JPH0336418B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a positive photosensitive resin composition for producing integrated circuits, and more specifically, to a positive photosensitive resin composition for producing an integrated circuit. The present invention relates to a positive photosensitive resin composition used as a heat-resistant photoresist for producing integrated circuits.

[Conventional technology]

Conventionally, as a photoresist for producing integrated circuits, a negative photoresist in which a bisazide compound is blended with cyclized isoprene rubber is known. However, this negative type photoresist has a limitation in resolution, and therefore has the disadvantage that it cannot sufficiently respond to higher integration of integrated circuits. On the other hand, in contrast to negative photoresists, positive photoresists have superior resolution and are therefore considered to be fully compatible with higher integration of integrated circuits.

Currently, positive photoresists commonly used in this field are made by blending an alkali-soluble resin with a 1,2-quinonediazide compound as a photosensitizer.

However, conventional positive photoresists
Crystals of the 1,2-quinonediazide compound are precipitated, and satisfactory results are not always obtained in various performances such as sensitivity, resolution, and residual film rate as a positive photoresist.

[Problem to be solved by the invention]

The object of the present invention is to eliminate the drawbacks of the above-mentioned conventional techniques, and to provide a 1,2-quinonediazide compound that does not cause crystal precipitation, has high sensitivity, high resolution, and high residual film rate, and has excellent developability. An object of the present invention is to provide a positive photosensitive resin composition for producing an integrated circuit that has heat resistance.

[Means to solve the problem]

The positive photosensitive resin composition for integrated circuit production of the present invention is prepared by the following general formula () with respect to 100 parts by weight of the alkali-soluble resin. Or the following general formula () (In the formula, l, m and n are the same or different,
means 0 or an integer from 1 to 2, R ₁ , R ₅ and
R ₇ is the same or different and is a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, or a 1,2-naphthoquinonediazide-5-sulfonyl group;
-benzoquinonediazide-4-sulfonyl group,
R ₂ , R ₆ , R ₈ and R ₁₁ are the same or different and are a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group,
Aryl group such as phenyl group, naphthyl group or alkoxy group, preferably alkoxy group having 1 to 7 carbon atoms such as methoxy group, phenoxy group, benzyloxy group, R ₃ , R ₄ , R ₉ and R ₁₀ are the same or different , a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, or an aryl group such as a phenyl group or a naphthyl group, R ₃ and R ₄ and R ₉ and R ₁₀ can form a ring through a carbon-carbon bond.

In the composition of the present invention, the compound represented by the general formula () or () used as a photosensitizer is produced, for example, by subjecting the phenolic hydroxyl group of a specific compound to a condensation reaction with 1,2-quinonediazide sulfonyl chloride. Ru.

That is, the compound represented by the above general formula () is the compound represented by the following general formula () (In the formula, R ₁₂ and R ₁₃ are the same or different,
hydrogen atom, alkyl group or aryl group, R ₁₄ and R ₁₅ are the same or different and mean a hydrogen atom, alkyl group, aryl group or alkoxy group,
_1,2 - _{naphthoquinonediazide} -4-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide, quinonediazide-5-sulfonyl chloride,
It is obtained by subjecting 1,2-quinonediazide sulfonyl chloride such as 1,2-benzoquinonediazide-4-sulfonyl chloride to a condensation reaction in the presence of a basic catalyst and then purifying it.

The amount of 1,2-quinonediazide sulfonyl chloride to be used for the compound represented by the general formula () in the condensation reaction is determined as appropriate depending on the number of hydroxyl groups in the compound represented by the general formula () to which the 1,2-quinonediazide sulfonyl chloride is to be condensed. It can be adjusted, and usually 1 equivalent of 1,2-quinonediazide sulfonyl chloride per equivalent of the number of hydroxyl groups.
Use moles.

Examples of the basic catalyst used in the condensation reaction include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and organic amines such as diethylamine and triethylamine. The amount of these basic catalysts used is usually 1 to 2 times the mole, preferably 1 to 1.3 times the mole of 1,2-quinonediazide sulfonyl chloride used. The condensation reaction is usually carried out in the presence of a solvent, such as water, dioxane, diethyl ether, tetrahydrofuran, acetone,
For example, methyl ethyl ketone, etc., per 100 parts by weight of the compound represented by the general formula (),
Usually 100 to 1000 parts by weight are used.

