JP2000119520A - Production of positive type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive type photosensitive resin composition having high sensitivity, a short development time and high resistance o formed pattern by treating a specific alkali-soluble polymer with an acetal or ketal compound and adding an ortho-quinone diazide compound to the treated polymer. SOLUTION: An alkali-soluble polymer of formula I (R1 is a >=2C trifunctional or tetrafunctional organic group; R2 is >=2C bifunctional organic group; R3 is H or a >=1C monofunctional organic group; (m) is 1 or 2; (n) is an integer of 3-1,000) is treated with at least one kind of a compound of formula II (R4 is H or a >=1C monofunctional organic group; R5 is H, a >=1C monofunctional organic group, nitrogen-containing organic group or oxygen-containing organic group; R6 is a >=1C monofunctional organic group) or formula III (R7 is a >=1C bifunctional organic group, nitrogen-containing organic group or oxygen- containing organic group; R8 is a >=1C monofunctional organic group). Then an ortho-quinone diazide compound being a photosensitizer is added to the polymer to give the objective positive type photosensitive resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a positive photosensitive resin composition, and more particularly, to a method for developing a positive photosensitive resin composition, which can be developed with an alkali developing solution, and which is further subjected to a heat treatment. The present invention relates to a photosensitive resin composition to be a polyimide heat-resistant resin applicable as an insulating film and a method for producing the same.

[0002]

2. Description of the Related Art Polyimide can be easily formed into a film, and has excellent heat resistance and mechanical properties. Therefore, polyimide is widely used as a surface protective film and an interlayer insulating film of a semiconductor device. When polyimide is used as a surface protective film and an interlayer insulating film, it is necessary to pattern the polyimide film for the purpose of forming through holes. For example, a solution of a polyamic acid, which is a polyimide precursor, is applied to a substrate, converted into polyimide by heat treatment, then a positive photoresist relief pattern is formed on the polyimide film, and the polyimide film is formed with a hydrazine-based etchant. Pattern processing is performed by a selective etching method. However, in the above polyimide pattern processing,
The process is complicated because it involves steps such as application and stripping of a photoresist. In addition, since the relief pattern is transferred to the polyimide film via the photoresist, the dimensional accuracy tends to decrease. For these reasons, a photosensitive resin composition which is a heat-resistant resin or a precursor which can be converted into a heat-resistant resin by heat treatment or the like and which itself can be subjected to pattern processing has been studied.

[0003] As for the photosensitive polyimide composition, a polyimide precursor composition having a photosensitive group introduced by an ester bond (Japanese Patent Publication No. 52-30307), a carbon-carbon diamine which can be dimerized or polymerized with a polyamic acid by actinic radiation. A polyimide precursor composition to which an amine compound containing a heavy bond is added (JP-B-59-52822) is known. When using the photosensitive polyimide composition, usually,
The solution is applied to the substrate in a solution state, dried, and irradiated with actinic rays through a mask. The above polyimide precursor composition is of a negative type in which unexposed portions are dissolved, and an organic solvent is used for development. When switching from a non-photosensitive polyimide patterning process using a conventional positive photoresist to a process using a negative photosensitive polyimide composition, it is necessary to change the mask of the exposure equipment and the development equipment. Was a problem. Further, from the viewpoint of preventing environmental pollution and improving the working environment, a photosensitive material that can be developed with an aqueous developer instead of an organic developer has been desired. For these reasons, alkali-developable positive photosensitive polyimides have been studied.

A polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (JP-A-60-3755)
No. 0), a mixture of a polyamic acid ester and an o-quinonediazide compound (JP-A-2-181149), a mixture of a polyamic acid having a phenolic hydroxyl group or a polyamic acid ester and an o-quinonediazide compound (JP-A-Hei. No. 3-115461), a mixture of a polyimide having a phenolic hydroxyl group and an o-quinonediazide compound (JP-A-3-177455), and a mixture of polyhydroxyamide and an o-quinonediazide compound (Japanese Patent Publication No. 1-46862). Gazette) was known.

