JPS62178562A - Production of 1,2-quinonediazide compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a positive-type resist sensitive to radiation when used together with an alkali-soluble resin, by reacting a polyhydroxyl compound with an acylation agent, a sulfonylation agent and a 1,2-quinonediazidation agent. CONSTITUTION:The objective compound can be produced by reacting a part of hydroxyl groups of a polyhydroxyl compound with an acylation agent (e.g. acetyl chloride) and/or sulfonylation agent (e.g. methanesulfonic acid chloride) at 0-40 deg.C and reacting a part of or whole remaining hydroxyl group of the polyhydroxyl compound with e.g. a 1,2-quinonediazidation agent at 0-40 deg.C. The total amount of the acylation agent, sulfonylation agent and 1,2- quinonediazidation agent is >=0.3mol per 1g-equivalent of the hydroxyl group of the polyhydroxyl compound.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a 1,2-quinonediazide compound, and more specifically, a method for producing a 1,2-quinonediazide compound and an alkali-soluble resin. A specific 1°2- The present invention relates to a method for producing a quinonediazide compound.

(Prior art) Conventionally, resists used to fabricate integrated circuits include a negative resist made by blending a bisazide compound with cyclized rubber, and a positive resist made by blending a 1,2-quinonediazide compound into an alkali-soluble resin. It is known as resist. In negative resists, the bisazide compound desorbs nitrogen when exposed to ultraviolet rays and becomes nitrene, which three-dimensionally crosslinks the cyclized rubber. Therefore, the solubility of the ultraviolet irradiated areas and the non-UV irradiated areas in a developing solution consisting of a cyclized rubber solvent is important. This causes a difference in patterning, but even though it is crosslinked, the UV irradiated area is not completely cured, so the resist pattern swells significantly in a developer made of a cyclized rubber solvent. The drawback is that 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 developer consisting of an alkaline aqueous solution.
Because it hardly swells, the 1,2-
Quinonediazide compound changes to indene carboxylic acid,
Even when developed with a developer consisting of an alkaline aqueous solution, there is extremely little change in the unirradiated portions of the resist pattern that are not irradiated with ultraviolet rays (a resist pattern that is faithful to the pattern of the pattern mask and has high resolution can be obtained. In recent years, with the demand for higher integration, such positive resists with excellent resolution have come into widespread use.

However, a positive resist made by dissolving an alkali-soluble resin and a 1,2-quinonediazide compound in a solvent can be stored after being filtered, for example, through a filter with a pore size of 0.2 μm.
If the positive resist containing the foreign particles is stored for a longer period of time, the formation of precipitates may eventually occur. Some of the foreign particles generated in such a positive resist have a particle size of 0.5 μm or more.

When a resist pattern is formed on a silicon wafer using a positive resist that contains such large foreign particles, the foreign particles remain in the areas where the resist is removed during development, resulting in a decrease in resolution and a reduction in yield when manufacturing integrated circuits. causes deterioration.

(Problems to be Solved by the Invention) The object of the present invention is to combine an alkali-soluble resin and a
．． Solving the problem of foreign matter occurring in a solution of a radiation-sensitive resin composition (hereinafter simply referred to as "resin composition") suitable for a positive resist prepared by dissolving a 2-quinonediazide compound in a solvent. Another object of the present invention is to provide a method for producing a 1,2-quinonediazide compound that can improve the resolution during resist pattern formation and the yield during integrated circuit production.