The condensation reaction temperature varies depending on the solvent used, but is generally -20 to 60°C, preferably 0 to 40°C.
It is ℃.

Examples of the compound represented by the general formula () include 2,3,4,2',3',4'-hexahydroxy-diphenylmethane, 2,3,4,2',
3′,4′-hexahydroxy-diphenylethane-
(1,1), 2,3,4,2',3',4'-hexahydroxy-diphenylpropane-(1,1), 2,
3,4,2',3',4'-hexahydroxy-diphenylpropane-(2,2), 2,3,4,2',3',
4'-hexahydroxy-diphenyl-n-butane-(1,1), 2,3,4,2',3',4'-hexahydroxy-diphenyl-n-pentane-(1,
1), 2,3,4,2',3',4'-hexahydroxy-diphenylcyclohexane-(1,1), 2,
3,4,2',3',4'-hexahydroxy-triphenylmethane, 2,4,6,2',4',6'-hexahydroxy-diphenylmethane, 2,4,6,
2',4',6'-hexahydroxy-diphenylethane-(1,1), 2,4,6,2',4',6'-hexahydroxy-diphenylpropane-(1,1),
2,4,6,2',4',6'-hexahydroxy-diphenylpropane-(2,2),2,4,6,2',
4',6'-hexahydroxy-diphenyl-n-butane-(1,1), 2,4,6,2',4',6'-hexahydroxy-diphenyl-n-pentane-(1,
1), 2,4,6,2',4',6'-hexahydroxy-diphenylcyclohexane-(1,1), 2,
4,6,2',4',6'-hexahydroxy-triphenylmethane, 2,3,4,2',3',4'-hexahydroxy-5,5'-dimethyl-diphenylpropane-( 2,2), 2,4,6,2',4',6'-hexahydroxy-3,3-dimethyl-diphenylpropane-(2,2), 2,3,4,2',3' , 4'-hexahydroxy-5,5'-dimethoxy-diphenylpropane-(2,2), 2,4,6,2',4',
Examples include 6'-hexahydroxy-3,3'-dimethoxy-diphenylpropane-(2,2).

These compounds represented by the general formula () are:
For example, it can be obtained in good yield by reacting the corresponding polyhydroxybenzene with aldehydes or ketones in the presence of an acidic catalyst such as hydrochloric acid.

The compound represented by the general formula () thus obtained can be purified by crystallization in an organic solvent such as alcohol, acetone, acetic acid, benzene, toluene, chlorobenzene, or a mixed solvent thereof.

In addition, the compound represented by the general formula () is the following general formula () (In the formula, R ₁₆ and R ₁₇ are the same or different,
_{1 ,} 1, 2-Naphthoquinone diazide-
It can be obtained by subjecting 4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-benzoquinonediazide-4-sulfonyl chloride, etc. to a condensation reaction in the presence of a basic catalyst and then purifying it.

The condensation reaction conditions in this case are the same as those for the compound represented by the general formula () and 1,2-quinonediazide sulfonyl chloride.

Examples of the compound represented by the general formula () used in this case include 2,3,4-trihydroxy-diphenylmethane, 2,4,6-trihydroxy-diphenylmethane, 2,3,4-trihydroxy-5-methyl -diphenylmethane, 2,
4,6-trihydroxy-3-methyl-diphenylmethane, 2,3,4-trihydroxy-5-methoxy-diphenylmethane, 2,4,6-trihydroxy-3-methoxy-diphenylmethane,
2,3,4-trihydroxy-4'-methyl-diphenylmethane, 2,4,6-trihydroxy-
4'-Methyl-diphenylmethane, 2,3,4-trihydroxy-4'-t-butyl-diphenylmethane, 2,3,4-trihydroxy-4'-t-butyl-diphenylmethane, 2,3,4-trihydroxy-4'-t-butyl-diphenylmethane Hydroxy-diphenylethane-(1,1),2,4,6
-trihydroxy-diphenylethane-(1,
1), 2,3,4-trihydroxy-diphenylpropane-(1,1), 2,4,6-trihydroxy-diphenylpropane-(1,1), and the like.

