JPH06332178A - Photosensitive polyimide precursor composition - Google Patents

Abstract

PURPOSE:To obtain the polyimide film easy in manufacture and enhanced in performance by curing after development by incorporating each of a specified polymer, a compound, a photoinitiator, a sensitizer, and a photoreactive monomer. CONSTITUTION:This composition contains the polymer composed essentially of structural units represented by formula I, the compound represented by formula II, the photoinitiator, the sensitizer, and the photoreactive monomer. In formulae I and II, R<1> is a tri- or tetra-valent organic group having at least 2C; R<2> is a divalent organic group having at least 2C; R<3> is an H; alkali metal ion, or ammonium ion, or a 1-30C organic group; n is 1 or 2; each of Y<1> and Y<2> is -O- or -NH-; R<4> is H or 1-10C lower alkyl; R<5> is an optionally substituted hydrocarbon group; and R<6> is an optionally substituted 1-10C hydrocarbon group, thus permitting the obtained composition to be easy in manufacture and enhanced in performance both as a negative type or a positive type.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide precursor composition, and more particularly to a photosensitive polyimide precursor composition applicable to both a negative type and a positive type.

[0002]

2. Description of the Related Art The following is known as a negative photosensitive polyimide precursor composition in which an exposed portion remains after development.

(A) A composition in which a polyamic acid is added with a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof (for example, Japanese Patent Publication No. 59-5).
2822).

(B) Photosensitive adducts of polyamic acid and an isocyanate compound having an unsaturated double bond (for example, JP-A-63-226639 and JP-A-63-2266).
40, GCDavis: ACS Symp. Ser., 242 (1984) 25.
9.).

(C) A composition containing a polyimide precursor having a carbon-carbon double bond group, a specific oxime compound, and a sensitizer (for example, JP-A-61-118423 and JP-A-61-184423). 62-184056, JP-A-62-1
273259).

The following have been known as positive-type photosensitive polyimide compositions.

(D) A photosensitive polyimide precursor obtained by introducing photodegradable photosensitivity into a polyamic acid by an ester group (for example, JP-A No. 01-61747).

(D) A photosensitive polyimide precursor formed by adding a naphthoquinonediazide compound having a specific structure to a polyamic acid having a specific structure and subjecting it to a heat treatment after exposure in a specific temperature range (for example, Proceedings of the Polymer Society of Japan, Volume 40, Issue 3, 8
21 (1991)).

However, each of these has only a negative type or positive type function, and a photosensitive polyimide precursor composition having both negative type and positive type functions with the same composition is as follows: Not known at all.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photosensitive polyimide precursor composition which is easy to manufacture and has excellent performance as a negative type and a positive type. is there.

[0011]

The object of the present invention is: (a) a polymer (A) containing a structural unit represented by the general formula (1) as a main component,

[Chemical 3] (Wherein R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen, an alkali metal ion Represents an ammonium ion or an organic group having 1 to 30 carbon atoms, n is 1 or 2.) (b) A compound (B) represented by the general formula (2), and

[Chemical 4] (In the formula, Y ¹ and Y ² each represent an —O— or —NH— group. R ⁴ is hydrogen or a lower alkyl group having 1 to 10 carbon atoms, and R ⁵ is a substituted or unsubstituted hydrocarbon. The group R ⁶ represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.) (C) A photoinitiator and / or a sensitizer and / or a photoreactive monomer are contained. Achieved by a photosensitive polyimide precursor composition.

The polymer (A) having a structural unit represented by the general formula (1) as a main component in the present invention means a polymer having an imide ring or other cyclic structure (hereinafter referred to as "polymer") by heating or a suitable catalyst. Polyimide-based polymer).

In the general formula (1), R ¹ is at least 2
A trivalent or tetravalent organic group having 4 carbon atoms.
From the viewpoint of heat resistance, R ¹ is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms. Specific examples thereof include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenyl sulfone group, a diphenylpropane group, a benzophenone group, and a biphenyltrifluoropropane group. .

In the above general formula (1), R ² is at least 2
Although it is a divalent organic group having 4 carbon atoms, R ² contains an aromatic ring or an aromatic heterocycle from the viewpoint of heat resistance,
Moreover, a divalent group having 6 to 30 carbon atoms is preferable. Specific examples thereof include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, a naphthalene group, a perylene group, a diphenyl ether group, a diphenyl sulfone group, a diphenylpropane group, a benzophenone group, and a biphenyltrifluoropropane group. .