(Means for Solving the Problems) The present invention provides (1) (a) a part of the hydroxyl group of the polyhydroxy compound is acylated and/or sulfonylated by reacting with an acylating agent and/or a sulfonylating agent; rear,
Further, part or all of the remaining hydroxyl groups of the polyhydroxy compound are reacted with a 1.2-quinone diazidating agent to 1.
2-quinone diazidation, or (b) some or all of the hydroxyl groups of the polyhydroxy compound are treated with an acylating agent and/or a sulfonylating agent and 1.2-
acylation and/or reaction with a quinone diazidating agent.
Alternatively, 1.2-quinone diazidation is performed simultaneously with sulfonylation, or (c) a part of the hydroxyl group of the polyhydroxy compound is reacted with a 1.2-quinone diazidating agent to give 1.2-quinone diazidation.
- After the quinone diazidation, some or all of the remaining hydroxyl groups of the polyhydroxy compound are further reacted with an acylating agent and/or a sulfonylating agent to acylate and/or
or sulfonylation step, and the total amount of the acylating agent, sulfonylating agent, and 1゜2-quinone diazidating agent is 0.3 mol or more per 1 gram equivalent of hydroxyl group of the polyhydroxy compound, and the acylating The ratio of the agent and/or sulfonylating agent [A] and the 1,2-quinonediazide agent [Q] is [A] / [Q] = 0.01.
The present invention provides a method for producing a 1,2-quinonediazide compound, characterized in that the molar ratio is 10.99 to 0.710.3.

The polyhydroxy compound used in the present invention contains at least two or more hydroxyl groups in the molecule, and specifically includes polyhydroxybenzene H12,4-dihydroxyphenylpropyl such as resorcinol, pyrogallol, and phloroglucinol. Ketones, polyhydroxyphenylalkyl ketones such as 2.4-dihydroxyphenyl-n-hexylketone, 2.3.4-) dihydroxyphenyl-n-hexylketone, 2,4-dihydroxybenzophenone, 2.3.4- ) dihydroxybenzophenone, 2,4.6-) dihydroxybenzophenone,
2.4.2', 4'-tetrahydroxybenzophenone, 2,3.4.4'-tetrahydroxybenzophenone, 2,3,4.2'.

4'-pentahydroxybenzophenone, 2,3°4.
2',6'-pentahydroxybenzophenone, 2.3
．． 4.3',4',5'-hexahydroxybenzophenone, 2,4.6.3',4'.

5'-hexahydroxybenzophenone, 2,3°4.
5.4”-pentahydroxybenzophenone, 2, 3
．． 4. 5. 3', 4'', 5''-hebutahydroxybenzophenone, 2,3.3'', 4', 5'-
Pentahydroxy-4-methoxybenzophenone, 2.
3,4.3",4",5'-hexahydroxy-5-chlorobenzophenone, 2,3.4°3',4',5'-
Polyhydroxyphenylarylketones such as hexahydroxy-5-benzoylbenzophenone, bis(2,
4-dihydroxyphenyl)methane, 2,2-bis(2
, 4-dihydroxyphenyl)propane, 2,2-bis(2,3,4-trihydroxyphenyl)propane and other bis(polyhydroxyphenyl)alkanes, 3.4.
5-) Polyhydroxybenzoic acid alkyl esters or polyhydroxybenzoic acid aryl esters such as propyl trihydroxybenzoate, phenyl 3.4.5-trihydroxybenzoate, bis(2,4-dihydroxybenzoyl)methane , 2. (2,3,4-)dihydroxybenzoyl)methane, bis(2,4,6-)dihydroxybenzoyl)methane, 2,2-bis(2,3,4-)
Bis(polyhydroxybenzoyl)alkanes such as dihydroxyphenyl)propane, p-bis(2,5-dihydroxybenzoyl)benzene, p-bis(2,3,4
-1 hydroxybenzoyl)benzene, p-bis(2
, 4,6-)dihydroxybenzoyl)benzene, etc., ethylene glycol di(3,5-dihydroxybenzoate),
Ethylene glycol di(3,4,5-trihydroxybenzoate), 1,4-butanediol di(3,4,5
-1-dihydroxybenzoate), alkanediol di(polyhydroxybenzoates) such as 1°8-octanediol di(3,4,5-) dihydroxybenzoate), diethylene glycol di(3,4,5-) dihydroxybenzoate) , triethylene glycol di(
polyethylene glycol di(polyhydroxybenzoate) such as 3,4゜5-trihydroxybenzoate), α-pyrone natural pigments having hydroxyl groups such as hispidin and gluterdine, chrysin, abigenin, quercetin, rutin, morin, naringenin, γ-pyrone natural pigments with hydroxyl groups such as brunetine, leucopterin,
Diazine natural pigments with hydroxyl groups such as entropterin, chrysopterin, and iodinine, atromentin,
muscarfine, nigerone, alizarin, purpurin,
Examples include quinone natural pigments having a hydroxyl group such as skyline, and resins having a hydroxyl group such as poly(hydroxystyrene), alkali-soluble novolak resin, and pyrogallol/acetone condensation resin. These polyhydroxy compounds may be used alone or in combination of two or more.

