JPH0990627A - Photosensitive polyimido precursor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the sensitivity by incorporating a polymer having specified structural units as a main component and a compound having an ethylenically unsaturated double bond and an amino and/or amido group and a specified oxime compound and an aromatic secondary or tertiary amine compound. SOLUTION: This composition contains the polymer composed mainly of the structural units each represented by formula I, the compound having an ethylenically unsaturated double bond and an amino and/or amido group, the compound represented by formula II, and the aromatic secondary or tertiary compound. In the formulae I and II, R1 is a tri- or tetra-valent organic group having >=2 carbon atoms; R2 is a divalent organic group having >=2 carbon atoms; R3 is H atom or an alkali metal atom ion or ammonium ion or a 1-30C organic group; (n) is 1 or 2; each of R4 and R5 is a l-20C organic group; R6 is an organic group having >=2C and 1-4 valences; and (m) is 1-4.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive polyimide precursor composition having good sensitivity.

[0002]

2. Description of the Related Art The following are known negative photosensitive polyimide precursor compositions in which exposed portions remain 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-
52822).

(B) A composition obtained by adding acrylamides to polyamic acid (for example, JP-A-3-170555).

(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).
JP-A-62-184056, JP-A-62-1840
273259).

In these conventional prior arts, when the film thickness of the photosensitive polyimide precursor is increased, the photosensitivity is lowered and the pattern side of the exposed portion is scooped out during development, resulting in an overshoot. -There was a problem of hanging.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and provide a negative photosensitive polyimide precursor composition having good sensitivity.

[0008]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
(A) a polymer (A) containing a structural unit represented by the general formula (1) as a main component,

Embedded image (R1 is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R2 is a divalent organic group having at least 2 or more carbon atoms, R3 is hydrogen, an alkali metal ion, an ammonium ion Or 1 to 30 carbon atoms
Represents an organic group. n is 1 or 2. ) A polymer having the structural unit [1] as a main component, and (b) a compound (B) having an ethylenically unsaturated double bond and an amino group and / or an amide group, (c) a general formula (2). ) An oxime compound (C) represented by

Embedded image (Wherein R4 and R5 are organic groups having 1 to 20 carbon atoms,
R6 is a monovalent to tetravalent organic group having at least 2 carbon atoms, and m is 1 to 4. ) (D) Aromatic secondary or aromatic tertiary amine compound (D)
And a photosensitive polyimide precursor composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer (A) containing a structural unit represented by the general formula (1) as a main component in the present invention has an imide ring or other cyclic structure by heating or a suitable catalyst. It can be a polymer (hereinafter referred to as a polyimide-based polymer).

In the general formula (1), R1 is at least 2
It is a trivalent or tetravalent organic group having one or more 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. Specifically, a phenyl group, a biphenyl group,
Examples thereof include, but are not limited to, a terphenyl group, a naphthalene group, a perylene group, a diphenylether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, a biphenyltrifluoropropane group, and the like.

In the general formula (1), R2 is at least 2
Although it is a divalent organic group having at least one carbon atom, R2 is preferably a divalent group having an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms from the viewpoint of heat resistance. Specific examples include a phenyl group, a biphenyl group, a ta-phenyl group, a naphthalene group, a perylene group, a diphenylether group, a diphenylsulfone group, a diphenylpropane group, a benzophenone group, and a biphenylhexafluoropropane group. It is not limited to these.

Further, in order to improve the adhesiveness to the substrate, R1 and R2 may be copolymerized with an aliphatic group having a siloxane structure within a range that does not lower the heat resistance. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane.

R3 represents hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms. Preferred examples of R3 include hydrogen, methyl group,
Examples thereof include, but are not limited to, ethyl group, isopropyl group, butyl group, ethyl methacrylate group, ethyl acrylate group, and o-nitrobenzyl group. R3 is preferably hydrogen.