These compounds represented by the general formula () are:
For example, polyalkoxy produced by reacting a corresponding benzyl chloride with polyhydroxybenzene or a derivative thereof, or by reacting a benzyl chloride with a polyalkoxybenzene or a derivative thereof in the presence of a Lewis acid catalyst. It is obtained by further treating the compound with aluminum chloride, sodium hydroxide, hydrochloric acid-pyridine, aqueous hydrogen iodide, boron tribromide, aqueous hydrogen bromide, and the like.

Specific examples of the compound represented by the general formula () obtained in this way include the following compounds.

2,3,4,2',3',4'-hexahydroxy-
Diphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid hexaester, 2,3,
4,2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid hexaester, 2,3,4,2',3',
4'-hexahydroxy-diphenylmethane-1,
2-benzoquinonediazide-4-sulfonic acid hexaester, 2,3,4,2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester,
2,3,4,2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, 2,3,4,
2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid triester, 2,3,4,2',3',4'-hexahydroxy-diphenylmethane-1, 2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4,2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2,3,
4,2',3',4'-hexahydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,
4,2',3',4'-hexahydroxy-diphenylpropane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,
4,2',3',4'-hexahydroxy-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,
4,2',3',4'-hexahydroxy-diphenyl-n-butane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,
3,4,2',3',4'-hexahydroxy-diphenyl-n-pentane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4,2',3',4'-hexahydroxy-diphenylcyclohexane-(1,1)-1,2
-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,4,2',3',4'-hexahydroxy-triphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester,
2,4,6,2',4',6'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,
2',4',6'-hexahydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-
5-sulfonic acid pentaester, 2,4,6,
2',4',6'-hexahydroxy-diphenylpropane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,
2',4',6'-hexahydroxy-diphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,
2',4',6'-hexahydroxy-diphenyl-n
-butane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,
6,2',4',6'-hexahydroxy-diphenyl-n-pentane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester,
2,4,6,2',4',6'-hexahydroxy-diphenylcyclohexane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,2' , 4',6'-hexahydroxy-triphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,
3,4,2',3',4'-hexahydroxy-5,
5'-dimethyl-diphenylpropane-(2,2)-
1,2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,2',4',6'-hexahydroxy-3,3'-dimethyl-diphenylpropane-(2,2)-1 , 2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,3,
4,2',3',4'-hexahydroxy-5,5'-dimethoxy-diphenylpropane-(2,2)-1,
2-naphthoquinonediazide-5-sulfonic acid pentaester, 2,4,6,2',4',6'-hexahydroxy-3,3'-dimethoxy-diphenylpropane-(2,2)-1,2 - Naphthoquinonediazide-5-sulfonic acid pentaester.

Further, specific examples of the compound represented by the general formula () include the following compounds.

2,3,4-trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid triester, 2,3,4-trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid triester, 2, 3, 4
-trihydroxy-diphenylmethane-1,2-
Benzoquinonediazide-4-sulfonic acid triester, 2,3,4-trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4-trihydroxy-diphenylmethane-1,2-naphtho Quinonediazide-5-sulfonic acid monoester, 2,4,
6-trihydroxy-diphenylmethane-1,2
-Naphthoquinonediazide-5-sulfonic acid diester, 2,3,4-trihydroxy-5-methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,4,6-
Trihydroxy-3-methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4-trihydroxy-5
-methoxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester,
2,4,6-trihydroxy-3-methoxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4-trihydroxy-4'-methyl-diphenylmethane-
1,2-naphthoquinonediazide-5-sulfonic acid diester-2,4,6-trihydroxy-4'-
Methyl-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,
3,4-trihydroxy-4'-t-butyl-diphenylmethane-1,2-naphthoquinonediazide-
5-sulfonic acid diester, 2,4,6-trihydroxy-4'-t-butyl-diphenylmethane-
1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,3,4-trihydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-4-sulfonic acid triester, 2,
3,4-trihydroxy-diphenylethane
(1,1)-1,2-naphthoquinonediazide-5-
Sulfonic acid triester, 2,3,4-trihydroxy-diphenylethane-(1,1)-1,2-
Benzoquinonediazide-4-sulfonic acid triester-2,3,4-trihydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid triester, 2,3,4-trihydroxy-diphenylethane -(1,1)-
1,2-naphthoquinonediazide-5-sulfonic acid monoester, 2,4,6-trihydroxy-diphenylethane-(1,1)-1,2-naphthoquinonediazide-5-sulfonic acid diester, 2,
3,4-trihydroxy-diphenylpropane-
(1,1)-1,2-naphthoquinonediazide-5-
Sulfonic acid diester, 2,4,6-trihydroxy-diphenylpropane-(1,1)-1,2-
Naphthoquinonediazide-5-sulfonic acid diester.

