JP2826978B2 - Composition for i-ray exposure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the present invention relates to a photosensitive composition suitable for forming an image using a short-wavelength light source, which will become mainstream in the semiconductor manufacturing process in the future, and obtaining a polyimide pattern.

[0002]

2. Description of the Related Art Polyimide resins have attracted attention as materials for microelectronics due to their high thermal and chemical stability, low dielectric constant, and excellent planarization ability. These are widely used as materials for semiconductor surface protection films, interlayer insulating films, multi-chip modules, and the like. By the way, in order to form a desired pattern using a lithography technique from a normal polyimide resin film, using a photoresist and a photomask on the formed polyimide film, after forming a photoresist pattern, An indirect method of patterning a polyimide resin by an etching method has been adopted.

However, in this method, a photoresist pattern is formed, the polyimide resin is etched using the photoresist pattern as a mask, and then the unnecessary photoresist pattern must be removed. On top of that, it is necessary to use a toxic substance such as hydrazine, and there is an unfavorable point that only a pattern with low resolution can be obtained by indirect pattern formation. For this reason, in recent years, a method of directly forming a pattern by introducing a photopolymerizable sensitive group into a polyimide precursor has been studied, and a compound having a double bond is bonded via an ester bond, an amide bond, an ionic bond, or the like. The polyamic acid derivative was insolubilized by a photoinitiator or the like,
A method has been proposed in which, after development processing, the photosensitive group is removed by heating to convert the photosensitive group component into a polyimide having thermal stability [Yamaoka, Table, "Polyfile", Vol. 27, No. 2, 14-18 (1990)]. This technology is
It is generally called photosensitive polyimide.

[0004] By the way, the demand for the degree of integration of semiconductor elements such as ICs, LSIs and VLSIs is increasing year by year.
At the same time, the development of a technology capable of fine processing has become necessary. As one of the techniques, a normal G light is used as a light beam for exposure at the time of forming a photoresist pattern.
Instead of the line (436 nm wavelength), an attempt has been made to use a short-wavelength beam for which high resolution can be desired, for example, an i-line having a wavelength of 365 nm, and this has been quite successful for ordinary photoresists. For this reason, it is expected that all the exposure apparatuses in the semiconductor manufacturing plant will use i-line as a light source in the future.

[0005] However, in the case of a photosensitive polyimide precursor composition, unlike a normal photoresist, the absorbance of the polyimide precursor as a main component with respect to i-line is relatively large. It is often used in applications where a film thickness of 6 μm or more is required due to its physical properties. Therefore, when the currently used one is used, the i-line does not sufficiently reach the bottom of the coating film, the curing of the lower surface of the coating film becomes insufficient, and the pattern is scooped from the bottom. It is known that it is difficult to use an i-line as a light source in order to obtain a polyimide having a certain thickness or more because of flowing. [“IEEE / SEMI Advanced Semico” Nectar Manufacturing Conference (C. Schckett, et a
l. , Advanced Semiconductor
Manufacturing Conferenc
e) ", Transactions, pp. 72-74 (1990)]. Therefore, when the i-line is used, the thin film patterns are stacked several times in order to obtain a sufficient film thickness, and the accuracy is not improved, and the process is complicated, which is not practical. As a polyimide precursor having a high i-line transmittance of a coating film, a polyimide precursor having a fluorine content has been known [Journal of Applied Polymer Science (T. Omote, T. Yamaoka. And
K. Kosei, J. et al. Appld. Polymer S
ci. 38), 389-402 (1989).
Year)〕. However, polyimide containing fluorine in the main skeleton obtained after heating and curing this precursor is used when forming a semiconductor device or a multilayer wiring board, and is used in combination with other materials such as a base inorganic material and an epoxy resin of a coating layer,
There is a drawback that the adhesive strength to metal for wiring is low and lacks practicality. For this reason, it has been the fact that a photosensitive polyimide precursor composition that can be used for pattern formation using i-line has not been obtained yet.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and provides a photosensitive polyimide precursor composition which can be used for forming a pattern by i-line with a film thickness of a certain value or more and which can be practically used. It was made for the purpose.

[0007]

Means for Solving the Problems The present inventors have conducted various studies on a photosensitive polyimide precursor composition capable of forming a pattern by i-line, and as a result, have found that it has several specific chemical structures and / or Or, using a photosensitive polyimide precursor composition containing a polyimide precursor having a specific amide bond concentration and prepared such that a film obtained after coating and drying shows a specific absorbance, a good pattern is formed by i-line. In addition, the polyimide obtained after heat curing the pattern shows excellent coating film properties and also has a good adhesive strength with epoxy resin, inorganic material and metal, and shows excellent water resistance. Based on this, the present invention has been completed.

That is, the present invention relates to (A) a compound represented by the general formula (I)
And a amide bond concentration of 1.
An aromatic polyimide precursor of 5 mol / kg or more (hereinafter, referred to as “polyimide precursor”);

[0009]

Embedded image

Wherein X is a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond, a sulfoxide, or a tetravalent aromatic group not containing a fluorine atom or an aromatic group not containing 2 to 4 fluorine atoms. A tetravalent organic group having a chemical structure bonded via at least one bond selected from a bond and a sulfone bond, wherein -COR and -COR 'and -CONH- groups are In the ortho position, and R and R ′ are each independently —O ^— N ⁺ R ₃ R ₄ R ₅
R ₆ or —OH (where R ₂ and R ₃ are each independently and not limited to one kind, an organic group partially having an ethylenically unsaturated bond, R ₄ , R ₅ and R ₆ are each a hydrogen atom or a carbon atom; Wherein R or R ′ in at least some of the repeating units is a residue other than —OH;
Is an aromatic group containing no divalent fluorine atom or 2 to 6 aromatic groups are a single bond, an ether bond, a thioether bond,
A divalent organic compound containing no fluorine atom and having a chemical structure interconnected via at least one bond selected from a carbonyl bond, a methylene bond, a 2,2-propylene bond, a sulfoxide bond and a sulfone bond. Is a group)

In the photosensitive composition for i-line exposure containing (B) a photopolymerization initiator and (C) a solvent, the polyimide precursor has (i) an amide bond concentration of 2.42 mol.
/ Kg or less, and / or (ii) X is a tetravalent group having a chemical structure of an aromatic group substituted with an aprotic electron-donating group in an aromatic group having a bonding group. And / or (iii-2) Y is a group represented by the general formula (II)

[0012]

Embedded image [Wherein A is _{-CH 2 -, - CO -,} - SO 2 -, - O
-, -S-, m-dioxyphenylene group, p-dioxyphenylene group or general formula (II-1)

[0013]

Embedded image (Wherein B is _{-CH 2 -, - CO -,} - SO 2 -, - O
-, -S-, m-dioxyphenylene group, p-dioxyphenylene group, k is 0 or 1), m is 0
Or 1) or a divalent group represented by (i)
ii-3) General formula (III)

[0014]

Embedded image

A divalent group represented by the formula:
(Iii-4) a divalent group having a chemical structure of an aromatic group having a bonding group or an aromatic group substituted by an aprotic electron-withdrawing group in an aromatic group adjacent thereto through an ether bond; Wherein the absorbance at a wavelength of 365 nm of a film of the photosensitive composition formed after applying and drying the photosensitive composition for i-ray exposure is 1.5 or less per 10 μm of film thickness. And a photosensitive composition for i-line exposure.

In the composition of the present invention, the polyimide precursor used as the component (A) is represented by the above general formula (I). Examples of the aromatic group represented by X or Y in the general formula (I) include a group having a benzene ring, a naphthalene ring, and an anthracene ring.
The polyimide coating film obtained by heating and curing the photosensitive composition of the present invention is preferable because the heat resistance of the polyimide coating film is increased. For the same reason, the aromatic bonding group includes a single bond, an ether bond,
One or two or more selected from a carbonyl bond and a sulfone bond are preferable.

The —COR group of the general formula (I) or —CO
When the R ′ group is represented by an amide group represented by the general formula (V-2) —CO—NHR ₂ (V-2) (wherein R ₂ has the same meaning as described above), As the group, N- (2-
Acryloyloxyethyl) -aminocarbonyl group, N
It is necessary to include a group having an ethylenically unsaturated bond such as-(2-methacryloyloxyethyl) -aminocarbonyl group, and in addition, a methylaminocarbonyl group,
Ethylaminocarbonyl group, N (2-ethoxyethyl)
It may contain a group containing no ethylenically unsaturated bond such as an aminocarbonyl group.

The —COR group or —COR ′ of the general formula (I)
Group is formulas (V-3) -CO-O - · N + R 3 R 4 R 5 R 6 ··· (V-3) (R 3 in the formula, R _4, R ₅ and R ₆ are the Having the same meaning as described above), the substituted ammonium addition salt type carboxylic acid residue may be a methacryloyloxyethyl / trimethylammonium addition salt type carboxylic acid residue. , Acryloyloxyethyl / dimethylammonium addition salt-type carboxylic acid residue, etc., and it is necessary that all of R ₃ , R ₄ , R ₅ , and R ₆ be a hydrogen atom or It may contain a group that is a hydrocarbon group.

