JPH07238168A - Regular polymer and composition - Google Patents

Abstract

PURPOSE:To obtain a regular polymer improved in pattern formation by polycondensing two specified aromatic tetracarboxylic diesters with an alcohol (derivative). CONSTITUTION:25-75mol% aromatic tetracarboxylic diester of formula I (wherein X is a group of formula II or III; and R1 is a 4-11 C group having a terminal ethylenic bond, provided that the group of formula IV and the group of formula V are ortho to each other in each pair) and 25-75mol% aromatic tetracarboxylic diester of formula VI (wherein R2 is at least one group selected from among methyl, ethyl, n-propyl, isopropyl and allyl) are polycondensed with at most 75mol% alcohol (derivative) of formula VII (wherein Y is at least one group selected from groups of formulas VIII and IX) to obtain a polyimide precursor comprising repeating units of formula X (wherein R is R1 or R2, provided that R1 and R2 cannot be present simultaneously in the same repeating unit, and that R1s account for 25-75mol% of Rs and R2s account for 25-75mol% of Rs). 130 pts.wt. this precursor is mixed with 1-15 pts.wt. polymerization initiator and 100-400 pts.wt. polar solvent to obtain the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel material useful as a raw material for electric and electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the present invention relates to a novel polyimide precursor having a good pattern formability and a polyimide film obtained after heating and curing having a good mechanical property, and a photosensitive composition thereof.

[0002]

2. Description of the Prior Art Polyimide resins are known for their high thermal and chemical stability, low dielectric constant and excellent planarization ability.
It is a material that has attracted attention in the microelectronics industry and is widely used as a surface protective film for semiconductors, an interlayer insulating film, a material for multichip modules, and the like. By the way, in order to form a polyimide coating film on a semiconductor device or the like in a desired pattern, a polyimide precursor is semi-cured by heating, and then a photoresist pattern is once formed on the coating film. After etching the polyimide resin using the mask as a mask, the photoresist pattern that is no longer needed is peeled off, and the polyimide coating film is heat-treated again to obtain the desired physical properties. However, there is a problem in that the condition setting and management in step 3 are likely to be insufficient, and the reproducibility of physical properties is insufficient. Further, it is also a process which is not preferable because the resolution is not sufficiently obtained by indirect patterning and a toxic substance such as hydrazine is used during etching.

Therefore, in recent years, in order to obtain a pattern of a polyimide coating film, a polyimide precursor polymer into which a photopolymerizable sensitive group is introduced is used, and a photosensitive composition is prepared by adding a photoinitiator or the like thereto. A method for obtaining a pattern by photo-curing a film, developing it, and then heating it to remove a photosensitive group component and converting it into polyimide has been proposed. This technique is generally called photosensitive polyimide. This technique is described in detail, for example, in "Polyfile" Vol. 27, No. 2, paragraphs 14-18. According to this technique, the problem when using the above-mentioned non-photosensitive process is improved, and therefore its adoption is expanding year by year as a method for obtaining a pattern of a polyimide coating film.

[0004]

In recent years, there has been an increasing demand for higher resolution of polyimide patterns on semiconductor devices and the like. One of the reasons for this is that the resolution was not so high in the previous process using non-photosensitive polyimide, so the semiconductor device and process were designed on the premise of that, but when using photosensitive polyimide This is because new semiconductor devices and processes using high resolution patterns have appeared because they have higher pattern resolution.

For example, in the case of a memory device or the like, a preparatory circuit is made in advance in order to increase the yield of the product, and an unnecessary circuit is cut off after the product is inspected. This was done before making the polyimide pattern, but with photosensitive polyimide, there is enough resolution to cut holes in the polyimide pattern to cut unnecessary circuits and cut the preliminary circuit after pattern formation. The preliminary circuit disconnection is closer to the final product, and the product yield is further improved.

In such applications, there is a demand for smaller holes for cutting circuits for higher integration of devices, and a photosensitive polyimide precursor composition which gives a pattern resolution higher than that at present is required. It is being done.
Further, the photosensitive polyimide precursor that gives a high resolution pattern is easy to take a process margin corresponding to high integration and high accuracy of semiconductor elements, and the higher the resolution, the better. These circumstances are the same when a polyimide pattern is formed for other uses such as a multi-chip module, and a polyimide pattern with higher resolution and higher accuracy corresponding to thicker polyimide film, multilayer wiring and higher wiring density. There is a need for a photosensitive polyimide precursor composition that gives

In addition, in recent years, the mechanical strength of polyimide coating films,
In particular, the demand for elongation is becoming higher. This is because, for example, in a semiconductor device, conventionally, a semiconductor chip was placed on a lead frame and bonded, so that no stress was applied to the polyimide, whereas in order to downsize the device, a polyimide pattern was formed on the semiconductor chip. This is because a high stress is applied to the polyimide coating film due to the fact that the lead frame has been bonded on top of this.

Also, in applications such as multi-chip modules, the pins for electrical connection become smaller as the device becomes higher in density, and the area where the pins are attached becomes smaller,
The stress applied to the polyimide coating film at the adhesion portion becomes relatively large. In order to meet these requirements, there has been a demand for a photosensitive polyimide precursor composition which gives a polyimide pattern having a higher elongation.

In addition, in the process of heating the photosensitive polyimide, a step of obtaining a polyimide pattern is performed, and the substrate and the polyimide are cooled to room temperature after the stress between the substrate and the substrate disappears at high temperature. The phenomenon in which stress occurs due to the difference in shrinkage ratio generally occurs. If this residual stress is high, problems occur in the reliability and durability of the semiconductor device, which is not preferable. Therefore, there has been a demand for a photosensitive polyimide that reduces the residual stress of the cured polyimide.

