JPH06273932A - Positive photosensitive polyimimido precursor composition - Google Patents

Abstract

PURPOSE:To facilitate the manufacturing method of this composition and to enhance its performance by incorporating a polymer composed essentially of specified structural units, a compound having an ethylenically unsaturated double bond and an amide group, and a photccpolymerization initiator and/or a sensitizer and/or a photopolymerizable monomer. CONSTITUTION:This composition comprises the polymer composed ssentially of the structural units each represented by formula I (R<1> is a tri- or tetra-valent organic group having at least 2C atoms; R<2> is a >=2C divalent organic group: R<3> is an H, alkali metal, or ammonium ion or a 1-30C organic group; and n is 1 or 2), the compound having an ethylenically unsaturated double bond and an amide group, and the photopolymerization initiator and/or the sensitizer and/or the photopolymerizable monomer. This polymer can be converted into a polymer having imido rings or other cyclic structures by heating or catalytic action.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a positive photosensitive polyimide precursor composition.

[0002]

2. Description of the Related Art The following are known as photosensitive polyimide precursor compositions.

(A) A composition obtained by adding a polyamic acid to a carbon-carbon double bond which is dimerizable or polymerizable by actinic radiation and an amino group or a quaternized salt thereof (for example, Japanese Examined Patent Publication Sho 59).
-52822 publication).

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

However, all of these are negative-working, in which the exposed portion remains after development. In the case of the negative type, if dust or the like adheres to a mask or the like used at the time of exposure, that portion becomes a defect and a pinhole is formed in the polyimide coating. Therefore, especially when a polyimide film is used as a protective film for semiconductor elements or an interlayer insulating film for multi-layer wiring for high-density packaging, there is a problem that the yield and reliability decrease. A body composition was sought.

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

(C) 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, in all of these, the method for producing the photosensitive polyimide precursor composition is complicated,
At present, there are problems in terms of performance and it has not been put to practical use.

[0010]

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

[0011]

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,

[Chemical 7] (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) having an ethylenically unsaturated double bond and an amide group, and (c) photoinitiation. And a sensitizer and / or a photoreactive monomer are contained in the positive-type 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 adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized as a diamine component as R ¹ and R ² within a range that does not lower the heat resistance. . Specifically, bis (3-aminopropyl) tetramethyldisiloxane or the like is used in an amount of 1 to 10
Examples include those copolymerized by mol%.

R ³ represents hydrogen, an alkali metal ion, an ammonium ion or an organic group having 1 to 30 carbon atoms.
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.

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 Things 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'-benzophenone tetracarboxylic dianhydride and paraphenylenediamine, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-diphenyl ether Tetracarboxylic acid dianhydride and para-phenylenediamine, 3,3
′, 4,4′-Biphenyltrifluoropropanetetracarboxylic dianhydride and paraphenylenediamine, 3,3
′, 4,4′-Biphenyltetracarboxylic dianhydride and ta-phenyldiamine, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4 ′
-Benzophenone tetracarboxylic dianhydride and paraphenylenediamine, 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) Tetramethyldisiloxane, pyromellitic dianhydride and 4,4'-diaminodiphenyl ether and bis (3
-Aminopropyl) tetramethyldisiloxane, 3,3
′, 4,4′-Biphenyltetracarboxylic dianhydride and 4,4′-diaminodiphenyl ether and bis (3
-Aminopropyl) tetramethyldisiloxane, and the like, but not limited to, polyamic acid and an esterified product thereof.

These polyamic acids and their esterified products are synthesized by known methods. 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-
It is synthesized by reacting in butyrolactone.
An esterified product of a polyamic acid is described in, for example, JP-A-61-17.
2022, Japanese Patent Publication No. 55-30207, and the like.

The component (b) having an ethylenically unsaturated double bond and an amide group is 10 mmHg at 80 ° C.
Compounds exhibiting the following vapor pressures are preferred. 10mmHg at 80 ℃
Most of the compounds having the above vapor pressure, such as N, N-dimethylacrylamide, are volatilized in the drying step of forming a film of the polyimide precursor composition on the substrate, and good photosensitivity cannot be obtained, which is not preferable. Further, a compound such as N-methylolacrylamide that reacts with the amide group of the polymer (A) to form a covalent bond in the drying step is also not preferable.

The compound having an ethylenically unsaturated double bond and an amide group is represented by the general formula (2), (3),
The compound represented by (4), (5) or (6) is preferable.

