JP2600487B2 - Photosensitive resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel positive photosensitive resin composition suitable for use in electric / electronic devices, particularly semiconductor devices.

[Prior Art] Polyimide resins have high mechanical strength, excellent electrical insulation properties, and excellent heat resistance. In particular, in recent years, its excellent electrical properties and heat resistance have been recognized, and its application to semiconductor devices that require the most reliability has been active.

With respect to the use of a polyimide resin in a semiconductor device, for example, a junction coat film, a moisture-proof film, a buffer coat film, an α-ray shielding film, an interlayer insulating film, and the like are known (functional materials, July 1983, p. 9).

When used for these purposes, a process of performing fine processing such as through-holes on the polyimide resin film is required for connection with the conductive parts of the upper and lower conductor layers and external lead wires. A chemical etching process is performed on the polyimide resin film to be used.

However, since the patterning of the polyimide resin film in the above steps includes steps such as application and stripping of a photoresist, the steps are extremely complicated as a whole. Therefore, in order to simplify the process, development of a polyimide resin that can be finely processed by direct light has been desired.

[Problems to be Solved by the Invention] As a method for imparting photosensitivity to a polyimide resin, for example, JP-A-54-116216 and JP-A-54-116217
JP-A-54-145794 and a method of chemically bonding a crosslinkable group to a soluble precursor described in JP-A-54-145794,
There is a method of mixing a crosslinkable monomer described in JP-A-57-168942.

The above-mentioned method is a so-called negative type in which exposed portions are cross-linked and insolubilized by light and only unexposed portions are dissolved with a developer. This method utilizes the fact that the polyimide resin precursor is soluble in a solvent, imparts photosensitivity to the precursor, performs optical processing, and then performs imide ring closure by heat treatment.

However, in the case of the negative type, there is a drawback inherent in the negative type that the exposed portion swells due to the developer and it is difficult to perform high-resolution fine processing.

On the other hand, as another method for imparting photosensitivity to a polyimide resin, US Pat. No. 4,093,461, JP-A-63-13032
And a method of mixing a photosensitive substance such as an orthoindiazide compound with a polyimide resin precursor or an organic solvent-soluble polyimide resin described in JP-A-64-60630. The above-mentioned method is a so-called positive type in which the exposed portion is easily dissolved by photolysis and only the exposed portion is dissolved with a developer.

The methods described in JP-A-63-13032 and JP-A-64-60630 are not photosensitive to the polyimide resin itself,
A method in which a photosensitive substance is mixed with an organic solvent-soluble polyimide resin having a specific molecular structure, and the polyimide resin is dissolved in an alkali at the same time by utilizing the fact that the photosensitive substance in an exposed portion becomes photosensitive and alkali-soluble. It is.

However, in this method, the polyimide resin itself must be soluble in an organic solvent, and for that purpose, there is a great limitation that the polyimide resin used is limited to one having a specific molecular structure.

The method described in U.S. Pat. No. 4,093,461 involves mixing a photosensitive substance with a polyamic acid, which is a precursor of a polyimide resin.

Since polyamic acid has high solubility in organic solvents, there is no restriction on the molecular structure of the polyimide resin used in this case.

However, since the polyamic acid dissolves in the alkali which is a developer, it is difficult to suppress the dissolution of the unexposed portion,
Also, the polyamic acid is susceptible to hydrolysis by alkali, such as the unexposed portion has insufficient resistance to alkali,
This was a major problem in pattern formation.

As described above, attempts have been made to impart photosensitivity to polyimide resins, but none of them has been satisfactory.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found the present invention.