Polyimide resins are known to cause a decrease in mechanical strength and a decrease in adhesive strength with a base material in a boiling test, which is not preferable because it may lead to a decrease in reliability of semiconductor devices and the like. . Therefore, there is a need for a photosensitive polyimide precursor composition that provides a more durable polyimide pattern. In short, a new photosensitive polyimide precursor composition having a required property of giving a pattern of a polyimide coating film having a higher elongation and a lower residual stress and a higher durability and a higher resolution is demanded. It was

There are many types of technology called photosensitive polyimide, depending on the chemical structure of the main skeleton of the polymer, the type of photosensitive group and the like. These are classified in detail in, for example, the 2nd Photo-Reaction / Electronic Materials Research Society Proceedings, 6th to 14th (1992) according to the table. Examples of these various photosensitive polyimides include those obtained by ionic bonding of a photosensitive group to a polyamic acid disclosed in Japanese Patent Publication No. 59-52822 by Hiramoto et al., Proc. No. 8, Item 2397 (1990)
A system in which a reactive monomer is mixed with the polyamic acid described in JP-A-3-220558 by Nader et al. And a system in which a polyamic acid partially esterified with a photosensitive group is used to develop in an aqueous system. There is also.

However, in the system using the polyimide precursor containing these carboxylic acid residues, the stability of the photosensitive composition is insufficient and the conditions are not constant, so that the pattern reproducibility is not good and the polyimide having good resolution is obtained. The pattern cannot be obtained with good reproducibility, and the exposed part is partially dissolved during development and the solubility difference from the unexposed part cannot be sufficiently taken, and the elution amount of the polymer from the exposed part remains after development and sufficient resolution is obtained. There was a phenomenon such as the occurrence of no pattern, which was unsuitable for obtaining the highly accurate pattern aimed at by the present invention. In the present invention, a polyimide precursor having a chemical structure of a polyamic acid ester that does not have the above-mentioned problems was studied.

Photosensitive compositions using a polyimide precursor having a polyamic acid ester chemical structure are known, for example, Lubner et al., Photograph. Sc
i. Eng. Those described in Item No. 303, Item 303 of 1979, M. Pottigger
38th. Electric Component
nts Conf. Examples thereof include those shown in Item 315 (1988), and each of them uses a polyamic acid ester in which only a 2-methacryloyloxyethyl group, which is a group having a terminal ethylene bond, is ester-bonded.

Polyamic acid esters obtained by ester-bonding a group having no terminal ester bond are also known. For example, Okabe et al.
The method described in item 7 in which a polyamic acid ester in which a group having no terminal ethylene bond is ester-bonded to a photosensitive composition is disclosed in Matsuoka et al., JP-A-61-29.
It is described in Japanese Patent No. 3204. The compositions shown by Lubner et al. And Pottiger et al. Are close to the above-mentioned photosensitive polyimide precursor compositions which are mainly used in the present semiconductor devices and the like. Is not yet satisfactory in terms of resolution and elongation and durability of the polyimide coating film.

Further, the composition shown by Matsuoka et al. Has a low sensitivity due to insufficient photocrosslinking by exposure, and at the same time, the exposed part is partially dissolved during development and a sufficient solubility difference from the unexposed part is obtained. However, there is a problem that the polymer elution from the exposed area remains after development and sufficient resolution cannot be obtained.

The present inventors have tried to improve a photosensitive polyimide precursor composition having a polyamic acid ester chemical structure as shown in Japanese Patent Application No. 4-257582.
As a result, as the organic group ester-bonded to the polyamic acid ester, (1) a hydrocarbon group having 1 to 3 carbon atoms,
(2) 2 of a group having a terminal ethylene bond having 4 or more carbon atoms
When both types of the mixture are used in a specific ratio, the polyimide pattern obtained after heat curing from the photosensitive composition has a higher elongation and is more water resistant than when either of the organic groups is used alone. It was found that it has high performance and at the same time has high resolution. Therefore, the present inventors continued their research in search of a photosensitive polyimide in which these performances were further improved and the residual stress of the polyimide after curing was low.

[0017]

SUMMARY OF THE INVENTION In view of the above points, the present inventors have aimed to improve the performance of the polyimide precursor disclosed in Japanese Patent Application No. 4-257582.
When (a) tetracarboxylic acid component, (b) ester group sequence and (c) diamine component were examined, by using specific ones for each of these three items,
The polyimide pattern obtained after thermosetting from the photosensitive composition has high elongation, high resolution, and high water resistance,
At the same time, the inventors have found a polyimide precursor having a low residual stress and completed the present invention.

That is, the present invention is that the aromatic tetracarboxylic acid diester represented by the following formula [I] is 25 to 75 mol%,

[Chemical 9] 25-75 mol% of an aromatic tetracarboxylic acid diester represented by the following formula [II],

[Chemical 10] (In the formula, R ₂ is a methyl group, an ethyl group, an n-propyl group,
It is one or more groups selected from an isopropyl group or an allyl group, and is the same as the formula [I] for others. )
And an aromatic tetracarboxylic acid diester consisting of

[Chemical 11] Provided is a polyimide precursor having a repeating unit represented by the following formula [IV], which is obtained by polycondensing Also,

[Chemical 12]

(A) A photosensitive composition containing the polyimide precursor described above, (B) a photopolymerization initiator, and (C) a solvent is provided. Further, (A) a polyimide precursor having a repeating unit represented by the following formula [V], (B) a polyimide precursor having a repeating unit represented by the following formula [VI], (C) a photopolymerization initiator, and ( D) A solvent is included, and the weight ratio of (A) and (B) contained is 0.75: 0.25 to 0.25: 0.
A photosensitive composition in the range of 75 is provided. Also,

[Chemical 13] (In the formula, R ₁ is the same as the formula [I], and the others are the same as the formula [IV].)

[Chemical 14] (In the formula, R ₂ is the same as the formula [II], and the others are the same as the formula [IV].)

There is provided a polyimide precursor as described above, wherein R ₁ is a polyimide precursor in which the group is represented by the formula [VII]. Also,

[Chemical 15] (In the formula, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group.) (A) A photosensitive composition as described above, which is a polyimide precursor in which R ₁ is a group represented by the formula [VII]. I will provide a.

[Chemical 16] (In the formula, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group.)

The present invention will be described in detail below. In the present invention, a method for producing a polyimide precursor having a chemical structure of a polyamic acid ester may be a known method, for example, the method used by Lubner et al., Used by Pottinger et al. Method, the method used by Matsuoka et al., Mentioned above, L. Minnema
Et al., Polym. Eng. Sci. 1988 v
ol. 28, No. The method described in paragraphs 12,815 and the method described in Japanese Patent Application Laid-Open No. 61-127731 by Matsuoka et al. Can be used.