In the composition of the present invention, compounds represented by general formula () or () can be used in combination.

In the composition of the present invention, the alkali-soluble resin to which the compound represented by the above general formula () and/or () is added is not particularly limited, but for example, a novolak resin obtained from phenol and formaldehyde, a novolak resin obtained from cresol and formaldehyde, etc. Examples include novolac resins obtained from hydroxystyrene polymers, aminostyrene polymers, copolymers of ethylenically unsaturated carboxylic acids and monoolefin compounds, and the like.

General formula () and/or in the composition of the present invention
The compounding amount of the compound represented by () is 5 to 100 parts by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin. If this amount is less than 5 parts by weight, the residual film rate after development will be insufficient, the pattern obtained will be easily deformed by heat, and a composition with high resolution will not be obtained. On the other hand, if this amount exceeds 100 parts by weight, a composition with high sensitivity cannot be obtained.

The composition of the present invention has the general formula () or ()
The amount of 1,2-quinonediazide compounds other than the compounds represented by the following formula is within a range that does not impede the effects of the present invention, for example, 100 parts by weight or less, preferably 50 parts by weight or less, particularly preferably 20 parts by weight, based on 100 parts by weight of the alkali-soluble resin. It can be blended in a proportion of less than 1 part.

Furthermore, in order to improve the developability, storage stability characteristics, etc. of the composition of the present invention, the composition of the present invention may be prepared by copolymerizing styrene and maleic anhydride, a natural resin such as rosin or silica copolymer, or copolymerizing styrene and acrylic resin. Synthetic resins such as acid, methacrylic acid or copolymers with these alkyl esters, acrylic ester polymers, vinyl acetal polymers, vinyl ether polymers, vinyl acetate polymers, vinyl alcohol polymers, vinyl pyrrolidone polymers,
It can also be added in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin.

Furthermore, storage stabilizers, pigments, and the like may be added to the composition of the present invention, if necessary. Furthermore, in order to improve the adhesive strength between the composition of the present invention and a substrate, depending on the selected substrate, for example, hexamethyldisilazane, chloromethylsilane, etc. may be applied as an adhesive to the substrate.

The composition of the present invention can be applied onto a substrate to be microfabricated, and a pattern can be formed by partially irradiating the composition with actinic light, such as ultraviolet rays, and developing it.

The composition of the present invention can be applied to a substrate by dissolving the composition of the present invention in an appropriate solvent to a concentration of 5 to 50% by weight, and applying the composition by spin coating, flow coating, or roll coating. An example of this method is to apply the agent by, for example, Suitable solvents used in this case include, for example, ketones such as cyclopentanone, cyclohexanone, and diacetone alcohol;
-Alcohols such as butanol, ethers such as dioxane, ethylene glycol dimethyl ether, ethyl glycol diethyl ether, alcohol ethers such as ethyl glycol monomethyl ether, ethylene glycol monoethyl ether, esters such as butyl acetate, cellosolve acetate, methoxyethyl acetate, etc. Class, 1, 1, 2
- Halogenated hydrocarbons such as trichloroethylene, polar solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, etc. are used alone or in combination.

The developer used in the composition of the present invention includes:
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, trisodium phosphate, sodium hydrogen phosphate, n-propylamine, di-n-propylamine, di-n-butylamine, methyldiethylamine. , pyrrole, 2,5-dimethylpyrrole, β
- Aqueous solutions of picoline, collidine, piperidine, piperazine, triethylenediamine, dimethylethanolamine, triethanolamine, diethylhydroxylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and aqueous ammonia.

Further, an appropriate amount of alcohols such as methanol and ethanol, sulfite stabilizers, or surfactants may be added to the developer.

〔Example〕

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

Example 1 (1) Synthesis of novolac resin A 500 ml three-neck separable flask was charged with 75 g of m-cresol and 25 g of p-cresol, and then 66 ml of a 37% by weight formalin aqueous solution and 0.04 g of oxalic acid were added. While stirring, the separable flask was immersed in an oil bath to adjust the reaction temperature to 100°C, and the reaction was allowed to proceed for 10 hours. After the reaction was completed, water was distilled off by reducing the pressure to 30 mmHg, and the internal temperature was further raised to 130°C to remove unreacted substances. The reaction product, molten alkali-soluble novolac resin, was then returned to room temperature and recovered.