That is, the present invention provides (1) a polyimide resin precursor comprising a copolymer of a repeating unit represented by the following general formula [I] and general formula [II], (A divalent organic group constituting wherein R _1, R ₃ good organic diamine optionally being the same or different, R ₂ and
R ₄ is a tetravalent organic group constituting a tetracarboxylic acid or a derivative thereof, and at least one of the tetravalent organic groups is a tetracarboxylate or a derivative thereof comprising four carbonyl groups not directly bonded to an aromatic ring. And X ₁ and X ₂ are an alkyl group having 1 to 8 carbon atoms which may be the same or different from each other. The constitutional ratio a of the repeating unit represented by the general formula [I] is
20 mol% ≦ a <100 mol%, the constitutional ratio b of the repeating unit represented by the general formula [II] is 80 mol% ≧ b> 0 mol%, and the reduced viscosity is 0.05 to 3.0 g / a photosensitive resin composition containing 1 to 100 parts by weight of an orthoquinone diazide compound per 100 parts by weight of a polyimide resin precursor having a dl (in N-methylpyrrolidone at a temperature of 30 ° C., a concentration of 0.5 dl / g) (2) R ₂ and R ₄ in the general formulas (I) and (II) are
The photosensitive resin composition according to the above (1), which is a tetravalent organic group constituting a tetracarboxylic acid comprising four carbonyl groups not directly bonded to an aromatic ring and a derivative thereof. The photosensitive resin composition according to the above (1), wherein R ₂ and R _{4 in the} formula [I] and the general formula [II] are cyclobutane residues. A polyimide resin precursor consisting of a repeating unit represented by the formula (III), and a mixture of a polyimide resin precursor consisting of a repeating unit represented by the general formula (III), (Wherein R ₅ and R ₇ are divalent organic groups constituting an organic diamine which may be the same or different, and R ₆ and R ₈
Is a tetravalent organic group constituting a tetracarboxylic acid or a derivative thereof, and at least one of the tetravalent organic groups is a tetracarboxylic acid or a derivative thereof composed of four carbonyl groups not directly bonded to an aromatic ring. X ₃ and X ₄ are alkyl groups having 1 to 8 carbon atoms which may be the same or different from each other. ) Constituent ratio c of the repeating unit represented by the general formula [III]
Is 20 mol% ≦ c <100 mol%, and the constitutional ratio d of the repeating unit represented by the general formula [IV] is 80 mol% ≧ d> 0
Mol%, and its reduced viscosity is 0.05 to 3.0 dl / g (temperature 30
A photosensitive resin composition comprising 1 to 100 parts by weight of an orthoquinodiazide compound per 100 parts by weight of a polyimide resin precursor having a concentration of 0.5 g / dl in N-methylpyrrolidone at a temperature of 5 ° C. ) R ⁶ R ⁸ in the general formulas [III] and [IV] is a tetravalent organic group constituting a tetracarboxylic acid composed of four carbonyl groups which are not directly bonded to an aromatic ring and derivatives thereof. (6) The photosensitive resin composition according to the above (4), wherein R ⁶ R ^{8 in the} general formulas (III) and (IV) is a cyclobutane residue. It relates to the photosensitive resin composition according to (4).

That is, the present invention relates to a composition having a positive photosensitive property comprising a polyimide resin precursor and an orthoxinonediazide compound, and the composition of the present invention is easily etched by an alkaline aqueous solution and has a predetermined pattern. By performing heat treatment after exposure and development using a mask, a polyimide resin coating film having a relief pattern with a fine shape and high dimensional accuracy can be obtained.

The polyimide resin precursor used in the present invention is characterized by having a polyamic acid component having a high affinity for an alkali as a developer and a polyamic acid ester component having a low affinity for an alkali at an appropriate ratio. When developing, a relief pattern having high solubility in exposed portions, less film loss in unexposed portions, and a fine shape and high dimensional accuracy can be easily obtained.

Further, it is possible to obtain a very high sensitivity and high resolution positive photosensitive characteristic by using a polyimide resin precursor having extremely excellent transparency as a constituent component.

The method for obtaining the polyimide resin precursor used in the present invention is not particularly limited.

Generally, it is common to react and polymerize an organic tetracarboxylic dianhydride with an organic diamine. In order to obtain polyamic acid which is one component of the polyimide resin precursor of the present invention, an organic tetracarboxylic dianhydride and an organic diamine may be directly reacted. To obtain a polyamic acid ester, a tetracarboxylic dianhydride and an alcohol are reacted to form a dicarboxylic diester, and then the carboxylic acid is chlorinated using a chlorinating agent such as thionyl chloride to form an organic tetracarboxylic diester dichloride. After that, it may be reacted with an organic diamine.