Further, in order to improve the adhesiveness to the substrate, R ¹ and R ² may be copolymerized with an aliphatic group having a siloxane structure within a range that does not lower the heat resistance. Specific examples of the diamine component include those obtained by copolymerizing bis (3-aminopropyl) tetramethyldisiloxane with 1 to 10 mol%.

R ³ represents hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms.
Preferable specific examples of R ³ include, but are not limited to, hydrogen, methyl group, ethyl group, isopropyl group, butyl group, ethyl methacrylate group, ethyl acrylate group, o-nitrobenzyl group and the like. Particularly, R ³ is preferably hydrogen.

In the polymer (A), R ¹ , R ² and R ³ may each be composed of one kind, or each of them may be ² kinds.
It may be a copolymer composed of one or more species.

The polymer (A) may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit.
At that time, the structural unit represented by the general formula (1) is 90 mol%
It is preferable to contain the above. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

Specific examples of the polymer (A) include pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4. ′ -Diaminodiphenyl ether, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether,
3,3 ', 4,4'-biphenyltrifluoropropane tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, 3,3', 4,4'-biphenylsulfone tetracarboxylic dianhydride and 4, 4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3'-
(Or 4,4 ') diaminodiphenyl sulfone, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 3,3'-(or 4,4 ') diaminodiphenyl sulfone, 3,3', 4,4'-biphenyl tetracarboxylic dianhydride 3,3 ′-(or 4,4 ′) diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4′-diaminodiphenyl sulfide, 3,3 ′,
4,4'-benzophenone tetracarboxylic acid dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3 ',
4,4'-biphenyltetracarboxylic dianhydride and 4,
4'-diaminodiphenyl sulfide, 3,3 ', 4
4'-benzophenone tetracarboxylic dianhydride and paraphenylenediamine, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine,
3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and paraphenylenediamine, 3,3 ′,
4,4′-biphenyltrifluoropropanetetracarboxylic dianhydride and paraphenylenediamine, 3,3 ′,
4,4'-biphenyltetracarboxylic dianhydride and terphenyldiamine, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride Anhydrous and para-phenylenediamine, pyromellitic dianhydride and 3,3 ',
4,4'-benzophenone tetracarboxylic dianhydride and 3,3 '-(or 4,4') diaminodiphenyl ether, pyromellitic dianhydride and 3,3 ', 4,4
′ -Biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldiamine Siloxane, pyromellitic dianhydride and 4,4 '
-Diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, 3,3 ', 4
4'-biphenyltetracarboxylic dianhydride and 4,4 '
Examples include, but are not limited to, polyamic acid and its ester compounds synthesized from diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane.

These polyamic acids and their esterified products are synthesized by known methods. That is, in the case of a polyamic acid, it is synthesized by selectively combining a tetracarboxylic dianhydride and a diamine and performing a polymerization reaction in an organic polar solvent. Here, the organic polar solvent means amides having no ethylenically unsaturated double bond, cyclic amides, lactones, N, N-dialkyl sulfones,
Refers to N, N-dialkyl sulfoxides. N, N-dialkylcarboxylamides, N-alkylcarboxylamides, cyclic amides and lactones having a low molecular weight and usually liquid are preferable. As specific examples, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N,
N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, N-acetyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylsulfone, N, N-dimethylsulfoxide , Hexamethylphosphoramide, 2-
Examples thereof include, but are not limited to, pyrrolidone. These organic polar solvents are used alone or as a mixture of two or more kinds. Further, other organic solvents such as xylene, acetone, ethanol, methanol, methyl cellosolve, ethyl cellosolve, diglyme, 2-
Used as a mixture with hydroxyethyl methacrylate and the like.

Examples of esterification products of polyamic acid include those disclosed in JP-A-61-272022 and JP-B-55-30207.
It is synthesized by the method described in the publication.

In the present invention, the compound (B) represented by the general formula (2) is contained as an essential component.

[0023]

[Chemical 5] In the general formula (2), Y ¹ and Y ² are each —O—
Or a -NH- group is shown. R ⁴ is hydrogen or 1 to 1 carbon atoms
10 is a lower alkyl group, R ⁵ is a substituted or unsubstituted hydrocarbon group, and R ⁶ is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. Here, as the substituent, an amino group,
Examples thereof include amide group, hydroxyl group, carbonyl group, carboxyl group, and cyano group, but are not limited thereto.

