JPH0820730B2 - Positive type radiation sensitive resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a positive-type radiation-sensitive resin composition, more specifically, a quinonediazide compound containing an alkali-soluble resin and a heat-modified 1,2-quinonediazide compound. And a positive-type radiation-sensitive resin composition suitable as a resist for producing an integrated circuit.

(Prior Art) Conventionally, as a resist for producing an integrated circuit, a negative type resist in which cyclized isoprene rubber is mixed with a bisazide compound is known. However, this type of resist has a limitation in resolution due to swelling during development, and thus has a drawback that it cannot sufficiently cope with high integration of integrated circuits. On the other hand, in contrast to this negative resist, the positive resist is a mixture of an alkali-soluble resin and a 1,2-quinonediazide compound,
Since it has excellent resolution, it is considered to be sufficiently compatible with high integration of integrated circuits.

However, if a positive resist obtained by dissolving an alkali-soluble resin and a 1,2-quinonediazide compound in a solvent is filtered through a filter with a pore size of 0.2 μm and then stored, foreign matter is generated and If the mold resist is stored for a longer period of time, it may eventually become possible to see the formation of precipitates. The foreign matter generated in such a positive resist may have a particle size of 0.5 μm or more. When a resist pattern is formed on a silicon wafer using a positive resist containing such a large foreign substance, the foreign substance remains in a portion where the resist is removed by development,
This lowers the resolution and further deteriorates the yield when manufacturing integrated circuits.

(Problems to be Solved by the Invention) An object of the present invention is to solve the above-mentioned problems of the prior art, to have excellent storage stability, and also to have positive sensitivity and high sensitivity with high resolution and high residual film rate. It is to provide a resin composition.

(Means for Solving Problems) The present invention provides a positive-type radiation-sensitive resin composition obtained by blending an alkali-soluble resin with a quinonediazide compound, wherein the quinonediazide compound is heat-modified 1,2-quinonediazide compound. And a non-modified 1,2-quinonediazide compound, and characterized in that the weight ratio of the heat-modified 1,2-quinonediazide compound and the unmodified 1,2-quinonediazide compound is 1/99 or more. The present invention provides a positive radiation-sensitive resin composition.

Examples of the alkali-soluble resin used in the present invention include an alkali-soluble novolac resin (hereinafter, simply referred to as “novolac resin”). The novolak resin is obtained by condensing phenols and aldehydes in the presence of an acid catalyst.

Examples of the phenols used at this time include 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, hydroquinone, catechol, resorcinol, 2-methylresorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid Esters and the like can be mentioned. Of these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2,3,5-
Trimethylphenol, 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, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,
Examples thereof include pn-butylbenzaldehyde, and formaldehyde, acetaldehyde and benzaldehyde are preferable among these aldehydes. These aldehydes can be used alone or in combination of two or more. The amount of aldehydes used is 1 phenol
Per mol, preferably 0.7 to 3 mol, particularly preferably
It is 0.7 to 2 mol.

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 preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols.

In the condensation reaction, water is usually used as the reaction medium, but when the phenols used in the condensation reaction do not dissolve in the aqueous solution of aldehydes and become a heterogeneous system from the initial stage of the reaction, a hydrophilic solvent is used as the reaction medium. Can also be used. Examples of the hydrophilic solvent used at this time 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 usually 20 to 1 per 100 parts by weight of the reaction raw material.
It is 000 parts by weight.

The reaction temperature and reaction time of the condensation reaction can be appropriately adjusted depending on the reactivity of the reaction raw materials, but usually 10 to
200 ℃, preferably 70 ~ 150 ℃ and 15 minutes ~ 12 hours,
It is preferably 30 minutes to 60 hours.

After the completion of the condensation reaction, the internal temperature is generally raised to 130 ° C. to remove unreacted raw materials, acid catalyst and reaction medium present in the system.
The temperature is raised to ˜230 ° C., the volatile matter is distilled off under reduced pressure, and then the molten novolac resin is cast on a steel belt or the like and collected.

Further, by the method of dissolving the reaction mixture in the hydrophilic solvent after completion of the condensation reaction and adding it to a precipitating agent such as water, n-hexane, n-heptane to deposit the novolac resin and heating and drying the deposit. Can be collected.