In the polymer (A), R1, R2 and R3 may each be composed of one type of these, or may be a copolymer composed of two or more types of each.

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. In this case, it is preferable that the content of the structural unit represented by the general formula (1) is 90 mol% or more. 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 and 4,4'- (or 3,4'-).
Diaminodiphenyl ether, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4'-
(Or 3,4 ′-) diaminodiphenyl ether,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-(or 3,4 '-) diaminodiphenyl ether, 3,3', 4,4'-biphenylhexafluoro Propane tetracarboxylic dianhydride and 4,4 '
-(Or 3,4 '-) diaminodiphenyl ether,
3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride and 4,4'-(or 3,4 '-) diaminodiphenyl ether, pyromellitic dianhydride and 3,3'
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′-biphenyltetracarboxylic dianhydride and 3,3 ′-(or 4,
4 '-) diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4'-diaminodiphenyl sulfide,
3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and 4,4′-diaminodiphenyl sulfide,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl sulfide, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride and paraphenylenediamine, 3,3 ', 4,4'-biphenylhexafluoropropanetetracarboxylic dianhydride and paraphenylenediamine, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and ta-phenyldiamine, 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 para-phenylenediamine, 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane,
Pyromellitic dianhydride and 4,4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 4, Examples thereof include, but are not limited to, polyamic acid and its ester compound synthesized from 4′-diaminodiphenyl ether and bis (3-aminopropyl) tetramethyldisiloxane.

These polyamic acid and its ester compound are synthesized by a known method. That is, in the case of polyamic acid, tetracarboxylic dianhydride and diamine are selectively combined, and these are mainly composed of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. Polar solvent or γ
-Synthesized by reacting in butyrolactone. Polyamide acid ester compounds are disclosed in, for example,
It is synthesized by the method described in JP-A No. 1-72022 or JP-A No. 55-30207.

The component (B) having an ethylenically unsaturated double bond and an amino group and / or an amide group used in the present invention includes an ethylenically unsaturated double bond and an amino group and / or an amide group. An organic compound having 3 to 30 carbon atoms is preferable. Furthermore, carbon number 3 to 3
An aliphatic organic compound of 0 is preferred. Examples of the organic group contained include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, and a urea group in addition to an amino group and an amide group.

Preferred specific examples of the compound having an ethylenically unsaturated double bond and an amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, N,
N-dimethylaminoethyl methacrylamide, N, N-
Dimethylaminopropyl methacrylamide, N, N-diethylaminoethyl methacrylamide, N, N-diethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide, Examples thereof include, but are not limited to, N, N-dimethylaminopropylacrylamide, N, N-diethylaminoethylacrylamide, N, N-diethylaminopropylacrylamide and the like.

Preferred specific examples of the compound having an ethylenically unsaturated double bond and an amide group are acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-ethylmethacrylamide and N-ethylacrylamide. , N-isopropylmethacrylamide, N-isopropylacrylamide,
N-butyl methacrylamide, N-butyl acrylamide, diacetone acrylamide, diacetone methacrylamide, N-cyclohexyl methacrylamide, N-cyclohexyl acrylamide, N-methyl acrylamide, acryloyl morpholine, methacryloyl morpholine, acryloyl piperidine, methacryloyl piperidine, Crotonamide, N-methylcrotonamide,
Examples thereof include, but are not limited to, N-isopropylcrotonamide, N-butylcrotonamide, acetic acid allylamide, and propionic acid allylamide. Particularly, amino acrylate derivatives and acrylamide derivatives are preferable in terms of sensitivity.

These are used alone or as a mixture of two or more kinds.

The compound (B) is 5 of all constitutional units of the polymer.
%, Preferably 30% or more and more preferably 5 times or less of the equivalents of all the carboxyl groups in the polymer. If the ratio is out of this range, the sensitivity is deteriorated and restrictions on development are increased.

The oxime compound (C) used in the present invention is represented by the following general formula (2).