Specific examples of the acylating agent used for acylation in the present invention include acetic acid chloride, acetic acid bromide, acetic acid fluoride, chloroacetic acid chloride, dichloroacetic acid chloride, trichloroacetic acid chloride, propionic acid chloride, propionic acid bromide, α-chloropropion Alkanecarboxylic acid halides such as acid chloride, butyric acid chloride, isobutyric acid chloride, valeric acid chloride, isovaleric acid chloride, trimethylacetic acid chloride, acrylic acid chloride, acrylic acid bromide, methacrylic acid chloride, methacrylic acid bromide, crotonic acid chloride, α-Ethyl acrylic acid chloride, β
-Methylcrotonic acid chloride, angelic acid chloride,
Tiglic acid chloride, α-ethyl crotonic acid chloride,
Alkene carboxylic acid halides such as 2-pentenoyl chloride, alkyne carboxylic acid halides such as propiol acid chloride, tetrolic acid chloride, ethylpropiol acid chloride, butylpropiol acid chloride, 2.4
- Alkadienecarboxylic acid halides such as pentadienoic acid chloride and 2,4-hexadienoic acid chloride, benzoic acid chloride, benzoic acid bromide, 4-methylbenzoic acid chloride, 4-propylbenzoic acid chloride, 4-chlorobenzoic acid chloride, 3.4.Arylcarboxylic acid halides such as 5-1-rimethoxybenzoic acid chloride, 3゜4.5-1-rimethoxybenzoic acid bromide, methoxyformic acid chloride, ethoxyformic acid chloride, propoxyformic acid chloride, 2-ethoxyethoxyformic acid Alkoxyalkane carboxylic acid halides such as chloride, methoxyacetic acid chloride, ethoxyacetic acid chloride, propoxyacetic acid chloride, 3-methoxypropionic acid chloride, 3-ethoxypropionic acid chloride, and methoxycarbonylacetic acid chloride, ethoxycarbonylpropionic acid chloride, ethoxycarbonyl Examples include alkoxycarbonylalkane carboxylic acid halides such as acetic acid chloride, ethoxycarbonylpropionic acid chloride, methoxycarbonylbutyric acid chloride, ethoxycarbonylbutyric acid chloride, methoxycarbonylvaleric acid chloride, and ethoxycarbonylvaleric acid chloride.

Although carboxylic acid halides are mainly used as the above-mentioned acylating agent, carboxylic acids or carboxylic acid anhydrides may also be used depending on the conditions of the acylation reaction. These acylating agents may be used alone or in combination of two or more.

Specific examples of the sulfonylating agent used for sulfonylation in the present invention include methanesulfonic acid chloride, methanesulfonic acid fluoride, ethanesulfonic acid chloride, propanesulfonic acid chloride, butanesulfonic acid chloride, pentanesulfonic acid chloride, and hexanesulfonic acid chloride. Alkanesulfonic acid halides such as chloride, alkenesulfonic acid halides such as ethylenesulfonic acid chloride, 1-propene-1-sulfonic acid chloride, benzenesulfonic acid chloride, benzenesulfonic acid fluoride, p-
) Arylsulfonic acid halides such as luenesulfonic acid chloride and p-xylenesulfonic acid chloride can be mentioned. These sulfonylating agents alone or in combination
Used in combination of more than one species.