Of these production methods, the content of ionic impurities is the smallest, and the planned polyamic acid ester can be produced in the highest chemical structure, and a photosensitive composition using this polyimide precursor can be produced. Since it has good storage stability, it has been disclosed by Matsuoka et al. In JP-A-61-293.
The manufacturing method shown in Japanese Patent No. 204 is most preferable. In the present invention, as a raw material for producing a polyimide precursor having a polyamic acid ester chemical structure, in any of the above production methods, (1) tetracarboxylic acid or its derivative, (2) diamine or its derivative, and (3 )
It is possible to use three kinds of alcohols or derivatives thereof, and also to use a dehydration condensation agent or the like depending on the production method.

As a raw material for producing the polyimide precursor in the present invention, a specific compound among the above is used. (1) The chemical structure of the tetracarboxylic acid or its derivative that can be used in the present invention is not particularly limited as long as it can be reasonably used in the synthesis reaction. It is preferable to use acid dianhydride as a raw material. Specific preferred examples thereof include pyromellitic dianhydride or 3,3 ′, 4.
It is 4'-biphenyltetracarboxylic dianhydride. These can be used alone or as a mixture.

(2) As the diamine or its derivative usable in the present invention, for example, trimethylsilylated diamine can be used, but the diamine itself is the simplest. Specific preferred examples of these diamines are paraphenylenediamine, metaphenylenediamine and 4,4'-diaminodiphenyl ether. These diamines can be used alone or in admixture of two or more.

(3) As the alcohol or its derivative used in the present invention, for example, the active alcohol derivative shown by Minema et al. Can be used.
These have a chemical structure that can be synthesized from alcohol, and it can be said that alcohol is used as the original raw material.

The polyimide precursor of the present invention has a polyamic acid ester chemical structure, and 25 to 75 mol% of ester-bonded organic groups are methyl groups represented by R ₂ of the above formula [II], One or two or more groups selected from ethyl group, n-propyl group, isopropyl group or allyl group, and 25 to 75 mol% of the ester-bonded organic groups have the formula [I ] is a polyimide precursor such that a group having a terminal ethylenic bond of carbon number 4-11 shown by R _1, the specific ratio of organic groups of the specific two types of chemical structure as the organic groups by ester bonds Have in. Therefore, as the alcohol used in the present invention, it is necessary to use alcohols having two specific chemical structures in a specific ratio.

First, as the alcohol having a chemical structure belonging to the first group, one or more alcohols selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol and allyl alcohol are all alcohols. 25 to 7
5 mol% is used. Then, as the alcohol having a chemical structure belonging to the second group, an alcohol having a terminal ethylene bond having 4 to 11 carbon atoms is used as the total alcohol.
5 to 75 mol% is used.

Specific preferred examples of alcohols in this group include 2-methacryloyloxyethyl alcohol, 2-acryloyloxyethyl alcohol and 1
-Methacryloyloxy-2-propyl alcohol, 1
-Acryloyloxy-2-propyl alcohol, 2-
Methacrylamidoethyl alcohol, 2-acrylamidoethyl alcohol, methylol vinyl ketone and 2-
Examples thereof include hydroxyethyl vinyl ketone.

The first four of these alcohols were listed.
The seed alcohol is more preferable from the viewpoint of solubility of the polymer. These alcohols can be used alone or in combination of two or more.

When the alcohol having a chemical structure belonging to the above-mentioned first group is used only at 25 mol% terminal, the photosensitive composition using the obtained polyimide precursor has a known photosensitivity in view of resolution. No difference from the polyimide precursor composition is observed, and there is no difference in the elongation and water resistance of the polyimide coating film obtained after heat treatment, which is not preferable. Therefore, the alcohol having the chemical structure belonging to the above second group can be used only at 75 mol% or less.

Further, when less than 25 mol% of the alcohol having the chemical structure belonging to the above-mentioned second group is used, the photosensitive composition using the obtained polyimide precursor has low sensitivity and resolution. It is not preferable because it is insufficient. Therefore, the alcohol having the chemical structure belonging to the above-mentioned first group can be used only at 75 mol% or less.

The polyimide precursor of the present invention was used 2
It is characterized by the arrangement in each repeating unit of the ester bond formed by a kind of alcohol. That is,
An ester group formed from two alcohols does not coexist on the same repeating unit, and two ester-bonded groups in one repeating unit must be R ₁ or a group represented by the formula [I]. _Two of R ₂ shown in [II] are bonded. R ₁ and R ₂ are loosely present on each repeating unit, using the photosensitive composition of polyimide precursor R ₁ and R ₂ coexist on the same repeating units, residues of polyimide pattern obtained after thermal curing It is not preferable because the stress becomes higher.

In the present invention, since it is necessary to take the above-mentioned specific ester bond, the method for producing a polyimide precursor having a repeating unit represented by the above-mentioned formula [IV] which is a copolymer is It is limited to the method used by Lubner et al. And the method by Matsuoka et al. In these, the above-mentioned two alcohols are separately used during the synthesis of the tetracarboxylic acid diester produced in the intermediate to obtain the compound of the above formula [I].
And a tetracarboxylic acid diester represented by the formula [II] are independently prepared, and the following polycondensation reaction is performed in a state where the two kinds are mixed to obtain a polyimide having the repeating unit represented by the formula [IV]. A precursor is obtained.

The above formula [V] and formula [V
The polyimide precursor having a repeating unit represented by the formula [I] can be produced independently by using any of the above-mentioned production methods. Examples of the photopolymerization initiator of the photosensitive composition of the present invention include benzophenone,
Methyl o-benzoylbenzoate, 4-benzoyl-4 '
Benzophenone derivatives such as methyldiphenylketone, dibenzylketone and fluorenone; acetophenone derivatives such as 2,2′-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone;

1-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2
Thioxanthone derivatives such as isopropylthioxanthone and diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethylketal and benzyl-β-methoxyethylacetal; benzoin derivatives such as benzoin benzoin methyl ether; 2,6-di (4'-diazidobenzal)- 4-methylcyclohexanone, 2,
Azides such as 6'-di (4'-diazidobenzal) cyclohexanone; 1-phenyl-1,2-butanedione-
2- (o-methoxycarbonyl) oxime,

1-phenyl-propanedione-2- (o
-Methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (O-Ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-
Oxime such as benzoyl) oxime is used,
Oximes are preferable in terms of photosensitivity. The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the polyimide precursor.