Examples of the lower alkyl group having 1 to 10 carbon atoms for R ⁴ include methyl group, ethyl group, propyl group, butyl group,
Examples include, but are not limited to, a pentyl group.
R ^5, is a substituted or unsubstituted hydrocarbon group, 1 to carbon atoms
10 compounds are preferred. Examples of the hydrocarbon group include, but are not limited to, a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, and the like. R ⁶ is a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group,
Examples thereof include, but are not limited to, a pentyl group, a cyclohexyl group, a phenyl group and a benzyl group.

Specific examples of the compound (B) include 1-methyl-3- (2-methacryloyloxyethyl) urea, 1-ethyl-3- (2-methacryloyloxyethyl) urea, 1-propyl-3-. (2-methacryloyloxyethyl) urea, 1-butyl-3- (2-methacryloyloxyethyl) urea, 1-pentyl-3-
(2-methacryloyloxyethyl) urea, cyclohexyl-3- (2-methacryloyloxyethyl) urea, 1-benzyl-3- (2-methacryloyloxyethyl) urea, 1-methyl-3- (2-methacryloyloxypropyl) Urea, 1-ethyl-3- (2-methacryloyloxypropyl) urea, 1-propyl-3
-(2-methacryloyloxypropyl) urea, 1-
Butyl-3- (2-methacryloyloxypropyl) urea, 1-pentyl-3- (2-methacryloyloxypropyl) urea, cyclohexyl-3- (2-methacryloyloxypropyl) urea, 1-benzyl-3-
(2-methacryloyloxypropyl) urea, 1-phenyl-3- (2-methacryloyloxypropyl) urea, methyl N- (2-methacryloyloxyethyl)
Urethane, ethyl N- (2-methacryloyloxyethyl) urethane, propyl N- (2-methacryloyloxyethyl) urethane, butyl N- (2-methacryloyloxyethyl) urethane, pentyl N- (2-methacryloyloxyethyl) urethane, Cyclohexyl N-
(2-methacryloyloxyethyl) urethane, benzyl N- (2-methacryloyloxyethyl) urethane,
Methyl N- (2-methacryloyloxypropyl) urethane, ethyl N- (2-methacryloyloxypropyl) urethane, propyl N- (2-methacryloyloxypropyl) urethane, butyl N- (2-methacryloyloxypropyl) urethane, pentyl N -(2-methacryloyloxypropyl) urethane, cyclohexyl N- (2-methacryloyloxypropyl) urethane,
Benzyl N- (2-methacryloyloxypropyl) urethane, phenyl N- (2-methacryloyloxypropyl) urethane, dimethylaminoethyl N- (2-methacryloyloxyethyl) urethane, dimethylaminoethyl N- (2-methacryloyloxypropyl) Urethane, diethylaminoethyl N- (2-methacryloyloxyethyl) urethane, diethylaminoethyl N- (2
-Methacryloyloxypropyl) urethane, and those in which the methacryloyl group is changed to an acryloyl group, but not limited thereto. Particularly, a compound having a methacryl group is desirable in terms of sensitivity. These compounds (B) are used alone or as a mixture of two or more.

The compound (B) is 20% of all the constitutional units of the polymer.
%, Preferably 50% or more, and more preferably 5 times or less the equivalent of all the carboxyl groups in the polymer. If it deviates from this range, the sensitivity will be deteriorated and there will be many restrictions on development.

The composition of the present invention contains a photoinitiator and / or a sensitizer and / or a photoreactive monomer.

As the photoinitiator, Michler's ketone, 4,
Aromatic amine compounds such as 4'-diethylaminobenzophenone, N-phenyldiethanolamine, N-phenylglycine, 1-phenylpropanedione-2- (O-
(Ethoxycarbonyl) oxime, 1-phenyl-1,2
-Butanedione-2- (O-methoxycarbonyl) oxime, 1-phenylpropanedione-2- (O-benzoyl) oxime, 1-2-diphenyl-ethanedione-
A chain oxime ester compound typified by 1- (O-benzoyl) oxime and a cyclic oxime ester compound typified by 3-phenyl-5-isoxazolone are effective, but not limited thereto. Particularly, an oxime ester compound is desirable in terms of sensitivity. These photoinitiators are used alone or as a mixture of two or more kinds.