1,2- used in 1,2-quinone diazidation in the present invention
Typical examples of quinonediazidating agents include 1,2-quinonediazide sulfonic acid halide, specifically 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-
naphthoquinonediazide-4-sulfonic acid chloride, 1,
Examples include 2-benzoquinonediazide-4-sulfonic acid chloride. These 1,2-quinone diazidating agents may be used alone or in combination of two or more.

The 1,2-quinonediazide compound of the present invention (hereinafter simply r
As a specific example of the method for producing QD compound (referred to as "QD compound"),
The following methods (1), (2), or (3) can be mentioned.

(1) The polyhydroxy compound is a7tone, dioxane,
After dissolving in a solvent such as tetrahydrofuran or methyl ethyl ketone, add an amount of acylating agent and/or sulfonylating agent to acylate and/or sulfonylate a portion of the hydroxyl groups of the polyhydroxy compound, preferably 1 gram equivalent of the hydroxyl groups of the polyhydroxy compound. 0.01-0.8 for
After adding molar amount and reacting, further add a 1,2-quinonediazidizing agent in an amount to convert some or all of the remaining hydroxyl groups of the polyhydroxy compound into 1,2-quinonediazide and react, and after the reaction is completed, A method of filtering the generated hydrochloride or adding water to dissolve the hydrochloride, reprecipitating with a large amount of acidic water such as dilute hydrochloric acid or dilute sulfuric acid, and then drying.

(2) After dissolving the polyhydroxy compound in the same solvent as above, add acylating agent and/or sulfonyl other agent to 1.2
- Add a quinone diazidating agent and react with it, and after the reaction is complete, filter the generated hydrochloride, or add water to dissolve the hydrochloride, and then add a large amount of dilute hydrochloric acid water, dilute sulfuric acid water, etc. A method in which the product is purified by reprecipitation with acidic water and then dried.

(3) After dissolving the polyhydroxy compound in the same solvent as above, add a 1,2-quinone diazidating agent in an amount to convert a part of the hydroxyl groups of the polyhydroxy compound into 1,2-quinone diazide, preferably the hydroxyl groups of the polyhydroxy compound. After adding 0.3 to 0.99 mol per 1 gram equivalent and reacting,
Further, adding an acylating agent and/or a sulfonylating agent in an amount to acylate and/or sulfonylate some or all of the remaining hydroxyl groups of the polyhydroxy compound,
React, and after the reaction is complete, filter the generated hydrochloride, or
Alternatively, after adding water to dissolve the hydrochloride, purifying it by reprecipitation with a large amount of acidic water such as diluted hydrochloric acid or diluted sulfuric acid, followed by drying.

The total amount of the acylating agent, sulfonylating agent, and 1,2-quinone diazidizing agent used in the present invention is 0.3 mol or more, preferably 0.4 mol, per gram equivalent of hydroxyl group of the polyhydroxy compound. or more, particularly preferably 0.5
It is more than 1 mole, and usually less than 1.2 mole. This is 0.
If the amount is less than 3 moles, the sensitivity, which is a characteristic of the resin composition, and the residual film rate when used as a positive resist will be unbalanced, and furthermore, problems will arise in resolution.

Acylating agent and/or sulfonylating agent [A] and 1.
2-quinone diazidating agent (Using ratio with Ql is [A]
/ [Q] =0.0110.99~0.710.3
[Molar ratio), preferably [A]/[Q]=0°011
0.99-0.610.4C molar ratio), particularly preferably [A] / [Q] = 0.110.9-0.6 /
The molar ratio is 0.4. Usage ratio [A] / [Q]
is less than 0゜0110.99C molar ratio], the proportion of acylated and/or sulfonylated hydroxyl groups of the polyhydroxy compound is smaller than the proportion of 1,2-quinone diazidation, and therefore the resin composition is It is not possible to stop the generation of foreign substances when storing in solution. On the other hand, when the usage ratio [A]/[Q] exceeds 0.710.3 [molar ratio], the proportion of 1,2-quinone diazidation of the hydroxyl groups of the polyhydroxy compound is acylated and/or sulfonylated. Since the ratio is small, the sensitivity, which is a characteristic of the resin composition, and the residual film rate when used as a positive resist are unbalanced, and furthermore, problems arise in resolution.