[0024]

Embedded image In the formula, R4 and R5 are organic groups having 1 to 20 carbon atoms, R6 is a monovalent to tetravalent organic group having at least 2 carbon atoms, and m is 1 to 4. R4 and R5 are specifically an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, a cycloalkyl group such as a cyclobutyl group and a cyclohexyl group, (unsubstituted or methyl, ethyl, propyl, butyl, etc. Examples include, but are not limited to, aromatic hydrocarbon groups such as (substituted) phenyl groups.

In the formula, R6 is a mono- to tetra-valent organic group having at least two carbon atoms, preferably a C2-C20 di- to tetra-valent organic group. Specifically, divalent hydrocarbon groups such as methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, phenyl, biphenyl, diphenyl ether, diphenyl sulfone, diphenyl propane, benzophenone, biphenyl hexa. Examples thereof include aromatic groups each having a valence of 2 to 4, and the like, but are not limited thereto.

Specific examples of the oxime compound (C) include, but are not limited to, the following.

Acetic acid (1-phenyl-1,2-propanedione-2-oxime) monoester, stearic acid (1-phenyl-1,2-propanedione-2-oxime) monoester, benzoic acid (1-phenyl -1,2-
Propanedion-2-oxime) monoester and the like.

Malonic acid (1-phenyl-1,2-propanedione-2-oxime) diester, succinic acid (1
-Phenyl-1,2-propanedione-2-oxime)
Diester, adipic acid (1-phenyl-1,2-propanedione-2-oxime) diester and the like.

Tele (or iso) phthalic acid (1-phenyl-1,2-propanedione-2-oxime) diester, 4,4'-benzophenone dicarboxylic acid (1-phenyl-1,2-propanedione-2- Oxime) diester, etc.

Trimellitic acid (1-phenyl-1,2
-Propanedion-2-oxime) triester, trimesic acid (1-phenyl-1,2-propanedione-
2-oxime) triester and the like.

Pyromellitic acid (1-phenyl-1,2
-Propanedione-2-oxime) tetraester,
3,3 ′, 4,4′-benzophenone tetracarboxylic acid (1-phenyl-1,2-propanedione-2-oxime) tetraester and the like.

The above phenyl is changed to methyl, ethyl, propyl, or butyl, and the above propanedione is changed to butanedione or hexanedione.

The amount of the oxime compound (C) is 0.1% by weight to 10% by weight, preferably 0.5% by weight to 5% by weight, more preferably 0.5 to 3% by weight, based on the polymer. Is desirable. If the ratio is out of this range, the sensitivity is deteriorated and restrictions on development are increased.

Furthermore, by adding an aromatic secondary or aromatic tertiary amine compound (D), a marked improvement in sensitivity can be achieved. Preferred specific examples include N-phenyldiethanolamine and N- (3-methylphenyl).
Diethanolamine, N- (4-methylphenyl) diethanolamine, N-phenylmonoethanolamine,
N-phenyl-N-methyl-monoethanolamine, N
-Phenyl-N-ethyl-monoethanolamine, N-
Examples thereof include ethylaniline, N, N-diethylaniline, N-benzyl-N-ethylaniline and N-arylglycine compounds. N- from the point of sensitivity improvement
Arylglycine compounds are particularly preferred. The N-arylglycine compound is a compound in which an aromatic ring is directly bonded to the nitrogen atom of glycine, and the aromatic ring here is
Benzene ring, naphthalene ring, anthracene ring, naphthoquinone ring, anthraquinone ring, etc. These aromatic rings may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a nitro group, a halogen group, a carboxyl group, a carboxyl ester group, a secondary or tertiary amino group, or the like. Further, the carboxyl group of glycine may be esterified. Specific preferred examples of the N-arylglycine compound include, but are not limited to, N-phenylglycine, N-naphthylglycine, N-phenylglycine ethyl ester, and N-naphthylglycine ethyl ester.

