JPH06208226A - Production of heat resistant photosensitive polymer composition and relief pattern - Google Patents

Abstract

PURPOSE:To dispense with a purifying process and to shorten a development time by incorporating a specified polymer, the compd. containing the unsatd. bond capable of dimerizing or polymerizing by actiniism and one amino group or its quaternary salt, azide, a photo sensitizer and a photo initiator. CONSTITUTION:The composition is constituted by incorporating the polymer expressed by the formula, the compd. containing one or plural unsatd. bond capable of dimerizing or polymerizing by actinism and one amino group or its quaternary salt and the compd. containing one or plural unsatd. bond capable of dimerizing or polymerizing by azide, a sensitizing agent, a photo initiator or actinism. In the formula, R1 is quadrivalent org. group of >=2C, R2 is bivalent org. group of >=2C, R3 is hydrogen or the pair ion of alkali metal, R4 is monovalent org. group inactive to actinism or-Si(S5)3 (R5 is hydrogen or monovalent org. group) and m+n=1.

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 more specifically, a polyimide-based heat-resistant composition which can be applied as a surface protective film or an interlayer insulating film for electronic parts such as semiconductor elements by heat treatment. The present invention relates to a heat-resistant photosensitive polymer composition which becomes a polymer and a method for producing a relief pattern using this 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 flattened surface. When polymide is used as a surface protective film or an interlayer insulating film, the step of forming through holes and the like is performed by an etching process using a photoresist. However, there is a problem in that the process includes coating and peeling of the photoresist and is complicated. Therefore, heat-resistant materials having photosensitivity have been studied for the purpose of streamlining the work process.

Regarding the photosensitive polyimide composition, a polymide precursor composition having a photosensitive group introduced by an ester bond (Japanese Patent Publication No. 52-30207) and a carbon-carbon dimer which can be dimerized or polymerized with polyamic acid by actinic radiation. A composition containing a compound containing a heavy bond and an amino group (Japanese Patent Publication No. 59-52822) is known. When these photosensitive polyimide compositions are used, they are usually applied on a substrate in a solution state, dried, irradiated with an actinic ray through a mask, and the unexposed portion is removed with a developing solution. However, among the photosensitive polymide compositions, a polyimide precursor composition in which a photosensitive group is introduced by an ester bond is required as a purification step for removing impurities and by-products when synthesizing the polymide precursor, which is economical. Also, the composition obtained by adding a compound containing a carbon-carbon double bond and an amino group that is dimerizable or polymerizable by actinic radiation to polyamic acid has a problem that the development time is long.

[0004]

DISCLOSURE OF THE INVENTION The present invention overcomes the above-mentioned problems of the prior art, requires no purification step in the synthesis of a polyimide precursor, and has a short development time. A method for producing a relief pattern using the composition is provided.

[0005]

The present invention comprises (a) general formula (I)

[Chemical 2] (In the formula, R ₁ represents a tetravalent organic group having 2 or more carbon atoms,
R ₂ means a divalent organic group having 2 or more carbon atoms, R ₃ means hydrogen or an alkali metal counterion, and R ₄ is a monovalent organic group inert to actinic radiation or —Si (R ₅ ) ₃ means (R ₅
Means hydrogen or a monovalent organic group), a polymer represented by m + n = 1, m is 0 <m <1, and n is 0 <n <1, A compound containing one or more unsaturated bonds capable of dimerization or polymerization and one amino group or a quaternized salt thereof, and (c) an azide, a sensitizer, a photoinitiator or a monomer which can be polymerized with actinic radiation. The present invention relates to a heat-resistant photosensitive polymer composition containing a compound containing one or more unsaturated bonds, and a method for producing a relief pattern using this composition.

In the present invention, the component (a) is, for example,
General formula (II)

[Chemical 3] (In the formula, R ₁ represents a tetravalent organic group having 2 or more carbon atoms,
R ₂ represents a divalent organic group having 2 or more carbon atoms, R ₆ represents a monovalent organic group inert to actinic radiation, and p represents an integer of 1 or more) And general formula (III)

[Chemical 4] (In the formula, R ₂ means a divalent organic group having 2 or more carbon atoms,
R ₇ represents hydrogen or a monovalent organic group) and is obtained by reacting both or either of the compounds represented by the formula (1) and, if necessary, other diamine and tetracarboxylic dianhydride in a solvent. .