In the 1,2-quinone diazidation reaction, it is necessary to use a basic reagent.

Examples of the basic reagent include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and organic amines such as triethylamine, tripropylamine, pyridine, and aniline. The amount of these basic reagents used is 1,2-quinonediazide and other agents.
Usually 0.8 to 2 mol, preferably 1 to 1 mol
．． It is 5 moles.

In addition, in the acylation and/or sulfonylation reaction, when using the carboxylic acid halide and/or sulfonic acid halide, it is necessary to use the base No. 1 reagent, and the amount used is Usually 0.00% per mole of halide.
8 to 2 mol, preferably 1 to 1.5 mol.

In addition, in the acylation reaction, when the carboxylic acid anhydride is used, the basic reagent is not particularly required, and when the carboxylic acid is used, the basic reagent is not present in the reaction system. It is necessary to do so.

Further, the reaction temperature in the above methods (1), (2) and (3) is usually -20 to 60°C, preferably 0 to 4°C.
It is 0°C.

The QD compound according to the present invention synthesized as described above can be used alone or as a mixture of two or more in an alkali-soluble resin when used as a resin composition.
The blending amount is preferably 5 to 100 parts by weight, particularly preferably 10 to 5 parts by weight, per 100 parts by weight of the alkali-soluble resin.
It is 0 parts by weight. If the amount of QD compound is too small,
Since the QD compound absorbs radiation and produces a small amount of carvone, patterning becomes difficult when the resin composition is used as a positive resist. All of the QD compounds cannot be decomposed, making development with a developer consisting of an alkaline aqueous solution difficult.

The alkali-soluble resin used in the resin composition containing the QD compound obtained by the production method of the present invention includes:
For example, an alkali-soluble novolak resin (hereinafter simply referred to as "novolak resin") can be mentioned. Novolac resins are synthesized by addition condensation of phenols and aldehydes in the presence of an acid catalyst.

The phenols used at this time include, for example, phenol, 0-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-cresol,
-Ethylphenol, 0-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 A1 dihydroxybenzoate,
Examples include gallic acid ester. These phenols may be used alone or in combination of two or more.

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

The acid catalyst includes non-ta acids such as hydrochloric acid, nitric acid, and sulfuric acid;
Alternatively, organic acids such as formic acid, oxalic acid, and acetic acid are used. The amount of these acid catalysts used is preferably 1 x 10''4 to 5 x 10-1 mol per mol of phenol.

Water is usually used as a reaction medium in the condensation reaction when synthesizing novolac resins, 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 early stage, , it is also possible to use hydrophilic solvents as reaction medium. 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 to 1000 parts by weight per 100 parts by weight of the reaction raw materials.

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

After the condensation reaction is complete, in order to remove the unreacted raw materials, acid catalyst, and reaction medium present in the system, volatile components are distilled off under reduced pressure, and then the molten novolac resin is poured onto a steel belt, etc. and collect it.

Examples of alkali-soluble resins other than the novolak resin include polyhydroxystyrene or derivatives thereof,
Examples include styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and carboxyl group-containing (meth)acrylic resin. These alkali-soluble resins may be used alone or in combination of two or more.

When applying a resin composition containing a QD compound obtained by the production method of the present invention to a substrate, the composition is
For example, it is dissolved in a suitable solvent to a concentration of 5 to 50% by weight, and applied to a substrate such as a silicon wafer by spin coating, flow coating, roll coating, or the like. Examples of solvents 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, ethyl 2-oxypropionate, and 2-oxypropion. Examples include monooxymonocarboxylic acid esters such as ethyl acid, aromatic hydrocarbons such as 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. In addition, if necessary, 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 acetonyl acetone and isophorone, and fatty acids such as caproic acid and caprylic acid are added. , 1-octatool, 1-nonanol, alcohols such as benzyl alcohol, or esters such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, ethylene carbonate, phenyl cellosolve acetate, etc. It is also possible to add high boiling point solvents such as.