[0023]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12] ^{R 4, R 7, R 8} , R 11, R 14, R 15 represents hydrogen or a lower alkyl group having 1 to 6 carbon atoms. R ⁵ , R ⁹ , R ¹² ,
R ¹³ and R ¹⁶ represent hydrogen or an organic group having 1 to 30 carbon atoms. The organic group having 1 to 30 carbon atoms, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, groups such as a cyclohexyl _{group, -C (CH 3) 2 CH} 2 COCH 3 group and the like. R ⁶ represents an aliphatic organic group having 3 to 30 carbon atoms or a cyclohexyl group. Where the carbon number is 3
It is important to be ~ 30. When the carbon number is less than 3, as described above, good photosensitivity cannot be obtained, or a negative image is formed, which is not preferable. The aliphatic organic group having 3 to 30 carbon atoms, a propyl group, a butyl group, dimethylaminoethyl group, dimethylaminopropyl group, diethylaminoethyl group, diethylaminopropyl _{group, -C (CH 3) 2 CH} 2 COCH 3 group, etc. The base is given. R ¹⁰ and R ¹⁸ represent a lower alkyl group having 1 to 6 carbon atoms. R ¹⁷ represents an organic group having 1 to 30 carbon atoms. Examples of the organic group having 1 to 30 carbon atoms include groups such as methylene group, ethylene group and propylene group.

As a preferred specific example, the general formula (2)
Examples of the compound represented by N-isopropylmethacrylamide, N-isopropylacrylamide, N-butylmethacrylamide, N-butylacrylamide, diacetoneacrylamide, diacetonemethacrylamide,
N-cyclohexyl methacrylamide, N-cyclohexyl acrylamide, N, N-dimethylaminoethyl (methacrylic or acrylic) amide, N, N-dimethylaminopropyl (methacrylic or acrylic) amide, N, N-diethylaminoethyl (methacrylic or acrylic) Examples of the compound represented by the general formula (3) such as amide and N, N-diethylaminopropyl (methacryl or acryl) amide include acryloylmorpholine and methacryloylmorpholine, and the compound represented by the general formula (4) include acryloyl. Examples of the compound represented by the general formula (5) such as piperidine and methacryloylpiperidine include crotonamide, N-methylcrotonamide, N-isopropylcrotonamide, N-butylcrotonamide, and the like. Examples of the compound represented by 6), acetic acid allyl amide, the like allyl amide propionic acid without limitation. These compounds (B) are used alone or as a mixture of two or more.

It is more preferable to add a compound containing an ethylenically unsaturated double bond and an amino group or a quaternized salt thereof, because the photosensitivity is further improved. As a preferred specific example, dimethylaminoethyl methacrylate,
Diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, N, N-dimethylaminoethyl (methacrylic or acrylic) amide, N, N-dimethylaminopropyl ( Methacrylic or acryl) amide, N, N-diethylaminoethyl (methacryl or acryl) amide, N, N-diethylaminopropyl (methacryl or acryl) amide, and the like, but are not limited thereto.

The compound (B) is 5 of all constitutional units of the polymer.
%, Preferably 30% or more equivalent amount, and it is desirable to mix at a ratio of 5 times or less of the equivalent amount of all carboxyl groups in the polymer. If it deviates from this range, the sensitivity will be deteriorated and there will be many restrictions on development.

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 may be used alone or in admixture of two or more.

The amount of the photoinitiator is desirably 1 to 100% by weight, preferably 5 to 50% by weight, based on the polymer component. 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 the sensitizer is preferably 0.1 to 20% by weight, preferably 0.2 to 10% by weight, based on the polymer component, from the viewpoint of sensitivity. As the photoreactive monomer, monomers such as 2-hydroxyethyl methacrylate, methacrylic acid, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate are added in an amount of 1 to 20% by weight based on the polymer. It can be expected to improve the sensitivity.

A combination of an oxime ester compound as a photoinitiator and a coumarin compound as a sensitizer is particularly effective for the positive photosensitive polyimide precursor composition of the present invention.

Examples of the photoreactive monomer include 2-hydroxyethyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate. These photoreactive monomers may be used alone or in admixture of two or more. If these photoreactive monomers are added in an amount of 1 to 20% by weight with respect to the polymer component, further improvement in sensitivity can be expected.

An actinic radiation-sensitive 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, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphorotriamide, γ-butyrolactone, N, N An aprotic polar solvent such as dimethylacrylamide is preferably used alone or as a mixture of two or more kinds, but is not limited thereto.