It is not necessary that the -COR group or -COR 'group of all the repeating units of the polyimide precursor be the group represented by the above (V-2) or (V-3). It is sufficient that some of the groups or -COR 'groups are the above groups, and others are carboxylic acid groups.

In the composition of the present invention, the polyimide precursor used as the component (A) has an amide bond concentration of 1.5.
mol / kg or more. The amide bond concentration referred to here, when the molecular weight of the repeating unit in the polyimide precursor or the polyimide precursor has several kinds of repeating units, divided by 2,000 by the average molecular weight calculated from the molecular weight and the mole fraction of each. Value
This is a parameter representing the number of moles of amide groups present in 1 kg of the polyimide precursor. When the amide bond concentration is less than 1.5 mol / kg, heat resistance is significantly reduced.

In the composition of the present invention, the aromatic polyimide precursor polymer used as the component (A) is already known as a precursor of a heat-resistant high-molecular compound, and is prepared by a known method, for example, Davis ( Davis) ["Chemical & Engineering News (Chem. & Eng. News)", September 26, 1983, p. 23] and the like. In addition, it can also be produced by the method described in JP-A-61-72022, JP-A-3-220558, and JP-B-59-52822.

According to these methods, the polyimide precursor is obtained by preparing an aromatic tetracarboxylic dianhydride (hereinafter referred to as ATC dianhydride) represented by the general formula (IV) and a polyimide precursor represented by the following general formula (V). It is produced by using the aromatic diamino compound to be used as a part of the raw material.

[0023]

Embedded image

H ₂ N—Y—NH ₂ (V) (wherein Y is as defined above) A compound having a fluorine-containing group such as a fluorine group and a trifluoromethyl group is prepared by using the polyimide precursor of the present invention. When used as a raw material for a body, polyimide containing a fluorine atom obtained after heat-curing the photosensitive composition is not preferred because it has low adhesiveness to other materials used in combination and lacks practicality.

In order to obtain the photosensitive composition of the present invention, it is necessary to use a polyimide precursor under specific conditions. Any of these species or a combination of two or more species can be used in the present invention as long as the other conditions of the composition are satisfied. Specifically, the polyimide precursor needs to satisfy at least one of (i) to (iii-4).

The amide bond concentration must be 1.5 mol / kg or more, and the composition of the present invention can be obtained regardless of the structure if the amide concentration is 2.42 mol / kg or less. Further, the lower the concentration of the amide bond in the polyimide precursor, the lower the i-line absorption value of the formed polymer coating film and the higher the water resistance of the polyimide film after the heat treatment. The amide bond concentration in the polyimide precursor is 2.
It is more preferable to use 0 to 2.45 mol / kg of a polyimide precursor because a polyimide film having higher mechanical strength and heat resistance can be obtained.

In the case of producing a polyimide precursor under the condition (ii), an aromatic group having a carboxylic acid anhydride group among ATC dianhydrides is replaced by an aprotic electron donating group. ATC having an aromatic group chemical structure
Use dianhydride. Here, the aprotic group means a group other than a group having active hydrogen, such as an alcohol, an amine and a carboxylic acid. In addition, the electron donating group here is Ham
A substituent in which the value of σp or σm in the mett relational rule has a negative value is referred to. For such a relational rule and numerical values, for example, Chemical Handbook, Basic Edition II, Item 365 (edited by The Chemical Society of Japan, Maruzen 1984) Etc. are widely known.

Specific preferred examples of the aprotic electron donating group include a dialkylamino group, an alkoxy group, an aryloxy group, a trialkylsilyl group, a benzyl group and an alkyl group. Specific preferred examples of the aromatic ATC dianhydride having the chemical structure of an aromatic group in which an aromatic group in which a compound group is present are substituted with an aprotic electron donating group include 3,3
3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 1,4-dimethoxy-2,3,5,6-benzenetetracarboxylic dianhydride, 1,4-ditrimethylsilyl-2,3,5 2,6-benzenetetracarboxylic dianhydride, 1,4-bis (3,4-dicarboxylphenoxy) benzene dianhydride, 1,3-bis (3,4-dicarboxylphenoxy) benzene dianhydride, 3 , 3 ',
4,4'-diphenylmethanetetracarboxylic dianhydride, bis (3,4-dicarboxylphenoxy) dimethylsilane dianhydride, bis (3,4-dicarboxylphenoxy) methylamine dianhydride, 4,4'- Screw (3
4-dicarboxylphenoxy) biphenyl dianhydride,
4,4'-bis (3,4-dicarboxylphenoxy)
And diphenylsulfone dianhydride.

In the present invention, as long as the absorbance at a wavelength of 365 nm of the film of the photosensitive composition of the present invention is 1.5 or less per 10 μm of film thickness, the film is represented by the general formula (VI) other than the above. When the ATC dianhydride is mixed with the above ATC dianhydride as required, or combined with a specific aromatic diamino compound described below, and / or used for an aromatic polyimide precursor having a specific amide bond concentration. Can be used alone.

Specific examples of such compounds include pyromellitic dianhydride, 2,3,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid Dianhydride, 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 2,3,5
6-pyridinetetracarboxylic dianhydride, 2,3,6
7-quinolinetetracarboxylic dianhydride, 3,3 ',
4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfoxidetetracarboxylic dianhydride And 1,2,8,9-anthracenetetracarboxylic dianhydride, 1,4-bis (3,4-dicarboxylphenylsulfonyl) benzene dianhydride, and the like.
1,4-bis (3,4-dicarboxylphenylthio)
Benzene dianhydride, 3,3 ", 4,4" -tert-phenyltetracarboxylic dianhydride, 4-phenylbenzophenone-3,3 ", 4,4" -tetracarboxylic dianhydride,
1,4-bis (3,4-dicarboxylbenzoyl)-
Benzene dianhydride, 3,3 "', 4,4'"-quatylphenyltetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxylphenoxy) benzophenone dianhydride, 4,4'bis (3,4-dicarboxylphenoxy) diphenylsulfoxide dianhydride can also be used.

In the case of producing a polyimide precursor satisfying the condition (iii-2), Y is represented by the aforementioned general formula (II)
An aromatic diamino compound which is a divalent group represented by the following formula is used. Specific preferred examples of these aromatic diamino compounds include, for example, 4,4'-bis (3-aminophenoxy) biphenyl, 1,3-bis (3-aminophenoxy) benzene, and 3,3'-diaminodiphenyl ,
3,3'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone,

3,3'-diaminobenzophenone,
3'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfide, 4,4'-bis (3-aminophenoxy) diphenylsulfone, 4,4'-bis (3-
Aminophenoxy) diphenylmethane, 4,4'-bis (3-aminophenoxy) diphenyl ether, 4,
4'-bis (3-aminophenoxy) diphenyl sulfide and the like.

When producing a polyimide precursor satisfying the condition of (iii-3), Y is represented by the above-mentioned general formula (II)
An aromatic diamino compound that is a divalent group represented by I) is used. Specific preferred examples of these aromatic diamino compounds include, for example, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone,
4,4'-diaminodiphenylsulfoxide, 4,
4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis (4-aminophenoxy) diphenylsulfoxide, 4,4'-bis (4-aminophenoxy) benzophenone, and the like.

When preparing a polyimide precursor satisfying the condition (iii-4), among the aromatic diamino compounds, an aromatic group having an amino group or an aromatic group adjacent thereto through an ether bond is used. An aromatic diamino compound having the chemical structure of an aromatic group substituted by an aprotic electron withdrawing group in the group is used. Here, the electron-withdrawing group refers to a substituent in which the value of δp or δm is 0.2 or more. Examples of the aprotic electron withdrawing group include an acyloxy group, an acylamino group, a halogen group, an amide group, an alkoxycarbonyl group, an alkylcarbonyl group, a nitrile group, an alkylsulfone group, a nitro group, and an alkoxysulfone group.

An aromatic group having the chemical structure of an aromatic group having an amino group or an aromatic group which is substituted by an aprotic electron-withdrawing group not containing a fluorine atom in an aromatic group adjacent thereto through an ether bond. Specific preferred examples of the aromatic diamino compound include 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone,
4'-diaminodiphenylsulfoxide, bis [4-
(4-aminophenoxy) phenyl] sulfone, 4,
4'-bis [4- (4-aminophenoxy) phenylsulfonyl] diphenyl ether, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) benzophenone, 1,4-
Bis (4-aminophenylsulfonyl) benzene,
1,4-bis [4- (4-aminophenoxy) phenylsulfonyl] benzene, 4,4'-bis (4-aminophenylsulfonyl) diphenyl ether, 3,5-
Ethyl diaminobenzoate, 2,4-diaminobenzamide, 3,5-diaminobenzophenone, 4-dimethylamino-3 ′, 5′-diaminobenzophenone,
3,5-diaminobenzoic acid (methacrylic acid-2-hydroxyethyl) ester, 3,5-diaminoacetanilide, 4-chloro-m-phenylenediamine, 3,5-diaminobenzonitrile, 5-nitro-m-phenylenediamine And the like.