Further, a copolymer of polyamic acid and polyamic acid ester may be obtained by reacting tetracarboxylic dianhydride and tetracarboxylic diester dichloride with an organic diamine. Further, it can also be obtained by using a so-called polymer reaction in which a prepolymerized polyamic acid is partially esterified or a polyamic acid ester is partially hydrolyzed.

R _{1 in the} general formula (I) and R _{3 in} the general formula (II), R _{5 in the} general formula (III) and R ₇ in the general formula (IV) may be the same or different from each other. The diamine constituting these is a diamine generally used when synthesizing a polyimide resin, and can be variously selected according to the characteristics of the produced polyimide resin, and is not particularly limited.
These may be used alone or in plural.

The specific examples thereof include P-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylpropane,
1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxybenzene), bis (4-amino3,5-diethylphenyl) methane, bis (4-amino-3,5- Diisopropylphenyl) methane, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone,
2,2-bis [4- (4-aminophenoxy) phenyl]
Propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
There are aromatic diamines such as bis [4- (3-aminophenoxy) phenyl] hexafluoropropane. In order to further lower the coefficient of thermal expansion of the resulting polyimide resin, benzidine, 3,3'-dimethoxy-4, 4'-diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-p-terphenyl, 9.1
Polycyclic aromatic diamines such as 0-bis (4-aminophenyl) anthracene are also included. And the like.

Other alicyclic diamines and aliphatic diamines may be used depending on the purpose.

R ₂ in the general formula [I] and R ₄ in the general formula [II], R ₆ in the general formula [III] and R ₈ in the general formula [IV] constitute tetracarboxylic acid and a derivative thereof. And at least one of the tetravalent organic groups is a tetracarboxylic acid composed of four carbonyl groups that are not directly bonded to an aromatic ring and derivatives thereof, and the remaining tetracarboxylic acids and the derivatives thereof. The derivative is not particularly limited.

 These may be used alone or in plural.

Specific examples of tetracarboxylic acid consisting of four carbonyl groups not directly bonded to an aromatic ring and derivatives thereof include:
Cyclobutane-1,2,3,4-tetracarboxylic dianhydride,
3,4-dicarboxy-1,2,3,4-tetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-
Naphthalene succinic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, bicyclo (2.2.2)
Alicyclic tetracarboxylic dianhydrides such as oct-4-ene 2,3,5,6-tetracarboxylic dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride; Can be mentioned.

Also, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride can be mentioned.

Furthermore, in the case of not a tetracarboxylic acid consisting of four carbonyl groups not directly bonded to an aromatic ring and its derivative,
Dare to give specific examples, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride And aromatic tetracarboxylic anhydrides such as 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride Can be.

In particular, in order to obtain high-sensitivity and high-resolution positive-type photosensitivity, it is effective to use an acid anhydride in which four carbonyl groups are not directly linked to an aromatic ring as an acid anhydride. Specific examples thereof include the above-mentioned alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride. Particularly, cyclobutanetetracarboxylic dianhydride is preferable.

The method for obtaining the organic tetracarboxylic diester chloride is not particularly limited, but usually, a tetracarboxylic dianhydride is reacted with an alcohol to form a dicarboxylic diester, and then the carboxylic acid is chlorinated using a chlorinating agent such as thionyl chloride. Is generally used. At this time, the alcohol to be reacted with the tetracarboxylic dianhydride is an alcohol constituting X ₁ , X _{2 in} the general formula [I], and X ₃ and X ₄ in the general formula [III], There is no particular limitation as long as it is an aliphatic alcohol having 1 to 8 carbon atoms.

If specific examples are given, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 2-methyl-2-propanol,
1-butanol, 2-butanol, 3-methyl-1-butanol, 1-pentanol, 1-hexanol, 1-butanol
Heptanol, 1-octanol and the like can be mentioned.