The amount of photoinitiator is from 1% by weight to the polymer.
It is desirable that 100% by weight, preferably 2 to 50% by weight, is mixed. If it deviates from this range, the sensitivity will be deteriorated and there will be many restrictions on development.

As the sensitizer, Michler's ketone, 4,4
′ -Diethylaminobenzophenone, 3,3′-carbonylbis (diethylaminocoumarin), “Coumarin” 339, “Coumarin” 338, manufactured by Kodak Corporation.
"Coumarin" 314, "coumarin" 7 and the like are effective, but are not limited thereto. Coumarin compounds are particularly desirable in terms of sensitivity. These sensitizers are used alone or as a mixture of two or more kinds.

The amount of sensitizer is 0.1% by weight based on the polymer.
It is desirable that they are mixed in an amount of ˜20% by weight, preferably 0.2% by weight to 10% by weight.

As the photoreactive monomer, an amino acrylate compound and / or an aminoacrylamide compound is effective, and the addition of these photoreactive monomers further improves the photosensitivity.

Specific examples of the amino acrylate compound include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, tert-butylaminoethyl methacrylate and dimethylamino-2-methacrylate. Examples include, but are not limited to, hydroxypropyl, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, and the like.

Specific examples of the aminoacrylamide compound include N, N-dimethylaminoethyl methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminoethyl methacrylamide,
N, N-diethylaminopropylmethacrylamide,
N, N-dimethylaminoethylacrylamide, N, N
-Dimethylaminopropyl acrylamide, N, N-diethylaminoethyl acrylamide, N, N-diethylaminopropyl acrylamide and the like, but not limited to.

The amino acrylate compound and / or amino acrylamide compound is one of all constitutional units of the polymer.
%, Preferably 5% or more and more preferably 5 times or less of the equivalents of all carboxyl groups in the polymer.

As the photoreactive monomer other than the above,
Further improvement in sensitivity can be expected by adding a monomer such as 2-hydroxyethyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, or ethylene glycol dimethacrylate in an amount of 1 to 20% by weight based on the polymer.

A photosensitive polyimide precursor composition is obtained by mixing the above-mentioned polymer (A), compound (B), and photoinitiator and / or sensitizer and / or photoreactive monomer with a solvent. As the solvent used at this time, a polar solvent containing N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, or the like as a main component, or γ-
Solvents such as butyrolactone and water are preferably used alone or as a mixture of two or more kinds, but are not limited thereto.

If necessary, the above precursor composition may be added with a surfactant for improving the wettability with the substrate, SiO ₂ ,
Inorganic particles such as TiO ₂ or particles of polyimide may be added.

Next, a method for forming a polyimide pattern using the photosensitive polyimide precursor composition of the present invention will be described.

The photosensitive polyimide precursor composition is coated on a substrate. The substrate may be, but is not limited to, silicon, alumina ceramic, glass ceramic, aluminum nitride, a semiconductor-formed substrate, or the like. Examples of the coating method include, but are not limited to, spin coating using a spinner, spray coating, dipping, and roll coating. Although the coating film thickness varies depending on the coating means, the solid content concentration of the composition, the viscosity, etc., it is usually coated so that the film thickness after drying will be 0.1 to 150 μm.

Next, the substrate coated with the polyimide precursor composition is dried to obtain a polyimide precursor composition coating film. Drying is preferably performed using an oven, a hot plate, infrared rays or the like at 50 to 100 ° C. for 1 minute to several hours.

Next, a mask having a desired pattern is placed on this film, and actinic rays are irradiated through the mask to expose it. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron rays, and X-rays. Ultraviolet rays and visible rays are particularly preferable.

The formation of a negative type polyimide pattern is achieved by removing the unexposed portion with a developing solution after exposure. As a developing solution, N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, N, N
-A polar solvent such as dimethylformamide, methanol, ethanol, isopropyl alcohol, xylene,
A developer combined with water or the like can be used. After development,
Rinse with alcohol such as ethanol or isopropyl alcohol. Also, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide,
An alkaline aqueous solution such as tetraethylammonium hydroxide or choline can also be used. In this case, the rinse liquid can be used and water can be used.