In addition, as long as the absorbance at 365 nm of the film of the photosensitive composition of the present invention is 1.5 or less per 10 μm, the film represented by the general formula (V) other than the aromatic diamino compound having the specific chemical structure described above. The aromatic diamino compound represented is optionally mixed with the aromatic diamino compound having the above specific chemical structure, or combined with the ATC anhydride having the above specific chemical structure, and / or a specific amide bond. When it is used for a polyimide precursor having a high concentration, it can be used alone.

Specific preferred examples of such aromatic diamino compounds include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide,
3,4'-diaminodiphenyl ether, 1,4-phenylenediamine, 2,7-naphthalenediamine, 3,
3'-dimethyl-4,4'-diaminobiphenyl, 3,
3'-dimethoxy-4,4'-diaminobiphenyl,
3,3'-dichloro-4,4'-diaminobiphenyl,
1,4-bis (4-aminophenoxy) benzene, 1,
3-bis (4-aminophenoxy) benzene, 5,8-
Diaminoquinoline, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) Benzene, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylmethane, 4,4'-bis (4-aminophenoxy) diphenyl sulfide, bis [2- (4 -Aminophenyl) -benzothiazolyl] oxide, bis [2- (4-
Aminophenyl) -benzimidazolyl] sulfoxide, bis [2- (4-aminophenyl) -benzoxazolyl], 4- (4-aminophenylsulfonyl)-
4'-aminobiphenyl, 4,4'-bis (4-aminophenyl) diphenyl ether, 1,4-di- (4-aminobenzoyloxy) butane and the like can be mentioned.

When a polyimide precursor is produced using an aromatic diamino compound in which Y is a divalent group represented by the aforementioned general formula (II) or (III) among these various aromatic diamino compounds, Heat resistance, strength, of the polyimide coating film obtained after heat curing from the obtained photosensitive composition,
It is more preferable because the water resistance is good. Also, among the aromatic diamino compounds listed here, bis [4- (3-aminophenoxy) phenyl] sulfone, 3,3'-diaminodiphenylsulfone, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl and bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4'-diaminobenzophenone, 4,4'-bis [4- (4-aminophenoxy) Phenoxy) diphenylsulfone, 4,
4'-diaminodiphenyl sulfoxide, 4,4'-
The use of diaminodiphenylsulfone is more preferable from the viewpoint of the physical properties of the polyimide coating film as described above.

As the photopolymerization initiator used as the component (B) of the photosensitive composition of the present invention, for example, benzophenone,
methyl o-benzoylbenzoate, 4-benzoyl-4 '
Benzophenone derivatives such as -methyldiphenylketone, dibenzylketone and fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenylketone; thioxanthone;
Thioxanthone derivatives such as 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethylketal and benzyl-β-methoxyethylacetal; benzoin derivatives such as benzoin and benzoin methyl ether; (4-azidobenzylidene)
Azides such as -4-methylcyclohexanone and 2,6'-di (4-azidobenzylidene) cyclohexanone;
1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propane Zeon-2- (O
-Ethoxycarbonyl) oxime, 1-phenyl-1,
2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (O
-Ethoxycarbonyl) oxime, 1-phenyl-3-
Ethoxy-propanetrione-2- (O-benzoyl)
Although oximes such as oximes are used, oximes are preferred in terms of photosensitivity. The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight based on 100 parts by weight of the polyimide precursor polymer.

The solvent used as the component (C) in the photosensitive composition of the present invention is preferably a polar solvent in terms of solubility. For example, N, N'-dimethylformamide, N-methylpyrrolidone, N-acetyl-2-yl Pyrrolidone, N,
N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like can be used, and these can be used alone or in combination of two or more.

These solvents are used in an amount of 100 to 4 parts by weight based on 100 parts by weight of the aromatic polyimide precursor depending on the coating film thickness and viscosity.
It can be used in the range of 00 parts by weight. To the photosensitive composition of the present invention, a compound having a reactive carbon-carbon double bond may be added, if desired, for improving photosensitivity, in addition to the essential components (A) to (C) described above. . Examples of such a compound include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, and an addition mole number of 2
-20, polyethylene glycol diacrylate, pentaerythritol diacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, methylenebisacrylamide, N-methylolacrylamide and the above acrylates or the corresponding methacrylates, methacrylamides and so on. These compounds are 1 to 30 parts by weight per 100 parts by weight of the polyimide precursor.
It is preferable to add in the range of parts by weight.

A sensitizer for improving photosensitivity can be added to the photosensitive composition of the present invention, if desired. Such sensitizers include, for example, Michler's ketone, 4,
4'-bis (diethylamino) benzophenone, 2,5
-Bis (4'-diethylaminobenzylidene) cyclopentanone, 2,6-bis (4'-diethylaminobenzylidene) cyclohexanone, 2,6-bis (4'-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6- Bis (4'-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, 2- (4'-dimethylaminocinnamylideneindanone , 2- (4'-dimethylaminobenzylidene indanone, 2- (p-4'-dimethylaminobiphenyl) -benzothiazole, 1,3-bis (4
-Dimethylaminobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,
3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3
-Ethoxycarbonyl-7-dimethylaminocoumarin,
3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, Np -Tolyldiethanolamine, N-phenylethanolamine,
4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamyl 4-diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole,
2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, -(P-dimethylaminobenzoyl) styrene and the like. From the viewpoint of sensitivity, it is preferable to use a compound having a mercapto group and a compound having a dialkylaminophenyl group in combination. These are used alone or in combination of 2 to 5 kinds, and the amount of addition is 0.1 to 100 parts by weight of the polyimide precursor.
10 parts by weight are preferred.

The photosensitive composition of the present invention may optionally contain an adhesion aid for improving the adhesion to the substrate. Examples of the adhesion aid include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-
Aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltri Methoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] Phthalamic acid, benzophenone-3,3'-bis (3-triethoxysilyl) propylaminocarbonyl-4,4'-dicarboxylic acid, benzene-1,4-bis (3-triethoxysilyl) propylaminocarbonyl Such as 2,5-dicarboxylic acid is used. The amount of these additives is 10%.
The range of 0.5 to 10 parts by weight relative to 0 parts by weight is preferable.

A thermal polymerization inhibitor can be added to the photosensitive composition of the present invention, if desired, in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of the thermal polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol,
Phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino)
Phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1
-Naphthyl) hydroxylamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl-phenylmethane) or the like is used in an amount of 0.005 to 5 with respect to 100 parts by weight of the polyimide precursor. A range of parts by weight is preferred.

The photosensitive composition of the present invention has an absorbance at the i-line, that is, a light having a wavelength of 365 nm, of a film after coating and drying, which is formed to have an absorbance of 1.times. It is necessary to make it 5 or less. If the absorbance is higher than this, the required amount of light cannot reach the bottom of the film, resulting in incomplete pattern formation. Such an absorbance is (A)
It can be prepared by appropriately adjusting the amounts of the essential components of (C) to (C) and other components added as desired. The photosensitive composition of the present invention can be obtained by mixing the above essential components (A) to (C) and other components. And a polyimide coating film can be obtained from the composition by the following method.

The photosensitive composition of the present invention can be applied to a substrate by, for example, a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, or a method of spray coating with a spray coater. it can. The obtained coating film is dried by air drying, heat drying using an oven or a hot plate, vacuum drying, or the like. The coating film thus obtained is exposed by an ultraviolet light source or the like using an exposure device such as a contact aligner, a mirror projection, and a stepper. In terms of pattern resolution and handleability, the light source wavelength is preferably i-line, and the apparatus is preferably a stepper. Development is
Any method can be selected from conventionally known photoresist developing methods, for example, a rotary spray method, a paddle method, an immersion method involving ultrasonic treatment, and the like.

The developer used is preferably a combination of a good solvent and a poor solvent for the polymer precursor. Examples of the good solvent include N-methylpyrrolidone and N-methylpyrrolidone.
Acetyl-2-pyrrolidone, N, N'-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, etc., and poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol And water. The ratio of the poor solvent to the good solvent is adjusted by the solubility of the used polyimide precursor. Each solvent may be used in combination.

For a composition containing a compound having a high carboxylic acid content, a developing solution obtained by adding an above-described solvent to an aqueous solution of an organic base such as choline hydroxide or tetramethylammonium hydroxide, if necessary. Is used. The patterned film of the polyimide precursor composition thus obtained is converted into polyimide by heating to volatilize the photosensitive component. The heat conversion can be performed by a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. Air may be used as the atmosphere gas for the heat conversion, and an inert gas such as nitrogen or argon may be used.

[0049]

Next, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited by these examples. The characteristics in each example were measured as follows. (1) Amide bond concentration The amide bond concentration is determined according to the following equation.

In the above formula, [M] _C represents the molecular weight of the tetracarboxylic acid unit, which is obtained by subtracting the atomic weight 32 of two oxygens from the molecular weight of the tetracarboxylic dianhydride used as a raw material. Tetracarboxylic dianhydride to 2
When more than one kind is used, the average molecular weight calculated from the molecular weight of each tetracarboxylic dianhydride and the molar ratio used is used.
[M] _A represents the molecular weight of the diamine unit,
From the molecular weight of the aromatic diamino compound used as the raw material,
It is obtained by subtracting the atomic weight 2 of each hydrogen atom. When two or more aromatic diamino compounds are used, the average molecular weight calculated from the molecular weight of each diamino compound and the number of moles used is used.