A compound having a reactive carbon-carbon double bond can be added to the photosensitive composition of the present invention for improving photosensitivity. Examples of such compounds include 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate having an addition mole number of 2 to 20, pentaerythritol diacrylate, dipentaerythritol hexaacrylate. ,

Examples include tetramethylolmethane tetraacrylate, methylenebisacrylamide, N-methylolacrylamide and the above acrylates or corresponding methacrylates and methacrylamides. These compounds are preferably added in the range of 1 to 30 parts by weight per 100 parts by weight of the polyimide precursor.

Next, a sensitizer for improving photosensitivity can be added to the photosensitive composition of the present invention. Examples of such sensitizers include Michler's ketone and 4,4 ′.
-Bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane,
2,6-bis (4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-dimethylaminobenzal) -4-methylcyclohexanone,

2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinna Millidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) Isonaphthothiazole,

1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) 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, dimethylaminobenzoate isoamyl, diethylaminobenzoate isoamyl, 2- Mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole,

2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl)
Examples thereof include benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, and 2- (p-dimethylaminobenzoyl) styrene.

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 addition amount thereof is 0.1 to 100 parts by weight of the polyimide precursor.
10 parts by weight is preferred.

Further, an adhesive aid may be added to the photosensitive composition of the present invention in order to improve the adhesiveness to the substrate.
Examples of this adhesion aid include γ-aminopropyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane,

Dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] Phthalamic acid, benzophenone-3,
3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzene-1,4
-Bis (N- [3-triethoxysilyl] propylamide) -2,5-dicarboxylic acid or the like is used. The amount of these adhesion promoters added is preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyimide precursor.

A thermal polymerization inhibitor may be added to the photosensitive composition of the present invention 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 ether diamine tetraacetic acid, 2,6-di-te
rt-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-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt and the like are used. The amount added is 100 parts by weight of the polyimide precursor,
The range of 0.005 to 5 parts by weight is preferable.

The solvent in the photosensitive composition of the present invention is preferably a polar solvent from the viewpoint of solubility, for example, N, N '.
-Dimethylformamide, N-methylpyrrolidone, N-
Acetyl-2-pyrrolidone, N, N′-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ
-Butyrolactone or the like is used. These can be used alone or in combination of two or more. The amount of the solvent used is 1 with respect to 100 parts by weight of the above-mentioned polyimide precursor.
The range of 00 to 400 parts by weight is preferable.

In the present invention, the method of applying the photosensitive composition onto the substrate is, for example, a method of applying a spin coater, a bar coater, a blade coater, a curtain coater, a screen printing machine or the like, or a spray coating with a spray coater. The method and the like can be used. As a method for drying the coating film, air drying, heat drying using an oven or a hot plate, vacuum drying and the like are used.

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, a stepper, etc., and then developed. The developer used for the development is preferably a combination of a good solvent and a poor solvent for the polyimide precursor, and as the good solvent, N-methylpyrrolidone, N-
Acetyl-2-pyrrolidone, N, N′-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone and the like, and poor solvents such as toluene, xylene, methanol, ethanol and isopropyl alcohol. And water are used.

The ratio of the poor solvent to the good solvent is adjusted by the solubility of the polymer used, and it is possible to use several kinds of each solvent in combination. The development can be performed by selecting any method from conventionally known photoresist development methods, such as a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment.

The pattern film of the composition thus obtained is heated to disperse the photosensitive components and converted into polyimide. As the method for heating conversion, various methods such as a method using a hod plate, a method using an oven, and a method using a temperature rising type oven capable of setting a temperature program can be selected. Air may be used as the atmospheric gas at the time of heat conversion, and an inert gas such as nitrogen or argon may be used.

When the polyimide precursor and the photosensitive composition of the present invention are used, the reduction rate of the film thickness upon heat curing is smaller than that when the conventional product of Lubner et al. Is used. The obtained polyimide coating film is a conventional product of Lubner et al. And Japanese Patent Application No. 4-257.
Higher density than that of 582. The pattern of the obtained polyimide coating film has a higher resolution than that of the conventional photosensitive polyimide precursor composition, and at the same time, has a higher elongation and a higher water resistance, and is useful with a low residual stress.

[0055]

The residual stress of the polyimide coating film obtained from the photosensitive polyimide precursor composition of the present invention has a residual stress of Japanese Patent Application No. 4-2575.
The reason why it is lower than that obtained from the composition shown in No. 82 is not clear, but it is considered that it is related to the molecular orientation of the polymer due to the higher density of the coating film. The particular ester group arrangement of the present invention is presumed to enhance the molecular orientation.

[0056]

The present invention will be described in more detail with reference to the following examples. In addition, the solution viscosity in each example and the residual stress of the polyimide coating film after heat curing were determined by the following methods. (1) Solution Viscosity and Composition Viscosity A sample solution was measured with an E-type viscometer (Tokyo Keiki, VISCONI
C-EMD type) was used and the viscosity was determined by comparison with a standard solution for viscosity calibration (Showa Shell Sekiyu JS2000) at 23 ° C.

(2) Measurement of residual stress The photosensitive composition obtained in each of the examples and comparative examples was applied to a 3-inch silicon wafer having a thickness of 370 μ so that the film thickness after curing was 10 to 10.
It was spin-coated to a thickness of 15 μm, dried at 90 ° C. for 1 hour, and further heated at 140 ° C. for 2 hours and 400 ° C. for 2 hours to obtain a polyimide coating film. After cooling, contact center surface roughness meter (SLOAN,
Curvature was measured using DEKTAK II A). The distance from the central part of the chord to the bow of the obtained figure that can be approximated to a bow is measured. Let this be D, the residual stress δ
Is represented by the following formula (1).

