JPH07181689A - Method for forming patterned polyimide coating film on substrate - Google Patents

Abstract

PURPOSE:To form a patterned polyimide coating film on a substrate. CONSTITUTION:A photocrosslinkable polymer compsn. obtd. by modifying a precursor of polyimide with a compd. having a photosensitive group is applied on a substrate to form a coating film, this film is imagewise exposed and developed and the film at the hardened exposed part is converted into a polyimide resin coating film by heating to form a patterned polyimide resin coating film. In this method, a solvent prepd. by adding 2-methyl-2-propanol to a good solvent or a mixed solvent consisting of the good solvent and a bad solvent is used as a developer in the developing process.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a protective film, an insulating film, an interlayer insulating film, a passivation film, a recording element, a plate making in the semiconductor manufacturing industry, microelectronics industry, photolithography, imaging field including hologram and laser recording. It relates to a method for producing a material or the like from a photocrosslinkable polymer composition obtained by modifying a polyimide precursor with a compound having a photosensitive group. More specifically,
It relates to a method for obtaining a predetermined pattern on a substrate by imagewise exposing a coating film obtained by applying the above-mentioned photocrosslinkable polymer composition onto the substrate and removing the unexposed portion.

[0002]

2. Description of the Related Art In recent years, in the semiconductor manufacturing industry and the microelectronics industry, a resin having a heterocyclic group in the molecular structure such as a polyimide resin having high heat resistance and excellent electrical and mechanical properties is an insulating film for integrated devices. It has also been used as a passivation film and as an interlayer insulating film of a high-density mounting substrate.

When an insulating film is formed of this resin, it may be necessary to form a circuit between a metal or a conductor which is a lower layer of the insulating film and another electronic element or device. In addition, when forming an interlayer insulating film with this resin, it is often necessary to provide a conductive path between the upper and lower layers to establish conduction. Therefore, a via hole is provided in the resin film and the upper and lower layers are connected via this via hole. It will be connected by a conductor. Then, such an insulating film or an interlayer insulating film is formed using a photosensitive polyimide precursor composition having excellent processability, and the insulating film or the interlayer insulating film has a desired patterned shape by a pattern forming method. Things have come to be done.

The pattern forming method using the above-mentioned photosensitive polyimide precursor composition is performed, for example, in the following steps. Application: A polyimide precursor composition varnish is applied on a substrate. Baking: The solvent in the above composition varnish is evaporated to form a coating film. Exposure: Exposure is performed using an ultraviolet exposure device and a predetermined photomask. Development: The unexposed area is dissolved and removed with a developing solution and washed with a rinse solution to obtain a pattern. Cure: It is converted into a polyimide resin by heating.

Further, in the fields of photolithography and imaging, optical recording materials such as plate-making materials obtained by using a photosensitive polyimide precursor composition have been attracting attention due to their excellent properties such as mechanical strength. Then, when a coating film of such a photosensitive polyimide precursor is imagewise exposed and the unexposed portion is dissolved and removed by a developing solution, examples of the developing solution include N-methyl-2-pyrrolidone, γ-butyrolactone,
A mixed solution of xylene, alcohols and water is used.

[0006]

However, when forming a polyimide pattern using a polyimide precursor,
Excellent in resolution and residual film characteristics. Prevents the generation of residues without fail, and considers the cost of development and rinsing liquid consumption. Good solvents and aromatics for polyimide precursors such as N-methyl-2-pyrrolidone and γ-butyrolactone. hydrocarbon,
Mixed solvents with poor solvents such as alcohols and esters are widely used as developers and rinses. At the same time, various standards and regulations that consider environmental protection and effects on the human body have been expanded, and as a result, aromatic hydrocarbon compounds have recently become subject to regulation and cannot be used as the developer or rinse solution as described above. The case is expected.