[M] _S represents the total molecular weight of the side chain substituents (R) and (R ') present in the carbonyl group bonded to the aromatic ring of the precursor polymer, and the same substituent is bonded. In this case, the molecular weight of the substituent may be multiplied by 2,
When two or more substituents are present, the average molecular weight calculated from the molecular weight of each substituent and the molar ratio used is multiplied by two. In the above calculation, the atomic weight of carbon is 12, the atomic weight of nitrogen is 14, the atomic weight of oxygen is 16, and the atomic weight of sulfur is 3
2. The value obtained by calculating the atomic weight of hydrogen as 1. In the formula, 2000 is a coefficient for calculating the number of moles of the amide bond present in 1 kg of the polyimide precursor.

(2) Absorbance of Polyimide Precursor Coating Film A solution of the polyimide precursor in N-methylpyrrolidone
After spin-coating on a quartz plate having a thickness of mm, it is dried in an oven at 80 ° C. for 40 minutes to form a coating film having a thickness of 10 μm. Next, the absorbance at 365 nm of this coating film was measured using a UV spectroscope (Shimadzu Corporation, UV-240 type), and represented by an absorption value according to the following equation. Absorbance = log ₁₀ I ₀ / I (where I ₀ is the intensity of incident light and I is the intensity of light transmitted through the film)

(3) Absorbance of the photosensitive composition coating film Measured in the same manner as in (2) above. (4) Viscosity number of polyimide precursor The polyimide precursor in N-methylpyrrolidone (1 g / d
l) Viscosity number (ηsp / c)
It was measured at 30 ° C. with AVL-2C (manufactured by Sun Electronics).

(5) Viscosity of photosensitive composition A solution of the composition sample was subjected to an E-type viscometer (manufactured by Tokyo Keiki, VISC).
(ONIC-EMD type) at 23 ° C. (6) Tensile strength and elongation of polyimide coating film In each case, the coating film on the wafer was subjected to the same treatment except that the coating film on the wafer was entirely exposed without using a photomask and was not developed. Peel the obtained polyimide coating from the wafer,
The tensile strength and elongation were determined according to ASTM D-882-88.
It was measured according to.

(7) Peeling Test The adhesion of the polyimide coating film to the epoxy resin was measured as follows. A pin having a diameter of 2 mm was joined to the polyimide coating on the silicon wafer after the heat treatment, using an epoxy resin adhesive (Araldite Standard, manufactured by Showa Polymer Co., Ltd.). The sample was subjected to a peeling test using a take-off tester (Sebastian 5 type, manufactured by Quad Group). Rating: peel strength 7kg / mm ² or more ... adhesion good 6-5kg / mm ² ··· usable 5kg / mm ² less than ... bad

(8) Water resistance test The polyimide coating film on the silicon wafer after the heat treatment was kept in boiling water for 48 hours, and then placed in a 50 ° C. oven.
After drying for an hour, the same peel test as above was performed. Rating: peel strength 7 kg / mm ² or more ... adhesion good 6-3kg / mm ² ··· Usable 3 kg / mm ² less than ... poor (9) ATC dianhydride used as a raw material preparation example Expressed by the following symbols. The following structural formula represents X in (VI).

[0057]

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[0058]

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The aromatic diamino compounds used in the production examples are represented by the following symbols. The following structural formula represents Y in the formula (V).

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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Production Example 1 16.1 g of (X-1) and 10.9 g of (X-11) were placed in a 500 ml separable flask.
g, (E-1) 27.0 g and γ-butyrolactone 6
0 ml, pyridine 1 while stirring under ice-cooling.
7.0 g were added. After stirring at room temperature for 16 hours, a solution of 41.2 g of dicyclohexylcarbodiimide in 40 ml of γ-butyrolactone was added under ice-cooling for 30 minutes, and then 35.0 g of (Y-1) was suspended in 70 ml of γ-butyrolactone. What was added was added in 60 minutes. After stirring for 3 hours under ice-cooling, 5 ml of ethanol was added, and the mixture was further stirred for 1 hour, and the solid produced in the above process was removed by filtration. The reaction solution was added to 10 l of ethanol, and the formed precipitate was separated by filtration and dried in vacuo. Thus, a polyimide precursor (A1-1) was produced. Table 5 shows the viscosity number, the amide bond concentration, and the absorbance of (A1-1).

(Production Example 2) A separable flask having a capacity of 500 ml was charged with 62.0 g of (X-2) and 462 ml of N, N'-dimethylacetamide (hereinafter referred to as DMAc), and 68.4 g of (Y-2) while stirring. DMA containing
After adding 100 ml of c and stirring at room temperature for 16 hours, 43.4 g of (E-2) was added under ice cooling and the mixture was stirred for 3 hours.
This reaction solution was added to 10 liters of ethanol, and the formed precipitate was filtered and dried under vacuum. Thus, a polyimide precursor (A2-1) was produced. Table 5 shows the viscosity number, the amide bond concentration, and the absorbance of (A2-1).

(Production Example 3) 76.8 g of (Y-3) was added to N-
Dissolved in 450 g of methylpyrrolidone (X-3) 71.6
g was added and reacted at 50 ° C. for 6 hours. (E-
3) A solution of 74.0 g in 110 g of N-methylpyrrolidone was slowly added at room temperature to obtain a solution of a polyimide precursor (A3-1). Table 5 shows the amide bond concentration and absorbance of (A3-1). (Production Example 4) 121.1 g of (Y-4) was dissolved in 687 g of N-methylpyrrolidone, 88.2 g of (X-8) was added, and the mixture was stirred at room temperature for 12 hours. Next, (E-4) 8
5.3 g was added and the mixture was stirred at 70 ° C. for 36 hours. Thus, a solution of the polyimide precursor (A4-1) was produced. Table 5 shows the amide bond concentration and absorbance of this (A4-1).
Shown in

(Production Example 5) 72.9 g of (X-4) was added to N-
Dissolved in 200 g of methylpyrrolidone, (E-1) 5.2
g and heated at 100 ° C. for 1 hour. This was cooled to 50 ° C., 44.4 g of (Y-5) was added together with 110 g of N-methylpyrrolidone, and the mixture was stirred at 50 ° C. for 5 hours. Next, 76.0 g of trifluoroacetic anhydride was added together with 280 ml of tetrahydrofuran.
Stir for hours. At this time, insoluble solid components were precipitated. Next, 52.0 g of (E-1) was added, and the mixture was stirred at 50 ° C. for 5 hours to dissolve the solid components to obtain a uniform solution. This solution was added to 10 l of water, and the formed precipitate was filtered, washed with water and dried in vacuo. Thus, a polyimide precursor (A5-1) was produced. Table 5 shows the viscosity number, amide bond concentration, and absorbance of (A5-1).

(Production Examples 6 to 17) ATC shown in Table 1
Polyimide precursors (A1-2) to (A1-17) in the same manner as in Production Example 1 except that dianhydride, aromatic diamino compound and R-containing compound were used in the amounts shown in Table 1, respectively.
Was manufactured. Table 5 shows the viscosity number, amide bond concentration, and absorbance of the obtained polyimide precursor. (Production Examples 18 to 25) A polyimide precursor was prepared in the same manner as in Production Example 3 except that the ATC dianhydride, the aromatic diamino compound and the other compounds shown in Table 2 were used in the amounts shown in Table 2, respectively. The bodies (A3-2) to (A3-9) were produced. Amide bond concentration of the obtained polyimide precursor,
Table 6 shows the absorbance.

(Production Examples 26 to 28) ATs shown in Table 2
A polyimide precursor (A5-
2) to (A5-4) were produced. Table 6 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor thus obtained. (Production Examples 29 and 30) A polyimide precursor (A1
-14) and (A1-15). Table 6 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor thus obtained.

(Production Example 31) In a 500-ml separable flask, 31.0 g of (X-2) and 17.0 pyridine were added.
g, 60 ml of γ-butyrolactone was added, and 27.0 g of (E-1) was added with stirring. The solution was heated to 40 ° C. and maintained for 4 hours. After stirring at room temperature for 16 hours, 41.2 g of dicyclohexylcarbodiimide γ-
A solution of 40 ml of butyrolactone was added under ice-cooling for 30 minutes, and then 40.4 g of (Y-8) was added to 80 ml of γ-
The butyrolactone suspension was added over 60 minutes. After stirring for 3 hours under ice-cooling, 5 ml of ethanol was added, and the mixture was further stirred for 1 hour. The reaction solution obtained by removing the solid produced by the above process by filtration was added to 10 l of ethanol, and the formed precipitate was separated by filtration. Dried. Thus, a polyimide precursor (A1-16) was produced.
Table 6 shows the viscosity number, amide bond concentration, and absorbance of (A1-16).