These tetracarboxylic dianhydrides are reacted with an alcohol to form a dicarboxylic diester, and then a chlorinating agent such as thionyl chloride is used to form a tetracarboxylic diester chloride to obtain a generally used acid chloride. What is necessary is just to follow a method.

The reaction method of these tetracarboxylate diester dichloride and diamine is not particularly limited.

In general, there are methods such as solution polymerization in an organic solvent in which both are uniformly dissolved, and interfacial polycondensation in an organic solvent / water system.

In the case of the solution polycondensation method in which the operation is relatively simple, tetracarboxylic diester chloride and diamine are reacted in a polar solvent such as N-methylpyrrolidone, dimethyl acedamide, or dimethylformamide. It is generally used as an agent for removing hydrochloric acid generated by the condensation reaction.

The reaction temperature at this time is −20 to 100 ° C., preferably 0 to 2 ° C.
0 ° C.

After completion of the reaction, the mixture is poured into a large amount of water or a poor solvent, and the precipitate is recovered, whereby a polyimide resin precursor can be obtained.

In order for the photosensitive resin composition of the present invention to have excellent photosensitive characteristics, it is important that the obtained polyimide resin precursor has an appropriate affinity for an alkali as a developer.

For this purpose, it is important to have a suitable repeating unit having a polyamic acid structure represented by the general formula [II] and / or the general formula [IV]. These repeating units having a polyamic acid structure may be contained in the form of a copolymer in the molecule of the polyamic acid ester structure, or in the form of a mixture of a molecule of the polyamic acid ester structure and a molecule of the polyamic acid structure. It may be included.

When the repeating unit having a polyamic acid structure is contained in the molecule in the form of a copolymer, the constituent ratio b of the repeating unit having a polyamic acid structure represented by the general formula [III] is 80 mol% ≧ b Any value of> 0 mol% can be selected. When the repeating unit having a polyamic acid structure is contained in the form of a mixture, the constitutional ratio d of the repeating unit having a polyamic acid structure represented by the general formula [IV] is 80 mol% ≧ d> Any value of 0 mol% can be selected.

Normally, sufficient photosensitivity is exhibited even when b = 0 and / or d = 0, but as b and / or d increase, the alkali affinity increases and the solubility of the exposed portion increases. On the other hand, if b and / or d are too large, the alkali resistance of the unexposed portion will be low. Therefore, the composition ratio b of the repeating unit represented by the general formula [II] and / or the composition ratio d of the repeating unit represented by the general formula [IV] is 50 mol% ≧ b> 0 mol%, 50 mol% ≧ d
> 0 mol% is preferred.

In addition, the reduced viscosity of the polyimide resin precursor of the present invention (temperature
N-methylpyrrolidone at 30 ° C., concentration 0.5 g / dl) is 0.05
3.03.0dl / g, particularly preferably 0.1 to 2.0.

When the reduced viscosity is 0.05 or less, the mechanical strength of a film formed from the obtained composition is reduced, and when the reduced viscosity is 3.0 or more, the viscosity of the obtained composition is significantly increased. Workability is extremely reduced.

The orthoquinonediazide compound constituting the positive photosensitive polyimide composition of the present invention is not particularly limited as long as it is a compound containing an orthoquinonediazide group in a molecule.

For example, an orthobenzoquinonediazide compound, an orthonaphthoquinonediazide compound, an orthoquinolinequinonediazide compound, and the like can be mentioned, and these are used in a so-called phenol novolak-based positive photosensitive resin composition. General. The above-mentioned orthoquinonediazide compound is usually used as orthoquinonediazidesulfonic acid ester.

These orthoquinonediazidesulfonic acid esters are usually obtained by a condensation reaction of orthoquinonediazidesulfonic acid chloride with a compound having a phenolic hydroxyl group.

As the orthoquinone diazide sulfonic acid component constituting the ortho quinone diazide sulfonic acid chloride,
For example, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid and the like can be mentioned.