As the alkali-soluble resin other than the novolac resin used in the present invention, for example, polyhydroxystyrene or its derivative, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, carboxyl group-containing methacrylic resin, etc. are used.

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

The heat-modified 1,2-quinonediazide compound used in the present invention is 1,2-quinonediazide compound used in a conventional positive resist.
It is obtained by heat-treating a quinonediazide compound. This is essentially different from drying the sensitizer by removing moisture.

The heat-modified 1,2-quinonediazide compound may be a conventionally used one, for example, a polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl halide, 1,2-naphthoquinonediazide-4-sulfonyl halide, It is obtained by an esterification reaction with a 1,2-quinonediazide agent such as 1,2-benzoquinonediazide-4-sulfonyl halide, and examples of these include 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 and the like (poly) hydroxybenzene 1,2-quinonediazidesulfonic acid esters, 2 , 4-Dihydroxyphenyl-propyl ketone-1,2-benzoquinonediazide-4- Sulfonic acid esters, 2,4-dihydroxyphenyl -n- hexyl ketone 1,2-naphthoquinonediazide-4-sulfonic acid esters, 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-trihydroxybenzophenone-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-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-
1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2
-Naphthoquinonediazide-4-sulfonic acid ester, 2,
3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, and 2,
2 ', 3,4,6'-pentahydroxybenzophenone, 2,
2 ', 3,3', 4-pentahydroxybenzophenone, 2,
3 ', 4', 5 ', 6-pentahydroxybenzophenone, 2,
3,3 ′, 4 ′, 5′-pentahydroxybenzophenone, 2,
3 ', 4,4', 5'-pentahydroxybenzophenone, 2,
3 ', 4', 5,5'-pentahydroxybenzophenone, 2,
2 ', 3', 4,4'-pentahydroxybenzophenone, 2,
2 ', 4,4', 6'-pentahydroxybenzophenone, 2,
2 ', 3,4,5'-pentahydroxybenzophenone, 2,
2 ', 4,5', 6-pentahydroxybenzophenone, 2,3,
3 ', 4,4', 5'-hexahydroxybenzophenone, 2,
2 ', 3,4,4', 6'-hexahydroxybenzophenone,
Or 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonate, 1,2-naphthoquinonediazide-4-sulfonate or 1,2- 1,2-quinonediazidesulfonic acid esters of (poly) hydroxyphenylalkylketones such as benzoquinonediazide-4-sulfonic acid ester or (poly) hydroxyphenylarylketones,
Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-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-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,4-dihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, Bis [(poly) such as 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonate
Hydroxyphenyl] alkane 1,2-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-sulfonate, propyl 3,4,5-trihydroxybenzoate-1,2-naphthoquinonediazide-5-sulfonate, 3,4,5
-Trihydroxybenzoic acid phenyl-1,2-naphthoquinonediazide-5-sulfonic acid ester and other (poly) hydroxybenzoic acid alkyl ester or (poly) hydroxybenzoic acid aryl ester 1,2-quinonediazide 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-trihydroxybenzoyl) benzene-1,2-naphthoquinonediazide-5-sulfonic acid ester, p-bis (2,4,6-trihydroxybenzoyl) benzene-1 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, Five
-Dihydroxybenzoate) -1,2-naphthoquinonediazide-5-sulfonic acid ester, ethylene glycol-di (3,4,5-trihydroxybenzoate) -1,2-naphthoquinonediazide-5-sulfonic acid ester, polyethylene glycol- Di (3,4,5-trihydroxybenzoate) -1,2-naphthoquinonediazide-5-sulfonate, etc. 1,2-quinonediazidesulfonate of (poly) ethylene glycol-di [(poly) hydroxybenzoate] , 1,2-quinonediazide sulfonic acid ester of α-pyrone natural dye having a hydroxy group, 1, γ-pyrone natural dye having a hydroxy group of 1,
Examples thereof include 2-quinonediazide sulfonic acid esters and 1,2-quinonediazide sulfonic acid esters of diazine-based natural dyes having a hydroxy group.

In addition to these 1,2-quinonediazide compounds, J. Kosar
Work "Light-Sensitive Systems" 339-352 (1965), Joh
n Wiley & Sons (New York) and WS De Forest “Ph
otoresist "50 (1975), McGraw-Hill, Inc., (New Yor
The 1,2-quinonediazide compounds listed in k) are mentioned.