(Production Example 32) 35.0 g of (Y-1) was converted into 70 ml of γ-butyrolactone by using the ATC dianhydride and the aromatic diamino compound shown in Table 2 in the amounts shown in Table 2, respectively. Instead of adding a suspension (Y-5)
A polyimide precursor (A1-17) was produced in the same manner as in Production Example 1, except that a 160 ml γ-butyrolactone solution containing 23.6 g was added. Table 6 shows the viscosity number, amide bond concentration, and absorbance of (A1-17).

(Production Example 33) The same procedure as in Production Example 2 was carried out except that the ATC dianhydride, amino compound and other compounds shown in Table 2 were used in the amounts shown in Table 2, respectively. A2-2) was produced. This (A2-
Table 6 shows the viscosity number, amide bond concentration, and absorbance of 2). (Production Example 34) 160.6 g of (Y-7) was dissolved in 770 g of N-methylpyrrolidone, 120 g of (X-11) was added, and the mixture was reacted at 50 ° C for 6 hours. To 50 g of this solution,
(E-9) A solution in which 2.5 g was dissolved in 50 g of N-methylpyrrolidone was added to obtain a polyimide precursor (A3-10). Table 6 shows the viscosity number, amide bond concentration, and absorbance of (A3-10).

(Production Examples 35 to 43) ATs shown in Table 3
Polyimide precursors (A1-18) to (A1-18) were prepared in the same manner as in Production Example 32 except that the amounts of C dianhydride, aromatic diamino compound and other compounds shown in Table 3 were used.
26). Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor. (Production Example 44) 22.8 g of (Y-20) and 150 g of N-methylpyrrolidone were dissolved, and 35.8 g of (X-3) was added and reacted at 50 ° C for 6 hours. (E-3) 3
A solution of 7.2 g in 66 g of N-methylpyrrolidone was slowly added at room temperature to obtain a polyimide precursor solution (A3
-11) was obtained. Table 7 shows the viscosity number, amide bond concentration, and absorbance of (A3-11).

(Production Examples 45 to 48) ATs shown in Table 3
Polyimide precursors (A1-28) to (A128) were prepared in the same manner as in Production Example 32 except that the amounts of C dianhydride, aromatic diamino compound, and other compounds shown in Table 3 were used.
-31). Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor. (Production Examples 49 to 50) A polyimide precursor solution (A) was prepared in the same manner as in Reference Example 4 except that the ATC dianhydride and the aromatic diamino compound shown in Table 3 were used in the amounts shown in Table 3.
4-2) and (A4-3) were produced. Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor solution.

(Production Examples 51 and 52) A polyimide precursor solution (A
3-12) and (A3-13). Table 7 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor solution. (Production Examples 53 to 58) A polyimide precursor (A1
-32) to (A1-37). Table 8 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor.

(Production Examples 59 and 60) A polyimide precursor (A5
-5) and (A5-6). Table 8 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor. (Production Example 61) A polyimide precursor (A1) was prepared in the same manner as in Production Example 32 except that the ATC dianhydride, aromatic diamino compound and other compounds shown in Table 4 were used in the amounts shown in Table 4, respectively. -38). Table 8 shows the viscosity number, amide bond concentration, and absorbance of the polyimide precursor.

Next, examples will be shown. Abbreviations for each component in the examples are as follows. (Photopolymerization initiator (component B)) I-1 Benzophenone I-2 Benzyl I-3 2-Isopropylthioxanthone I-4 1,3-Diphenylpropanetrione-2-
(O-ethoxycarbonyl) oxime I-5 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime

(Compound having a reactive carbon-carbon double bond) M-1 tetraethylene glycol dimethacrylate M-2 pentaerythritol diacrylate M-3 methylenebisacrylamide M-4 N-methylolacrylamide M-5 trimethylolpropane Triacrylate

(Sensitizer) S-1 Michler's ketone S-2 4,4'-bis (diethylamino) benzophenone S-3 2- (p-dimethylaminostyryl) benzoxazole S-4 2- (p-dimethylaminobenzoyl) ) Styrene S-5 N-phenyldiethanolamine S-6 Np-tolyldiethanolamine S-7 N-phenylethanolamine S-8 2-mercaptobenzimidazole S-9 1-phenyl-5-mercapto-1,2,2
3,4-tetrazole S-10 2-mercaptobenzothiazole

(Adhesion Aid) F-1 γ-Glycidoxypropylmethyldimethoxysilane F-2 3-Methacryloxypropyltrimethoxykilan F-3 3-Methacryloxypropylmethyldimethoxysilane F-4 N- [3- (Triethoxysilyl) propyl] phthalamic acid F-5 benzophenone-3,3'-bis [N- (3
-Triethoxysilyl) propylamide] -4,4'-
Dicarboxylic acid

(Thermal polymerization inhibitor) Z-1 N-nitrosodiphenylamine Z-2 bis (4-hydroxy-3,5-tert-
Butylphenyl) methane Z-3 2,6-di-tert-butyl-p-methylphenol Z-4 2-nitroso-1-naphthol

Reference Example 1 Polyimide precursor (A1-
1) 50 g, (I-1) 2 g, (M-1) 6 g, (S-
1) 0.05 g, (S-5) 1 g, (S-8) 1.5
g, (F-1) 1 g and (Z-1) 0.05 g
-Methylpyrrolidone was dissolved in 75 g to prepare a photosensitive composition (W-1). The absorbance of the coating film of this composition was 1.5, and the viscosity was 73.5 poise. This composition was spin-coated on a 3-inch silicon wafer and dried to form a 13 μm thick coating. An i-line stepper EPA20 was applied to this coating film using a reticle with a test pattern.
An energy of 800 mJ / cm ² was irradiated with 01iI (manufactured by Canon). Next, the wafer was spray-developed with γ-butyrolactone and xylene (50/50 (%)), and rinsed with isopropyl alcohol, whereby a sharp pattern with a resolution of 10 μm line / space was obtained.

The wafer was placed in an inert oven at 140 ° C. for 1 hour in a nitrogen atmosphere, then at 300 ° C.
For 1 hour to obtain a 7 μm thick polyimide film. In both the peeling test and the water resistance test, the epoxy resin was broken at a stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. The polyimide film has a tensile strength of 14
kg / mm ² and elongation was 30%.

(Example 2) Polyimide precursor (A2-
1) 20 g, (I-2) 0.3 g, (M-2) 0.5
g, (S-2) 0.02 g, (S-9) 0.1 g, (F
-3) 0.15 g of (Z-2) methane and 0.01 g of methane were dissolved in 40 g of N-methylpyrrolidone to prepare a photosensitive composition (W-2). The absorbance of the coating film of this composition was 1.5, and the viscosity was 44 poise. Next, this composition was spin-coated on a 3-inch silicon wafer and dried to obtain a 13 μm-thick coating film. This coating film was exposed to an energy of 400 mJ / cm ² from an i-ray light source through a reticle using an i-ray stepper exposure machine NSR1505i (manufactured by Nikon). The wafer was then treated with tetramethylammonium hydroxide / methanol / water (0.3 / 2.
7/97 (volume%)) and rinsed with water to obtain a 10 μm line / space resolving sharp pattern.

This was baked on a hot plate at 200 ° C. for 10 minutes, further placed in a vertical curing furnace, and heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere to obtain a 7 μm-thick polyimide pattern. This film has a stress of 8 kg / in both the peeling test and the water resistance test.
At the time of mm ² , the epoxy resin was broken, and both the adhesive strength and the water resistance were good. The polyimide film had a tensile strength of 20 kg / mm and an elongation of 9%.

Example 3 Polyimide Precursor (A3-
In 77 g of the solution of 1), 0.2 g of (I-3) and (M-3)
0.8 g, (S-3) 0.02 g, (S-6) 0.3
g, (S-10) 0.15 g, (F-3) 0.1 g and (Z-3) 0.01 g were dissolved, and the photosensitive composition (W-
3) was prepared. The absorbance of a coating film of this composition is 0.8,
The viscosity was 55.0 poise. Next, this composition was added to 3
Spin on an inch silicon wafer and dry
A coating having a thickness of 7 μm was obtained. An i-line bandpass filter UVD36C (manufactured by Toshiba Colored Glass) is passed through a photomask through a photomask through a PLA 50 IF exposure machine (manufactured by Canon).
Through 1000 mJ / cm ² . This wafer was treated with N, N'-dimethylacetamide /
After spray development with a developing solution of ethanol (80/20 (vol%)), rinsing with isopropyl alcohol gave a sharp pattern with a resolution of 10 μm line / space.

This was heat-treated in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour and 300 ° C. for 1 hour to obtain 8 μm.
An m-thick polyimide pattern was obtained. This film is
In both the peeling test and the water resistance test, the epoxy resin was broken at a stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. The polyimide film had a tensile strength of 12 kg / mm ² and an elongation of 70%.

Reference Example 4 Polyimide precursor (A4-
In 33.3 g of the solution of 1), 0.6 g of (I-4) and (M-
4) 0.8 g, (S-4) 0.03 g, (S-7) 0.
2 g, 0.1 g of (S-8), 0.1 g of (F-4) and 0.01 g of (Z-4) were dissolved and the photosensitive composition (W-
4) was prepared. The absorbance of a coating film of this composition is 1.5,
The viscosity was 38 poise.