[0058]

[Equation 1] E: Young's modulus of silicon wafer V: Poisson's ratio of silicon wafer D: Measurement length Ts: Thickness of silicon wafer T: Coating film thickness (after curing)

Here, the underlined portion of the equation is a value specific to the silicon wafer, and is therefore a constant in this measurement. Therefore, the residual stress, δ, is expressed by the following equation (2).

[Equation 2] When the value of K is calculated here, it becomes K = 3.91 [kg / mm ² ]. Then, the coating film is scratched, the coating film thickness T is measured using the same contact type surface roughness meter, and from T, Δ and K, the formula (2) is obtained.
Then, the value of residual stress δ was obtained.

(Example 1) 52.3 g of pyromellitic dianhydride (hereinafter referred to as PMDA) and 2-methacryloyloxyethyl alcohol (hereinafter referred to as "methacryloyloxyethyl alcohol") were placed in a 2 liter separable flask (hereinafter referred to as "container A"). 62.4 g and γ-butyrolactone (hereinafter referred to as γ)
-BL) (190 ml) was added, and while stirring under ice cooling, 38.5 g of pyridine (hereinafter referred to as Py) was added, and after the generation of heat, the mixture was allowed to cool to room temperature and left for 16 hours.

Separately, 34.9 g of PMDA, 14.7 g of ethyl alcohol (hereinafter referred to as EtOH) and γ-BL1 were placed in a 1-liter flask (hereinafter referred to as container B).
Add 30 ml and stir under ice cooling while stirring Py25.7
After the completion of heat generation, the solution was allowed to cool to room temperature and left standing for 16 hours, and the entire amount of the resulting solution was added to the container B. Then, a solution of 166 g of dicyclohexylcarbodiimide in 120 ml of γ-butyrolactone was stirred under ice cooling while stirring 4
The mixture was added for 0 minutes, and then a suspension of 74.5 g of 4,4′-diaminodiphenyl ether in 150 ml of γ-butyrolactone was added for 60 minutes while stirring under ice cooling.

After stirring for 2 hours at room temperature, 30 ml of ethyl alcohol was added and stirred for 1 hour, 250 ml of dimethylacetamide and 400 ml of tetrahydrofuran were added, and the precipitate was filtered off to obtain a reaction solution of 15
After adding to liter of ethyl alcohol and filtering off the formed precipitate, it was vacuum dried to obtain a polymer powder. This is S
It is called -40. In N-methylpyrrolidone of S-40,
The viscosity of the 30 wt% solution was 28.3 ps.

50 g of S-40, 2 g of 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, 0.1 g of Michler's ketone, 3 g of acetylene glycol diacrylate, 1 g of 2-mercaptobenzothiazole, N- Phenyldiethanolamine 2g, 3
-Methacryloxypropyldimethoxysilane 0.5 g,
A photosensitive composition was prepared by dissolving 0.02 g of 2-nitroso-1-naphthol in 88.5 g of N-methylpyrrolidone. This composition is called WS-40. The viscosity of WS-40 was 142 ps.

The residual stress of the polyimide coating film obtained from WS-40 was 2.0 kg / mm ² at a film thickness of 11.0 μm. WS-40 was spin-coated on a silicon wafer and dried in an oven at 80 ° C. for 80 minutes to form a coating film having a thickness of 40 μm. A contact aligner (PLA501F type manufactured by Canon Inc., 250 W super high pressure mercury lamp) is used for this coating film, and a reticle with a test pattern is set to 55 cmH.
A hard contact was made with a suction pressure of g and exposure was performed for 100 seconds. Cyclohexanone / methanol [4
9/1 (vol / vol)] is used as a developing solution and isopropyl alcohol is used as a rinsing solution, and paddle development is performed with a developing machine (D-SPIN636 type manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a pattern of a polyimide precursor. It was This wafer was heated at 20 ° C. in a nitrogen atmosphere by using a temperature rising program type curing furnace (VF-2000 type, manufactured by Koyo Lindbergh Co., Ltd.).
Heat treatment was performed at 0 ° C. for 1 hour and 350 ° C. for 3 hours to obtain a polyimide pattern having a film thickness of 25 μm. In the obtained polyimide pattern, 20 μm square via holes were resolved.

A pin having a diameter of 2 mm was adhered on the polyimide film of this wafer using an epoxy adhesive (Showa Polymer Co., Ltd., Araldite Standard), and this was tested by a tensile tester (Quad Group Co., Sebastian 5 type).
When a peeling test was conducted by using, the epoxy resin was broken and the peeling stress was measured to be 8 kg / mm ² or more. The upper wafer was left in a pressure cooker at 133 ° C., 2 kg / mm ² , 100% RH for 100 hours, dried at 60 ° C. for 20 minutes, and then peeled off in the same manner as above. ,
The peeling stress was kept at 6 kg / mm ^2, and it was found that the adhesive had sufficient water resistance.

In addition to the above wafer, WS-40
Is similarly applied and dried to expose the coating film on the entire surface, and then heat-treated under the same condition as it is without development to obtain a polyimide coating film, which is a dicing saw (manufactured by DISCO, DAD-2H16T). 3 mm width using a mold, and peeling from the wafer with 20% hydrofluoric acid to make a polyimide tape, measuring instrument (manufactured by Toyo Baldwin, TENSILON, UTM-II).
-20 type) was used to measure the mechanical properties,
The tensile strength was 14 kg / mm ² and the elongation was 73%.

The same polyimide coating film was applied on a silicon wafer in a pressure cooker at 133 ° C. for 2 k.
After being left under conditions of g / mm ² and 100% RH for 100 hours, it was dried at 60 ° C. for 20 minutes, and then mechanical properties were measured in the same manner. Tensile strength was 13 kg / mm.
² , the elongation was kept at 55%, which was a sufficient value, and it was found that the water resistance of mechanical properties was also sufficient.