Further, as described in JP-A-58-17112, a resin obtained by condensing a 1,2-quinonediazide agent with a hydroxyl group of the novolak resin at an equivalent ratio of 0.001 to 0.5 is 1,2.
It can also be used as a quinonediazide compound.

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

Although the details of the structure of the heat-modified 1,2-quinonediazide compound obtained by heat-treating the 1,2-quinonediazide compound are unknown, it is a polymerized version of the 1,2-quinonediazide compound. It is estimated that there is.

Here, the temperature of the heat treatment is preferably 30 to 100 ° C, more preferably 40 to 90 ° C.

In the present invention, the weight ratio of the heat-modified 1,2-quinonediazide compound and the unmodified 1,2-quinonediazide compound is 1/99 or more, preferably 1/99 to 50/50, more preferably 1/99. Heat-denatured 1,2 blended in a ratio of 99-30 / 70
-When the blending ratio of the quinonediazide compound is less than 1% by weight, the storage stability deteriorates.

In the present invention, for example, 1,2
-A part of the quinonediazide compound may be heat-modified 1,2-quinonediazide compound may be used.
A mixture of a -quinonediazide compound and an unmodified 1,2-quinonediazide compound can be easily obtained.

(A) The heat denaturing conditions vary depending on the type of 1,2-quinonediazide compound to be heat-denatured, but generally, in an air or nitrogen atmosphere, the internal temperature is preferably 30 to 100 ° C, more preferably 40 to 90 ° C. The drying time is appropriately adjusted according to the internal temperature.

When the internal temperature is less than 30 ° C, the heat treatment time is too long to be practical, and when the internal temperature exceeds 100 ° C, the 1,2-quinonediazide compound gradually undergoes thermal decomposition, which is not desirable. The heat denaturation temperature may be low when the heat denaturation time is long within the above temperature range and may be short when the heat denaturation temperature is high. Specifically, the relationship between the heat denaturation temperature and the heat denaturation time is preferably within the shaded range defined by FIG. 1 (the range shown in FIG. 1 is shown by the following mathematical formula), and outside the shaded range, It is difficult to exert the effect.

Further, if the heat denaturation temperature is lower than 30 ° C, the heat treatment time is too long to be practical, and if it exceeds 100 ° C, 1,2-
This is not desirable because the quinonediazide compound gradually undergoes thermal decomposition.

However, 30 <T (° C.) <100 (b) The 1,2-quinonediazide compound is dissolved in a hydrophilic solvent, coagulated with water and dispersed in water for heat denaturation. As the hydrophilic solvent, acetone, tetrahydrofuran, dioxane, dimethylformald, N-methyl-
2-pyrrolidone, dimethyl sulfoxide and the like can be mentioned. The concentration of the 1,2-quinonediazide compound is 5 to 60
Weight% is preferable, and 5-40 weight% is especially preferable. When the concentration is less than 5% by weight, the amount of water that coagulates the 1,2-quinonediazide compound in this solution is large, which is not practical. On the other hand, when the concentration exceeds 60% by weight, the 1,2-quinonediazide compound is difficult to dissolve in the hydrophilic solvent, which makes it difficult to form a solution. This solution contains a polyhydroxy compound and 1,
The solution obtained by reacting the 2-quinonediazide agent may be used as it is. This solution is preferably mixed with water in an amount of 1 to 100 times, particularly preferably 3 to 30 times by weight.
-Coagulate the quinonediazide compound and stir well to disperse into a slurry. If the amount of water is too low, 1,2
-The quinonediazide compound is hard to coagulate and tends to become a candy-like substance. In order to facilitate coagulation, protic acids such as hydrochloric acid and sulfuric acid are added to water in an amount of 0.01 to 10% by weight, especially 0.05
It is desirable to add ~ 5% by weight. The amount of protic acid is 10
If it exceeds 5% by weight, the protic acid remains in the 1,2-quinonediazide compound and it is difficult to completely remove it.