These aromatic secondary or aromatic tertiary amine compounds are used alone or as a mixture of two or more kinds. The preferred addition amount is 0.1% by weight based on the polymer.
˜20% by weight, more preferably 0.2% by weight to 10% by weight.

The ratio of the oxime compound (C) to the aromatic secondary or tertiary amine compound (D) ((C) /
(D)) is preferably 1 or less, more preferably 0.5 or less.

Further, coumarins may be added to improve the sensitivity to g-ray exposure. Specific examples of preferable coumarins include 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, 3- (4-cyanobenzoyl) coumarin, and 7-methoxy-3- (4-
Methoxybenzoyl) coumarin, 3-benzoyl-7-
Methoxycoumarin, 3- (4-cyanobenzoyl) -7
-Methoxycoumarin, 5,7-dimethoxy-3- (4-
Methoxybenzoyl) coumarin, 3-benzoyl-5,
7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxycoumarin, 3-benzoyl-
7-diethylaminocoumarin, 7-diethylamino-3
-(4-Dimethylaminobenzoyl) coumarin, 3,3
′ -Carbonylbiscoumarin, 3,3′-carbonylbis (7-methoxycoumarin), 5,7-dimethoxy-
3,3'-carbonylbiscoumarin, 5,7,7'-trimethoxy-3,3'-carbonylbiscoumarin, 3,
3'-carbonylbis (5,7-dimethoxycoumarin), 7-diethylamino-3,3'-carbonylbiscoumarin, 7-diethylamino-5 ', 7'-dimethoxy-3,3'-carbonylbiscoumarin, 3, 3'-Carbonylbis (7-diethylaminocoumarin), 9-
(7-diethylamino-3-coumarinoyl) -1,2,
4,5-Tetrahydro-3H, 6H, 10H [l] benzopyrano [9,9a, l-gh] quinolazin-10-one, 9,9'-carbonylbis (1,2,4,5-tetrahydro-3H, 6H, 10H [l] benzopyrano [9,9a, l-gh] quinolazin-10-one), and the like, but are not limited thereto.

These coumarins are used alone or as a mixture of two or more kinds. The preferred addition amount is 0.1% by weight to 20% by weight, more preferably 0.2% by weight to 10% by weight, based on the polymer.

Further, a sensitizer other than the above may be added. Specific examples include Michler's ketone, fluorenone,
Aromatic carbonyl compounds such as benzanthrone, 3-
[4- (Dimethylamino) phenyl] -1-phenyl-
2-propen-1-one, 1- (3-chlorophenyl)-
An amino aromatic unsaturated ketone such as 5- [4- (dimethylamino) phenyl] -1,4-pentadiene-3-one,
Although methylenethiazole derivatives such as 1-methyl-2-benzoylmethylene-1,2-dihydronaphtho [1,2, d] thiazole and merocyanine dyes are effective,
It is not limited to these. These sensitizers are used alone or as a mixture of two or more kinds. The preferred addition amount is 0.1% by weight to 20% by weight, more preferably 0.2% by weight to 10% by weight, based on the polymer.

In addition to the composition of the present invention, as a photoreactive monomer, 2-hydroxyethyl methacrylate, trimethylol propane triacrylate, trimethylol.
It is permissible to add a monomer such as rupropane trimethacrylate or ethylene glycol dimethacrylate in an amount of 1 to 20% by weight based on the polymer.

The above-mentioned polymer (A), compound (B), oxime compound (C), aromatic secondary or aromatic tertiary amine compound (D), and optionally coumarins and other sensitizers, A photosensitive polyimide precursor composition is obtained by mixing the photoreactive monomer with a solvent. As the solvent used at this time, N-methyl-2-pyrrolidone,
A polar solvent containing N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, etc. as a main component, or a solvent such as γ-butyrolactone, N, N-dimethylacrylamide, or a mixture of two or more thereof. It is preferably used, but is not limited thereto. In addition, if necessary, a surfactant for improving the wettability of the above precursor composition with the substrate, SiO ₂ , or TiO ₂ .
Inorganic particles such as ₂ or polyimide particles 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 of the present invention is mainly used for forming a negative type polyimide pattern.