(Examples 2 to 4, Comparative Examples 1 and 2) Amounts of PMDA, HEMA, γ-BL and Py charged in the container A, and PMDA, RtOH, γ-BL and P charged in the container B.
A polymer powder was obtained in the same manner as in Example 1 except that the amount of y was changed. However, in Examples 3 and 4 and Comparative Example 1, the order of addition was changed such that 250 ml of dimethylacetamide was added immediately after the addition of 4,4′diaminodiphenyl ether. Table 1 shows the amounts of raw materials, the name of the obtained polymer and the viscosity of a 30 wt% solution in N-methylpyrrolidone. Then, a photosensitive composition was prepared by using the same amount as in Example 1 except for the amount of N-methylpyrrolidone in the same amount. The name of the composition, the amount of N-methylpyrrolidone and the viscosity of the composition are shown in Table 1.

Table 2 shows the residual stress values of the polyimide coating film obtained from the obtained photosensitive composition. Further, a coating film having a thickness of 40 μm was formed from this composition in the same manner as in Example 1. From this coating film, a polyimide pattern and a tape were obtained in the same manner as in Example 1. The film thickness of the obtained pattern and the size (resolution) of the smallest via hole that was resolved, and the peeling stress before and after the pressure cooker treatment (PCT), the pressure cooker treatment (PCT)
The front and rear mechanical properties were measured in the same manner as in Example 1, and the results are shown in Table 2 together with the name of the varnish.

[0070]

[Table 1]

[0071]

[Table 2]

(Comparative Example 3) 87.2 g of pyromellitic dianhydride, 62.4 g of 2-methacryloyloxyethyl alcohol, 14.7 g of ethyl alcohol and 320 m of γ-butyrolactone were placed in a 2 liter separable flask.
1 l, and while stirring under ice cooling, 64.2 g of pyridine
Was added. After the completion of heat generation, the mixture was left to cool to room temperature for 16 hours and then a solution of 166 g of dicyclohexylcarbodiimide in 120 ml of γ-butyrolactone was added for 40 minutes while stirring under ice cooling, followed by 74.5 g of 4,4′-diaminodiphenyl ether. Γ-butyrolactone 1
What was suspended in 50 ml was stirred under ice cooling while stirring 60
Added in minutes.

After stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour, 250 ml of dimethylacetamide and 400 ml of tetrahydrofuran were added, and the precipitate was removed by filtration to obtain a reaction liquid of 15
After adding to liter of ethyl alcohol and filtering off the formed precipitate, it was vacuum dried to obtain a polymer powder. This is T
It is called -40. In N-methylpyrrolidone of T-40,
The viscosity of the 30 wt% solution was 23.1 ps.

50 g of T-40, 2 g of 1-phenyl-3-ethoxypropanetrione-2- (o-benzoyl) oxime, 0.1 g of Michler's ketone, 3 g of diethylene glycol diacrylate, 1 g of 2-mercaptobenzothiazole, N-phenyldiethanolamine. 2g, 3
-Methacryloxypropyldimethoxysilane 0.5 g,
A photosensitive composition was prepared by dissolving 0.02 g of 2-nitroso-1-naphthol in 84.4 g of N-methylpyrrolidone. This composition is designated as WT-40. The viscosity of WT-40 was 131 ps.

The residual stress of the polyimide coating film obtained from WT-40 was 3.4 kg / mm ² . A polyimide pattern having a film thickness of 23 μm was obtained from WT-40 in the same manner as in Example 1. In the resulting polyimide pattern,
A 20 μm square via hole was resolved. A peeling test was conducted using this wafer in the same manner as in Example 1. As a result, the epoxy resin broke and the peeling stress was determined to be 8 kg / mm ² or more. The above wafer was placed in a pressure cooker at 133 ° C. and 2 kg / m.
After leaving for 100 hours under the condition of m ² and 100% RH,
When it was dried at 60 ° C. for 20 minutes and then subjected to a peeling test as described above, the peeling stress was 6 kg /
It was found that the water resistance of the adhesive strength was sufficient while holding mm ² .

Separately from the above wafer, the mechanical properties of WT-40 were measured in the same manner as in Example 1. The tensile strength was 14 kg / mm ² and the elongation was 72%.
Same as this polyimide coating film on a silicon wafer in a pressure cooker at 133 ° C., 2 kg / mm ² ,
Leave at 100% RH for 100 hours, then 60 ℃
It was dried at 20 ° C. for 20 minutes, and the mechanical properties were measured in the same manner. Tensile strength was 12 kg / mm ² , elongation was 57
%, A sufficient value was maintained, and it was found that the mechanical properties had sufficient water resistance.

Comparative Examples 4 to 10 Polymer powders were obtained in the same manner as in Example 1 except that the amounts of 2-methacryloyloxyethyl alcohol (HEMA) and ethyl alcohol (EtOH) were changed. However, Comparative Examples 5, 6, 7, and 1
Regarding 0, the order of addition was changed by adding 250 ml of dimethylacetamide immediately after adding 4,4'diaminodiphenyl ether. Amount of raw material, name of polymer obtained and 30 wt% in N-methylpyrrolidone
The viscosities of the% solutions are given in Table 1. Then, a photosensitive composition was prepared by using the same amount as in Example 1 except for the amount of N-methylpyrrolidone in the same amount. The name of the composition, the amount of N-methylpyrrolidone and the viscosity of the composition are listed in Table 3.

The residual stress of the polyimide coating film obtained from the obtained photosensitive composition is shown in Table 4. Further, a coating film having a thickness of 40 μm was formed from this composition in the same manner as in Example 1. From this coating film, a polyimide pattern and a tape were obtained in the same manner as in Example 1. The thickness of the obtained pattern and the size of the smallest via hole (resolution) that was resolved,
The peeling stress before and after the pressure cooker treatment (PCT) and the mechanical properties before and after the pressure cooker treatment (PCT) were measured in the same manner as in Example 1, and the results are shown in Table 4 together with the name of the varnish.

[0079]

[Table 3]

[0080]

[Table 4]

(Examples 5 to 7 and Comparative Examples 11 to 12) The same as Example 1 except that T-0 and T-100 were mixed and used as a polymer and the amount of N-methylpyrrolidone was the same. The photosensitive composition was prepared using only the amount. T-0
Table 5 shows the amounts of T and T-100 used, the name of the composition, the amount of N-methylpyrrolidone, and the viscosity of the composition.