[0007] Therefore, as a poor solvent which replaces the aromatic hydrocarbon compound, it exhibits substantially the same resolution and developing ability as residual film characteristics as when an aromatic hydrocarbon compound is used, and in a series of steps of forming a polyimide pattern. There is a demand for a solvent that can be used as a developing solution under the same process control (for example, developing time) as when an aromatic hydrocarbon compound is used. Here, it is possible to obtain equivalent properties without being inferior or superior to aromatic hydrocarbon compounds which are widely used from the cost advantage, by starting by applying the above-mentioned polyimide precursor composition. It is very important in that the productivity of the whole process can be maintained without changing the production line that carries out a series of processes for curing and forming a pattern made of a polyimide resin.

In the case of obtaining a polyimide film patterned by the above method so that the resolution is excellent and the unexposed portion does not remain, the development time becomes extremely long, and the process control and the productivity are reduced. It was not preferable. In order to solve this drawback, it has been attempted to shorten the baking time of the above-mentioned composition varnish, or to shorten the developing time by lowering the baking temperature. Another problem arises in that the unexposed parts are degraded and cannot be completely removed, and there is also an undercut in which the bottom of the film is shaved. Therefore, there is a demand for elucidation of a developing method that does not cause such a problem.

[0009]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems of the prior art, and as a result, they are obtained by applying a photosensitive polyimide precursor composition onto a substrate. The present invention has been completed by developing a developing solution capable of performing imagewise exposure on a coating film, shortening the development time when developing the same, and simultaneously forming a pattern with a high resolution without leaving an unexposed portion. That is, the present invention is a photocrosslinkable polymer composition obtained by modifying a polyimide precursor derived from an aromatic tetracarboxylic acid or its mono- or diacid anhydride and an aromatic diamine with a compound having a photosensitive group. Was prepared and applied on a substrate to form a film, and the film was imagewise exposed to cure the exposed part, and the unexposed part was dissolved and removed with a developer to remove the remaining exposed part. In a method of forming a patterned polyimide resin coating on a substrate by heating the coating to convert it to a polyimide resin, 2-methyl-2-propanol as a developer is used in an amount of 10% by weight or more and 80% by weight or less. It is characterized by using a mixed solvent containing it.

By using the above-described developing / rinsing solution according to the present invention, the developing / rinsing solution containing an aromatic hydrocarbon compound which has been conventionally used has a developing ability equal to or higher than that of the conventional developing / rinsing solution. There is no unexposed portion remaining in terms of film rate, and there is no need to change process control when an aromatic hydrocarbon compound is used, that is, the equipment for pattern formation is not changed.

The photocrosslinkable polymer composition used in the present invention has the following general formula (I):

[Chemical 1] Where R ¹ contains at least 2 carbon atoms
A valent group, R ² contains at least 2 carbon atoms 2
A valent group, R ³ , R ⁴ , R ⁵ and R ⁶ are all monovalent aliphatic groups having 1 to 11 carbon atoms, monovalent cyclic aliphatic groups,
A monovalent group in which an aromatic group and an aliphatic group are bonded, a group in which these groups are substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group or a hydrogen atom, These four Rs may be the same or different,

Specific examples of R ¹ include, for example,

[Chemical 2]

Specific examples of R ² are:

[Chemical 3] n represents a repeating unit of one or more polyamic acid) or a polyimide precursor derived from an aromatic diamine and an aromatic tetracarboxylic acid or an acid monoanhydride or an acid dianhydride, that is, a polyamic acid. It is obtained by modification with a compound having a photosensitive group.

Specific examples of R ³ , R ⁴ , R ⁵ and R ⁶ include CH ₃ —, CH ₃ CH ₂ —, CH ₃ (CH ₂ ) ₂ —, CH
_{3 (CH 2) 3 -,} CH 3 (CH 2) 5 -, CH 3 (CH 2) 11 -, C
_{H 3 (CH 2) 13 -} , CH 3 (CH 2) 15 -, CH 3 (CH 2)
_{17 -, CH 3 (CH 2} ) 19 -, CH 3 (CH 2) 21 -, CF 3 (C
H ₂ ) ₁₅ − and the like.

Specific examples of the aromatic tetracarboxylic dianhydride used in the production of the above polyamic acid include pyromellitic dianhydride (PMDA), 3,4,3 ', 4'.
-Benzophenone tetracarboxylic acid dianhydride (BTD
A) 1,4,5,5-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,
4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride Thing, screw (3,4
-Dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride and perylene-3,4,9,10-tetracarboxylic dianhydride, diphenylthioether tetracarboxylic dianhydride , And diphenylsulfone tetracarboxylic dianhydride, and mixtures thereof.