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

Next, a method for forming a positive type polyimide pattern using the positive type 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, aluminum, aluminum nitride, alumina ceramics, glass ceramics, sapphire, a semiconductor-formed substrate, or the like. Examples of the coating method include, but are not limited to, spin coating using a spinner, spray coater, dipping, and roll coating. The coating thickness varies depending on the coating means, the solid content concentration of the composition, the viscosity, etc., but usually the coating thickness after drying is
It is applied so as to have a thickness of 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, 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 beams, and X-rays. Ultraviolet rays and visible rays are particularly preferable.

In the present invention, it is important to carry out a treatment such that the unexposed portion of the coating has a higher degree of curing than the exposed portion of the coating after exposure. The unexposed film is more exposed than the exposed film.
As the treatment for increasing the degree of curing, heat treatment, infrared irradiation treatment, microwave irradiation treatment, etc. are effective, and particularly preferable because heat treatment is simple. The heat treatment is preferably performed for 1 minute to several hours at the same temperature as or higher than the drying step. Specifically, it is 60 to 180 ° C., more preferably 90.
The temperature is ˜170 ° C. By performing these treatments after the exposure, the unexposed film has a higher degree of curing than the exposed film, so that the resistance to the developing solution is high, and when developed, the exposed part is removed earlier than the unexposed part. , A positive image is formed.

The term "curing" as used herein refers to a component other than polyimide, for example, a compound having an amino group and / or an amide group, a photoinitiator, from a film of a polyimide precursor composition.
It means that photoreactive monomers, solvents, ring-closing water, etc. are volatilized. As the film of the polyimide precursor composition cures, the film thickness becomes thinner, and when the cure is completed, that is,
When it becomes a polyimide coating, it has a certain thickness. The difference in the degree of cure between the unexposed portion coating and the exposed portion coating after the treatment for increasing the curing degree is expressed by the film thickness ratio (that is, curing degree ratio = unexposed portion coating thickness / exposed portion coating). Film thickness). The curing degree ratio is preferably 0.98 or less, though it varies depending on the exposure amount and the processing conditions for promoting curing. More preferably, it is 0.97 or less. When the hardening process is not performed (hardness ratio 1.000), a negative image is formed for a moment at the beginning of development, but then disappears.

After the processing, development is performed to remove the exposed portion.
The removal can be performed by peeling, melting, etching or the like. Specific examples thereof include mechanical peeling, plasma etching, and a method using a developing solution. Particularly, the method using a developing solution is preferable because it is simple.

As the developing solution, an alkaline aqueous solution of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline or the like is desirable. Further, a developer obtained by combining these alkalis with a polar solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide or an alcohol such as methanol, ethanol or isopropyl alcohol, N-methyl-2-pyrrolidone or N. ，
Polar solvent such as N-dimethylacetamide and xylene,
Developers in combination with water can also be used.

After development, it is preferable to rinse with water or an alcohol such as methanol, ethanol or isopropyl alcohol.

Further, by curing, the polyimide precursor is imidized to obtain a polyimide insulating film. Curing after development is carried out for 5 minutes to 5 hours by selecting the temperature and gradually raising the temperature or by selecting a certain temperature range and continuously raising the temperature. The maximum temperature of this curing is 250 to 500 ° C., preferably 300 to 450 ° C. For example,
Heat treatment is performed at 130 ° C., 200 ° C., and 400 ° C. for 30 minutes each. Alternatively, the temperature may be linearly raised from room temperature to 400 ° C. over 2 hours.

The polyimide coating formed from the positive 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 multilayer wiring for high-density packaging, and the like.

[0047]

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.). N-isopropylacrylamide 11 was added to this solution.
3.16 g (equivalent to all carboxyl groups in polymer), 3-
Phenyl-5-isoxazolone 23.6 g, 3,3'-
2.36 g of carbonylbis (diethylaminocoumarin) and 315 g of γ-butyrolactone were added to obtain a photosensitive polyimide precursor composition.

This polyimide precursor composition was applied onto a 4-inch silicon wafer and dried at 60 ° C. for 30 minutes in a nitrogen atmosphere to form a film having a thickness of 5.18 μm. 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 4.12 μm, the exposed film had a film thickness of 4.44 μm, and the curing ratio was 0.928. Next, when it was immersed in a developing solution consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, the exposed areas dissolved and the unexposed areas became
An image was formed which remained 2.34 μm. 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, instead of the developing solution consisting of a 2.38% aqueous solution of tetramethylammonium hydroxide, N--
A positive type pattern was obtained by immersing in a developer containing 700 g of methyl-2-pyrrolidone, 300 g of xylene and 100 g of water.