This slurry-like 1,2-quinonediazide compound is heated to preferably 30 to 100 ° C., more preferably 40 to 90 ° C. in an air or nitrogen atmosphere, and the heating time is appropriately adjusted according to the internal temperature. The range of the above heat denaturation conditions is within the shaded area in FIG. 1, and the reason is the same as the reason given in (a). The 1,2-quinonediazide compound in a slurry form after heat denaturation is dehydrated and filtered to collect solids, which are then placed in a vacuum dryer at 40 ° C. to remove water and dried for 12 hours.

In the present invention, the heat-modified 1,2-quinonediazide compound and the unmodified quinonediazide compound are preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. To be When the amount is less than 5 parts by weight, the amount of the quinonediazide compound used for the alkali-soluble resin is insufficient because the amount of the quinonediazide compound used for the alkali-soluble resin is insufficient. It is difficult to form a resist pattern because it is impossible to make a difference in solubility in a developing solution composed of an aqueous solution. On the other hand, if the amount exceeds 100 parts by weight, all quinonediazide compounds cannot be decomposed by irradiation for a short time and a part of them remains, making it difficult to develop with a developer composed of an alkaline aqueous solution when used as a positive resist. Becomes

The heat-modified 1,2-quinonediazide compound and the unmodified 1,2-quinonediazide compound may be used alone or in combination of two or more.

A sensitizer can be added to the composition of the present invention in order to improve the sensitivity as a resist. Examples of the sensitizer include 2H-pyrido [3,2-b] -1,4-oxazin-3 [4H] ones and 10H-pyrido [3,2-b]-[1,4].
-Benzothiazines, urazoles, hydantoins,
Examples thereof include barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxans and maleimides. The compounding amount of the sensitizer is usually 100 parts by weight or less, preferably 4 to 60 parts by weight, based on 100 parts by weight of the quinonediazide compound.

Further, a surfactant can be added to the composition of the present invention in order to improve the coating properties such as striation and the developability of the radiation-irradiated area after the formation of a dry coating film. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether and other polyoxyethylene alkylphenols. Ethers, and polyethylene glycol dilaurate,
Nonionic surfactants of polyethylene glycol dialkyl ethers such as polyethylene glycol distearate, F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) , Florard FC430, FC431 (Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382,
Fluorine-based surfactants such as SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) Polymer Polyflow No.7
5, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. 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 alkali-soluble resin and the quinonediazide compound in the composition of the present invention.

Furthermore, in order to improve the adhesiveness, the composition of the present invention contains
A coloring agent may be added as an adhesion aid, or in order to visualize the latent image on the radiation irradiated portion and to reduce the effect of halation during radiation irradiation.

Examples of the adhesion aid include 3-aminopropyltriethoxysilane, vinyltrichlorosilane, 2- (3,4-
Silicon compounds such as epoxycyclohexylethyl) trimethoxysilane are used. The amount of these adhesion promoters to be added is usually 4 parts by weight or less, preferably 2 parts by weight or less, per 100 parts by weight of the alkali-soluble resin and quinonediazide compound in the composition of the present invention.

The amount of the colorant compounded is usually 6 parts by weight or less, preferably 4 parts by weight or less, per 100 parts by weight of the alkali-soluble resin and the quinonediazide compound in the composition of the present invention.

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

In the composition of the present invention, the alkali-soluble resin, the quinonediazide compound and the various compounding agents are dissolved in a solvent, for example, so that the solid content concentration becomes 5 to 50% by weight, and the mixture is filtered with a filter having a pore size of about 0.2 μm. By
Is prepared.

Examples of the solvent used at this time include ketones such as cyclopentanone, cyclohexanone and diacetone alcohol, alcohols such as n-butanol, dioxane, ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether, and ethylene glycol monomethyl. Ether, alcohol ethers such as ethyl glycol monoethyl ether, butyl acetate,
Esters such as ethyl cellosolve acetate and methoxyethyl acetate, methyl 2-oxypropionate, 2
-Alcohol esters such as ethyl oxypropionate, halogenated hydrocarbons such as 1,1,2-trichloroethylene, and polar solvents such as dimethylacetamide, dimethylsulfoxide, dimethylformamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

If necessary, a high-boiling solvent, for example, ethers such as benzyl ethyl ether and dihexyl ether, glycol ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether, ketones such as acetonylacetone and isophorone, caproic acid and caprylic acid. Fatty acids such as 1-octanol, 1-
Nonanol, alcohols such as benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate,
Esters such as propylene carbonate and phenyl cellosolve acetate can also be added and used.