Specific examples of the other aromatic diamine used in the production of the above polyamic acid include m- or p-phenylenediamine, 4,4'- or 3,3'-diaminobiphenyl, 4,4'- or 3,3'-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3 3,3'-thiodianiline, bis- (4-aminophenyl) bis (trifluoromethyl) methane, 4,4 '
-Diaminobenzophenone, 1,5-diaminonaphthalene, bis- (4-aminophenyl) -dimethylsilane,
Bis- (4-aminophenyl) -diethylsilane, bis- (4-aminophenyl) -diphenylsilane, bis-
(4-Aminophenyloxy) -dimethylsilane, bis-
(4-Aminophenyl) -ethylphosphine oxide, N- [bis- (4-aminophenyl)]-N-methylamine, N- [bis- (4-aminophenyl)]-N
-Phenylamine, 4,4'-methylenebis- (o-chloroaniline), 4,4'-methylenebis- (3-methylaniline), 4,4'-methylenebis- (2-ethylanilene), 4,4'- Methylenebis- (2-methoxyaniline), 5,5'-methylenebis- (2-aminophenol), 4,4'-methylenebis- (2-methylaniline), 4,4'-oxybis- (2-methoxyaniline) 4,4'-oxybis- (2-chloroaniline), 5,5-oxybis- (2-aminophenol), 4,4'-thiobis- (2-methylaniline),
4,4'-thiobis- (2-methoxyaniline), 4,
4'-thiobis- (2-chloroaniline), 4,4'-
Sulfonylbis- (2-methylaniline), 4,4'-
Sulfonylbis- (2-ethoxyaniline), 4,4 '
-Sulfonylbis- (2-chloroaniline), 5,5 '
-Sulfonylbis- (2-aminophenol), 3,
3'-dimethyl-4,4'-diaminobenzophenone,
3,3'-dimethoxy-4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 4,4'-oxydianiline, 4,4'-isopropylidenedianiline, 3 , 3'-dichlorobenzidine,
3,3'-Dimethylpentidine, 3,3'-dimethoxybenzidine, 3,3'-dicarboxybenzidine, diaminotoluene, 4,4'-methylenebis- (3-carboxyaniline) and various esters thereof Kind, 5-
Amino-1- (4-aminophenyl) -1,3,3-trimethylindane and 6-amino-1- (4'-aminophenol) -1,3,3-trimethylindane, and mixtures thereof. .

The modification of the polyimide precursor with a compound having a photosensitive group is carried out by mixing a compound having a photosensitive group into the polyimide precursor or by introducing a photosensitive group into a side chain of the polyimide precursor. Be seen. The compound having a photosensitive group to be mixed with the polyimide precursor is a compound known as a photosensitive monomer, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N, Examples thereof include (meth) acrylates such as N-dimethylaminoethyl methacrylate, mercapto compounds such as thioglycolic acid, maleimides such as phenylsulfonylmaleimide, and isocyanates such as ethylmethacrylate methacrylate. These photosensitive monomers are mixed in the polyimide precursor in an amount of 0.01% by weight to 100% by weight.

As the photosensitive group introduced into the side chain of the polyimide precursor, a group having a carbon-carbon double bond is typical, and vinyl group, allyl group, acryl group, methacryl group, cinnamyl group, maleimide. Examples thereof include groups having a group, but are not limited thereto. Then, these photosensitive groups are introduced into the side chain of the polyimide precursor through a chemical bond such as an ester bond, an ether bond, an amide bond, a urethane bond, and a urea bond, or directly into an aromatic nucleus. To impart photosensitivity to the polyimide precursor. The photosensitive polyimide precursor of the present invention is produced by polycondensing the above-mentioned tetracarboxylic dianhydride and aromatic diamine in an organic polar solvent solution with stirring.