In order to form a positive type polyimide pattern, it is important to carry out a treatment for increasing the degree of curing of the unexposed portion of the coating after the exposure to that of the exposed portion and the selection of the developer composition. is there. Heat treatment, infrared irradiation treatment, microwave irradiation treatment and the like are effective as the treatment for increasing the degree of curing of the unexposed film than the exposed film, and the heat treatment is particularly preferable because it is simple. The heat treatment is preferably performed for 1 minute to several hours at a temperature equal to or higher than that of the previous drying step. Specifically, the temperature is 60 to 180 ° C, more preferably 90 to 170 ° C. By performing these treatments after the exposure, the unexposed film has a higher degree of curing than the exposed film, and the resistance to the developer is different between the unexposed film and the exposed film. . When the unexposed film is more resistant to the developing solution than the exposed film, the exposed film is removed faster than the unexposed film, and a positive image is formed. In the opposite case, that is, when the exposed film is more resistant to the developing solution than the unexposed film, the unexposed part is removed faster than the exposed part, and a negative image is formed. .

The term "curing" as used herein refers to a component other than polyimide, for example, the compound (B) from the film of the polyimide precursor.
And photoinitiators, photoreactive monomers, solvents, ring-closing water, etc. are volatilized. The film of the polyimide precursor composition becomes thinner as the curing progresses, and has a constant film thickness at the time when the curing is completed, that is, when the film becomes a polyimide film. The difference in the degree of cure between the unexposed film and the exposed film after the treatment for increasing the curing degree is expressed by the film thickness ratio, that is, (curing ratio = film thickness of unexposed film ÷ exposed film The film thickness of the coating). The degree of cure differs depending on the amount of exposure and the processing conditions that promote curing, but it is preferably 0.98 or less for forming a positive polyimide pattern.

As a developing solution suitable for forming a positive type polyimide pattern, an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline or the like is preferably used. Also,
An organic solvent-based developer obtained by combining a polar solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide with methanol, ethanol, isopropyl alcohol, xylene, water or the like gives a negative image. After development, rinse with water or an alcohol such as methanol, ethanol or isopropyl alcohol. After development, curing is performed to obtain a polyimide insulating film.

Curing after development is carried out for 5 minutes to 5 hours while selecting the temperature and gradually raising the temperature or selecting a certain temperature range and continuously raising the temperature. The maximum temperature of this cure is 250 ~
It is good to carry out at 500 ° C., preferably 300 to 450 ° C. For example, 30 at 130 ℃, 200 ℃, and 400 ℃
Heat treatment for minutes. Alternatively, the temperature may be linearly raised from room temperature to 400 ° C. over 2 hours.

The polyimide film formed from the photosensitive polyimide precursor according to the present invention is used as a passivation film for semiconductors, a protective film for semiconductor elements, an interlayer insulating film for multi-layer wiring for high-density packaging, and the like.

[0049]

EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.

Example 1 80.55 g of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 54.53 g of pyromellitic dianhydride, 2.3 g of ethanol and 549 g of N-methyl-2-pyrrolidone
The reaction was carried out at 70 ° C. for 3 hours. After that, it was cooled to 20 ° C. and 95.10 g of 4,4′-diaminodiphenyl ether.
And 6.20 g of bis (3-aminopropyl) tetramethyldisiloxane were added and further reacted at 60 ° C. for 3 hours to obtain a polymer (A) solution having a viscosity of 122 poise (25 ° C.). 201.21 g of ethyl N- (2-methacryloyloxyethyl) urethane, 23.6 g of 3-phenyl-5-isoxazolone, 3,3'-carbonylbis (diethylamino) were added to this solution in an amount equivalent to all the carboxyl groups in the polymer. Coumarin) 2.36 g of γ-butyrolactone 3
A solution dissolved in 15 g was added to obtain a polyimide precursor composition.

This polyimide precursor composition was coated on a 4-inch silicon wafer, and was heated on a hot plate at 80 ° C. for 3 hours.
After minute drying, a film with a thickness of 6.69 μm was formed. 1000 mJ / cm ² (365n) using a photo mask made of chrome using an ultraviolet exposure device PLA-501F made by Canon Inc.
m UV intensity) exposed. After the exposure, heat treatment was performed on a hot plate at 140 ° C. for 3 minutes. By this treatment, the unexposed film had a thickness of 3.73 μm, the exposed film had a thickness of 5.45 μm, and the curing ratio was 0.684. Next, it was immersed in a developer composed of a 2.38% aqueous solution of tetramethylammonium hydroxide for development. After rinsing with water, it was blown with nitrogen and dried. The positive type pattern thus obtained was cured at 130 ° C., 200 ° C. and 400 ° C. for 30 minutes in a nitrogen atmosphere to form a positive type polyimide pattern.