Further, as the compound having a phenolic hydroxyl group, for example, 2,4-dihydroxybenzophenone, 2,3,4
-Trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'- Dihydroxydiphenyl sulfone and the like can be mentioned.

In general, a part or all of the phenolic hydroxyl groups of these compounds are substituted and reacted with the above-mentioned orthoquinonediazidesulfonic acid group, and the di-substituted, tri-substituted and tetra-substituted compounds are generally used alone or as a mixture thereof. It is.

The amount of the orthoquinonediazide compound is 1 to 100 parts by weight based on 100 parts by weight of the organic solvent-soluble polyimide. If the compounding amount is less than 1 part by weight, the sensitivity of the obtained composition at the time of exposure is low, and pattern formation cannot be performed.

On the other hand, if the amount is more than 100 parts by weight, the mechanical properties, electrical properties, etc. of the film formed from the composition obtained are reduced.

When the positive photosensitive resin composition of the present invention is used for an electric / electronic device or the like, it is used as a solution dissolved in an organic solvent.

The organic solvent is not particularly limited as long as it can uniformly dissolve the polyimide resin precursor and the orthoquinonediazide compound.

Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, m-cresol, and γ-butyllactone.

In addition, other organic solvents may be mixed and used as long as the solubility of the composition is not inhibited according to the purpose.

The method for dissolving the polyimide resin precursor and the orthoquinonediazide compound is not particularly limited. The orthoquinone diazide compound may be dissolved in the solution obtained by reacting and polymerizing the polyimide resin precursor, and the polyimide resin precursor precipitated and recovered using a poor solvent may be dissolved in the organic solvent together with the orthoquinone diazide compound. Good.

The concentration of the organic solvent solution of the positive photosensitive resin composition is not particularly limited as long as the polyimide resin precursor and the orthoquinonediazide compound are uniformly dissolved in the organic solvent. The range of 1 to 50% by weight is generally used from the viewpoint of ease of processing.

The positive photosensitive resin composition of the present invention can be spin-coated on a glass plate or a silicon wafer and then pre-dried at 50 to 80 ° C. to form a film.

At this time, even better adhesion can be obtained by using a substrate treated with a silane coupling agent such as 3-aminopropyltriethoxysilane.

By mounting a mask having a predetermined pattern on the above-described film, irradiating the film with light, and then developing the film with an alkali developing solution, an exposed portion is washed out and a sharp relief pattern on an end face is obtained. The developing solution used in this case is an aqueous alkali solution, such as an aqueous solution of an alkali metal hydroxide such as caustic potassium and caustic soda, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and ethanolamine. And aqueous solutions of amines such as propylamine and ethylenediamine.

This composition has high solubility in the exposed area, and the above development can be easily performed at room temperature.

Furthermore, by subjecting the obtained substrate having the relief pattern to heat treatment, the polyimide resin precursor can be converted to polyimide. The heat treatment temperature at this time is 20
The temperature is 0 to 400 ° C, more preferably 250 to 350 ° C.

Thus, a polyimide resin coating film having excellent heat resistance, chemical resistance, and electrical properties and having a good relief pattern can be obtained.

[Effect of the Invention] The present invention is easy to etch with an alkaline aqueous solution,
The present invention relates to a resin composition having a positive photosensitive property that can easily obtain a polyimide resin coating film having a fine relief pattern by performing a heat treatment after exposure and development.

The polyimide resin precursor used in the present invention does not need to restrict the molecular structure of the polyimide resin to a specific one, and has high resistance to a developing solution.

In addition, by appropriately containing a repeating unit having a polyamic acid structure, alkali developability can be adjusted.Furthermore, a highly transparent polyimide precursor is used as a component, and a highly sensitive, high resolution positive type. It is possible to obtain photosensitive characteristics.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
It is not limited to these.