A sensitizer can be added to the resin composition containing the QD compound obtained by the production method of the present invention in order to improve sensitivity. As this sensitizer, for example, 2H-
Pyrido(3,2-b)-1゜4-oxazine-3[4H
) ons, 10H-pyrido(3,2-b)(1,4)-
Benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides, as well as Japanese Patent Publication No. 4B-12242, Japanese Patent Publication No. 48-3
Examples include sensitizers described in JP-A No. 5402, JP-A-58-37641, JP-A-58-149042, and the like. The blending amount of these sensitizers is usually 100 parts by weight or less per 100 parts by weight of the QD compound.

Furthermore, the resin composition containing the QD compound obtained by the production method of the present invention may contain surfactants, etc. in order to improve the coating properties, for example, the developability of the IJ any and the radiation irradiated area after forming the dry coating film. can be blended. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Nonionic surfactants of polyethylene glycol dialkyl ethers such as oxyethylene alkyl phenyl ethers, polyethylene glycol dilaurate, and polyethylene glycol distearate;
F-TOP EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173
(manufactured by Dainippon Ink Co., Ltd.), JP-A-57-178242
Straight fluorine-based surfactants having a fluorinated alkyl group or perfluoroalkyl group as exemplified in the above publication, Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-38
2, 5C101, 5C102, 5C103, 5C104
, 5CIO5, 5C106 (manufactured by Asahi Glass Co., Ltd.), fluorine-based surfactants, organosiloxane polymer KP34
1 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co)polymer Polyflow 75, l1h95
(manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). The blending amount of these surfactants, etc. is based on the solid content of the resin composition containing the QD compound obtained by the production method of the present invention.
It is usually 2 parts by weight or less per 0 parts by weight.

In addition, the resin composition containing the QD compound obtained by the production method of the present invention is coated with a coloring agent in order to visualize the latent increase in the radiation irradiated area and to reduce the effect of halation during radiation irradiation. Adhesion aids can also be added to improve the properties.

Furthermore, the resin composition containing the QD compound obtained by the production method of the present invention may also contain a storage stabilizer, an antifoaming agent, etc., if necessary.

A resin composition containing a QD compound obtained by the production method of the present invention is prepared by dissolving a predetermined amount of an alkali-soluble resin, a QD compound, and various compounding agents in a solvent.
．． It is prepared by filtering through a filter of about 2 μm.

Examples of the developer for the resin composition containing the QD compound obtained by the production method of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate,
Inorganic alkalis such as sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, and secondary amines such as diethylamine and di-n-propylamine.
amines, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, or virol, Piperidine, 1°8-diazabicyclo(5,4,
0) -7-undecene, 1,5-diazabicyclo(4
An alkaline aqueous solution prepared by dissolving a cyclic amine such as ,3,0)-5-nonane is used.

Further, the developer may contain a water-soluble organic solvent, such as methanol,
An aqueous solution containing an appropriate amount of an alcohol such as ethanol or a surfactant can also be used as the developer.

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

Example 1 (1) 5Q Q with stirrer, dropping funnel and temperature needle
Into a 12 separable flask, add ethylene glycol di(3,4,5
-) hydroxybenzoate) (H) 8.9 g,
1.2-Naphthoquinonediazide-5-sulfonic acid chloride [Q] 32.6 as a 2-quinonediazide agent
g ([Q] / (H) = 5 C molar ratio]), propionic acid chloride [A] as acylating agent 2.3
g ([A] / [Q] = 0.1710.83 [molar ratio]) and 240 g of dioxane as a solvent were charged and dissolved with stirring. Further add 16.2 to the dropping funnel.
g of triethylamine was charged.

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. Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of diluted hydrochloric acid to precipitate the QD compound. The precipitate was collected and dried in a heated vacuum dryer controlled at 40° C. all day and night.

The yield of the QD compound obtained was 98%.