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 carried out using an oven, hot plate, infrared ray or the like at a temperature of 50 to 100 ° C. for 1 minute to several hours.

Next, a mask having a desired pattern is placed on this coating, and actinic radiation is 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.

Formation of the polyimide pattern is achieved by removing the unexposed portion with a developing solution after the exposure. As the developing solution, polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide, and methanol, ethanol, isopropyl alcohol, xylene, water and the like are used. A combined developer can be used. After development,
Rinse with an alcohol such as alcohol or isopropyl alcohol.

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 the mixture was further reacted at 60 ° C. for 3 hours to obtain a polymer solution of structural unit (1) having a viscosity of 122 poise (25 ° C.). In this solution, 113.16 g of N-isopropylacrylamide (equivalent to all carboxyl groups in the polymer), isophthalic acid (1-phenyl-1,2-propanedione-2-oxime) diester, 2.36 g, 11.82 g of N-phenylglycine and γ-butyrolactone 315g
Was added to obtain a polyimide precursor composition. This polyimide precursor composition was coated on a 4-inch silicon wafer and dried at 60 ° C. for 30 minutes in a nitrogen atmosphere to give a film thickness of 5.18 μ.
m film was formed. Canon Inc. UV exposure machine P
Using LA-501F, it was exposed to 150 mJ / cm ² (ultraviolet intensity of 365 nm) through a photomask made of chromium. After the exposure, a heat treatment was performed on the hot plate at 80 ° C. for 1 minute. Next, this is N-methyl-2-pyrrolidone 70
It was dipped in a developer containing 0 g, xylene 300 g, and water 100 g, rinsed with isopropyl alcohol, and then blown with nitrogen to obtain a negative pattern. The thus obtained negative pattern was cured at 130 ° C., 200 ° C. and 400 ° C. for 30 minutes in a nitrogen atmosphere to form a negative polyimide pattern.

Example-2 4,4 was added to the polymer solution of the structural unit (1) obtained in Example-1.
′ -Benzophenonetetracarboxylic acid (1-methyl-
1,2-propanedione-2-oxime) tetraester, 2.36 g, N-phenyldiethanolamine 11.82
g, 315 g of γ-butyrolactone and 185.0 g of N, N-diethylaminoethyl methacrylate were added to prepare a polyimide precursor composition. This polyimide precursor composition was applied on a 4-inch silicon wafer and dried at 80 ° C. for 3 minutes on a hot plate to form a polyimide precursor film having a thickness of 5.40 μm. Using a UV exposure machine PLA-501F manufactured by Canon Inc., exposure was performed at 200 mJ / cm ² (UV intensity of 365 nm) through a photomask made of chromium. After the exposure, a heat treatment was performed on the hot plate at 80 ° C. for 1 minute. 900 g of N-methyl-2-pyrrolidone and 100 g of water
Was rinsed with isopropyl alcohol and then blown with nitrogen to obtain a negative type pattern.

Example 3 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 147.1 g, 2-hydroxyethyl methacrylate 3
2.5 g, with N-methyl-2-pyrrolidone 471 g, 7
The reaction was carried out at 0 ° C for 3 hours. Thereafter, the mixture was cooled to 20 ° C., 37.84 g of paraphenylenediamine, 25.03 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. And viscosity 600 poise (25
° C) to obtain a polymer solution of the structural unit (1). 2.16 g of terephthalic acid (1-phenyl-1,2-butanedione-2-oxime) diester, 10.8 g of N-phenylglycine, 0.54 g of 3,3′-carbonylbis (diethylaminocoumarin) and 171 g of γ-butyrolactone were added to this polymer solution.
And 78.65 g of dimethylaminoethyl methacrylate
Was added to prepare a polyimide precursor composition having a viscosity of 120 poise (25 ° C.).