However, a polyimide precursor having an o-nitrobenzyl group introduced by an ester bond has a problem in that the sensitivity is low because the photosensitive wavelength is mainly 300 nm or less. A mixture of a polyamic acid ester and an o-quinonediazide compound has a problem that the developing time is long and the sensitivity is low because the dissolving rate in an alkali developing solution is low. A mixture of a polyamic acid having a phenolic hydroxyl group and an o-quinonediazide compound is too large in solubility in an alkali developing solution, so that it can be applied only to a dilute alkali developing solution, and the unexposed portion swells with the developing solution. Therefore, there is a problem in that fine pattern processing is difficult. Polyamides having phenolic hydroxyl groups, polyimides having phenolic hydroxyl groups, or those obtained by mixing an o-quinonediazide compound with polyhydroxyamide, the solubility in an alkali developing solution is improved to some extent, but the solubility is adjusted. However, there is a problem in that it is necessary to change the polymer composition and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a positive photosensitive resin composition which can easily adjust the solubility in an alkali developing solution. An object of the present invention is to provide a positive photosensitive resin composition in which the dissolution rate in an alkali developer is adjusted to a practically desirable rate.

[0007]

According to the present invention, there is provided a method for producing a positive photosensitive resin composition comprising an alkali-soluble polymer and an o-quinonediazide compound, wherein the alkali-soluble polymer represented by the general formula (1) is represented by the general formula: A method for producing a positive photosensitive resin composition, characterized by treating with at least one compound represented by formula (2) or formula (3).

[0008]

Embedded image (In the general formula (1), R1 represents a trivalent or tetravalent organic group having 2 or more carbon atoms, R2 represents a divalent organic group having 2 or more carbon atoms, and R3 represents a hydrogen atom or a carbon atom having 1 or more carbon atoms. Represents a monovalent organic group, m represents an integer of 1 or 2, and n represents 3 to 1.
Indicates an integer of 000. )

Embedded image (In the general formula (2), R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R5 represents a hydrogen atom or 1 carbon atom.
Any of the above monovalent organic groups, nitrogen-containing organic groups, and oxygen-containing organic groups is shown, and R6 is a monovalent organic group having 1 or more carbon atoms. )

Embedded image (In the general formula (3), R7 represents any one of a divalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group;
8 represents a monovalent organic group having 1 or more carbon atoms. )

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the general formula (1) represents a structural unit of a polyamide. R1 in the general formula (1) is a trivalent or tetravalent organic group having 2 or more carbon atoms, R2 is a divalent organic group having 2 or more carbon atoms, and R3 is a hydrogen atom or an organic group having 1 or more carbon atoms. It is preferably a group.

The polymer represented by the general formula (1) is obtained by reacting a tetracarboxylic dianhydride represented by the general formula (4) with a diamine compound represented by the general formula (5).

[0011]

Embedded image (In the general formula (4), R1 is the same as the general formula (1).)

Embedded image (In the general formula (5), R2 is the same as the general formula (1).) Examples of the tetracarboxylic dianhydride represented by the general formula (4) include pyromellitic dianhydride,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride, 1,2,2
3,4-cyclobutanetetracarboxylic dianhydride, 1,
2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3 ′ , 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 2,2
Tetracarboxylic dianhydrides such as -bis (3,4-dicarboxyphenyl) hexafluoropropanetetracarboxylic dianhydride are used alone or in combination of two or more.

Examples of the diamine compound represented by the general formula (5) include, for example, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '
-Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4 '
-Diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 1,4-phenylenediamine,
1,3-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, Bis [4- (4-aminophenoxy)
Phenyl] ether, diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, and 2,2-bis (3
-Amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxybenzidine, 2,4-
Diamine compounds having a phenolic hydroxyl group such as diamino-6-hydroxypyrimidine, 4,5-diamino-6-hydroxypyrimidine, 2,3-diaminophenol, and 2,4-diaminophenol; 2,5-diaminobenzoic acid; 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,5-diaminoterephthalic acid, bis (4-amino-3-carboxyphenyl) methylene, bis (4-
Amino-3-carboxyphenyl) ether, 4,4 ′
-Diamino-3,3'-dicarboxybiphenyl, 4,
4'-diamino-5,5'-dicarboxy-2,2'-
Diamine compounds having a carboxyl group such as dimethylbiphenyl are exemplified. These diamine compounds are used alone or in combination of two or more.

For the purpose of improving the adhesion to the substrate, a diamine compound having a siloxane structure can be used as long as the heat resistance is not reduced. As the diamine compound having a siloxane structure, for example, bis (3-aminopropyl) tetramethyldisiloxane, bis (3-aminopropyl) tetraphenyldisiloxane and the like are used.

The polymer represented by the general formula (1) is obtained by reacting a diamine compound represented by the general formula (5) with a tetracarboxylic dianhydride represented by the general formula (4) by a known method. Synthesized by That is, N-methyl-2
-Pyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, 1,
It is synthesized by reacting in an organic solvent containing 3-dimethylimidazolidinone, hexamethylphosphoramide, γ-butyrolactone, cresol or the like as a main component.

The compound of the general formula (2) is an acetal or ketal compound. R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R5 represents any one of a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group; Represents a monovalent organic group having 1 or more carbon atoms. Specifically, N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide dibutyl acetal, N, N-dimethylformamide dibenzyl Acetal, N, N-dimethylformamide bis [2- (trimethylsilyl) ethyl] acetal,
N-dimethylacetamide diethyl acetal, trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthobenzoate, triethyl orthobenzoate, and the like, preferably N, N -Dimethylformamide dimethyl acetal,
N, N-dimethylformamide diethyl acetal,
N, N-dimethylformamide dipropyl acetal,
N, N-dimethylformamide dibutyl acetal,
N, N-dimethylformamide dibenzyl acetal.

The compound represented by the general formula (3) is a cyclic carbonyl compound acetal or ketal compound. R7 represents any one of a divalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group, and R8 represents a monovalent organic group having 1 or more carbon atoms. Specifically, N-methyl-2
-Pyrrolidone dialkyl acetal, 1,3-dimethylimidazolidinone dialkyl acetal, ethylene dialkyl acetal, propylene dialkyl acetal, γ-butyrolactone dialkyl acetal, cyclohexanone dimethyl acetal, preferably N-methyl-2-pyrrolidone dimethyl acetal ,
N-methyl-2-pyrrolidone diethyl acetal, γ-
Butyrolactone dimethyl acetal and γ-butyrolactone diethyl acetal.

The polymer represented by the general formula (1) is dissolved in a solvent, and one or more compounds of the general formula (2) or the general formula (3) are directly added to the solution, or the solution is mixed and stirred. By doing so, it can be processed. After polymerizing the polymer represented by the general formula (1), one or more compounds of the general formula (2) or the general formula (3) are directly used in the solution, or the solution is mixed and stirred for treatment. You can also. The carboxyl group in the polymer represented by the general formula (1) can be esterified by treating with at least one compound of the general formula (2) or the general formula (3). During this treatment, an imidization reaction as a side reaction also proceeds, but the ratio of the imidization reaction to the esterification reaction can be suppressed by selecting reaction conditions, that is, by selecting a reaction solvent and a reaction temperature. is there. As a reaction solvent, N
Aprotic polar solvents such as -methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, γ-butyrolactone; Preferably, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide are more preferable. Reaction temperature is from 0 ° C to 20
It is in the range of 0 ° C, preferably 20 ° C to 100 ° C, more preferably 30 ° C to 80 ° C. If the reaction temperature is lower than 0 ° C., the time required for the reaction to be completed becomes long, which is not practical. On the other hand, when the reaction temperature exceeds 200 ° C., the ratio of the imidization reaction increases, and problems such as a decrease in the transparency of the polymer and the generation of a gel component are likely to occur.

At least one compound represented by the general formula (2) or the general formula (3) may be used in order to accelerate the reaction by using an acid such as trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid or phosphoric acid. Is represented by the general formula (2) or the general formula (3)
0.01 to the total amount of any one or more compounds
To 10 mol% in combination.

The ratio of the compound represented by the general formula (2) or the general formula (3) to the polymer represented by the general formula (1) is determined by the ratio of the carboxyl group /
The total amount (molar ratio) of the latter compound is from 100/1 to 100 /
1000. Preferably, 100/10 to 100
/ 200500, more preferably 100/20
To 100/100200. The optimum ratio is determined by considering the structure of the polymer represented by the general formula (1) and the process conditions of pattern processing to be applied. The amount of residual carboxyl groups in the polymer after the treatment is preferably 0.001 to 5 mol / kg, and more preferably 2 mol / kg or less.

The o-quinonediazide compound which is a photosensitizer used in the present invention includes 1,2-benzoquinone-2-azido-4-sulfonic acid ester or sulfonic acid amide,
There are 1,2-naphthoquinone-2-diazide-5-sulfonic acid ester or sulfonic acid amide, 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester and sulfonic acid amide. These include, for example, 1,2-benzoquinone-2-azido-4-sulfonyl chloride,
1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-
It can be obtained by subjecting an o-quinonediazide sulfonyl chloride such as a sulfonyl chloride to a condensation reaction with a polyhydroxy compound or a polyamine compound in the presence of a dehydrochlorination catalyst.

Examples of polyhydroxy compounds include hydroquinone, resorcinol, catechol, pyrogallol, hydroxyhydroquinone, bisphenol A, bis (4-
Hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1- Screw (4
-Hydroxyphenyl) ethyl] benzene, 1-naphthol, 2-naphthol, methyl gallate, ethyl gallate and the like.

Examples of the polyamine compound include 1,4-phenylenediamine, 1,3-phenylenediamine,
4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide and the like.

Examples of the polyhydroxypolyamine compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine.

The o-quinonediazide compound is preferably used in an amount of 1 to 1 based on 100 parts by weight of the alkali-soluble polymer.
00 parts by weight, more preferably 5 to 40 parts by weight. If the amount is less than 1 part by weight, sufficient sensitivity cannot be obtained, and if it exceeds 100 parts by weight, the heat resistance of the resin composition may be reduced.

The photosensitive resin composition of the present invention is preferably used in the form of a solution in which an alkali-soluble polymer and o-quinonediazide are dissolved in a solvent. Examples of the solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, γ-butyrolactone, tetramethyl An aprotic polar solvent such as urea is used alone or in combination of two or more. For the purpose of improving the uniformity of the coating film, propylene glycol monomethyl ether,
Propylene glycol monomethyl ether acetate,
Solvents such as ethers or esters such as ethyl lactate may be mixed and used.

The photosensitive resin composition of the present invention can contain an organic silane compound or an aluminum chelate compound as an adhesion aid. As the organic silane compound, for example, 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane,
3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. Examples of the amino chelate compound include aluminum tris (acetylacetate) and aluminum acetylacetate diisopropylate.
The adhesion aid is used in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble polymer.

From the photosensitive resin composition of the present invention, a relief pattern can be obtained as follows. That is, the photosensitive resin composition is spin-coated with a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride, and then a hot plate. Dry using an oven or the like. Next, the resin composition coated on the supporting substrate is irradiated with actinic rays through a mask. As the actinic ray, ultraviolet ray, visible ray, radiation, etc. can be used.
A wavelength of from 00 to 500 nm is preferred, and more preferably an i-line (365 nm) and an h-line (405 n) of a mercury lamp.
m) and g-line (436 nm). A relief pattern is obtained by removing the exposed portion with a developing solution. Examples of the developer include, but are not limited to, aqueous solutions of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide and the like. The concentration of these aqueous solutions is preferably from 0.1 to 10% by weight. Further, an alcohol or a surfactant may be added to the developer for use. Each of these is preferably added to the developer in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Next, the resulting relief pattern is subjected to a heat treatment at 150 to 450 ° C., whereby a relief pattern of a heat-resistant polymer having an imide ring or another cyclic group is obtained.

[0028]

The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 17.58 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a nitrogen atmosphere
(48 mmol) and 0.50 g (2 mmol) of bis (3-aminopropyl) hexamethyldisiloxane in 79 g of dried N-methyl-2-pyrrolidone were added to a solution of 3,3 ′, 4,4′-benzophenonetetrane. 15.17 g (49 mmol) of carboxylic dianhydride was mixed and stirred, and reacted at 50 ° C. for 5 hours. Further, 14.72 g of N, N-dimethylformamide diethyl acetal (10.
0 mmol) and stirred at 50 ° C. for 5 hours to obtain a partially esterified polyamic acid solution (A).

The obtained polyamic acid solution (A) was added with o-
Quinonediazide compound 4NT-300 (manufactured by Toyo Gosei Kogyo Co., Ltd .: 1 mol of 2,3,4,4'-tetrahydroxybenzophenone is reacted with 3 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride) After dissolving 6.77 g of the obtained ester, the solution was filtered through a 0.5 μm membrane filter to prepare a photosensitive composition.

The photosensitive composition was spin-coated on a 6-inch silicon wafer by a spinner and heated on a hot plate at 120 ° C. for 3 minutes to form a 9.0 μm-thick photosensitive composition layer. The coating film g-line stepper exposing machine (manufactured by Nikon, NSR-1505G6) through a reticle, the exposure was carried out from 50 mJ / cm ² to 1000 mJ / cm ² at 50 mJ / cm ² intervals. As the reticle, one having an evaluation pattern of 5, 10, 15, 20, 30, 40, and 50 μm was used. Next, NMD-3
(A 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 90 seconds.
Washed for 2 seconds.

[0032] As a result, the portion irradiated with the exposure amount 400 mJ / cm ^2, it was confirmed that the pattern is formed (sensitivity 400mJ / cm ^2). At this time, the film thickness of the unexposed portion was 7.2 μm, and the film reduction by development was 1.
It was as good as 8 μm. Further, when the cross section of the pattern was observed by an electron microscope, it was found that the smallest pattern of 5 μm in the pattern formed was well resolved (resolution 5 μm).

Example 2 The amount of N, N-dimethylformamide diethyl acetal in Example 1 was changed to 17.67 g (120 mmol).
In place of 1), a polymer solution (B) was obtained.

A photosensitive composition was prepared in the same manner as in Example 1,
An evaluation was performed. The results are shown in Table 1. In a practical light irradiation amount and a development time, film loss was small and a good pattern was formed.

Example 3 The amount of N, N-dimethylformamide diethyl acetal used in Example 1 was changed to 11.78 g (80 mmol).
And a polymer solution (C) was obtained.

A photosensitive composition was prepared in the same manner as in Example 1,
An evaluation was performed. The results are shown in Table 1. In a practical light irradiation amount and a development time, film loss was small and a good pattern was formed.

Example 4 A polymer solution (D) was obtained by changing N, N-dimethylformamide diethyl acetal in Example 1 to N, N-dimethylformamide dimethyl acetal.

A photosensitive composition was prepared in the same manner as in Example 1,
An evaluation was performed. The results are shown in Table 1. In a practical light irradiation amount and a development time, film loss was small and a good pattern was formed.

Example 5 Under nitrogen atmosphere, 9.61 g (48 mmol) of 4,4'-diaminodiphenyl ether and 0.5 g (2 mmol) of bis (3-aminopropyl) hexamethyldisiloxane
Was dissolved in 59 g of dried N-methyl-2-pyrrolidone, and 15.20 g (49 mmo) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride was added to this solution.
1) was mixed and stirred, and reacted at 50 ° C. for 5 hours. Further, 11.78 g (80 mmol) of N, N-dimethylformamide diethyl acetal was added, and the mixture was stirred at 50 ° C. for 5 hours to obtain a partially esterified polyamic acid solution (E).
I got

A photosensitive composition was prepared in the same manner as in Example 1,
An evaluation was performed. The results are shown in Table 1. In a practical light irradiation amount and a development time, film loss was small and a good pattern was formed.

Example 6 18.31 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a nitrogen atmosphere
(50 mmol) was dissolved in 59 g of dried N-methyl-2-pyrrolidone, and 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride 15.20 was added to this solution.
g (49 mmol) was mixed and stirred, and reacted at 50 ° C. for 5 hours. Further, 22.08 g (150 mmol) of N, N-dimethylformamide diethyl acetal was added,
Stirred at 50 ° C. for 5 hours. After returning the reaction solution to room temperature,
The polymer was poured into a mixed solution of 1 liter of water / 0.1 liter of methanol to precipitate a polymer. After the polymer was collected by filtration, the polymer was dried with a vacuum dryer at 80 ° C. for 24 hours to obtain a partially esterified polyamic acid.

14 g of this partially esterified polyamic acid was dissolved in 26 g of N-methyl-2-pyrrolidone to obtain a polymer solution (F). An o-quinonediazide compound MG-300 (manufactured by Toyo Gosei Co., Ltd .: 3 moles of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride is reacted with 1 mole of methyl gallate) to this polymer solution (F). 2.8 g of an ester obtained by the reaction) and an adhesion improver (a polyamic acid prepared from 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride and bis (3-aminopropyl) hexamethyldisiloxane) After mixing and dissolving 1.4 g, the mixture was filtered through a 0.5 μm membrane filter to prepare a photosensitive composition.

Table 1 shows the results of the evaluation performed in the same manner as in Example 1.
It was shown to. In a practical light irradiation amount and a development time, film loss was small and a good pattern was formed.

Comparative Example 1 17.58 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a nitrogen atmosphere
(48 mmol) and 0.50 g (2 mmol) of bis (3-aminopropyl) hexamethyldisiloxane were dissolved in 79 g of dried N-methyl-2-pyrrolidone.
15.3 g (49 mmol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was mixed and stirred,
By reacting at 50 ° C. for 5 hours, a polyamic acid solution (F) was obtained.

In the same manner as in Example 1, 6.77 g of the o-quinonediazide compound (4NT-300) used in Example 1 was dissolved in the obtained polyamic acid solution (G).
The mixture was filtered through a 5 μm membrane filter to prepare a photosensitive composition.

Next, the photosensitive composition was spin-coated on a 4-inch silicon wafer by a spinner.
Heat on a hot plate at 0 ° C. for 3 minutes to a thickness of 9.0.
A photosensitive composition layer having a thickness of μm was formed. When exposed and developed in the same manner as in Example 1, all the films dissolved in 20 seconds,
I couldn't get the pattern.

Comparative Example 2 17.58 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane under a nitrogen atmosphere
(48 mmol) and 0.50 g (2 mmol) of bis (3-aminopropyl) hexamethyldisiloxane in 79 g of dried N-methyl-2-pyrrolidone were added to a solution of 3,3 ′, 4,4′-benzophenonetetrane. 15.17 g (49 mmol) of carboxylic dianhydride was mixed and stirred, and reacted at 50 ° C. for 5 hours to obtain a polyamic acid solution. Further, a reflux condenser equipped with a moisture meter was attached, 50 g of toluene and 2 g of 2-ethyl-4-methylimidazole were added, and the mixture was stirred and refluxed at 120 ° C. for 3 hours. After returning the reaction solution to room temperature, 1 liter of water /
The polymer was poured into a mixed solution of 0.1 liter of methanol to precipitate a polymer. After the polymer was collected by filtration, it was dried with a vacuum dryer at 80 ° C. for 24 hours to obtain a reddish brown polyimide.

14 g of this polyimide was treated with N-methyl-2-
The polymer was dissolved in 26 g of pyrrolidone to obtain a polymer solution (H).
After 2.8 g of the o-quinonediazide compound (4NT-300) used in Example 1 was mixed and dissolved in the polymer solution (H), the solution was filtered through a 0.5 μm membrane filter to prepare a photosensitive composition.

Table 1 shows the results of the evaluation performed in the same manner as in Example 1.
It was shown to. The practical light irradiation amount (100
(0 mJ / cm ² or less), it took time to dissolve the exposed portion, and a 7 μm film remained in the exposed portion even after 10 minutes of development, and pattern formation was not possible.

Comparative Example 3 50 g of pyromellitic dianhydride and 300 ml of ethanol
Was placed in a 500 ml flask, 0.2 ml of pyridine was added, and the mixture was stirred at 30 ° C. for 10 hours under a nitrogen atmosphere. Excess ethanol was distilled off under reduced pressure, and the residue was dried in vacuum to obtain pyromellitic acid diethyl ester.

The obtained pyromellitic acid diethyl ester 31.4 g (100 mmol), thionyl chloride 100 m
was placed in a flask, stirred at room temperature for 1 hour, and then refluxed for 3 hours. Excess thionyl chloride was removed with an aspirator to obtain chloride.

The obtained chloride was converted to γ-butyrolactone 60
g, and kept at 0 ° C. for 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 3
6.62 g (100 mmol) and pyridine 50 ml
-Methyl-2-pyrrolidone was dropped into a solution dissolved in 200 ml. After stirring at 0 ° C. for 3 hours, the temperature was further increased to 30 ° C.
For 3 hours. After filtering the insoluble matter, the filtrate was poured into 5 liters of water to precipitate a polymer.

The obtained polyamic acid diethyl ester 1
4 g was dissolved in 26 g of N-methyl-2-pyrrolidone to obtain a polyamic acid ester solution (I). After 2.8 g of the o-quinonediazide compound (4NT-300) used in Example 1 was mixed and dissolved in the polymer solution (I),
The mixture was filtered through a 0.5 μm membrane filter to prepare a photosensitive composition.

Table 1 shows the results of the evaluation performed in the same manner as in Example 1.
It was shown to. The practical light irradiation amount (100
(0 mJ / cm ² or less), it took time to dissolve the exposed portion, and a film of 5 μm remained in the exposed portion even after 10 minutes of development, and the pattern could not be formed.

Comparative Example 4 Under nitrogen atmosphere, 9.61 g (48 mmol) of 4,4′-diaminodiphenyl ether and 0.5 g (2 mmol) of bis (3-aminopropyl) hexamethyldisiloxane
Was dissolved in 59 g of dried N-methyl-2-pyrrolidone, and 15.20 g (49 mmo) of 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride was added to this solution.
1) was mixed and stirred, and reacted at 50 ° C. for 5 hours to obtain a polyamic acid solution (J).

A photosensitive composition was prepared in the same manner as in Example 1,
Evaluation was performed, but all the films were dissolved by development for 20 seconds, and a pattern could not be obtained.

[0057]

[0058]

[Table 1]

[0059]

According to the process for producing a positive photosensitive resin composition of the present invention, the dissolution rate of a polymer in an alkali developer can be easily adjusted arbitrarily. The resin composition has high sensitivity, short development time, and high heat resistance of the formed pattern, and can be used for a surface protective film, an interlayer insulating film, and the like of a semiconductor element and the like.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 22, 1998 (1998.10.
22)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image (In the general formula (1), R1 represents a trivalent or tetravalent organic group having 2 or more carbon atoms, R2 represents a divalent organic group having 2 or more carbon atoms, and R3 represents a hydrogen atom or a carbon atom having 1 or more carbon atoms. Represents a monovalent organic group, m represents an integer of 1 or 2, and n represents 3 to 1.
Indicates an integer of 000. )

Embedded image (In the general formula (2), R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R5 represents a hydrogen atom or 1 carbon atom.
Any of the above monovalent organic groups, nitrogen-containing organic groups, and oxygen-containing organic groups is shown, and R6 is a monovalent organic group having 1 or more carbon atoms. )

Embedded image (In the general formula (3), R7 represents any one of a divalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group;
8 represents a monovalent organic group having 1 or more carbon atoms. )

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction contents]

The ratio of the compound represented by the general formula (2) or the general formula (3) to the polymer represented by the general formula (1) is determined by the ratio of the carboxyl group /
The total amount (molar ratio) of the latter compound is from 100/1 to 100 /
1000. Preferably, 100/10 to 100
/ 500 , more preferably from 100/20 to 1
Is a 00/200. The optimum ratio is determined by considering the structure of the polymer represented by the general formula (1) and the process conditions of pattern processing to be applied.
The amount of residual carboxyl groups in the polymer after the treatment is 0.0%
It is preferably from 0.01 to 5 mol / kg, more preferably from 2 to 5 mol / kg.
More preferably, it is not more than mol / kg.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

The photosensitive resin composition of the present invention can contain an organic silane compound or an aluminum chelate compound as an adhesion aid. As the organic silane compound, for example, 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, vinyltriethoxysilane,
3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. Examples of the aluminum chelate compound include aluminum tris (acetylacetate) and aluminum acetylacetate diisopropylate.
The adhesion aid is used in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble polymer. ────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 27, 1999 (September 9, 1999
7)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction contents]

The compound represented by the general formula (3) is a cyclic carbonyl compound acetal or ketal compound. R7 represents any one of a divalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group, and R8 represents a monovalent organic group having 1 or more carbon atoms. Specifically, N-methyl-2
- pyrrolidone dialkyl acetals, 1,3-dimethylimidazolidinone dialkyl acetal, ethylene carbonate dialkyl acetal, propylene carbonate dialkyl acetal, .gamma.-butyrolactone dialkyl acetal, cyclohexanone di alkyl acetal and the like, preferably N- methyl-2-pyrrolidone dimethyl Acetal, N-methyl-2-pyrrolidone diethyl acetal,
γ-butyrolactone dimethyl acetal and γ-butyrolactone diethyl acetal.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

Examples of the polyamino compound, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4
-Diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane,
3,4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfone, 3,4-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfide, 3,4
-Diaminodiphenyl sulfide and the like.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

Further, as the polyhydroxy amino compounds, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxy-benzidine, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA01 AA04 AA10 AB16 AB17 AC01 AD03 BE01 CB25 CB52 FA03 FA17 FA29 4J043 ZB22

Claims (2)

[Claims] 1. A method for producing a positive photosensitive resin composition comprising an alkali-soluble polymer and an o-quinonediazide compound, wherein the alkali-soluble polymer represented by the following general formula (1) is replaced by the following general formula (2) Alternatively, a method for producing a positive photosensitive resin composition, comprising treating with at least one compound represented by any of the general formulas (3). Embedded image (In the general formula (1), R1 represents a trivalent or tetravalent organic group having 2 or more carbon atoms, R2 represents a divalent organic group having 2 or more carbon atoms, and R3 represents a hydrogen atom or a carbon atom having 1 or more carbon atoms. Represents a monovalent organic group, m represents an integer of 1 or 2, and n represents 3 to 1.
Indicates an integer of 000. ) (In the general formula (2), R4 represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R5 represents a hydrogen atom or 1 carbon atom.
Any of the above monovalent organic groups, nitrogen-containing organic groups, and oxygen-containing organic groups is shown, and R6 is a monovalent organic group having 1 or more carbon atoms. ) (In the general formula (3), R7 represents any one of a divalent organic group having 1 or more carbon atoms, a nitrogen-containing organic group, and an oxygen-containing organic group;
8 represents a monovalent organic group having 1 or more carbon atoms. ) 2. The method for producing a positive photosensitive resin composition according to claim 1, wherein the alkali-soluble polymer represented by the general formula (1) is treated with an N, N-dimethylformamide dialkyl acetal.