Production Example-1 6.01 g of 4,4'-diaminodiphenyl ether (hereinafter abbreviated as DDE) and 8.91 g of cyclobutanetetracarboxylic acid dimethyl ester dichloride were dissolved in 135 g of N-methylpyrrolidone (hereinafter abbreviated as NMP), and sodium carbonate was dissolved therein.
7.5 g was added and reacted at room temperature for 6 hours.

After the completion of the reaction, this solution was poured into water of 1.5, and the precipitate was filtered and dried to obtain 12.59 g of a white powder.

The reduced viscosity η _{sp / c} of the obtained polyamic acid ester is
It was 0.27 dl / g.

3 g of this resin powder was redissolved in 17 g of NMP to prepare a solution having a solid content of 15% by weight.

Production Example-2 4.00 g of DDE, 4,23 g of pyromellitic dianhydride in 47 g of NMP
And reacted at room temperature for 6 hours. The reduced viscosity η _{sp / c} of the obtained polyamic acid was 0.37 dl / g.

Production Example-3 4.0 g of DDE, cyclobutanetetracarboxylic dianhydride
3.80 g was dissolved in 44 g of NMP and reacted at room temperature for 6 hours.
The reduced viscosity η _{sp / c} of the obtained polyamic acid was 0.44 dl / g.

Example 1 Polyamic acid ester solution 18 obtained in Production Example-1
g and 2 g of the polyamic acid solution obtained in Production Example-3 to prepare a mixed solution of a polyamic acid ester and a polyamic acid having a solid content of 15% by weight, and 2,3,4,4'-
3-hydroxy substituted compound of 1,2-naphthoquinone-2-diazido-5-sulfonic acid of tetrahydroxybenzophenone
After adding 0.90 g and stirring at room temperature for 3 hours, the mixture was filtered through a 1.0 μm filter.

As a silane coupling agent, a 0.1% methanol solution of 3-glycidoxypropyltrimethoxysilane was spin-coated on a glass plate at 3000 rpm, and then spin-coated at 2300 rpm on a substrate treated at 80 ° C. for 10 minutes. , 7
It was dried in a circulating drying oven at 0 ° C. for 30 minutes to obtain a coating film having a thickness of 1.2 μm. The coating film was irradiated with ultraviolet rays for 2 minutes by a UV irradiation apparatus UVL-21 manufactured by UVP through a test mask. The ultraviolet intensity on the exposed surface was 350 mW / cm ^{2 at} 350 nm (measured by an ultraviolet irradiator UV-M01 manufactured by Oak Manufacturing Co., Ltd.).

NMD-3 (manufactured by Tokyo Ohka Co., Ltd.) at about 20 ° C after exposure
For 7 minutes to develop, and washed with pure water to obtain a good positive relief. The film thickness after development was 1.0 μm.

When this substrate was subjected to a heat treatment at 300 ° C. for 30 minutes in a circulating drying furnace, no pattern disorder was observed at all, and the film thickness was 0.9%.
A good relief pattern of μm was obtained. Also, as a result of measuring the infrared absorption spectrum of this coating film, 1780 cm ⁻¹ , 79
An imide group peak was observed at 0 cm ^-1 .

Comparative Example 1 The same orthonaphthoquinonediazide compound as in Example 1 was added to 20 g of the polyamic acid solution obtained in Production Example-2.
After adding 0.90 g and stirring at room temperature for 3 hours, the mixture was filtered through a 1.0 μm filter. This solution was spin-coated at 2800 rpm on a glass substrate that had been subjected to the same coupling treatment as in Example 1, and dried in a circulating drying oven at 70 ° C. for 30 minutes to obtain a 1.0 μm-thick coating film. The same operation as in Example 1 was performed with the ultraviolet light irradiation time set to 5 minutes for this coating film, but the entire coating film began to dissolve after 4 minutes from the development time, and no good positive relief was obtained. Was.

After the development, the coating film swelled severely, and the film thickness could not be measured.