Table 6 shows the residual stress of the polyimide coating film obtained from the obtained photosensitive composition. Further, a coating film having a thickness of 40 μm was formed from this composition in the same manner as in Example 1. From this coating film, a polyimide pattern and a tape were obtained in the same manner as in Example 1. The thickness of the obtained pattern and the size of the smallest via hole (resolution) that was resolved,
The peel stress before and after the pressure cooker treatment (PCT) and the mechanical properties before and after the pressure cooker treatment (PCT) were measured in the same manner as in Example 1, and the results are shown in Table 6 together with the name of the varnish.

[0083]

[Table 5]

[0084]

[Table 6]

(Example 8) 58.8 g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) was placed in a 2-liter separable flask.
52.0 g of 1-acryloyloxy-2-propyl alcohol (hereinafter referred to as 2HPA), γ-BL320m
1 l, and while stirring under ice cooling, 64.2 g of pyridine
Was added. After the fever is completed, leave it at room temperature for 2 hours, then PM
43.2 g of DA and 18.4 g of EtOH were further added.

After the completion of heat generation, the mixture was allowed to cool to room temperature and left for 16 hours, then dicyclohexylcarbodiimide was added in the same manner as in Example 1, followed by 37.3 g of 4,4'diaminodiphenyl ether and 20.1 g of metaphenylenediamine.
Was added to 150 ml of γ-butyrolactone, and Suspension II was added in the same manner as in Example 1 and then treated in the same manner as in Example 1 to obtain a polymer powder. This is referred to as D-50. D-50
The viscosity of a 30 wt% solution of N-methylpyrrolidone is 1
It was 9.3 ps.

Comparative Example 13 PMDA and EtOH were BT
A polymer powder was obtained in the same manner as in Example 8 except that DA and 2HPA were added at the same time. This is referred to as C-50. C
A similar viscosity of -50 was 20.3 ps.

(Comparative Example 14) 117.6 g of BTDA,
2 HPA (104 g) and metaphenylenediamine (40 g).
A polymer powder was obtained in the same manner as in Example 8 except that 2 g was used and PMDA, EtOH, and diaminodiphenyl ether were not used. This is referred to as D-0. The viscosity of a 30 wt% solution of D-0 in N-methylpyrrolidone was 13.2 ps.

(Examples 8 to 11, Comparative Examples 13 and 14) Each polymer shown in Table 7, 3 g of benzophenone and 4,4'-
Bis (diethylamino) benzophenone 0.2 g, benzyl dimethyl ketal 2.5 g, pentaerythritol triacrylate 4 g, 1-phenyl-5-mercaptotetrazole 2 g, γ-aminopropyltrimethoxysilane 0.5 g, ethylenediaminetetraacetic acid 0.003 g and N-methylpyrrolidone (NMP) in the amounts listed in Table 7
To prepare a photosensitive composition. Table 7 shows the name and viscosity of each composition.

Table 8 shows the residual stress values of the polyimide coating films obtained from the above compositions. Also, this composition was spin-coated on a silicon wafer, and then applied on a hot plate for 10 minutes.
It was dried at 0 ° C. for 240 seconds to form a coating film having a thickness of 15 μm.
A reduced projection exposure device (stepper manufactured by Nikon Corporation,
The test pattern was exposed for 1.4 seconds using a NSR1505G2A type, 500 W ultra-high pressure mercury lamp.

This wafer was treated with N-methylpyrrolidone / xylene / water [12/12/1 (vol / vol / vo
1)] was used as a developing solution and xylene / isopropyl alcohol [50/50 (vol / vol)] was used as a rinsing solution, and spray development was carried out in the same apparatus as in Example 1 to obtain a polyimide precursor pattern. This wafer was used in Example 1.
In the same equipment as above, under nitrogen atmosphere, 140 ° C for 1 hour, 350
A heat treatment was performed at 1 ° C. for 1 hour to obtain a polyimide pattern.

A polyimide tape was obtained in the same manner as in Example 1. The same evaluations as in Example 1 were performed on these samples. The film thickness of the obtained pattern and the size (resolution) of the smallest via hole that was resolved, and the peeling stress before and after the pressure cooker treatment (PCT), the pressure cooker treatment (PCT)
The front and rear mechanical properties were measured in the same manner as in Example 1, and the results are shown in Table 8 together with the name of the varnish.

[0093]

[Table 7]

[0094]

[Table 8]

(Example 12) BPDA (70.6 g), 2-acryloyloxyethyl alcohol (55.7 g) and pyridine (64.2 g) were added to a 2-liter parable flask by γ.
-Butyrolactone was added to 320 ml and stirred at 40 ° C for 2 hours to obtain a uniform solution. Then 47.0 g of BPDA
And 18.6 g of allyl alcohol were added, and the mixture was stirred at 40 ° C. for 2 hours. Dicyclohexyl was then added as in Example 1, then paraphenylenediamine 38.
What added 7 g to 250 ml of N, N- dimethylacetamide was added over 40 minutes, stirring under ice-cooling.

A polymer powder was obtained in the same manner as in Example 1 below. This is referred to as E-40. The viscosity of a 30 wt% solution of E-40 in N-methylpyrrolidone is 18.0 ps.
Met. A photosensitive composition was prepared in the same manner as in Example 8 except that 50 g of E-40 was used instead of D-50.
This composition is designated as YE-40. The viscosity of YE-40 was 35.1 ps.

When the same evaluation as in Example 5 was carried out using YE-40, the obtained polyimide pattern was 8.
1 μm, resolution 8 μm, peeling stress PCT
6 kg / mm ² before, 5 kg / mm ² after PCT, mechanical strength is 16 kg / mm ² before PCT, 14 k after PCT
g / mm ² , elongation is 45% before PCT, 35 after PCT
%Met. The residual stress of the polyimide coating film obtained from YE-40 was 2.3 kg / mm ² .