Examples of the organic polar solvent which can be used in this polycondensation reaction include N, N-dimethylformamide, N,
N, -diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methylcaprolactam,
Dimethyl sulfoxide, N-methyl-2-pyrrolidone,
Examples thereof include dimethyl sulfone, hexamethylphosphoamide, tetramethyl sulfone, N-acetyl-2-pyrrolidone and the like. These solvents may be used alone or in combination of two or more. The photocrosslinkable polymer composition thus prepared is preferably dissolved in a solvent and diluted for application to a substrate to reduce its viscosity. As the solvent used at this time, N, N'-dimethylformamide, N, N'-dimethylacetamide, γ-
Examples thereof include butyrolactone and N-methylpyrrolidone, but are not limited thereto.

The photocrosslinkable polymer composition diluted with a solvent is then applied onto the substrate. As a method of applying this substrate, a spin coater, a roll coater, etc. are typical, and as a substrate, a silicon wafer, gallium, arsenic wafer, glass, ceramics, a copper plate, or a substrate having elements formed on these substrates is typical. Take as an example. The coating film of the photocrosslinkable polymer composition thus applied on the substrate is then subjected to a drying step. In this drying step, baking with a circulating oven, a hot plate, or an infrared heater is generally used, but the baking is not limited to these. The baking temperature is preferably 50 to 130 ° C. The drying time varies depending on the film thickness, but is 3 minutes to 15 hours. The film thickness after drying is preferably 1 to 50 μm, but is not limited to this film thickness.

The coating of the photocrosslinkable polymer composition thus applied to the substrate and dried is then subjected to imagewise exposure. As an exposure method, a method of irradiating ultraviolet rays through a photomask by an ultraviolet exposure device used in a usual photoresist process is used. Although the exposure time varies depending on the photocrosslinkable polymer, the kind and amount of the additive, the light intensity of the exposure machine, etc., the optimum time is generally set to 1 second to 1 hour. A heat treatment may be further performed after the exposure, but the heat treatment temperature at that time is 40 to 150 ° C., and the time is 1
Seconds to 1 hour are good. As a heating method at that time, a circulation oven, a hot plate, an infrared heater, or the like is used as in the baking method.

Then, the coating film after the imagewise exposure is subjected to a developing step. The development is carried out by removing the portion which is cured by the imagewise exposure and becomes insoluble in the solvent on the substrate, and the unexposed portion which is soluble in the solvent is dissolved and removed by the solvent. In the present invention, the solvent used for this development, that is, the developing solution is a good solvent for the polymer alone or a mixed solvent in which a good solvent and a poor solvent are combined, whereas 2-methyl-2- is used as the poor solvent. It is characterized by using the one to which propanol is added. 2-methyl-2-
By adding propanol, the rate of developing the polyimide precursor is increased, and it is possible to form a pattern with less unexposed areas and improved resolution.

As the good solvent, N, N'-dimethylformamide, N, N'-dimethylacetamide, cyclopentanone, cyclohexanone, N-methylpyrrolidone, γ
-Butyrolactone, dimethyl sulfoxide, hexamethylphosphoric triamide, acetonitrile, tetrahydrofuran and the like can be mentioned, but not limited to these as long as the polymer can be dissolved therein. These may be used alone or as a mixture of two or more kinds. Examples of the poor solvent include methanol, ethanol, isopropyl alcohol, water, toluene, xylene, ethylbenzene, isopropylbenzene, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, n-propyl alcohol, isobutyl alcohol, and the like. Not limited to. Further, these may be used alone or as a mixture of two or more kinds.

The mixed solvent of the developing solution used in the present invention is a mixture of 2-methyl-2-propanol as a poor solvent and a good solvent alone, or a mixed solution of a good solvent and a poor solvent. In this case, the above-mentioned solvent is selected and used as a good solvent, but γ-butyrolactone is preferable in consideration of pattern processability, development rate and the like. 2-Methyl-2-propanol is 10 to 80 in the mixed solvent.
Although it is used in an amount in the range of wt%, the optimum amount may be selected depending on the kind of the polymer, the kind of the additive, or the mixing ratio of the good solvent and the poor solvent. In the present invention, by using such a developing solution, the developing speed can be increased, and a patterned polyimide resin film having a high resolution can be stably formed. However, the 2-methyl-2-propanol used has a melting point of about 25.
Since it has a freezing point as high as ℃, even when used as a mixed solvent, the coagulation of 2-methyl-2-propanol at low temperature,
There is a possibility of separation. Therefore, in order to prevent coagulation and separation of 2-methyl-2-propanol, it is desirable to mix any one of n-propanol, isopropanol, n-butanol, isobutanol or a combination thereof in the range of 5 to 20% by weight. If it is outside the range of 5 to 20% by weight, the pattern workability inherent in the developing solution will be impaired.