This polyimide precursor composition was applied onto a 4-inch silicon wafer and dried at 70 ° C. for 90 minutes with a dryer to form a polyimide precursor film having a thickness of 40 μm. Using Canon Inc. UV exposure machine PLA-501F,
An L-42 optical filter was attached, and the film was exposed to 250 mJ / cm ² (ultraviolet intensity of 436 nm) through a photomask made of chromium. After the exposure, a heat treatment was performed on the hot plate at 80 ° C. for 1 minute. Next, N-methyl-2-pyrrolidone 70
A developing solution consisting of 0 g, 300 g of xylene, and 100 g of water was dropped, developed by the paddle method, and rinsed with isopropyl alcohol to obtain a negative pattern having a vertical cross section.

[0054]

[Table 1] Comparative Example-1 In Example-1, isophthalic acid (1-phenyl-1,
A polyimide precursor composition was prepared without the 2-butanedione-2-oxime) diester.

This polyimide precursor composition was coated on a 4-inch silicon wafer, and exposed and developed in the same manner as in Example-1. A negative pattern was obtained with an exposure dose of 150 mJ / cm ² (ultraviolet intensity of 365 nm), but the cross section was hollowed out and the shape was an overhang.

Comparative Example-2 A polyimide precursor composition was prepared without adding N-phenylglycine in Example-3. This polyimide precursor composition was applied onto a 4-inch silicon wafer, and exposed and developed in the same manner as in Example-5. 250mJ / cm
^A negative pattern was obtained with an exposure dose of ² (ultraviolet intensity of 436 nm), but the cross section was hollowed out and had an overhang shape.

[0057]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a polymer having a structural unit represented by the general formula (1) as a main component, a compound having an ethylenically unsaturated double bond and an amino group and / or an amide group. The composition containing the specific oxime compound and the aromatic amino compound was able to exhibit excellent performance as a negative photosensitive polyimide precursor. 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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location H01L 21/027 H01L 21/312 B 21/312 21/30 502R

Claims (6)

[Claims] 1. A polymer (A) comprising a structural unit represented by the general formula (1) as a main component, (R1 is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, R2 is a divalent organic group having at least 2 or more carbon atoms, R3 is hydrogen, an alkali metal ion, an ammonium ion Or 1 to 30 carbon atoms
Represents an organic group. n is 1 or 2. ) A polymer having the structural unit [1] as a main component, and (b) a compound (B) having an ethylenically unsaturated double bond and an amino group and / or an amide group, (c) a general formula (2). ) And an oxime compound (C) (Wherein R4 and R5 are organic groups having 1 to 20 carbon atoms,
R6 is a monovalent to tetravalent organic group having at least 2 carbon atoms, and m is 1 to 4. ) (D) Aromatic secondary or aromatic tertiary amine compound (D)
A photosensitive polyimide precursor composition comprising: 2. The photosensitive polyimide precursor composition according to claim 1, wherein the aromatic secondary or aromatic tertiary amine compound is an N-arylglycine compound. 3. The photosensitive polyimide precursor composition according to claim 1, which contains a coumarin (E). 4. The oxime compound (C) represented by the general formula (2) is contained in an amount of 3% by weight or less of the polymer (A) containing the structural unit represented by the general formula (1) as a main component. The photosensitive polyimide precursor composition according to claim 1, wherein 5. The ratio ((C) / (D)) of the oxime compound (C) represented by the general formula (2) and the aromatic secondary or aromatic tertiary amine compound (D) is 1 or less. The photosensitive polyimide precursor composition according to claim 1, wherein the photosensitive polyimide precursor composition is present. 6. The photosensitive polyimide precursor composition according to claim 1, which is a negative type.