(Comparative Example 15) 11,3 g of 3,3 ', 4,4'-biphenylcitracarboxylic acid dianhydride, 55.7 g of 2-acryloyloxyethyl alcohol, and 18 of allyl alcohol were placed in a 2-liter parable flask. .6
g, 64.2 g of pyridine, 320 m of γ-butyrolactone
The solution was added to the mixture and stirred at 40 ° C. for 2 hours to obtain a uniform solution. Then add dicyclohexyl as in Example 1,
Then, 38.7 g of paraphenylenediamine added to 250 ml of N, N-dimethylacetamide was added over 40 minutes while stirring under ice cooling.

A polymer powder was obtained in the same manner as in Example 1 below. This is called U-40. The viscosity of a 30 wt% solution of U-40 in N-methylpyrrolidone is 18.0 ps.
Met. A photosensitive composition was prepared in the same manner as in Example 8 except that 50 g of U-40 was used instead of D-50.
This composition is designated as YU-40. The viscosity of YU-40 was 36.5 ps. When the same evaluation as in Example 5 was performed using YU-40, the obtained polyimide pattern was 8.0 μm, the resolution was 8 μm, the peeling stress was 6 kg / mm ² before PCT, and 5 kg / after PCT. m
m ² , mechanical strength before PCT is 16 kg / mm ² , PCT
14 kg / mm ² after, elongation is 35% before PCT, PC
It was 25% after T. The residual stress of the polyimide coating film obtained from YU-40 was 3.7 kg / mm ² .

Comparative Example 16 A polymer powder was obtained in the same manner as in Example 9 except that 92.8 g of 2-acryloyloxyethyl alcohol was used and no allyl alcohol was used. This is called U-0. The viscosity of a 30 wt% solution of U-0 in N-methylpyrrolidone was 20.3 ps.
A photosensitive composition was prepared in the same manner as in Example 9 except that U-0 was used instead of U-40. This composition is YU-
Called 0. The viscosity of YU-0 was 40.8 ps.

When the same evaluation as in Example 5 was performed using YU-0, the obtained polyimide pattern was 7.3.
μm, resolution is 15 μm, peeling stress is PCT
5 kg / mm ² before, 1 kg / mm ² after PCT, mechanical strength is 16 kg / mm ² before PCT, 13 k after PCT
g / mm ² , elongation is 20% before PCT and 5% after PCT
Met. The residual stress of the polyimide coating film obtained from YU-0 was 4.2 kg / mm ² .

Comparative Example 17 A polymer was synthesized in the same manner as in Example 7 except that 6.4 g of allyl alcohol was used instead of 92.8 g of 2-acryloyloxyethyl alcohol. It was solidified into a gel and a precipitate could not be obtained with ethyl alcohol, and no polymer powder was obtained.

Reference Example 1 T-0, T-15, T-2
5, T-40, T-67, T-80, and T-100 were each dissolved in N-methylpyrrolidone at a concentration of 30 wt% to prepare a solution. Each was spin-coated on a silicon wafer and dried in an oven at 80 ° C. for 40 minutes to obtain a polyimide precursor film. After peeling off this film, it was put into a density gradient tube made of carbon tetrachloride / xylene system, and the density of each film was measured. The measured value (unit: g / cm ³ ) is 1.328 for T-0,
T-15 is 1.331, T-25 is 1.333, T-4
0 was 1.337, T-67 was 1.344, T-80 was 1.348, and T-100 was 1.355.

Similarly, S-15, S-25, S-4
The densities of 0, S-67, and S-80 were measured and found to be S-
15 is 1.330, S-25 is 1.347, S-40 is 1.346, S-67 is 1.348, S-80 is 1.3.
It was 51.

(Reference Example 2) 1H NMR spectra of S-40 and T-40 were measured. 8.0-8.1
The S vector of the proton bonded to the benzene ring of ppm pyromellitic acid is S with the ester group bonded symmetrically.
While almost one is observed at -40, the spectrum of the same site in T-40 in which the ester group has a bilaterally symmetric component and a bilaterally asymmetric component is mixed has a complicated pattern that can be approximated to a triplet type. This shows that the structures of the two are different.

[0106]

EFFECT OF THE INVENTION When the polyimide precursor and the photosensitive composition of the present invention are used, higher elongation, higher water resistance and lower residual than the polyimide coating film obtained from the conventionally used photosensitive polyimide composition. A stressed polyimide coating can be obtained with higher resolution. It provides new and useful materials for the production of electric and electronic materials such as semiconductor devices and multilayer wiring boards.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03F 7/038 504 H05K 1/03 7011-4E

Claims (5)

[Claims] 1. An aromatic tetracarboxylic acid diester represented by the following formula [I] is added in an amount of 25 to 75 mol%: 25-75 mol% of an aromatic tetracarboxylic acid diester represented by the following formula [II]: (In the formula, R ₂ is a methyl group, an ethyl group, an n-propyl group,
It is one or more groups selected from an isopropyl group or an allyl group, and is the same as the formula [I] for others. )
An aromatic tetracarboxylic acid diester consisting of and and the following formula [III] A polyimide precursor having a repeating unit represented by the following formula [IV], which is obtained by polycondensing [Chemical 4] 2. A photosensitive composition comprising (A) the polyimide precursor according to claim 1, (B) a photopolymerization initiator, and (C) a solvent. 3. (A) a polyimide precursor having a repeating unit represented by the following formula [V], (B) a following formula [VI]
A polyimide precursor having a repeating unit represented by
(C) A photopolymerization initiator, and (D) A solvent is included, and the weight ratio of (A) and (B) contained is 0.75 to 0.25.
A photosensitive composition in the range of 0.25 to 0.75. [Chemical 5] (In the formula, R ₁ is the same as the formula [I], and the others are the same as the formula [IV].) (In the formula, R ₂ is the same as the formula [II], and the others are the same as the formula [IV].) 4. The polyimide precursor according to claim 1, wherein R ₁ is a polyimide precursor which is a group represented by the formula [VII]. [Chemical 7] (In the formula, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group.) 5. The photosensitive composition according to claim 2 or 3, wherein (A) R ₁ is a polyimide precursor which is a group represented by the formula [VII]. [Chemical 8] (In the formula, R ₃ and R ₄ are each independently a hydrogen atom or a methyl group.)