(2) Synthesis of photosensitizer In a 500 ml three-neck separable flask, add 63 g of pyrogallol, 20 g of acetone, and 100 g of dioxane.
ml, and 10 ml of hydrochloric acid water was added while stirring. After reacting this solution at 60°C for 10 hours and then at room temperature for 48 hours, it was mixed with 40% acetic acid aqueous solution 1 to precipitate the product, and further recrystallized in dioxane. ',3',4'-hexahydroxy-diphenylpropane-(2,2) was obtained.

In a 500ml three-necked separable flask under light-shielding conditions,
2,3,4,2',3',4'-hexahydroxy-diphenylpropane-(2,2) 14.6 g, 1,2-
naphthoquinonediazide-5-sulfonyl chloride
53.7 g and 250 ml of dioxane were charged and dissolved. To this solution, 23 g of triethylamine was gradually added while stirring, and the mixture was reacted at room temperature for 2 hours. After the reaction, the contents were dropped into a large amount of 1% by weight hydrochloric acid solution to precipitate the product, washed with water and vacuum dried at 40°C for 20 hours to obtain 2,3,4,2',3',4'- Hexahydroxy-diphenylpropane-(2,2)-
1,2-naphthoquinonediazide-5-sulfonic acid tetraester (hereinafter referred to as photosensitizer A) was obtained.

(3) Preparation and evaluation of composition 20 g of alkali-soluble novolac resin obtained in (1) and 5 g of photosensitizer A obtained in (2) were mixed under light shielding.
Dissolved in 75g of cellosolve acetate, pore size
A solution of the composition of the present invention was prepared by filtration through a 0.2 μm membrane filter. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

The obtained solution was applied onto a silicon oxide film wafer using a spinner, and then heated in an oven at 90°C.
A composition film with a thickness of 1 μm was obtained by pre-baking for 25 minutes. A test pattern mask manufactured by Toppan Printing Co., Ltd. was placed in close contact with the wafer, and ultraviolet rays of 12.6 mJ/cm ² (model manufactured by Optical Associates, Inc.) were applied to the wafer.
205UV measured by a power meter).
Tetramethylammonium hydroxy 2.0% by weight
When developed with an aqueous solution at 20℃ for 60 seconds, the line width was
We were able to resolve a 1.0μm pattern. It can be seen that the composition of the present invention has excellent sensitivity and resolution. Furthermore, the residual film rate in the unexposed area was as high as 91%, and there was no development residue, the pattern was clear, and the developability was extremely excellent.

Example 2 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
Diphenylpropane-(2,2) 14.6g, 1,2
2,3,4,2',3',4'-hexahydroxy -Diphenylprone-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as photosensitizer B) was obtained.

(2) Preparation and evaluation of composition 20 g of the alkali-soluble novolac resin obtained in Example 1 (1) and 5 g of photosensitizer B were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Further, the residual film ratio in the unexposed area was as high as 92%, and as in Example 1, the developability was also extremely excellent.

Example 3 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
2,3,
4,2',3',4'-hexahydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as photosensitizer C) was obtained.

(2) Preparation and evaluation of composition 20 g of the alkali-soluble novolak resin obtained in Example 1 (1) and 5 g of photosensitizer C were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Further, the residual film ratio in the unexposed area was as high as 89%, and as in Example 1, the developability was also extremely excellent.

Example 4 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
Diphenylcyclohexane-(1,1) 16.6g,
2,3,4,2',3',4' -hexahydroxy-diphenylcyclohexane-(2,2)-
1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as photosensitizer D) was obtained.

(2) Preparation and evaluation of composition 20 g of the alkali-soluble novolak resin obtained in Example 1 (1) and 5 g of photosensitizer D were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Further, the residual film ratio in the unexposed area was as high as 91%, and as in Example 1, the developability was also extremely excellent.

Example 5 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
2,3,
4,2',3',4'-hexahydroxy-triphenylmethane-1,2-naphthoquinonediazide-5-
A sulfonic acid pentaester (hereinafter referred to as photosensitizer E) was obtained.