The composition was spin-coated on a 3-inch silicon wafer and dried to obtain a 13 μm-thick coating film. An i-line stepper FPA is applied to this coating using a pattern reticle.
800 mJ / cm ² by 2000iI (manufactured by Canon)
Exposure. This wafer was treated with choline hydroxide / ethanol / water (0.5 / 9.5 / 90 (vo
1%)), and rinsed with water to obtain a sharp pattern with a resolution of 10 μm line / space.

This was heat-treated in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour and at 300 ° C. for 1 hour to give 7 μm.
An m-thick polyimide pattern was obtained. This film is
In both the peeling test and the heat resistance test, the epoxy resin was broken at a stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. The polyimide film had a tensile strength of 18 kg / mm ² and an elongation of 12%.

Reference Example 5 Polyimide precursor (A5-
1) 50 g, (I-5) 2 g, (M-5) 3 g, (S-
3) 0.1 g, (S-9) 0.5 g, (F-5) 1 g and (Z-4) 0.02 g were mixed with N-methylpyrrolidone 7
The resultant was dissolved in 5 g to prepare a photosensitive composition (W-5). The absorbance of the coating film of this composition was 1.0, and the viscosity was 47.0 poise. This composition was spin-coated on a 3-inch silicon wafer and dried to obtain a coating having a thickness of 19 μm. This coating film was coated with an i-line stepper FPA2001iI (manufactured by Canon Inc.) using a reticle with a test pattern at 600 mJ.
/ Cm ² . When this wafer was rinsed with a paddle developer and isopropyl alcohol with a cyclohexanone / xylene (70/30 (vol%)) developer, a sharp pattern with a resolution of 15 μm line / space was obtained.

This wafer was heat-treated in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour and at 350 ° C. for 2 hours to obtain a polyimide pattern having a thickness of 10 μm.
In this film, in both the peeling test and the water resistance test, the epoxy resin was broken at a stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. Also,
This polyimide coating film had a tensile strength of 18 kg / mm ² and an elongation of 18%.

(Reference Examples 6 to 18) 50 g of various polyimide precursors shown in Table 9, 2 g of (I-5), and (M-5) 3
g, (S-3) 0.3 g, (S-9) 0.5 g, (F-
5) 1 g and 0.02 g of (Z-4) were dissolved in 75 g of N-methylpyrrolidone to prepare photosensitive compositions (W-6) to (W-6).
-18) was prepared. Table 9 shows the viscosity of these compositions and the absorbance of the coating film.

These compositions were spin-coated on a 3-inch silicon wafer and dried. Table 9 shows the thickness of the obtained coating film. These coating films were exposed at an energy of 800 mJ / cm ² by an i-line stepper FPA2001iI (manufactured by Canon) using a reticle with a test pattern. This wafer was treated with cyclohexanone / xylene (70
/ 30 (vol%)), followed by rinsing with isopropyl alcohol, and the resulting resolution is shown in Table 9. These wafers were placed in an inert oven at 140 ° C. for 1 hour and 350 ° C.
Heat treatment was performed for a time to obtain a polyimide pattern. Table 9 shows the results of the peeling test and the water resistance test, tensile strength, elongation, and film thickness of the polyimide coating film.

(Examples 19 to 26) Photosensitive compositions (W-19) to (W-26) were prepared in the same manner as in Example 3 by using 77 g of various polyimide precursor solutions shown in Table 10. . Table 10 shows the viscosity of these compositions and the absorbance of the coating film.
Shown in Using these compositions, a coating film was formed in the same manner as in Example 3, and the resolution and the peeling test of the polyimide coating film after the heat treatment, the results of the water resistance test, and the tensile strength, elongation, and film thickness were measured. It is shown in Table 10.

(Reference Examples 27 to 28) Polyimide precursor (50 g), (I-5) 2 g, (M-5) 3 shown in Table 10
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) 1 g and 0.02 g of (Z-4) were dissolved in 75 g of N-methylpyrrolidone to form photosensitive compositions (W-27) to
(W-28) was prepared. Table 10 shows the viscosities and the absorbances of the coating films. The resolution of the pattern obtained by treating in the same manner as in Example 1 using these compositions, and the peeling test, water resistance test, film thickness, tensile strength and elongation of the polyimide coating film after heat curing were performed. It is shown in Table 10.

(Comparative Examples 1 and 2) 50 g of the polyimide precursor shown in Table 10, 2 g of (I-5), 3 g of (M-5),
(S-3) 0.05 g, (S-9) 0.5 g, (F-
5) 1 g and 0.02 g of (O-4) were dissolved in 75 g of N-methylpyrrolidone to prepare photosensitive compositions (WR-1) and (WR-2). Table 10 shows the viscosities of these compositions and the absorbance of the coating films.

Next, when these compositions were treated in the same manner as in Reference Example 6, in Comparative Example 1, a line / space line flowed due to the strong inverted trapezoidal pattern cross-sectional shape. In the case of these, lines flow due to the stronger cross-sectional shape of the inverted trapezoidal pattern, and all of them have practical problems. Table 10 shows a peeling test, a water resistance test, a film thickness, a tensile strength, and an elongation of the polyimide coating film after the heat curing.

(Comparative Example 3) Polyimide precursor (A1-
A photosensitive composition (WR-3) was prepared in the same manner as in Comparative Example 1, except that the polyimide precursor (A1-14) was used instead of 7). The viscosity of this composition was 66.3 poise, and the absorbance of the coating film was 0.41. This composition was spin coated on a 3 inch silicon wafer and dried to 27 μm
A thick coating was obtained. In the pattern obtained by treating this coating film in the same manner as in Example 1, the swelling of the exposed portion was strong and the line / space could not be resolved. This film had a stress of 8 kg / m in both the peeling test and the water resistance test.
At the time of m ² , the epoxy resin was good in breaking, adhesive strength and water resistance. The polyimide film has a tensile strength of 9
kg / mm ² and elongation were 120%.

Reference Example 29 Polyimide precursor (A1-
17) 50 g, (I-1) 2 g, (M-1) 6 g, (S
-1) 0.05 g, (S-5) 1 g, (S-10) 1.
5 g, (F-1) 1 g, and (Z-1) 0.05 g were dissolved in N-methylpyrrolidone 75 g to prepare a composition (W-29). The viscosity of this composition was 78 poise, and the absorbance of the coating film was 1.5.

This composition was treated in the same manner as in Reference Example 1 with 13
After forming and developing a coating film having a thickness of μm, the film was rinsed with xylene to obtain a sharp pattern with a resolution of 10 μm line / space. This wafer was heat-treated in the same manner as in Example 1 to obtain a 7 μm-thick polyimide pattern. In this film, in both the peeling test and the water resistance test, the epoxy resin was broken at the time of the stress of 8 kg / mm ² , and both the adhesive strength and the water resistance were good. The tensile strength of this polyimide coating was 15 kg /
mm ² and elongation were 14%.

Reference Example 30 Polyimide precursor (A2-
2) 0.3 g of (I-2) and 0.5 g of (M-2) in 55.6 g.
5 g, (S-2) 0.02 g, (S-9) 0.1 g,
(F-2) 0.15 g and (Z-2) 0.01 g were dissolved to prepare a photosensitive composition (W-30). The viscosity of this composition was 129 poise, and the absorbance of the coating film was 1.5.
A 13 μm-thick coating film was formed from this composition in the same manner as in Example 2 and developed. As a result, a 10 μm line / space resolving sharp pattern was obtained. This wafer was heat-treated in the same manner as in Example 2 to obtain a polyimide pattern having a thickness of 7 μm. In the peel test, the film was broken at the time of 5 to 6 kg / mm ² ,
In the water resistance test, the peel strength was reduced to 3 kg / mm ² . The polyimide film has a tensile strength of 17k.
g / mm ² and elongation was 10%.

Example 31 Polyimide Precursor (A3-
A photosensitive composition (W-31) was prepared in the same manner as in Example 3, except that the polyimide precursor (A3-10) was used instead of 1). The viscosity of this composition was 50 poise, and the absorbance of the coating film was 1.4. A 17 μm thick coating film was formed from this composition in the same manner as in Example 3 and developed.
A sharp pattern resolving a line / space of μm was obtained. This wafer was heat-treated in the same manner as in Example 3 to obtain a 9 μm-thick polyimide pattern. In this film, the epoxy resin was broken at a stress of 8 kg / mm ^{2 in} both the peeling test and the water resistance test,
Both adhesive strength and water resistance were good. The polyimide film has a tensile strength of 16 kg / mm ² and an elongation of 10%.
Met.