(2) In a 2β separable flask equipped with a stirrer, 336 g of m-cresol, 224 g of p-cresol,
37% by weight, 400 g of formaldehyde aqueous solution and 0.24 g of oxalic acid were prepared, linear polymerization was carried out at 100°C for 3 hours, and then heat treatment was performed to obtain Novolac resin 260.
g, 39 g of the QD compound obtained in (1), 720 g of ethyl cellosolve acetate and 18 g of γ-butyrolactone.
0 g was added and stirred thoroughly at room temperature to dissolve. After dissolution, it was filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution of the composition. When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign particles larger than 0.5 μm was 10 (llil/mI2).Then, the solution was heated at 40°C.
When stored for one month in a thermostatically controlled oven, the number of foreign particles larger than 0.5 μm measured using an automatic particulate counter was 15 particles/mβ, which showed almost no increase. In addition, when we conducted a performance evaluation as a resist, we found that 40
There was no change in the sensitivity or residual film rate between the sample before and after the storage stability test at ℃, indicating that the sample had high storage stability.

Comparative Example 1 Into a 500 m β separable flask equipped with a stirrer, dropping funnel, and thermometer, ethylene glycol rouge (
3,4,5-trihydroxyhenshade) (H)9.
7g, 1.2-naphthoquinonediazide-5-sulfonic acid chloride (Q335.6g ([Q] / (H) =
5 (molar ratio)) and 240 g of dioxane,
Dissolved with stirring.

Furthermore, 14.7 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the product was collected and dried to obtain a non-acylated QD compound.

Next, a solution of the composition was prepared in the same manner as in Example 1 (2) except that the QD compound described above was used instead of the QD compound used in Example 1 (2). When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, it was found to be 0.5 μm.
The number of foreign substances was 15/ml. Then add the solution to 4
When stored in a constant temperature bath controlled at 0°C for one month, the number of foreign particles larger than 0.5 μm measured using an automatic particle counter increased to 1200 pieces/ml.

Examples 2 to 1O Example 1 In place of the propionic acid chloride used as the acylating agent in (1), [A]/[Q]=0.171
Example 1 except that the acylating agent or sulfonylating agent [A] shown in Table 1 was used under conditions such that the molar ratio was 0.83 [molar ratio].
A QD compound was obtained in the same manner as in (1). Next, these Q
Using Compound D, solutions of the compositions were prepared in the same manner as in Example 1 (2). Ti! l! 0.5 for each solution immediately and stored in a constant temperature bath at 40°C for 1 month.
When the number of foreign particles of μm or larger was measured using an automatic particle counter, no increase in foreign particles was observed in any of the solutions.

The results are shown in Table 1.

Examples 11 to 18 QD compounds were obtained in the same manner as in Example 1 (1) except that the compounds shown in Table 2 were selected as polyhydroxy compounds (H). Next, using these QD compounds, composition solutions were prepared in the same manner as in Example 1 (2). When the number of foreign particles of 0.5 μm or larger was measured using an automatic particle counter for each solution immediately after preparation and stored in a constant temperature bath at 40°C for one month, no increase in the number of foreign particles was observed in any of the solutions. I couldn't. The results are shown in Table 2.

Example 19 In a 500 ml separable flask equipped with a stirrer, a dropping funnel and a temperature needle, 8°9 g of ethylene glycol di(3°4.5-)lihydroxybenzoate) (H) (1 acyl) was added as a polyhydroxy compound under the cover of light. 2.3 g of propionic acid chloride [A] and 1 dioxane as a curing agent.
00g was charged and dissolved while stirring. Furthermore, 16.2 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the reaction solution was stirred for 30 minutes. Furthermore, 32.6 liters of 1,2-naphthoquinonediazide-5-sulfonic acid chloride was added to the dropping funnel as a 1,2-quinonediazide agent.
g ([Q]/(H)=5C molar ratio], [A]/
A solution prepared from [Q]=0.1'I10.83 (molar ratio) and 140 g of dioxane was charged.