The developing method is spray development, dip development,
Examples include ultrasonic development and paddle development. The developed and patterned polyimide precursor coating is immediately rinsed with a rinse to remove the developer and dissolved polyimide precursor. Examples of the rinse solution include acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, toluene, xylene, ethylbenzene, water, 1-methoxy-2-propanol, and the like, but are not limited thereto. Not done. Further, these may be used alone or as a mixture of two or more kinds.

In the present invention, a mixed solvent containing 5 to 40% by weight of cyclohexanone, which is a good solvent, is used as the rinsing liquid, and when the rinsing liquid containing less than 5% by weight of cyclohexanone is used for cleaning, a pattern edge is formed. There is a problem that peeling occurs between the substrate and the formed polyimide resin coating in a portion, and when rinsing (washing) with a mixed solvent containing 40% by weight or more of a good solvent, cyclohexanone, the polyimide resin coating is There is a problem that the cross-section of the pattern formed in 1 is distorted. As another solvent to be mixed with cyclohexanone as a rinse solution, it is used in combination with a developer in the developing step, and the solubility parameter of the developer (for example, using the cohesive energy density δ represented by the SMALL equation below) is used. It is desired to exhibit a solubility similar to that of, in particular, 2-methyl-2-propanol, and it is therefore preferred to use isobutanol.

[0027]

By patterning a photocrosslinkable polymer composition using the method of the present invention, it has been widely used in the past due to its cost efficiency. It can be used in the polyimide pattern forming method as a developing solution of a mixture with a good solvent instead of a poor solvent of an aromatic hydrocarbon, at which time the resolution, the developing rate and the crack, swelling, or the resolution higher than that of the aromatic hydrocarbon can be obtained. It is possible to form a polyimide-coated photosensitive polyimide precursor pattern which is free from peeling and has a reduced remaining film ratio in the unexposed area. Next, the present invention and its effects will be described by way of examples, but the present invention is not limitedly interpreted by these examples.

Preparation Example of Polyimide Precursor A mixture of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4'-oxydianiline in a weight ratio of N-methyl-2-pyrrolidone is used. After mixing with N-methyl-2-pyrrolidone so as to be 10% to 40%, the mixture was stirred at 25 ° C. to complete the polymerization to obtain a polyamic acid polymer. Here, the molar ratio of the diamine to the acid anhydride is in the range of 0.8 to 1.25, preferably 0.98. The obtained polyamic acid polymer was mixed with N-methyldiethanolamine dimethacrylate so that the molar ratio was in the range of 0.1 to 1.0, and the mixture was stirred at 25 ° C. Further, to the resulting mixture, 4,4 '-(diethylamine) benzophenone 0.5%, 2-mercaptobenzoxazole 2%,
2% of bis (2-ortho-chlorophenyl-4,5-diphenyl) imidazole was mixed in a weight ratio with respect to the polyamic acid polymer to obtain a photosensitive polyamic acid precursor solution.

Example 1 A solution of a photosensitive polyimide precursor obtained by using a spin coater was applied on a silicon wafer. The coating conditions are 2
It was 000 rpm and 30 seconds. Next, apply this coating to 85 ℃ 3
After that, baking was performed on a hot plate under the conditions of 120 ° C. for 3 minutes to obtain a polyimide precursor coating film having a thickness of about 20 μm. A photomask on which a line-and-space of 5 to 200 μm is printed is brought into close contact with this film, and a Canon P
It was exposed with an energy of 160 mJ / cm ² using a LA-501F exposure machine, using the I line of a 365 nm mercury lamp. After exposure, a polyimide precursor is prepared by using a developer containing 70% by weight of γ-butyrolactone and 30% by weight of 2-methyl-2-propanol, and a rinse solution containing 85% by weight of isobutanol and 15% by weight of cyclohexanone. The coating film was developed to obtain a pattern. The developing time at this time was 25 seconds, and the dissolution rate of the polyimide precursor in the unexposed portion with the developing solution was 18 mg / s. Also,
The ratio of the film thickness after development to the film thickness before development in the exposed portion, that is, the residual film ratio was 95%.

