) Add "glycol ether esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate" after "cellosolve esters such as acetate" on the second line from the bottom of page 22 of the specification.

(5) "29 parts by weight of compound" on the 6th line from the bottom of page 26 of the specification has been changed to "29 parts by weight of compound a j.

(6) rHrAc/ROYC on page 27, line 9 of the specification
' was changed to 'HIACROYCJ.

(7) "2" on page 29, line 9 and line 10 of the specification
'' are respectively changed to '2J.

(8) ``2.2 mol'' on page 29, line 12 of the specification, ``3 mol'' on line 133, and ``2.6 mol'' on line 144 of the specification, each with an average of 2.2 mol.'' , "Average 3 moles", "
2.6 moles on average.

(9) "Dimethylaniline" in Example 6 in Table 1 on page 31 of the specification is changed to "benzylamine."

(10) "632" in Example 9 of Table 1 on page 31 of the specification
" is changed to '320J.

that's all

Claims (1)

[Claims] (1) 100 parts by weight of an alkali-soluble resin, 5 to 100 parts by weight of a 1,2-quinonediazide compound, and at least one nitrogen-containing compound selected from alkylamines, arylamines, aralkylamines, and nitrogen-containing heterocyclic compounds. .001 to 5 parts by weight of a positive radiation-sensitive resin composition.