The compound represented by the general formula (II) can be obtained, for example, by dehydration condensation of a tetracarboxylic acid diester and a diamine. The tetracarboxylic acid diester is obtained, for example, by reacting a tetracarboxylic dianhydride with a compound having a hydroxy group.

Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4 '.
-Benzophenone tetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, cyclopentane tetracarboxylic 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, 4,4'-sulfonyldiphthalic dianhydride,
Known acid anhydrides such as 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride are used alone. Alternatively, two or more kinds are used in combination.

Examples of the compound having a hydroxy group include methanol, ethanol, propanol, butanol, pentanol, hexanol and phenol. For the reaction between the tetracarboxylic dianhydride and the compound having a hydroxy group, for example, N-methyl-2-pyrrolidone,
An inert solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone or p-chlorophenol is used.

The tetracarboxylic acid diester is produced by reacting a tetracarboxylic dianhydride and a compound having a hydroxy group in the above-mentioned inert solvent by heating or adding a catalyst such as pyridine. General formula (II)
The compound represented by is obtained by dehydration condensation of a tetracarboxylic acid diester and a diamine in the above inert solvent using, for example, carbodiimides.

Examples of diamines are 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone,
Aromatic diamine compounds such as 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine and 2,6-naphthalenediamine, the following general formula (IV):

[Chemical 5] (Wherein R ₈ represents an alkylene group, R ₉ represents an alkyl group, and q represents an integer of 1 or more), for example,

[Chemical 6] And other compounds can be used. These diamines can be used alone or in combination of two or more.

As the compound represented by the general formula (III),

[Chemical 7] And so on.

Further, as the other diamine used as necessary, the diamines exemplified above, the general formula (V)

[Chemical 8] (In the formula, Ar means an aromatic group, and Y is SO ₂ or C.
Means O, diaminoamide compounds represented by one located in an ortho position to each other with an amino group and -Y-NH ₂ in), for example, 4,4'-diaminodiphenyl ether -
Use of compounds such as 3-sulfonamide, 3,4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4-sulfonamide You can also These diamines may be used alone or in combination of two or more.

As the tetracarboxylic acid dianhydride, the tetracarboxylic acid dianhydride exemplified above is used alone or in combination of two or more kinds.

The molar ratio of the compound represented by the general formula (II), the compound represented by the general formula (III) and other diamines used as necessary to the tetracarboxylic dianhydride is Preferably 80: 100 to 100: 8
The reaction is carried out at a ratio of 0, more preferably 90: 100 to 100: 90.

In the component (a), the ratio of m and n is such that the compound represented by the general formula (II) and the general formula (II
It depends on the ratio of the compound represented by I), the diamine used as necessary, and the tetracarboxylic dianhydride. From the viewpoint of the difference in dissolution rate between the exposed area and the unexposed area and the development time, m and n are preferably 0.1 ≦ m ≦ 0.8 and 0.2.
≦ n ≦ 0.9, more preferably 0.2 ≦ m ≦ 0.6,
0.4 ≦ n ≦ 0.8.

Tetracarboxylic acid dianhydride, general formula (II)
For the reaction with the compound represented by the formula (I), the compound represented by the general formula (III) and optionally other diamine, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide,
Dimethyl sulfoxide, hexamethylphosphoramide,
An inert solvent such as tetramethylene sulfone or p-chlorophenol is used.

When the polymer which is the component (a) is produced,
Preferably, first, a compound represented by the general formula (II), a compound represented by the general formula (III) and other diamines used as necessary are treated with an inert solvent such as N-methyl-2-pyrrolidone or N. , N-dimethylformamide,
After dissolving in N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, tetramethylene sulfone, p-chlorophenol, etc., tetracarboxylic dianhydride is added, preferably at about 80 ° C. or less, especially near room temperature or thereabout. Stir while maintaining the following temperature.
As a result, the reaction proceeds promptly, the viscosity of the reaction system gradually increases, and a polymer is produced.

As the component (b) used in the present invention, the compound containing one or more unsaturated bonds dimerizable or polymerizable by actinic radiation and one amino group or a quaternized salt thereof is: For example, general formula (VI)

[Chemical 9] (In the formula, R ₁₀ and R ₁₁ mean an alkyl group having 1 to 5 carbon atoms, R ₁₂ means an alkylene group having 2 to 6 carbon atoms, and R ₁₃ is hydrogen or 1 to 6 carbon atoms. And an X represents —O— or —NH—). In particular,

[Chemical 10] And so on. The component (b) is preferably 0.2 relative to the carboxyl group of the polymer as the component (a), from the viewpoint of the difference in dissolution rate between the exposed and unexposed areas and the allowable range of development conditions.
To 3 equivalents, more preferably 0.5 to 2 equivalents.