(Reference Examples 32-36 and Comparative Examples 4-6)
Various polyimide precursors and other components shown in Table 11 were dissolved in 75 g of N-methylpyrrolidone to prepare a composition (W-3
2) to (W-36) and (WR-4) to (WR-6)
Was prepared. Table 12 shows the viscosity and the absorbance of the coating film.
Shown in These compositions were spin-coated on a 3-inch silicon wafer and dried. Table 12 shows the thickness of the obtained coating film.
Shown in Using a reticle with a test pattern on this coating film, an i-line stepper FPA200liI (manufactured by Canon)
Exposure was performed at the exposure energy shown in Table 11 below. This wafer was treated with cyclohexanone / xylene (70/30 (vol.
%)), And rinsed with a solvent shown in Table 11, and the obtained resolution is shown in Table 12. In each of the examples, a sharp pattern was obtained. These wafers were heat-treated at 140 ° C. for 1 hour, 350 ° C. for 2 hours under a nitrogen atmosphere using an inert open,
A polyimide pattern having the thickness shown in Table 12 was obtained. Table 12 shows the results of the peeling test and the water resistance test, and the tensile strength and elongation of the polyimide coating film.

Reference Examples 37 to 40 50 g of various polyimide precursors shown in Table 13, 2 g of (I-1), and (M-1)
6 g, (S-1) 0.05 g, (S-5) 1 g, (S-
8) 1.5 g, (F-1) 1 g, (Z-1) 0.05 g
Was dissolved in 75 g of N-methylpyrrolidone to obtain a composition (W-
37) to (W-40) were prepared. Table 13 shows the viscosity and the absorbance of the coating film.

The compositions were spin-coated on a 3-inch silicon wafer and dried. Table 13 shows the thickness of the obtained coating film. This coating film was exposed using a reticle with a test pattern under an i-line stepper and exposure conditions shown in Table 13. When this wafer was rinsed with a spray developer and xylene with a developer of γ-butyrolactone / xylene (50/50 (vol%)), a sharp pattern was obtained in each case. Table 13 shows these resolutions. This wafer was heat-treated in an inert oven under a nitrogen atmosphere at 140 ° C. for 1 hour and at 300 ° C. for 1 hour. Are shown in Table 13.

Reference Examples 41 and 42 To 33.3 g of the polymer precursor shown in Table 13, 0.6 g of (I-4) and (M
-4) 0.8 g, (S-4) 0.03 g, (S-7)
0.2 g, (S-8) 0.1 g, (F-4) 0.1 g,
(Z-4) 0.01 g of a photosensitive composition (W-4)
1) and (W-42) were prepared. Table 13 shows the viscosities of these compositions and the absorbance of the coating films. This composition was treated in the same manner as in Reference Example 5 except that the exposure energy was changed to 500 mJ / cm ^2, and a sharp pattern was obtained in each case. Table 13 shows these resolutions. This wafer was heat-treated in an inert oven at 140 ° C. for 1 hour and at 350 ° C. for 1 hour in a nitrogen atmosphere. Are shown in Table 13.

(Examples 43 to 45) To 77 g of the polymer precursor shown in Table 13, 0.2 g of (I-3) and (M-3)
0.8 g, (S-3) 0.02 g, (S-6) 0.3
g, (S-10) 0.15 g, (F-3) 0.1 g,
(Z-3) 0.01 g of a photosensitive composition (W-4)
3) to (W-45) were prepared. Table 13 shows the viscosities of these compositions and the absorbance of the coating films.

The compositions were spin-coated on a 3-inch silicon wafer and dried. Table 13 shows the thickness of the obtained coating film. The coating film was exposed through a reticle using an i-line light source under the exposure conditions shown in Table 13. N,
N'-dimethylacetamide / ethanol = 80/20
(Vol%)), and a sharp pattern was obtained by rinsing with a spray developer and isopropyl alcohol. Table 13 shows these resolutions. The wafer was heat-treated at 140 ° C. for 1 hour and at 350 ° C. for 1 hour in a nitrogen atmosphere using an inert open to obtain a polyimide pattern having a thickness shown in Table 13. Table 13 shows the results of the peeling test and the water resistance test, tensile strength, and elongation of this polyimide coating film.

Reference Example 46 Polyimide precursor (A1-
31) 50 g, (I-1) 2 g, (M-1) 6 g, (S
-1) 0.05 g, (S-5) 1 g, (S-10) 1.
5 g, 1 g of (F-1) and 0.05 g of (Z-1)
-Soluble in 75 g of methylpyrrolidone
-46) was prepared. The viscosity of this composition is 43 poise,
The absorbance of the coating film was 1.5.

This composition was spin-coated on a 3-inch silicon wafer and dried to obtain a 13 μm-thick coating film. An i-line light source of 600 mJ was applied to this coating film through a reticle using an i-line stepper exposure machine NSR-1505i (manufactured by Nikon).
/ Cm ² . Γ-
Butyrolactone / xylene = 50/50 (vol / vo)
1%), and rinsed with xylene to obtain a sharp pattern with a resolution of 10 μm line / space. The wafer was heat-treated at 140 ° C. for 1 hour and 300 ° C. for 1 hour in a nitrogen atmosphere using an inert open to obtain a 7 μm-thick polyimide pattern. This film had a stress of 8 kg / mm ^{2 in} both the peeling test and the water resistance test.
At this point, the epoxy resin was broken, and the adhesive strength and water resistance were all good. The polyimide film has a tensile strength of 1
It was 4 kg / mm ² and the elongation was 15%.

Reference Examples 47 and 48 50 g of the polymer precursor, 2 g of (I-5), and (M-5) 3 shown in Table 14
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) Photosensitive compositions (W-47) to (W-48) obtained by dissolving 1 g and 0.02 g of (Z-4) in N-methylpyrrolidone.
Was prepared. Table 14 shows the viscosities of these compositions and the absorbance of the coating films.

This composition was spin-coated on a 3-inch silicon wafer and dried. Table 14 shows the thickness of the obtained coating film.
Shown in An i-line stepper NSR-1505i
(Manufactured by Nikon), using an i-line light source through a reticle
For 47 for 500mJ / cm ^2, W-48 were exposed with an energy of 600 mJ / cm ^2. This wafer was subjected to cyclohexanone / xylene = 70/30 (v
ol / vol%) of the developing solution, followed by rinsing with isopropyl alcohol, and a sharp pattern was obtained in each case. Table 14 shows the resolution.
This wafer was heat-treated at 140 ° C. for 1 hour and at 350 ° C. for 1 hour in a nitrogen atmosphere using an inert oven.
A polyimide pattern having a thickness shown in FIG. Table 14 shows the results of the peeling test and the water resistance test, and the tensile strength and elongation of the polyimide coating film.

Reference Example 49 Polyimide precursor (A1-
A photosensitive composition (W-49) was prepared in the same manner as in Reference Example 46 except that 31) was replaced with (A1-34). The viscosity of this composition was 44 poise, and the absorbance of the coating film was 1.0. The composition was exposed to an exposure energy of 200 mJ / cm ^2.
Was processed in the same manner as in Reference Example 46 to obtain a coating film having a thickness of 20 μm, and the resolution of the developing solution was measured.
A sharp pattern resolving m lines / space was obtained. This wafer was heat-treated in the same manner as in Example 46 to obtain a polyimide pattern having a thickness of 11 μm. This film has a stress of 8 kg / in both the peeling test and the water resistance test.
At the time of mm ² , the epoxy resin was broken, and both the adhesion and the water resistance were good. The polyimide film had a tensile strength of 14 kg / mm ² and an elongation of 30%.

(Reference Examples 50 and 51) 50 g of a polyimide precursor, 2 g of (I-5) and (M-5) 3 shown in Table 14
g, (S-3) 0.1 g, (S-9) 0.5 g, (F-
5) 1 g and 0.02 g of (Z-4) were dissolved in N-methylpyrrolidone to prepare photosensitive compositions (W-50) and (W-5).
1) was prepared. Table 14 shows the viscosities and the absorbances of the coating films. These compositions were exposed to an energy of W-5.
200 mJ / cm ² for 0, 500 for W-51
Processing was performed in the same manner as in Reference Example 5 except that mJ / cm ^{2 was used,} and a sharp pattern was obtained. Table 14 shows the resolution. This wafer was heat-treated at 140 ° C. for 1 hour and 350 ° C. for 1 hour in an atmosphere of nitrogen using an inert open. It is shown in Table 14.

(Reference Example 52) A polyimide precursor (A1
-31) was replaced with (A1-37), and a photosensitive composition (W-52) was prepared in the same manner as in Example 46, except that 80 g of N-methylpyrrolidone was used. The viscosity of this composition was 30 poise, and the absorbance of the coating film was 1.2. This composition was treated in the same manner as in Reference Example 46 to obtain a coating film having a thickness of 13 μm, and the resolution after development was measured. As a result, a sharp pattern with a resolution of 10 μm line / space was obtained.
This wafer was heat-treated in the same manner as in Reference Example 46 to obtain a 7 μm-thick polyimide pattern. This film fractured the epoxy resin at a stress of 8 kg / mm ^{2 in} both the peeling test and the water resistance test, and both the adhesive strength and the water resistance were good. The polyimide film has a tensile strength of 14
kg / mm ² and elongation was 25%.

(Reference Examples 53 and 54) Photosensitive compositions (W-53) and (W-54) were prepared in the same manner as in Reference Example 6, except that 50 g of various polyimide precursors shown in Table 15 were used.
Was prepared. Table 15 shows the viscosities of these compositions and the absorbance of the coating films. The resolution of the pattern obtained by treating these compositions in the same manner as in Reference Example 6, the peeling test of a polyimide coating film after heat curing, the result of a water resistance test and the film thickness, tensile strength, Table 15 shows the elongation.