Example 3 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime 2 was added to the polymer (A) solution obtained in Example 1.
3.6 g, "coumarin" 339 2.36 from Kodak Corporation
g, N, N-dimethylacetamide (315 g) and crotonamide (42.6 g), and N, N-dimethylaminopropylmethacrylamide (85.0 g) were added to prepare a photosensitive 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 coating having a film thickness of 5.40 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 is 4.29μm and the exposed film is 4.65μm.
The film thickness was μm, and the curing ratio was 0.923. 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 polyimide pattern.

Example 4 To the polymer (A) solution obtained in Example 1 was added 3-phenyl-5-
Photosensitive polyimide precursor composition in which isoxazolone 23.6 g, 3,3′-carbonylbis (diethylaminocoumarin) 2.36 g, γ-butyrolactone 315 g and diacetone acrylamide were added in an equivalent amount (169.22 g) to all carboxyl groups in the polymer. I adjusted things.

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 6.83 μm-thick polyimide precursor film 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 is 4.54 μm and the exposed film is 5.51
The film thickness was μm, and the cure ratio was 0.823. 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 polyimide pattern.

Example 5 To the polymer (A) solution obtained in Example 1 was added 3-phenyl-5-
A photosensitive polyimide precursor composition was prepared by adding 23.6 g of isoxazolone, 2.36 g of 3,3′-carbonylbis (diethylaminocoumarin), 315 g of γ-butyrolactone, 49.6 g of acetic acid allylamide and 92.5 g of diethylaminoethyl methacrylate.

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 4.55 μm-thick polyimide precursor film 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 3.61 μm and the exposed film was 4.44
The film thickness was μm, and the curing ratio was 0.813. 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 polyimide pattern.

Example 6 In place of N-isopropylacrylamide in Example 1, 141.17 g of acryloylmorpholine was added,
A photosensitive polyimide precursor composition was prepared.

This polyimide precursor composition was coated on a 4-inch silicon wafer, and the composition was heated at 80 ° C. for 3 hours on a hot plate.
After minute drying, a polyimide precursor film having a thickness of 4.54 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 to obtain a positive photosensitive polyimide precursor coating. By this treatment, the unexposed film had a thickness of 3.55 μm, the exposed film had a film thickness of 4.02 μm, and the curing ratio was 0.883. 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 polyimide pattern.

[0059]

As described above, the present invention provides a polymer containing a structural unit represented by the general formula (1) as a main component, a specific compound having an ethylenically unsaturated double bond and an amide group, and an optical compound. A composition containing an initiator and / or a sensitizer and / or a photoreactive monomer has an unexpected effect of exhibiting excellent performance as a positive photosensitive polyimide precursor. is there. The positive photosensitive polyimide precursor composition of the present invention can be easily produced, and by developing and curing, a positive polyimide coating having excellent performance can be obtained.

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[Procedure amendment]

[Submission date] July 14, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Furthermore, in order to improve the adhesion to the substrate, and the R ^1, R ² without compromising the heat resistance may be copolymerized an aliphatic group having a siloxane structure. Specific examples thereof include copolymers of bis (3-aminopropyl) tetramethyldisiloxane and the like in an amount of 1 to 10 mol%.

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Claims (3)

[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) a compound (B) having an ethylenically unsaturated double bond and an amide group, and (c) photoinitiation. A positive photosensitive polyimide precursor composition comprising an agent and / or a sensitizer and / or a photoreactive monomer. 2. The positive photosensitive polyimide precursor according to claim 1, wherein the compound having an ethylenically unsaturated double bond and an amide group is a compound having a vapor pressure of 10 mmHg or less at 80 ° C. Composition. 3. A compound having an ethylenically unsaturated double bond and an amide group is represented by the general formula (2), (3), (4),
The positive photosensitive polyimide precursor composition according to claim 1, which is at least one selected from the group of compounds represented by (5) or (6). [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] (Wherein R ⁴ , R ⁷ , R ⁸ , R ¹¹ , R ¹⁴ and R ¹⁵ are hydrogen or a lower alkyl group having 1 to 6 carbon atoms, R ⁵ ,
R ⁹ , R ¹² , R ¹³ and R ¹⁶ are hydrogen or an organic group having 1 to 30 carbon atoms, R ⁶ is an aliphatic organic group having 3 to 30 carbon atoms or a cyclohexyl group, and R ¹⁰ and R ¹⁸ are 1 to 1 carbon atoms. 6 is a lower alkyl group, R ¹⁷ is an organic group having 1 to 30 carbon atoms. )