Examples of the method of applying the composition of the present invention to a substrate such as a silicon wafer include a method of applying by spin coating, flow coating, roll coating and the like.

The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, primary amines such as ethylamine and n-propylamine. , 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, tetraethyl Quaternary ammonium salts such as ammonium hydroxide, or pyrrole, piperidine, 1,8-diazabicyclo (5,
4,0) -7-Undecene, 1,5-diazabicyclo (4,3,
An alkaline aqueous solution prepared by dissolving a cyclic amine such as 0) -5-nonane is used.

Further, a water-soluble organic solvent, for example, an alcoholic solution such as methanol or ethanol, or an alkaline aqueous solution to which an appropriate amount of a surfactant is added can be used as a developing solution.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Comparative Example 1 (1) In a 500 ml separable flask equipped with a stirrer, a dropping funnel and a thermometer, 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone [H] 5 g, 1, 2-naphthoquinonediazide-5-sulfonic acid chloride [Q] 32.6 g
([Q] / [H] = 5 [molar ratio]) and 240 g of dioxane as a solvent were charged and dissolved while stirring. Furthermore, 16.2 g of triethylamine was charged into the dropping funnel. The separable flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., triethylamine was slowly added dropwise to this solution so that the internal temperature did not exceed 35 ° C. Then, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to precipitate a quinonediazide compound. The precipitate is then collected,
It was dried overnight with a heating vacuum dryer controlled at 40 ° C. The yield of the obtained 2,3,3 ', 4,4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester was 98%.

(2) In a 2 l separable flask with a stirrer, protected from light,
Charge 336 g of m-cresol, 224 g of p-cresol, 400 g of 37% by weight aqueous formaldehyde solution and 0.24 g of oxalic acid, condense at 100 ° C for 3 hours, and heat to remove unreacted raw materials under reduced pressure. A resin was obtained.

(3) 39 g of the quinonediazide compound obtained in (1),
260 g of the novolak resin obtained in (2), 720 g of ethyl cellosolve acetate and 180 g of γ-butyrolactone were added, and the mixture was well stirred at room temperature to dissolve it. After melting, pore size 0.2μ
m membrane filter to prepare a solution of the composition. The number of foreign particles in the solution immediately after preparation was measured with an automatic particle counter, and the number of foreign particles with a particle size of 0.5 μm or more was 10 /
ml. Next, when the solution was placed in a constant temperature bath controlled at 40 ° C. and stored for 1 month, the number of foreign particles having a particle size of 0.5 μm or more measured by an automatic particle counter increased to 1000 particles / ml.

Example 1 The quinonediazide compound obtained in Comparative Example 1 (1) was placed in a dryer whose internal temperature was controlled to 45 ° C., and heat-denatured for 7 days in an air atmosphere to obtain a heat-denatured 1,2-quinonediazide compound. A quinonediazide compound having a weight ratio ([X] / [Y]) of [X] and unmodified 1,2-quinonediazide compound [Y] of 0.026 was obtained.

Then, a solution of the composition was prepared in the same manner as in Comparative Example 1 (3) except that the above quinonediazide compound was used instead of the quinonediazide compound used in Comparative Example 1 (3). The number of foreign particles in the solution immediately after preparation was measured with an automatic particle counter, and the number of foreign particles with a particle size of 0.5 μm or more was 15 pieces / ml.
Met. Next, the solution was placed in a constant temperature bath controlled at 40 ° C. and stored for 1 month, and the number of foreign substances having a particle size of 0.5 μm or more measured by an automatic fine particle counter was 15 particles / ml, which was hardly increased. In addition, when the performance of the resist was evaluated, it was found that there was no change in the sensitivity and residual film ratio before and after the storage stability test at 40 ° C, indicating high storage stability. It was

Example 2 40 g of the quinonediazide compound obtained in Comparative Example 1 (1)
Was added to 360 g of dioxane and dissolved by stirring well at room temperature. After the dissolution, 4 kg of 0.2 wt% hydrochloric acid was added dropwise at room temperature to coagulate the quinonediazide compound, and well stirred to obtain a slurry state.