The component (c) used in the present invention is a compound containing one or more unsaturated bonds dimerizable or polymerizable by an azide, a sensitizer, a photoinitiator or actinic radiation. From the viewpoint of sensitivity, the component (c) is preferably blended in an amount of 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (a). Examples of azides include 4-azidobenzalacetophenone, 4-azidobenzalbenzophenone and other monoazides, bis (4-azidophenyl) sulfonyl, bis (3-azidophenyl) sulfonyl, bis (4-azidophenyl) sulfide, bis. (4-azido-3-methoxyphenyl), 2,6- (4'-azidobenzal) cyclohexanone, 2,6- (4'-azidobenzal) -4-methylcyclohexanone, 2,6-
Examples include bisazides such as (4'-azidobenzal) -4-carboxycyclohexanone.

Examples of the sensitizer include phenyl such as N-phenylethylamine, N-phenyldiethylamine, N-phenylethanolamine, N-phenyldiethanolamine, N-ethyl-N-phenylamine and N-phenyl-N-ethanolamine. Amines, 7-diethylamino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 3- (2'-benzimidazolyl)-
Coumarins such as 7-diethylaminocoumarin, 3- (2'-benzthiazolyl) -7-diethylaminocoumarin, 7-diethylamino-3-cenoylcoumarin, 3,3-carbonylbis (7-diethylaminocoumarin), Michler's ketone, benzanthrone , 2,6-di (4'-
Diethylaminobenzal) -N-methylazacyclohexanone and the like.

As the photoinitiator, 3,3 ', 4,4'-
Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone.

Compounds containing one or more unsaturated bonds dimerizable or polymerizable by actinic radiation include
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, ethylene glycol dimethacrylate, glycerin dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate and the like can be mentioned.

The photosensitive polymer composition of the present invention can be obtained in a solution state by dissolving the components (a), (b) and (c) in a suitable organic solvent. Examples of the organic solvent used at this time include N-methyl-
2-pyrrolidone, N, N-dimethylformamide, N,
N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone,
An inert solvent such as N-acetyl-ε-caprolactam is used.

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.),
This 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. Then, the photosensitive polymer composition which has formed a film on the supporting substrate is irradiated with an actinic ray such as ultraviolet ray, visible ray, electron beam or radiation through a mask. A relief pattern is obtained by removing the unexposed portion with a developing solution. Examples of the developer include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, N-acetyl-ε-caprolactam and the like. Can be used alone or as a mixed solution with water, methanol, ethanol, isopropanol, toluene, xylene and the like. Then, the relief pattern thus obtained is subjected to a heat treatment at 150 to 450 ° C. to form a relief pattern of a heat resistant polymer having an imide ring or other cyclic group.

[0026]

EXAMPLES The present invention will be described below with reference to examples. Example 1 Methanol 64.0 in a 0.5 liter flask equipped with stirrer, thermometer, nitrogen inlet tube, Dimroth condenser.
Charge 9 g and 43.62 g pyromellitic dianhydride,
The mixture was refluxed at 65 ° C. for 8 hours for reaction. Then, excess methanol was distilled off, and further vacuum dried to obtain 53.62 g of tetracarboxylic acid diester (α).
Then, in a 0.5 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, Dimroth condenser tube, N-methyl-
2-Pyrrolidone (150.0 g) was charged, and tetracarboxylic acid diester (α) was 28.22 g, 4,4′-diaminodiphenyl ether (38.05 g) and 1,3-bis (3-).
2.48 g of aminopropyl) -1,1,3,3-tetramethyldisiloxane was added and dissolved with stirring. Dicyclohexylcarbodiimide 41.27 with stirring under ice cooling
A solution prepared by dissolving 2 g of N-methyl-2-pyrrolidone in 20.0 g was added dropwise over 30 minutes. After returning to room temperature and stirring for 3 hours,
The formed precipitate was filtered off. The obtained solution was poured into 3 liters of water, and the resulting precipitate was recrystallized to obtain 33.6 g of the diamine compound (β). Into a 0.5 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a Dimroth condenser tube, 130.4 g of N-methyl-2-pyrrolidone was charged, 32.57 g of the diamine compound (β) was added, and the mixture was stirred. Dissolved. Next, add 1 part of pyromellitic dianhydride to this solution.
0.91 g was added, and the mixture was reacted by stirring at 25 ° C for 6 hours and then at 60 ° C for 5 hours. Obtained polyamic acid (m = n =
The solution of 0.5) had a nonvolatile concentration of 25% by weight and a viscosity of 80 poise. To 100.0 g of this solution, 9.04 g of 2-dimethylaminoethyl methacrylate and 0.75 g of N-phenyldiethanolamine were added and dissolved with stirring. This solution was pressure-filtered using a Teflon filter having 1 μm pores 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 100 ° C. for 3 minutes to obtain a coating film of 5.2 μm. This coating film was contact-exposed through a photomask from a distance of 30 cm for 150 seconds using a 500 w high-pressure mercury lamp. Then N-
Paddle development was performed with a developing solution containing 70 parts by weight of methyl-2-pyrrolidone and 30 parts by weight of methanol, and washed with ethanol to obtain a relief pattern. The time required for development was 60 seconds. The obtained relief pattern was heat-treated in a nitrogen atmosphere at 140 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 350 ° C. for 1 hour to obtain a polyimide film pattern.