The separable flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, the prepared solution was slowly added dropwise to the reaction solution so that the internal temperature did not exceed 35°C. , the product was collected and dried to obtain the QD compound. The yield of the QD compound obtained was 9
It was 7%.

Next, the solution of the composition was cleaved using the QD compound in the same manner as in Example 1 (2). When the number of foreign substances in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign substances with a diameter of 0.5 μm or more was 13 pieces/ml. Then add 40% of the solution
When stored in a constant temperature bath controlled at ℃ for one month, the number of foreign particles of 0.5 μm or more was measured with an automatic particle counter to 21 (hard/m1, and almost no increase in the number of foreign particles was observed.

Example 20 Into a 500ml separable flask equipped with a stirrer, a dropping funnel and a thermometer, 8°9 g of ethylene glycoluge (3°4.5-1-lyhydroxybenzoate) (H) as a polyhydroxy compound was added under protection from light. .1,2-naphthoquinonediazide-5 as a 2-quinonediazidating agent
-Sulfonic acid chloride [Q] 32.6 g ([Q]
/ (H) = 5 C molar ratio]) and dioxane 2
40g was charged and dissolved while stirring. Furthermore, 16.2 g of triethylamine was charged into the dropping funnel. Example 1 After reacting while dropping triethylamine in the same manner as in (1), the reaction solution was stirred for 30 minutes. Furthermore, propionic acid chloride [A] was added to the dropping funnel as an acylating agent.
) 2.3 g ([A] / [Q] =0.171
0.83 (molar ratio) was charged. The separable flask was immersed in a water bath controlled at 30°C, and when the internal temperature became constant at 30°C, the acylating agent was slowly added dropwise to the reaction solution so that the internal temperature did not exceed 35°C. After that, the product was collected and dried to obtain a QD compound. The yield of the QD compound obtained was 98%.

Next, using the QD compound, a solution of the composition was prepared in the same manner as in Example 1 (2). When the number of foreign particles in the solution immediately after preparation was measured using an automatic particle counter, the number of foreign particles with a diameter of 0.5 μm or more was 12 pieces/ml. Next, the solution was stored in a constant temperature bath controlled at 40°C for one month, and the particle size was 0.5 μm as measured with an automatic particle counter.
The number of foreign substances was 15 pieces/ml, and almost no increase in foreign substances was observed.

(Effects of the Invention) By using the specific 1,2-quinonediazide compound obtained by the production method of the present invention and an alkali-soluble resin, the generation of foreign matter is extremely small, and the resolution during resist pattern formation is improved. It is possible to obtain a radiation-sensitive resin composition suitable as a positive resist that can improve the properties and yield during the production of integrated circuits.

Claims (1)

[Claims] (1) (a) After reacting a part of the hydroxyl group of the polyhydroxy compound with an acylating agent and/or a sulfonylating agent to acylate and/or sulfonylate it, further part of the remaining hydroxyl group of the polyhydroxy compound or all 1
, 2-quinonediazidating agent to form 1,2-quinonediazide, or (b) some or all of the hydroxyl groups of the polyhydroxy compound are reacted with an acylating agent and/or a sulfonylating agent to form 1,2-quinonediazide.
acylation and/or reaction with a quinone diazidating agent.
or 1,2-quinonediazide at the same time as sulfonylation, or (c) some of the hydroxyl groups of the polyhydroxy compound are 1,2-
After reacting with a quinone diazidating agent to form 1,2-quinone diazidation, some or all of the remaining hydroxyl groups of the polyhydroxy compound are further reacted with an acylating agent and/or a sulfonylating agent to form acylation and/or sulfonylation. and the total amount of the acylating agent, sulfonylating agent, and 1,2-quinone diazidizing agent is 0.3 per gram equivalent of hydroxyl group of the polyhydroxy compound.
The ratio of the acylating agent and/or sulfonylating agent [A] and the 1,2-quinonediazidating agent [Q] is set to be at least 1 mol [A]/[Q]=0.01/0.99 to 0. 7/
A method for producing a 1,2-quinonediazide compound, characterized in that the molar ratio is 0.3.