The slurry-like quinonediazide compound (hereinafter referred to as "slurry solution") was placed in a warmer whose internal temperature was controlled to 50 ° C, and heat-denatured for 1 day in an air atmosphere. The slurry solution is dehydrated and filtered to collect solids,
The weight ratio ([X] / [Y] of the heat-modified 1,2-quinonediazide compound [X] and the unmodified 1,2-quinonediazide compound [Y], which was dried for one day in a heating vacuum dryer controlled at ° C. ]) Was 0.029 to obtain a quinonediazide compound.

Then, a solution of the composition was prepared in the same manner as in Comparative Example 1 (3) except that the above quinonediazide compound was used instead of the quinonediazide compound used in Comparative Example 1 (3). The number of foreign particles in the solution immediately after preparation was measured with an automatic particle counter, and the number of foreign particles with a particle size of 0.5 μm or more was 13 / ml.
Met. Next, the solution was placed in a constant temperature bath controlled at 40 ° C. and stored for 1 month, and the number of foreign particles having a particle size of 0.5 μm or more measured by an automatic fine particle counter was 13 particles / ml, which was hardly increased. In addition, when the performance of the resist was evaluated, it was found that there was no change in the sensitivity and residual film ratio before and after the storage stability test at 40 ° C, indicating high storage stability. It was

Examples 3 to 8 The compounds shown in Table 1 were selected as the polyhydroxy compound [H], quinonediazide compounds were obtained by the method shown in Comparative Example 1 (1), and then heat-denatured in the same manner as in Example 1. 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, these quinonediazide compounds were used in Comparative Example 1 (3).
A solution of the composition was prepared in the same manner as in Comparative Example 1 (3), using the quinonediazide compound used in Example 1 above. Immediately after preparation and for each solution stored at 40 ° C for 1 month in a constant temperature bath, the number of foreign particles with a particle size of 0.5 μm or more was measured with an automatic particle counter, and the number of foreign particles increased in any solution. Was hardly recognized. The results are shown in Table 1.

Examples 9 to 14 The compounds shown in Table 2 were selected as the polyhydroxy compound [H], quinonediazide compounds were obtained by the method shown in Comparative Example 1 (1), and then heat-modified in the same manner as in Example 1, 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, these quinonediazide compounds were used in Comparative Example 1 (3).
A solution of the composition was prepared in the same manner as in Comparative Example 1 (3), using the quinonediazide compound used in Example 1 above. Immediately after preparation and for each solution stored at 40 ° C for 1 month in a constant temperature bath, the number of foreign particles with a particle size of 0.5 μm or more was measured with an automatic particle counter, and the number of foreign particles increased in any solution. Was hardly recognized. The results are shown in Table 2.

Comparative Example 2 (1) 500 ml with stirrer, dropping funnel and thermometer
2,3 ', 4,4', 5'-Pentahydroxybenzophenone [H] 5.7 g, 1,2-naphthoquinonediazide-5-sulfonic acid chloride [Q] 32.6 g in a separable flask in the dark.
([Q] / [H] = 4 [molar ratio]) and 290 g of dioxane as a solvent were charged and dissolved with stirring. Further, 18.2 g of triethylamine was charged into the dropping funnel.
The separable flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., triethylamine was slowly added dropwise to this solution so that the internal temperature did not exceed 35 ° C. Then, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to precipitate a quinonediazide compound. Then, the precipitate was collected and dried in a heating vacuum dryer controlled at 40 ° C. for 24 hours. The obtained 2,3 ', 4,4', 5'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-
The yield of sulfonate ester was 99%.

(2) Comparative Example 1 The quinonediazide compound obtained in (1) above was used in place of the quinonediazide compound used in (3), and 720 g of ethyl cellosolve acetate and 180 g of γ-butyrolactone were used instead of 900 g of ethyl cellosolve acetate. A solution of the composition was prepared in the same manner as in Comparative Example 1 (3) except for the above. When the number of foreign matters in the solution immediately after preparation was measured by an automatic fine particle counter, the number of foreign matters having a particle size of 0.5 μm or more was 5 / ml. Next, when the solution was placed in a constant temperature bath controlled at 40 ° C. and stored for 1 month, the number of foreign matters having a particle size of 0.5 μm or more measured by an automatic particle counter increased to 920 particles / ml.