Comparative Example 2 The same orthonaphthoquinonediazide compound as in Example 1 was added to 20 g of the polyamic acid solution obtained in Production Example-3.
After adding 90 g and stirring at room temperature for 3 hours, the mixture was filtered through a 1.0 μm filter. This solution was spin-coated at 3500 rpm on a glass substrate subjected to the same coupling treatment as in Example 1, and dried in a circulating drying oven at 70 ° C. for 30 minutes to obtain a 1.2 μm-thick coating film. The ultraviolet light irradiation time was 2 minutes for this coating film,
The same operation as in Example 1 was performed, but after 5 minutes from the development time, the entire coating film began to dissolve, and no favorable positive relief was obtained.

After the development, the coating film swelled severely, and the film thickness could not be measured.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-639 (JP, A) JP-A-2-181149 (JP, A) JP-A-4-120171 (JP, A) JP-A-4- 168441 (JP, A)

Claims (6)

(57) [Claims] 1. A polyimide resin precursor comprising a copolymer of a repeating unit represented by the following general formula [I] and general formula [II], (A divalent organic group constituting wherein R _1, R ₃ good organic diamine optionally being the same or different, R ₂ and
R ₄ is a tetravalent organic group constituting a tetracarboxylic acid or a derivative thereof, and at least one of the tetravalent organic groups is a tetracarboxy acid having four carbonyl groups not directly bonded to an aromatic ring and a derivative thereof. And X ₁ and X ₂ are an alkyl group having 1 to 8 carbon atoms which may be the same or different from each other. ) The constitutional ratio a of the repeating unit represented by the general formula [I] is 20
Mol% ≦ a <100 mol%, and the composition ratio b of the repeating unit represented by the general formula [II] is 80 mol% ≧ b> 0 mol%
Having a reduced viscosity of 0.05 to 3.0 dl / g (N at a temperature of 30 ° C.)
-A photosensitive resin composition comprising 1 to 100 parts by weight of an orthoquinodiazide compound per 100 parts by weight of a polyimide resin precursor having a concentration of 0.5 dl / g in methylpyrrolidone. Wherein R ₂ and in Formula (I) and formula (II)
2. The photosensitive resin composition according to claim 1, wherein R ₄ is a tetravalent organic group constituting a tetracarboxylic acid comprising four carbonyl groups which are not directly bonded to an aromatic ring and a derivative thereof. 3. The compound represented by the formula (I) or (II) wherein R _{2 is}
The photosensitive resin composition according to claim 1, wherein R ₄ is a cyclobutane residue. 4. A polyimide resin precursor represented by the following general formula [II
I) a polyimide resin precursor consisting of a repeating unit represented by, and a mixture of a polyimide resin precursor consisting of a repeating unit represented by the general formula (IV), (Wherein R ₅ and R ₇ are divalent organic groups constituting an organic diamine which may be the same or different, and R ₆ and R ₈
Is a tetravalent organic group constituting a tetracarboxylic acid or a derivative thereof, and at least one of the tetravalent organic groups is a tetracarboxylic acid or a derivative thereof composed of four carbonyl groups not directly bonded to an aromatic ring. X ₃ and X ₄ are alkyl groups having 1 to 8 carbon atoms which may be the same or different from each other. ) The constitutional ratio c of the repeating unit represented by the general formula [III] is 2
0 mol% ≦ c <100 mol%, and the constitutional ratio d of the repeating unit represented by the general formula [IV] is 80 mol% ≧ d> 0 mol%
Having a reduced viscosity of 0.05 to 3.0 dl / g (N at a temperature of 30 ° C.)
-A photosensitive resin composition comprising 1 to 100 parts by weight of an orthoquinodiazide compound per 100 parts by weight of a polyimide resin precursor having a concentration of 0.5 dl / g in methylpyrrolidone. 5. R ₂ and R ₄ in the general formulas (III) and (IV) each represent a tetracarboxylic acid comprising four carbonyl groups which are not directly bonded to an aromatic ring, and a tetravalent group constituting a derivative thereof. The photosensitive resin composition according to claim 4, which is an organic group. 6. The photosensitive resin composition according to claim ₄ , wherein R ₂ and R _{4 in} formulas [III] and [IV] are cyclobutane residues.