Example 2 Methanol 64.0 was placed in a 0.5 liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a Dimroth condenser tube.
9 g and 58.84 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride were charged and reacted at 65 ° C for 15 hours under reflux. Then, excess methanol is distilled off,
Further, by vacuum drying, 63.91 g of tetracarboxylic acid diester (γ) was obtained. Next, stirrer,
0.5 equipped with a thermometer, nitrogen inlet tube, Dimroth condenser tube
In a liter flask, 225.0 g of N-methyl-2-pyrrolidone was charged, and 53.75 g of tetracarboxylic acid diester (γ), 57.07 g of 4,4′-diaminodiphenyl ether and 1,3-bis (3-amino) were added. Propyl) -1,1,3,3-tetramethyldisiloxane 3.
73 g was added and dissolved by stirring. While stirring under ice cooling, a solution of 61.91 g of dicyclohexylcarbodiimide dissolved in 30.0 g of N-methyl-2-pyrrolidone was added dropwise over 30 minutes. After returning to room temperature and stirring for 3 hours, the generated precipitate was filtered off. The resulting solution was poured into 4.5 liters of water, and the resulting precipitate was recrystallized to diamine compound (δ) 5
5.0 g was obtained. In a 0.5 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, Dimroth condenser tube,
153.3 g of -methyl-2-pyrrolidone was charged, 36.38 g of the diamine compound (δ) was added, and the mixture was dissolved with stirring.
Next, 14.71 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was stirred at 25 ° C. for 8 hours and then at 70 ° C. for 7 hours for reaction. The resulting solution of polyamic acid (m = n = 0.5) had a nonvolatile concentration of 25% by weight and a viscosity of 75 poise. This solution 1
2-dimethylaminoethyl methacrylate 7.69 g and N-phenyldiethanolamine 0.75 in 00.0 g
g was added and dissolved by stirring. This solution was pressure-filtered using a Teflon filter having 1 μm pores 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 100 ° C. for 3 minutes to obtain a coating film of 5.2 μm. This coating film was contact-exposed through a photomask from a distance of 30 cm for 150 seconds using a 500 w high-pressure mercury lamp. Then, paddle development was performed with a developing solution containing 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of methanol, and washed with ethanol to obtain a relief pattern. The time required for development was 67 seconds. The obtained relief pattern was heat-treated in a nitrogen atmosphere at 140 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 350 ° C. for 1 hour to obtain a polyimide film pattern.