Example 2 In Example 1, after the exposure, no heat treatment was performed and N-methyl-
A negative type pattern was obtained by immersing in a developer containing 700 g of 2-pyrrolidone, 300 g of xylene and 100 g of water, rinsing with isopropyl alcohol, and blowing with nitrogen.

Example 3 After exposure in Example 1, without heat treatment, the sample was immersed in a developing solution containing a 0.48% aqueous solution of tetramethylammonium hydroxide for development. After rinsing with water, nitrogen blowing was performed to obtain a negative pattern.

Example 4 1-propyl-3 was added to the polymer (A) solution obtained in Example 1.
214 g of-(2-methacryloyloxyethyl) urea,
3-phenyl-5-isoxazolone 23.6 g, 3,3
´-Carbonylbis (diethylaminocoumarin) 2.36
A solution of 315 g of N-methyl-2-pyrrolidone dissolved in 315 g was added to prepare a polyimide precursor composition.

This polyimide precursor composition was coated on a 4-inch silicon wafer, and was heated at 80 ° C. for 3 hours on a hot plate.
After minute drying, a polyimide precursor film having a thickness of 6.56 μm was formed. Using a UV exposure machine PLA-501F manufactured by Canon Inc., 1000 mJ /
It was exposed to cm ² (ultraviolet intensity of 365 nm). After the exposure, heat treatment was performed on a hot plate at 140 ° C. for 3 minutes. By this treatment, the unexposed film was 4.41 μm and the exposed film was 5.83 μm.
The film thickness was μm, and the cure ratio was 0.756. Next, immersion development was performed in a developing solution composed of a 2.38% aqueous solution of tetramethylammonium hydroxide, rinsed with water, and then blown with nitrogen to obtain a positive image.

Example 5 In Example 4, after the exposure, no heat treatment was performed and N-methyl-
A negative type pattern was obtained by immersing in a developer containing 700 g of 2-pyrrolidone, 300 g of xylene and 100 g of water, rinsing with isopropyl alcohol, and blowing with nitrogen.

Reference Example Compound (B) used in Example 1 of the present invention, ethyl N-
(2-methacryloyloxyethyl) urethane is 2-
Methacryloyloxyethyl isocyanate (Showa Rhodia Co., Ltd.) 115.15 g (1 mol) and ethanol 4
60.7 g (10 mol) was reacted and excess ethanol was distilled off under reduced pressure to synthesize.

Compound (B) and 1-propyl-3- (2-methacryloyloxyethyl) urea used in Example 4 of the present invention were 2-methacryloyloxyethyl isocyanate (Showa Rhodia Co., Ltd.) 115.15 g.
(1 mol) was reacted with 59.11 g (1 mol) of n-propylamine in 300 g of N-methyl-2-pyrrolidone to synthesize. This was used as a solution as it was.

[0059]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a polymer containing a structural unit represented by the general formula (1) as a main component, a compound (B) represented by the general formula (2), and a photoinitiation. A composition comprising an agent and / or a sensitizer and / or a photoreactive monomer and having an unexpected effect of exhibiting excellent performance as a positive-type or negative-type photosensitive polyimide precursor Is. The photosensitive polyimide precursor composition of the present invention can be easily produced, and a polyimide film having excellent performance can be obtained by curing after development.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/039 H01L 21/027

Claims (1)

[Claims] 1. A polymer (A) comprising a structural unit represented by the general formula (1) as a main component, (Wherein R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen, an alkali metal ion Represents an ammonium ion or an organic group having 1 to 30 carbon atoms, n is 1 or 2.) (b) The compound (B) represented by the general formula (2), and (In the formula, Y ¹ and Y ² each represent an —O— or —NH— group. R ⁴ is hydrogen or a lower alkyl group having 1 to 10 carbon atoms, and R ⁵ is a substituted or unsubstituted hydrocarbon. The group R ⁶ represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.) (C) A photoinitiator and / or a sensitizer and / or a photoreactive monomer are contained. Photosensitive polyimide precursor composition.