Example 2 A 20 μm thick polyimide precursor coating film was obtained in the same manner as in Example 1. The exposure energy after that is 160 mJ /
It was cm ² . Development is performed using a developing solution containing 50% by weight of N-methyl-2-pyrrolidone and 50% by weight of 2-methyl-2-propanol and a rinse solution containing 70% by weight of isobutanol and 30% by weight of cyclohexanone. The pattern was obtained. The developing time was 20 seconds, the dissolution rate of the unexposed area was 20 mg / s, and the residual film rate was 96%.

Example 3 A coating film having a thickness of 20 μm was obtained in the same manner as in Example 1, and 160 mJ
Exposure was carried out with an I-line of / cm ² . γ-butyrolactone is 6
4% by weight, 27% by weight of 2-methyl-2-propanol and 9% by weight of n-butanol, and a rinse solution of 90% by weight of isobutanol and 10% by weight of cyclohexanone are used for development. The pattern was obtained. Development time is 23 seconds, dissolution rate of unexposed area is 1
The residual film rate was 8.5 mg / s and 95%.

Comparative Examples 1 to 3 A coating film was formed in the same manner as in Examples, exposed with I-line having an energy of 160 mJ / cm ² , and then spray-developed with the following combination of a developing solution and a rinsing solution. And rinsed to form a polyimide precursor pattern. The development time, the dissolution rate of the unexposed area and the residual film rate in each case are as shown in Table 1.

Developer (wt%) Rinse (wt%) Comparative Example 1 γ-butyrolactone / 2-methyl-isobutanol / cyclo-2-propanol = 15/85 Hexanone = 85/15 2 γ-butyrolactone / 2-methyl -Isobutanol / cyclo-2-propanol = 90/10 hexanone = 70/30 3 γ-butyrolactone / 2-methyl-isobutanol / cyclo-2-propanol / n-butanol hexanone = 90/10 = 60/15/25 or more Table 1 summarizes the conditions and results of Examples and Comparative Examples.
Shown in.

[0034]

[Table 1]

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Claims (5)

[Claims] 1. A photocrosslinkable polymer composition obtained by modifying a polyimide precursor derived from an aromatic tetracarboxylic acid or its mono- or di-anhydride and an aromatic diamine with a compound having a photosensitive group. To form a film on the substrate, imagewise expose this film, dissolve and remove the unexposed part with a developing solution, and heat the remaining exposed part of the film to convert it to a polyimide resin. In the method for forming a patterned polyimide resin film on a substrate according to, a mixed solvent containing 2-methyl-2-propanol in an amount of 10% by weight or more and 80% by weight or less is used as a developer. The above method. 2. The method for forming a patterned polyimide resin film on a substrate according to claim 1, wherein the mixed solvent as the developing solution contains γ-butyrolactone. 3. The mixed solvent which is the developing solution is further n-
The patterned polyimide on a substrate according to claim 2, wherein any one of propanol, isopropanol, n-butanol, and isobutanol or a mixed solution thereof is contained in an amount of 5% by weight or more and 20% by weight or less. A method of forming a resin film. 4. A method of forming a patterned polyimide resin film on a substrate using the photosensitive polyimide precursor according to claim 1, wherein one of cyclohexanone, isobutanol, and n-butanol is used as a rinse liquid. Alternatively, a mixed solvent containing the mixed solution is used, and the above method. 5. The photosensitive polyimide precursor according to claim 4, wherein the rinsing liquid mixed solvent contains cyclohexanone in an amount of 5% by weight or more and 40% by weight or less. A method of forming a patterned polyimide resin coating.