Example 3 Ethanol 90.1 was placed in a 0.5 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube and Dimroth condenser.
2 g and 58.84 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride were charged and reacted at 65 ° C for 20 hours under reflux. Next, excess ethanol was distilled off, and vacuum drying was performed to obtain 71.09 g of tetracarboxylic acid diester (ε). Next, in a 0.5 liter flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a Dimroth condenser tube, N-methyl-2-pyrrolidone 22 was added.
Charge 5.0 g, tetracarboxylic acid diester (ε)
57.95 g, 4,4'-diaminodiphenyl ether 57.07 g and 1,3-bis (3-aminopropyl)-
3.73 g of 1,1,3,3-tetramethyldisiloxane
Was added and dissolved by stirring. While stirring under ice cooling, 61.91 g of dicyclohexylcarbodiimide was added to N-methyl-
A solution dissolved in 30.0 g of 2-pyrrolidone was added dropwise over 30 minutes. After returning to room temperature and stirring for 3 hours, the generated precipitate was filtered off. The resulting solution was poured into 4.5 liters of water, and the resulting precipitate was recrystallized to diamine compound (ζ) 5
3.3 g was obtained. In a 0.5 liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, Dimroth condenser tube,
153.3 g of -methyl-2-pyrrolidone was charged, 37.78 g of the diamine compound (ζ) was added, and the mixture was dissolved with stirring.
Next, 14.71 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was stirred at 25 ° C. for 8 hours and then at 70 ° C. for 6 hours for reaction. The resulting solution of polyamic acid (m = n = 0.5) had a nonvolatile concentration of 25% by weight and a viscosity of 83 poise. This solution 10
0.05 g of 3-dimethylaminopropyl methacrylate 8.15 g and N-phenyldiethanolamine 0.75
g was added and dissolved by stirring. This solution was pressure-filtered using a Teflon filter having 1 μm pores 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 100 ° C. for 3 minutes to obtain a coating film of 5.2 μm. This coating film was contact-exposed through a photomask from a distance of 30 cm for 150 seconds using a 500 w high-pressure mercury lamp. Then, paddle development was performed with a developing solution containing 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of methanol, and washed with ethanol to obtain a relief pattern. The time required for development was 82 seconds. The obtained relief pattern was heat-treated in a nitrogen atmosphere at 140 ° C. for 30 minutes, 200 ° C. for 30 minutes, and 350 ° C. for 1 hour to obtain a polyimide film pattern.

Comparative Example 1 176.1 g of N-methyl-2-pyrrolidone was placed in a 0.5 liter flask equipped with a stirrer, a thermometer, a nitrogen introducing tube and a Dimroth condenser, and 4,4'-diamino was added. 19.02 g of diphenyl ether and 1.24 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane were added and dissolved with stirring. Next, 29.42 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride was added to this solution, and the mixture was heated at 25 ° C. for 8 hours and then at 70 ° C.
The mixture was stirred for 4 hours and reacted. The resulting polyamic acid solution had a nonvolatile concentration of 22% by weight and a viscosity of 75 poise. 2 to 100.0 g of the obtained polyamic acid solution
-Dimethylaminoethyl acrylate 12.68 g and N
-Phenyldiethanolamine 0.75g was added and dissolved with stirring. This solution was pressure-filtered using a Teflon filter having 1 μm pores to obtain a photosensitive polymer composition. The resulting photopolymer composition was spin coated on a silicon wafer using a spinner and heated on a hot plate at 100 ° C. for 5 hours.
Heat drying was performed for an hour to obtain a coating film of 5.8 μm. 500w from a distance of 30cm to this coating through a photomask
Contact exposure was carried out for 150 seconds using the high-pressure mercury lamp. Then, paddle development was performed with a developing solution containing 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of methanol, and washed with ethanol to obtain a relief pattern. The time required for development was 315 seconds.

[0030]

EFFECT OF THE INVENTION The photosensitive polymer composition of the present invention does not require a purification step during the production of a polyimide precursor, has a short development time, and can be used as a surface protective film for semiconductor devices or an interlayer insulating film. Can be used.

Continuation of front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location G03F 7/075 511 (72) Inventor Sato Court 4-13-1 Higashimachi, Hitachi-shi, Ibaraki Hitachi Chemical Yamazaki Factory Co., Ltd.

Claims (2)

[Claims] 1. (a) General formula (I): (In the formula, R ₁ represents a tetravalent organic group having 2 or more carbon atoms,
R ₂ means a divalent organic group having 2 or more carbon atoms, R ₃ means hydrogen or an alkali metal counterion, and R ₄ is a monovalent organic group inert to actinic radiation or —Si (R ₅ ) ₃ (R ₅ means hydrogen or a monovalent organic group), and m + n = 1, m is 0 <m <1, and n is 0 <n <1. A compound containing (b) one or more unsaturated bonds dimerizable or polymerizable by actinic radiation and one amino group or a quaternized salt thereof, and (c) an azide,
A heat-resistant photosensitive polymer composition comprising a sensitizer, a photoinitiator or a compound containing one or more unsaturated bonds dimerizable or polymerizable by actinic radiation. 2. A method for producing a relief pattern, which comprises coating the heat-resistant photosensitive polymer composition according to claim 1 on a supporting substrate, drying, exposing and developing.