Comparative Example 7 Polymer Precursor (A1-8)
In place of (A1-38), a photosensitive composition (WR-7) was prepared in the same manner as in Reference Example 6. The viscosity of this composition was 60.2 poise, and the absorbance of the coating film was 2.0.
Next, these compositions were treated in the same manner as in Reference Example 6 to give 1
When a 2 μm coating film was obtained and the resolution after development was measured,
Due to the strong inverted trapezoidal pattern cross-sectional shape, a line / space line flows, and there is a practical problem. A 7 μm-thick polyimide pattern was obtained from this wafer in the same manner as in Reference Example 6. This film breaks at a stress of 5 kg / mm ² in the peeling test and 3 kg in the water resistance test.
/ Mm ² or less. The polyimide film had a tensile strength of 14 kg / mm ² and an elongation of 30%.

<Other Physical Properties Tests> Various physical properties of the photosensitive composition and the polyimide coating film obtained therefrom were measured, and the results are shown in Tables 16 to 17. The measurement method and evaluation are as follows. (1) Storage stability test The photosensitive compositions (W-1) to (W-54) and (WR-) produced in Examples, Reference Examples 1 to 54 and Comparative Examples 1 to 6
1) to (WR-6) were kept in an open at 40 ° C. for 5 days. The thermal stability of the composition was examined by measuring the change in viscosity after holding and the pattern forming ability. Evaluation: Application and pattern formation possible as before holding without viscosity change of ± 5% or more ... Good (O) Viscosity change up to ± 25% is observed, but application and pattern formation by changing the application rotation speed Possible: No problem in practical use (△) Viscosity change exceeding ± 25% is observed, but coating is impossible ... Poor (×)

(2) Effect of Long-Term Development Under the same conditions as in Examples 1 to 54 and Comparative Examples 4 and 6, the photosensitive compositions (W-1) to (W-54), (WR-4) and (WR-4) WR-6) was used for coating and exposure, followed by development for 30% longer than the development performed in Examples, Reference Examples 1 to 54 and Comparative Examples 4 and 6, followed by rinsing to obtain a pattern. . Evaluation: A sharp pattern was obtained .............. Good (○) Slight swelling of the pattern ・ ・ ・ ・ ・ ・ ・ ・ ・ No problem in practical use (△) Part of the exposed portion swelled, Dissolves and does not resolve ... poor (x)

(3) Heat resistance test of polyimide coating film The polyimide films obtained in Examples, Reference Examples 1-28 and Comparative Example 3 were (i) placed in a solder bath at 280 ° C. for 20 seconds, and ii) Changes in the film when a metal lever heated to 300 ° C. was pressed for 2 seconds were observed. Evaluation: (i) No change: good (○) Shrinkage occurred, partial swelling: No problem in practical use (△) Unrecoverable ・ ・ ・ ・ ・ ・ Defective (×) (ii) No significant change ・ ・ ・ ・ ・ ・ Good (○) Marks appear ・ ・································· Poor (×)

(4) Elongation of polyimide film Reference Examples 8, 27, 28, 30 and 54, Comparative Examples 1 and 2
After holding the polyimide films obtained in Steps 7 and 8 in boiling water for 48 hours, they were dried in an oven at 50 ° C. for 2 hours, and the elongation of the films was measured. Reference Examples 8 and 2
The elongation after boiling of the films from 7, 28 is 90
% Is 85%, 27% is 30%, 65% is 65%,
Almost no change in the elongation of the film in boiling water was observed. In Reference Examples 30 and 54, 10% was 5%, respectively.
%, Below 30% to 15%. Comparative Examples 1 and 7
In each case, 30% dropped to 22% and 30% dropped to 10%. In Comparative Example 2, 8% was 2% or less, and the elongation could not be measured.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Table 6]

[0130]

[Table 7]

[0131]

[Table 8]

[0132]

[Table 9]

[0133]

[Table 10]

[0134]

[Table 11]

[0135]

[Table 12]

[0136]

[Table 13]

[0137]

[Table 14]

[0138]

[Table 15]

[0139]

[Table 16]

[0140]

[Table 17]

[0141]

According to the photosensitive composition of the present invention, a polyimide pattern can be obtained at a high resolution by an i-ray exposure process which will be generalized in a photolithography process in the production of semiconductor devices in the future. Therefore, a polyimide coating film can be easily obtained without using a non-photosensitive polymer using a complicated and toxic substance as in the related art. In addition, the polyimide film obtained from the photosensitive composition of the present invention after heat conversion is excellent in water resistance and adhesion to a substrate.

Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI G03F 7/031 G03F 7/031 H01L 21/027 H01L 21/30 502R (56) References JP-A-5-156006 (JP, A) JP JP-A-2-157845 (JP, A) JP-A-1-113460 (JP, A) JP-A-63-317553 (JP, A) JP-A-63-27834 (JP, A) JP-A-60-198537 (JP, A) JP-A-4-52647 (JP, A) JP-A-3-71633 (JP, A) JP-A-62-276045 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB G03F 7/038 G03F 7/027 C08G 73/10 C08L 79/08

Claims (6)

(57) [Claims] (A) an aromatic polyimide precursor having a repeating unit represented by the general formula (I) and having an amide bond concentration of 1.5 mol / kg or more: [Wherein X is an aromatic group containing no tetravalent fluorine atom or 2
Chemistry in which ~ 4 aromatic groups not containing a fluorine atom are bonded via at least one bond selected from a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond, a sulfoxide bond and a sulfone bond A tetravalent organic group having a structure, comprising -COR group and -CO
The R ′ group and the —CONH— group are located ortho to each other;
And R 'are each independently _{^{- O - N + R 3 R}} 4 R 5 R 6 or -
OH (however, R ₂ and R ₃ are each independently and not limited to one kind, and may be an organic group having an ethylenically unsaturated bond,
R ₄ , R ₅ and R ₆ are each hydrogen or a hydrocarbon group having 1 to 6 carbon atoms);
R 'is a residue other than -OH; Y is a divalent aromatic group containing no fluorine atom or 2 to 6 aromatic groups having a single bond, an ether bond, a thioether bond, a carbonyl bond, a methylene bond. A divalent organic group containing no fluorine atom and having a chemical structure interconnected via at least one bond selected from a 2,2-propylene bond, a sulfoxide bond and a sulfone bond] ( In the photosensitive composition for i-line exposure containing B) a photopolymerization initiator and (C) a solvent, (i) in the aromatic polyimide precursor polymer described above.
An amide bond concentration of not more than 2.42 mol / kg, and / or (ii) X has a chemical structure of an aromatic group in which an aromatic group having a bonding group is substituted by an aprotic electron donating group. Being a tetravalent group, and / or (iii-2) Y is a group represented by the general formula (II): [Wherein A is _{-CH 2 -, - CO -,} - SO 2 -, - O
-, -S-, m-dioxyphenylene group, p-dioxyphenylene group or general formula (II-1) (Wherein B is _{-CH 2 -, - CO -,} - SO 2 -, - O
-, -S-, m-dioxyphenylene group, p-dioxyphenylene group, k is 0 or 1), m is 0
Or 1) a divalent group represented by the formula: or (iii-3) a compound represented by the general formula (III): Or (iii-4) substituted by an aprotic electron-withdrawing group in an aromatic group having a bonding group or an aromatic group adjacent thereto via an ether bond. A divalent group having a chemical structure of an aromatic group, and the wavelength of the film of the photosensitive composition for i-ray exposure formed after the photosensitive composition for i-ray exposure is applied and dried. A photosensitive composition for i-line exposure , wherein the absorbance at 365 nm is 1.5 or less per 10 μm of film thickness. 2. The photosensitive composition for i-line exposure according to claim 1, wherein the aromatic polyimide precursor satisfies the condition (i) in claim 1. 3. The photosensitive composition for i-line exposure according to claim 1, wherein the aromatic polyimide precursor satisfies the condition (iii-2) or (iii-3) in claim 1. 4. An aromatic group having 2 to 4 X's in the general formula (I) mutually connected via at least one bond selected from a single bond, an ether bond, a carbonyl bond and a sulfone bond. 2. A tetravalent organic group having a defined chemical structure.
A photosensitive composition for i-line exposure . 5. An aromatic group having 2 to 6 Y's in the general formula (I) is interconnected via at least one bond selected from a single bond, an ether bond, a carbonyl bond and a sulfone bond. The photosensitive composition for i-line exposure according to claim 1, which is a divalent organic group having the following chemical structure. 6. The following steps: (A) a step of applying a photosensitive composition for i-line exposure to a substrate, which comprises an aromatic polyimide precursor (a), a photopolymerization initiator (b) and a solvent (c). , (B) an exposure step of i-line coating as a light source, (C) the step of removing the non-exposed portion by a developing solution, and (D) consists of a heat treatment step of the obtained pattern, the photosensitive for the i-ray exposure i sex composition of claim 1
A method for forming a polyimide pattern, which is a photosensitive composition for line exposure .