(2) Preparation and evaluation of composition 20 g of the alkali-soluble novolac resin obtained in Example 1 (1) and 5 g of photosensitizer E were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Further, the residual film ratio in the unexposed area was as high as 92%, and as in Example 1, the developability was also extremely excellent.

Example 6 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
5,5'-dimethyldiphenylpropane-(2,2)
16.0 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 67.3 g, dioxane 300 ml and triethylamine 29 g were reacted in the same manner as in Example 1 to obtain 2,3,4,2',3',4'-Hexahydroxy-5,5'-dimethyldiphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as photosensitizer F) was obtained.

(2) Preparation and evaluation of composition 20 g of the alkali-soluble novolac resin obtained in Example 1 (1) and 5 g of photosensitizer F were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Furthermore, the residual film ratio in the unexposed area was as high as 90%, and as in Example 1, the developability was also extremely excellent.

Example 7 (1) Synthesis of photosensitizer 2,3,4,2',3',4'-hexahydroxy-
5,5'-dimethoxydiphenylpropane-(2,
2) 17.6g, 1,2-naphthoquinonediazide-5
-Sulfonyl chloride 67.3g, dioxane 300ml
and 29 g of triethylamine, Example 1
2,3,4,2',3',4'-
Hexahydroxy-5,5'-dimethoxydiphenylpropane-(2,2)-1,2-naphthoquinonediazide-5-sulfonic acid pentaester (hereinafter referred to as
A photosensitive agent G) was obtained.

(2) Preparation and evaluation of composition 20 g of alkali-soluble novolak resin obtained in Example 1 (1) and 5 g of photosensitizer G were added to 75 g under light shielding.
A solution of the composition of the present invention was prepared by dissolving the composition in cellosolve acetate and filtering it through a membrane filter with a pore size of 0.2 μm. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate.

When the obtained solution was evaluated in the ^same manner as in Example 1 (3), the line width was
A 1.0 μm pattern could be resolved. Furthermore, the residual film ratio in the unexposed area was as high as 83%, and as in Example 1, the developability was also extremely excellent.

Example 8 (1) Synthesis of photosensitizer 10.8 g of 2,3,4-trihydroxy-diphenylmethane, 1,2-naphthoquinonediazide-5-
Example 1 (2) using 13.4 g of sulfonyl chloride, 150 ml of dioxane and 10 g of triethylamine
The reaction was carried out in the same manner as above to obtain 2,3,4-trihydroxy-diphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid diester (hereinafter referred to as photosensitizer H).

(2) Preparation and evaluation of composition A solution of the composition of the present invention was prepared under the same light conditions as in Example 3, except that photosensitizer H was used instead of photosensitizer C. Even when this solution was stored for a long period of time, crystals of the photosensitizer did not precipitate. When the obtained solution was evaluated in the same manner as in Example 1 (3),
A pattern with a line width of 1.0 μm could be resolved with 13.5 mJ/cm ² of ultraviolet irradiation. Furthermore, the residual film ratio in the unexposed area was as high as 87%, and as in Example 1, the developability was also extremely excellent.

〔Effect of the invention〕

The composition of the present invention does not precipitate crystals of the 1,2-quinonediazide compound, has high sensitivity, high resolution, high residual film rate, and has excellent developability, and is suitable for integrated circuit production. It is useful as a positive photoresist with heat resistance for
It is also useful as a positive photoresist for mask production.

Claims (1)

[Claims] 1. For 100 parts by weight of alkali-soluble resin, the following general formula () Or the following general formula () (In the formula, l, m and n are the same or different,
means 0 or an integer from 1 to 2, R ₁ , R ₅ and
R ₇ is the same or different and is a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, or a 1,2-naphthoquinonediazide-5-sulfonyl group;
-benzoquinonediazide-4-sulfonyl group,
R ₂ , R ₆ , R ₈ and R ₁₁ are the same or different; hydrogen atoms, alkyl groups, aryl groups or alkoxy groups; R ₃ , R ₄ , R ₉ and R ₁₀ are the same or different;
5 to 100% by weight of at least one compound represented by a hydrogen atom, an alkyl group, or an aryl group, in which R ₃ and R ₄ and R ₉ and R ₁₀ can form a ring with a carbon-carbon bond. 1. A positive photosensitive resin composition for producing an integrated circuit, comprising: