JPH107796A - Positive heat-resistant photopolymer composition and production of relief pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-resistant photopolymer composition which has high sensitivity an can be used for, e.g. a surface protective film for electronic components, such as a semiconductor element, and an interlaminar insulating film by selecting a specified polymer composition. SOLUTION: This composition contains a polymer represented by formula I [wherein R<1> is a 2C or higher tetravalent organic group; R<2> is a 2C or higher divalent organic group having a carboxyl or phenolic hydroxyl group; R<3> is a trivalent organic group containing an aromatic ring; R<4> is H or a 1C or higher monovalent organic group; an the ratio of m to n is (20 to 90):(80 to 10)] and an o-quinonediazide compound. This composition is applied to a supporting base plate and dried, and then exposed, developed and heat treated to give a relief pattern. The polymer represented by formula I is obtained by reacting an amide-forming derivative of a compound represented by formula II (wherein X is a group that reacts with an amine, such as halogeno or hydroxyl) with H2 N-R<2> -NH2 and H2 N-R<3> -NH2 .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant photosensitive polymer composition and a method for producing a relief pattern using the composition. More specifically, the present invention relates to a surface protection film for electronic parts such as semiconductor devices by heat treatment, The present invention relates to a heat-resistant photosensitive polymer composition which becomes a polyimide-based heat-resistant polymer applicable as an interlayer insulating film and the like, and a method for producing a relief pattern using the composition.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance and mechanical properties.
Further, it is widely used as a surface protective film and an interlayer insulating film of a semiconductor element because of its advantages such as easy film formation and flattening of the surface. When polyimide is used as a surface protective film and an interlayer insulating film, the process of forming through holes and the like is performed mainly by an etching process using a positive photoresist. However, there is a problem that the process involves coating and peeling of a photoresist, which is complicated. Accordingly, heat-resistant materials having both photosensitivity have been studied for the purpose of streamlining work steps.

With respect to the photosensitive polyimide composition,
(A) a polyimide precursor composition having a photosensitive group introduced through an ester bond (Japanese Patent Publication No. 52-30207);
(B) A polyimide precursor composition (JP-B-3-36861) in which a compound containing a carbon-carbon double bond and an amino group and an aromatic bisazide which can be dimerized or polymerized by actinic radiation to a polyamic acid is added is known. Have been. When the photosensitive polyimide composition is used, it is usually applied in a solution state on a substrate, dried, irradiated with an actinic ray through a mask, and the exposed portion is removed with a developer to form a pattern.

[0004] However, the polyimide precursor compositions (a) and (b) are negative type and use an organic solvent for development. Therefore, in order to switch from an etching process using a positive photoresist to a negative photosensitive polyimide, there is a problem that a mask of an exposure apparatus and development equipment need to be changed. On the other hand, as for the positive type photosensitive polyimide, (c) a polyimide precursor having an o-nitrobenzyl group introduced through an ester bond (Japanese Patent Application Laid-Open No.
No.-37550), (d) a mixture of a polyamic acid ester and an o-quinonediazide compound (Japanese Unexamined Patent Publication No.
181149) is known.

However, the polyimide precursor (c) has a problem that the sensitivity is low because the photosensitive wavelength is mainly 300 nm or less. The resin composition (d) has a problem in that the sensitivity is low because the dissolution rate of the polyamic acid ester in an aqueous alkali solution as a developer is low.

[0006]

SUMMARY OF THE INVENTION The first aspect of the present invention overcomes the above-mentioned problems of the prior art, and provides a high-sensitivity heat-resistant photosensitive polymer composition and the production of a relief pattern using the composition. It provides the law. The invention described in claim 2 provides a method for producing a relief pattern using the composition.

[0007]

According to the present invention, there are provided (a) a compound represented by the following general formula (I):

Embedded image (Wherein, R ¹ represents a 2 or more tetravalent organic group having a carbon number, R ²
Represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group and having 2 or more carbon atoms, and R ³ represents 3 containing an aromatic ring.
R ⁴ represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R ⁵ represents a monovalent organic group having 1 or more carbon atoms, and the ratio of m to n is m Is 20 to 90% and n is 80 to 10%), (b) o-
The present invention relates to a heat-resistant photosensitive polymer composition containing a quinonediazide compound. The present invention also relates to a method for producing a relief pattern in which the heat-resistant photosensitive polymer composition is coated on a support substrate, dried, exposed, developed, and heat-treated.

In the general formula (I), more specifically, R ¹ is a residue of a tetracarboxylic anhydride serving as a raw material of polyimide or polyimide isoindoloquinazolinedione, and has 4 to 25 carbon atoms. Are particularly preferred;
² is a residue excluding the amino group of a diamine compound having a carboxy group or a phenolic hydroxyl group, and preferably has 2 to 25 carbon atoms excluding the carboxy group, and R ³ is polyimide or polyimide isoindoloquinazolinedione. Residue of a diamine compound used as a raw material for
Preferably, R ⁴ is a monovalent organic group, and R ⁵ is preferably an organic group having 1 to 10 carbon atoms, particularly preferably a hydrocarbon group having 1 to 10 carbon atoms.
If m in the general formula (I) is too small, the solubility in an aqueous alkali solution will be poor, and if m is too large, film loss will increase during development.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the component (a)
General formula (II)

Embedded image (Wherein, R ¹ , R ⁴ and R ⁵ are the same as in the general formula (I), and X represents a reactive group with an amine such as a halogen such as chlorine or bromine or a hydroxyl group). Amide-forming derivatives of tetracarboxylic diamide compounds and the general formula (III)

Embedded image (Wherein R ² is the same as in the general formula (I)) and a diamine compound represented by the general formula (IV)

Embedded image (Wherein R ³ is the same as in the general formula (I)). In this case, the reaction is preferably performed in an organic solvent in the presence of a dehydrochlorination catalyst.

Examples of the amide-forming derivative of the tetracarboxylic diamide compound include tetracarboxylic diamide dichloride.

The tetracarboxylic diamide dichloride has a general formula (V)

Embedded image (Wherein, R ¹ is the same as in the general formula (I)) and a tetracarboxylic dianhydride represented by the general formula (VI)

Embedded image (Wherein, R ⁴ and R ⁵ are the same as those in the general formula (I)).

Embedded image (Wherein, R ¹ , R ⁴ and R ⁵ are the same as those of the general formula (I)).

Examples of the tetracarboxylic dianhydride represented by the general formula (V) include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',
4,4'-biphenylethertetracarboxylic 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,
Known tetracarboxylic dianhydrides such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride may be used alone or in combination of two or more.

The amine compound represented by the general formula (VI) includes, for example, methylamine, ethylamine, n-
Known compounds such as propylamine, isopropylamine, n-butylamine, isobutylamine, n-amylamine, isoamylamine, n-hexylamine, dimethylamine and diethylamine are used alone or in combination of two or more.

The diamine represented by the general formula (III) includes, for example, 2,5-diaminobenzoic acid,
3,4-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 '
Diamine compounds having a carboxyl group such as -diamino-5,5'-dicarboxy-2,2'-dimethylbiphenyl, 1,3-diamino-4-hydroxybenzene,
1,3-diamino-5-hydroxybenzene, 3,3 '
-Diamino-4,4'-dihydroxybiphenyl, 4,
4'-diamino-3,3'-dihydroxybiphenyl,
Bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl)
Sulfone, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (4-amino-3-
A diamine compound having a phenolic hydroxyl group such as hydroxyphenyl) hexafluoropropane alone or 2
Used in combination of more than one species.

The diamine compound represented by the general formula (IV) includes 4,4'-diaminodiphenyl ether,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzine, m-phenylenediamine, p-
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, 1,4-bis (4-aminophenoxy)
There are aromatic diamine compounds such as benzene.

The diamine represented by the general formula (IV) further includes a diamine represented by the general formula (VIII)

Embedded image (Where R ⁷ represents an alkylene group having 1 to 5 carbon atoms or a phenylene group which may be substituted with an alkyl group having 1 to 4 carbon atoms, and R ⁸ represents an alkyl group having 1 to 4 carbon atoms or A phenyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, and q is an integer of 1 to 200);

Embedded image And the like.

Commercially available products are those having q of 1 and an average of about 10 when R ⁷ is a trimethylene group and R ⁸ is a methyl group in general formula (VIII). About 20 on average, about 30 on average,
Those with an average of around 50 and those with an average of around 100 are LP-7100, X-22-161AS, and X-2, respectively.
2-161A, X-22-161B, X-22-161
C and X-22-161E (all are trade names of Shin-Etsu Chemical Co., Ltd.).

Further, the diamine compounds included in the general formula (IV) include 4,4'-diaminodiphenylether-3-sulfonamide, 3,4'-diaminodiphenylether-4-sulfonamide, and 3,4'- Diaminodiphenyl ether-3'-sulfonamide, 3,
3'-diaminodiphenylether-4-sulfonamide, 4,4'-diaminodiphenylether-3-carboxamide, 3,4'-diaminodiphenylether
Diaminoamide compounds such as 4-carboxamide, 3,4'-diaminodiphenylether-3'-carboxamide, and 3,3'-diaminodiphenylether-4-carboxamide can also be used, but these are used for improving heat resistance. And 15 of the total amount of the diamine compound
It is preferably used in an amount of not more than mol%, more preferably in the range of 0.5 to 10 mol%. These diamine compounds of the general formula (III) can be used alone or in combination of two or more.

A method for synthesizing the tetracarboxylic diamide compound represented by the general formula (VII) is known.
For example, tetracarboxylic dianhydride and an excess of the general formula (V
It is obtained by mixing the amine compounds represented by I), reacting them by heating, and then removing excess amine compounds. The preferred ratio (molar ratio) of the carboxylic dianhydride to the amine compound represented by the general formula (VI) is 1/2 to 1 /
20 and a more preferable ratio is 1 / 2.5 to 1
/ 10. The preferred reaction temperature is 30 to 13
At 0 ° C., the preferred reaction time is 3 to 24 hours.

A method for synthesizing tetracarboxylic diamide dichloride is known. For example, it is obtained by reacting a tetracarboxylic diamide compound with an excess of thionyl chloride by heating and then removing excess thionyl chloride. The preferred ratio (molar ratio) of tetracarboxylic diamide to excess thionyl chloride is in the range of 1/2 to 1/10,
A more desirable ratio is in the range of 1 / 2.2 to 1/5. The preferred reaction temperature is 0 to 100 ° C, and the preferred reaction time is 1 to 10 hours.

The polymer of the component (a) has the general formula (II)
I), a diamine compound represented by (IV) and a dehydrochlorination catalyst such as pyridine and lutidine are dissolved in an organic solvent, and tetracarboxylic diamide dichloride dissolved in the organic solvent is dropped and reacted. It is obtained by pouring into a poor solvent, filtering off the precipitate and drying. General formula (III),
The preferred ratio (molar ratio) of the total amount of the diamine compound represented by (IV) and the tetracarboxylic diamide dichloride is
The range is 0.95 / 1 to 1 / 0.95, and a more preferable ratio is in the range of 0.98 / 1 to 1 / 0.98.
The preferred reaction temperature is -30 to 40 ° C, the preferred reaction time is 1 to 10 hours, and the preferred weight average molecular weight (polystyrene conversion value by gel permeation chromatography) is 10,000 to 100,000.

The preferred ratio of the dehydrochlorination catalyst to the tetracarboxylic diamide dichloride is the former / the latter (molar ratio),
The range is 0.95 / 1 to 1 / 0.95, and a more preferable ratio is in the range of 0.98 / 1 to 1 / 0.98.
The use ratios of the diamine compounds represented by the general formulas (III) and (IV) are respectively 20 to 90 mol% and 10
It is used so that the total is 100 mol% at 80 mol%. The compound represented by the general formula (III) is used for imparting solubility of an aqueous alkali solution to a polymer. When the amount is too small, the solubility of the aqueous alkali solution is poor, and when the amount is too large, the film loss is large during development with the aqueous alkali solution. Become.

The o-quinonediazide compound which is a photosensitizer of the component (b) used in the present invention is 1,2-benzoquinone-2-diazide-4-sulfonic acid ester or sulfonamide, 1,2-naphthoquinone-. 2-diazide-5
Sulfonic acid esters or sulfonic acid amides, 1,2-
Examples include naphthoquinone-2-diazide-4-sulfonic acid ester or sulfonic acid amide. These are, for example,
1,2-benzoquinone-2-diazide-4-sulfonyl chloride, 1,2-naphthoquinone-2-diazide-5
An o-quinonediazidosulfonyl chloride such as sulfonyl chloride, 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and a polyhydroxy compound or a polyamine compound can be subjected to a condensation reaction in the presence of a dehydrochlorination catalyst.

As the polyhydroxy compound, for example,
Hydroquinone, resorcinol, pyrogallol, 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'-tetrahydroxy Benzophenone, 2,3,4,2 ', 3'-pentahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane , Bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,
Examples include 10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane. Examples of the polyamine compound include p-phenylenediamine,
m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide and the like can be mentioned.

It is preferable to mix the o-quinonediazidosulfonyl chloride with the polyhydroxy compound or polyamine compound in an amount of 0.5 to 1 equivalent of the hydroxy group or the amine group per 1 mol of the o-quinonediazidosulfonyl chloride. A preferable ratio of the dehydrochlorination catalyst to o-quinonediazide sulfonyl chloride is 0.95 / 1.
１ ／ 1 / 0.95. The preferred reaction temperature is 0
４０40 ° C., and the preferred reaction time is 1-10 hours.
As a reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N
-A solvent such as methylpyrrolidone is used. Examples of the catalyst for dehydrochlorination include sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, pyridine and the like.

The component (b) is preferably from 5 to 100 parts by weight, more preferably from 100 parts by weight of the component (a), from the viewpoint of the dissolution rate difference between the exposed part and the unexposed part and the allowable range of sensitivity. It is blended in the range of 10 to 40 parts by weight.

The photosensitive polymer composition of the present invention is preferably used as a solution by dissolving the components (a) and (b) in a solvent. As the solvent, for example, N-
An aprotic polar solvent such as methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, γ-butyrolactone, alone or in combination of two or more Used in combination.

The heat-resistant photosensitive polymer composition of the present invention may contain an organic silane compound or an aluminum chelate compound as an adhesion aid. Examples of the organic silane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. Can be Examples of the aluminum chelate compound include aluminum tris (acetylacetate) and aluminum acetylacetate diisopropylate. The adhesion aid is preferably 0.1 to 20 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of the component (a).
It is used in the range of 10 to 10 parts by weight.

From the heat-resistant photosensitive polymer composition of the present invention, a relief pattern of a polyimide compound can be obtained as follows. That is, a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO _2, etc.),
The heat-resistant photosensitive polymer composition is spin-coated on a supporting substrate such as silicon nitride using a spinner or the like, and then dried using a hot plate, an oven, or the like. Next, the photosensitive polymer composition coated on the supporting substrate is irradiated with actinic light such as ultraviolet light, visible light, or radiation through a mask. A relief pattern is obtained by removing the exposed portion with a developing solution. Examples of the developer include an aqueous solution of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide and the like. The aqueous solution preferably has a base concentration of 0.1 to 10% by weight.

Further, an alcohol or a surfactant may be added to the above-mentioned developer for use. Each of these is preferably 0.01 to 100 parts by weight of the developer.
10 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. Then, 15
By performing the heat treatment at 0 to 450 ° C., a relief pattern of a heat-resistant polymer having an imide ring or another cyclic group is obtained.

[0031]

The present invention will be described below with reference to examples. Example 1 In a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 93.07 g of 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, n-
Hexylamine (142.97 g) was charged and reacted at 95 ° C. with stirring for 5 hours. Excess n-hexylamine was distilled off under reduced pressure to obtain 3,3 ', 4,4'-biphenylethertetracarboxylic acid di-n-hexylamide. Next, 0.5 g equipped with a stirrer, a thermometer, and a Dimroth condenser tube.
3,3 ', 4,4'-biphenylethertetracarboxylic acid di-n-hexylamide 7
1.49 g, thionyl chloride 46.40 g, toluene 2
5.00 g was charged and reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 154 g of N-methylpyrrolidone was added,
A solution (α) of 3 ′, 4,4′-biphenylethertetracarboxylic acid di-n-hexylamide dichloride was obtained.

Next, 103 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 13.70 g of 3,5-diaminobenzoic acid and 4,4'-diamino After adding 12.01 g of diphenyl ether and dissolving with stirring, pyridine 2
While adding 3.73 g, keeping the temperature at 5-10 ° C,
The solution (α) of 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid di-n-hexylamide dichloride was added to 1
After dropwise addition over time, stirring is continued for 1 hour. The solution was poured into 4 liters of water, the precipitate was collected, washed, and dried under reduced pressure to obtain polyamic acid n-hexylamide. The weight average molecular weight was 18,000.

This polyamic acid n-hexylamide 3
0.00g, o-quinonediazide compound (4NT-30
0, Toyo Gosei Kogyo Co., Ltd., 2,3,4,4'-
1,2 per mole of tetrahydroxybenzophenone
-Naphthoquinone-2-diazide-5-sulfonyl chloride (3 mol), an ester obtained by the reaction) 6.00 g,
γ-glycidoxypropyltrimethoxysilane 0.90
g was stirred and dissolved in 70.00 g of N-methylpyrrolidone (NMP). This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 5 minutes on a hot plate to obtain a 6 μm coating film. This coating film is coated with an exposure device PLA600F (Canon
200-600 mJ / cm ² through a mask
Was exposed. Subsequently, paddle development was performed for 100 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. Appropriate exposure dose is 400mJ / c by pattern observation
m ² was determined. The resulting relief pattern was heated in a nitrogen atmosphere at 140 ° C. for 30 minutes, at 200 ° C. for 30 minutes, and at 350 ° C. for 1 hour to obtain a polyimide film pattern.

Example 2 96.67 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and n-amylamine were placed in a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser. 156.89 g was charged and reacted by stirring at 90 ° C. for 6 hours. Excess n-amylamine was distilled off under reduced pressure to obtain 3,3 ', 4,4'-benzophenonetetracarboxylic acid di-n-amylamide. Next, 69.08 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid di-n-amylamide, 46.40 g of thionyl chloride were placed in a 0.5 liter flask equipped with a stirrer, thermometer, and Dimroth condenser. Charge 25.00 g of toluene at 40 ° C.
For 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 124 g of N-methylpyrrolidone was added to obtain a solution (β) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid di-n-amylamide dichloride.

Next, 103 g of N-methylpyrrolidone was charged into a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 14.83 g of 3,5-diaminobenzoic acid and 4,4'-diamino 9.01 g of diphenyl ether, 1.86 g of LP-7100 (manufactured by Shin-Etsu Chemical)
Was added, and the mixture was stirred and dissolved. Then, 23.73 g of pyridine was added, and while keeping the temperature at 5 to 10 ° C., 3,3 ′, 4,
A solution (β) of 4′-benzophenonetetracarboxylic acid di-n-amylamide dichloride was added dropwise over 1 hour, and then 1
Continue stirring for hours. The solution was poured into 4 liters of water, and the precipitate was collected and washed, and then dried under reduced pressure to remove polyamic acid n.
-Amylamide is obtained. The weight average molecular weight is 30,00
It was 0.

The polyamic acid amylamide 30.00
g, 6.00 g of an o-quinonediazide compound (ester obtained by reacting 2 mol of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride with respect to 1 mol of 4,4'-diaminodifephenyl ether) To NMP8
The mixture was dissolved in 0.00 g with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition. The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating on a hot plate at 80 ° C. for 5 minutes to obtain a 6 μm coating film. This coating was exposed to 200 to 600 mJ / cm ² through a mask using PLA-600F. Subsequently, paddle development was performed for 90 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and washed with pure water to obtain a relief pattern. By pattern observation,
The appropriate exposure was determined to be 400 mJ / cm ² . The obtained relief pattern was treated at 140 ° C. for 30 minutes in a nitrogen atmosphere for 200 minutes.
Heat treatment was performed at 30 ° C. for 30 minutes and at 350 ° C. for 1 hour to obtain a polyimide film pattern.

Example 3 Polyamic acid amylamide obtained in Example 2 30.0
0 g of an o-quinonediazide compound (1,4 moles of 4,4'-diamino-3,3-dihydroxybiphenyl,
Ester obtained by reacting 4 mol of 2-naphthoquinone-2-diazide-5-sulfonyl chloride) 5.00 g
Was dissolved in 80.00 g of NMP with stirring. This solution is
The mixture was filtered under pressure using a Teflon filter having a pore size of μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 5 minutes on a hot plate to obtain a 6 μm coating film. This coating was exposed to 200 to 600 mJ / cm ² through a mask using PLA-600F. Subsequently, paddle development was performed for 100 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, followed by washing with pure water to obtain a relief pattern. By pattern observation, the appropriate exposure was determined to be 350 mJ / cm ² . The obtained relief pattern was placed in a nitrogen atmosphere at 140 ° C. for 30 minutes,
Heat treatment was performed at 00 ° C. for 30 minutes and at 350 ° C. for 1 hour to obtain a polyimide film pattern.

Comparative Example 1 In a 0.5-liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, 93.07 g of 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, n-
133.41 g of butyl alcohol was charged and reacted by stirring at 90 ° C. for 5 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ', 4,4'-biphenylethertetracarboxylic acid di-n-butyl ester.
Then, the obtained 3,3 ′, obtained was placed in a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser.
4,4'-biphenylethertetracarboxylic acid di-n-
63.36 g of butyl ester, 46.40 of thionyl chloride
g of toluene and 25.00 g of toluene were reacted at 40 ° C. for 3 hours. Excess thionyl chloride was azeotroped with toluene under reduced pressure and removed. 138 g of N-methylpyrrolidone was added to obtain a solution (γ) of 3,3 ′, 4,4′-biphenylethertetracarboxylic acid di-n-butyl ester dichloride.

Next, 120 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer, a thermometer and a Dimroth condenser, and 30.04 g of 4,4'-diaminodiphenyl ether was added and dissolved by stirring. rear,
23.73 g of pyridine was added, and a solution (γ) of 3,3 ′, 4,4′-biphenylethertetracarboxylic acid di-n-butyl ester dichloride was added dropwise over 1 hour while maintaining the temperature at 5 to 10 ° C. Thereafter, stirring is continued for 1 hour. After the precipitate was separated by filtration, the solution was poured into 4 liters of water, and the precipitate was collected and washed.
-Butyl ester was obtained. The weight average molecular weight is 35,0
00. This polyamic acid n-butyl ester 3
0.00 g, 4,4'-diaminodiphenyl ether 1
6.00 g of a compound obtained by reacting 2 mol of naphthoquinone-1,2-diazide-5-sulfonyl chloride with respect to the mol was dissolved in 80.00 g of NMP with stirring. This solution was filtered under pressure using a Teflon filter having a pore size of 1 μm to obtain a photosensitive polymer composition.

The obtained photosensitive polymer composition was spin-coated on a silicon wafer using a spinner, and dried by heating at 80 ° C. for 3 minutes on a hot plate to obtain a coating film of 5 μm. This coating was exposed to 200 to 600 mJ / cm ² through a mask using PLA-600F. Next, paddle development was performed for 100 seconds using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as a developing solution, and washing was performed with pure water, but no relief pattern was obtained.

[0043]

The photosensitive polymer composition according to claim 1 has high sensitivity and can be used for a surface protective film, an interlayer insulating film and the like of a semiconductor device. A useful resist pattern can be easily obtained by the method of claim 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03F 7/037 501 G03F 7/037 501

Claims (2)

[Claims] (A) General formula (I) (Wherein, R ¹ represents a 2 or more tetravalent organic group having a carbon number, R ²
Represents a divalent organic group having a carboxyl group or a phenolic hydroxyl group and having 2 or more carbon atoms, and R ³ represents 3 containing an aromatic ring.
R ⁴ represents a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R ⁵ represents a monovalent organic group having 1 or more carbon atoms, and the ratio of m to n is m Is 20 to 90% and n is 80 to 10%), (b) o-
A heat-resistant photosensitive polymer composition comprising a quinonediazide compound. 2. A method for producing a relief pattern, comprising applying the heat-resistant photosensitive polymer composition according to claim 1 onto a supporting substrate, drying, exposing, developing and heating.