Examples 15 to 17 The compounds shown in Table 3 were selected as the polyhydroxy compound [H], quinonediazide compounds were obtained by the method shown in Comparative Example 2 (1), and then heat-modified in the same manner as in Example 1. 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, these quinonediazide compounds were used in Comparative Example 2 (2).
A solution of the composition was prepared in the same manner as in Comparative Example 2 (2), except that the quinonediazide compound used in Example 2 was used instead. Immediately after preparation and for each solution stored in a constant temperature bath at 40 ° C for 1 month, the number of foreign particles with a particle size of 0.5 μm or more was measured with an automatic particle counter. Little increase was observed. The result is the third
Shown in the table.

Examples 18 to 20 The compounds shown in Table 4 were selected as the polyhydroxy compound [H], quinonediazide compounds were obtained by the method shown in Comparative Example 2 (1), and then heat-denatured in the same manner as in Example 2. 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, these quinonediazide compounds were used in Comparative Example 2 (2).
A solution of the composition was prepared in the same manner as in Comparative Example 2 (2), except that the quinonediazide compound used in Example 2 was used instead. Immediately after preparation and for each solution stored at 40 ° C for 1 month in a constant temperature bath, the number of foreign particles with a particle size of 0.5 μm or more was measured with an automatic particle counter, and the number of foreign particles increased in any solution. Was hardly recognized. The results are shown in Table 4.

Examples 21 to 27 As the polyhydroxy compound [H], compounds shown in Table 5 were selected, quinonediazide compounds were obtained by the method shown in Comparative Example 2 (1), and then heat-modified in the same manner as in Example 1, 1. 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, a quinonediazide compound A containing these heat-modified 1,2-quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] and a quinonediazide compound B other than A shown in Table 5 were prepared. Comparative example 1
It was used in place of the quinonediazide compound used in (3), and a solution of the composition was prepared in the same manner as in Comparative Example 2 (2). Immediately after preparation and for each solution stored at 40 ° C for 1 month in a constant temperature bath, the number of foreign particles with a particle size of 0.5 μm or more was measured with an automatic particle counter, and the number of foreign particles increased in any solution. Was hardly recognized. The results are shown in Table 5.

Examples 28 to 34 As the polyhydroxy compound [H], the compounds shown in Table 6 were selected, quinonediazide compounds were obtained by the method shown in Comparative Example 2 (1), and then heat-modified in the same manner as in Example 1, 2
A quinonediazide compound containing a -quinonediazide compound [X] and an unmodified 1,2-quinonediazide compound [Y] was obtained.

Next, a mixture of these quinonediazide compound A and a quinonediazide compound B other than A shown in Table 6 was prepared in Comparative Example 1
It was used in place of the quinonediazide compound used in (3), and a solution of the composition was prepared in the same manner as in Comparative Example 2 (2). Immediately after preparation, and for each solution stored at 40 ° C for 1 month in a constant temperature bath, the number of foreign particles with a particle size of 0.5 μm or more was measured by an automatic fine particle counter. No increase was observed. The results are shown in Table 6.

(Effect of the invention) According to the present invention, by using a heat-modified 1,2-quinonediazide compound and an unmodified 1,2-quinonediazide compound, generation of foreign matters is extremely small and storage stability is excellent, and Sensitivity in resist pattern formation, resolution,
It is possible to obtain a radiation-sensitive resin composition suitable as a positive resist having a good residual film rate and a good yield in the production of integrated circuits.

[Brief description of drawings]

FIG. 1 is a relationship diagram between heat denaturation temperature and heat denaturation time showing a preferable range of heat denaturation conditions for a 1,2-quinonediazide compound in the present invention.

Claims (1)

[Claims] 1. A positive-type radiation-sensitive resin composition comprising an alkali-soluble resin and a quinonediazide compound blended therein, wherein the quinonediazide compound is heat-modified 1,2-quinonediazide compound and unmodified 1,2-quinonediazide. A positive radiation-sensitive resin composition comprising a compound and having a weight ratio of a heat-modified 1,2-quinonediazide compound and an unmodified 1,2-quinonediazide compound of 1/99 or more. .