JP2009155609A - Polyimide precursor composition, photosensitive polyimide precursor composition, and electronic component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide precursor composition and a photosensitive polyimide precursor composition having original polyimide resin properties such as heat resistance, electric properties, mechanical properties, and incombustibility, high flexibility, and high adhesiveness, being only slightly curved, and having high alkali resistance and to provide electronic components produced by using the same. <P>SOLUTION: The polyimide precursor composition and the photosensitive polyimide precursor composition comprises at least one type of aromatic tetracarboxylic acid dianhydride that is a polyimide precursor obtained from aromatic tetracarboxylic acid dianhydride and aromatic diamine, wherein the aromatic tetracarboxylic acid dianhydride contains 3,4,3',4'-biphenyltetracarboxylic acid dianhydride as an essential component and at least 2 types of aromatic diamine of 4,4'-oxydianiline, paraphenylenediamine, 4,4'-diaminobenzanilide, 1,3-bis-(3-aminophenoxy)benzene, and methylenedianiline. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an electronic component including a polyimide precursor composition, a photosensitive polyimide precursor composition, and a coverlay (circuit protection) formed using the photosensitive polyimide precursor composition.

A coverlay film for a flexible printed wiring board (hereinafter referred to as “FPC”) is used for the purpose of circuit protection of a conductor circuit pattern formed using a copper-clad laminate (hereinafter referred to as “CCL”). As a method for attaching this cover lay film, “CCL on which a circuit is formed is prepared by previously punching a hole in a predetermined position of a cover lay film such as polyimide resin whose one surface is treated with an adhesive. The method of “laminate or press the plate” is generally used.

However, at the present time when the miniaturization of FPC circuits is rapidly progressing, “the circuit pattern and the circuit pattern after the holes and windows matching the terminal portions of the FPC circuit and the joints are formed in the coverlay film in advance. The method of “adhering the cover lay film to the CCL plate while aligning” is limited in terms of workability and position accuracy, and has a problem that the yield is poor and the process is complicated.

As another method, “a hole is formed only in the coverlay film at a predetermined position of the coverlay film by laser etching or the like after thermocompression bonding of the film on which the adhesive is treated on the FPC having the circuit formed”. There is also a method. Although this method can improve the accuracy of the drilling position with respect to the circuit pattern, there is a problem that the drilling process takes time and the manufacturing cost increases. In addition, there is a problem that an expensive processing apparatus is required to implement this method.

In recent years, a method using a photosensitive coverlay film and a method using a photosensitive resin composition have been proposed for such problems. In the former method, a photosensitive cover lay film is thermocompression-bonded on a CCL on which a circuit is formed, and then a photomask pattern is placed on the photosensitive cover lay film, exposed, and developed with a chemical solution. A hole can be accurately drilled at a predetermined position of the coverlay film. This cover lay film serves as a circuit insulating film and protective film. In the latter method, a photosensitive resin composition is applied and dried on a CCL board on which a circuit is formed, and then a photomask pattern is placed on the dried coating film of the photosensitive resin composition, and near ultraviolet rays or the like. After exposure and development with a weak alkaline solution, the dried coating film is thermally cured to form a coverlay film. In addition, the coating film formed in this way plays a role as an insulating film or a protective film of an electric circuit.

By the way, such a cover lay film is required to have many characteristics such as adhesive strength with an FPC board, electrical insulation, flexibility, incombustibility, and heat resistance. Moreover, when a coverlay film is formed from the photosensitive resin composition, the reduction | decrease of the curvature (curl) at the time of shaping | molding etc. is requested | required. In recent years, a method of forming a cover lay film using a photosensitive resin composition has become mainstream from the viewpoints of position accuracy and manufacturing cost at the time of drilling.

Conventionally, as such a photosensitive resin composition, a photosensitive polyimide resin composition and a photosensitive polyimide precursor composition having high adhesion to a substrate and small warpage during molding have been proposed (for example, Patent Document 1). And 4). In addition, a coverlay film excellent in heat resistance, flame retardancy, and flex resistance has also been proposed (see, for example, Patent Document 2). Furthermore, a photosensitive resin composition in which a silane coupling agent is blended in order to improve the adhesion to the substrate has also been proposed (see, for example, Patent Document 3).

However, in these conventional technologies, since polyimide, urethane, siloxane, or epoxy is mixed or copolymerized, the electrical characteristics, mechanical characteristics, heat resistance, etc. inherent to the polyimide resin are inherent. There are problems such as deterioration of the excellent characteristics of the steel, and deterioration of heat resistance, dielectric strength, incombustibility, etc. for soldering. Furthermore, in the prior art, an organic solvent or an organic alkaline solution is used as a developer for the photosensitive resin, so that there are concerns about environmental and work safety problems in the prior art. In such a reality, a coverlay film that satisfies all of the above-mentioned required characteristics has not been developed yet, and in the industry, a coverlay film having excellent characteristics of polyimide resin can be produced and there is a concern about environmental pollution. A photosensitive polyimide resin composition and a photosensitive polyimide precursor composition that can be developed with a small amount of a weak alkaline inorganic alkali aqueous solution are desired.
JP 2004-285129 A JP 2003-287886 A Japanese Patent Laid-Open No. 10-20499 JP 2002-206056 A

The object of the present invention is to form a cover lay film having heat resistance, electrical properties, mechanical properties, nonflammability, etc. inherent in polyimide resin, excellent adhesion, flexibility, etc., and small warpage during molding. Another object of the present invention is to provide a polyimide precursor composition or a photosensitive polyimide precursor composition that is excellent in resistance to processes such as alkaline degreasing and washing, and an electronic component using the same.

As a result of diligent research, the present inventors have obtained a polyimide precursor obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, and the aromatic tetracarboxylic dianhydride is 3,4, At least one aromatic tetracarboxylic dianhydride having 3 ′, 4′-biphenyltetracarboxylic dianhydride as an essential component, 4,4′-oxydianiline, paraphenylenediamine, 4,4′- By using a polyimide precursor composed of at least two aromatic diamines among diaminobenzoanilide, 1,3-bis- (3-aminophenoxy) benzene and methylenedianiline, heat resistance and electrical properties inherently possessed by the polyimide resin are obtained. , Mechanical properties and non-flammability, excellent adhesion and flexibility, small warpage during molding, alkaline degreasing and washing Found to be able to mold the superior cover lay film with resistance to manufacturing process of.

The polyimide precursor composition according to the present invention is a polyimide precursor obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, and the aromatic tetracarboxylic dianhydride is 3,4,3 ′, It consists of at least one kind of aromatic tetracarboxylic dianhydride having 4′-biphenyltetracarboxylic dianhydride as an essential component, and the aromatic diamine is 4,4′-oxydianiline, paraphenylenediamine, 4,4 It is a polyimide precursor composition comprising at least two kinds of aromatic diamines among '-diaminobenzoanilide, 1,3-bis- (3-aminophenoxy) benzene, and methylenedianiline.

The aromatic diamine contains 4,4′-diaminobenzoanilide as an essential component, and 4,4′-oxydianiline, paraphenylenediamine, 1,3-bis- (3-aminophenoxy) benzene, and methylenedianiline. It is a polyimide precursor composition which consists of at least 1 type of aromatic diamine.

The aromatic diamine is a polyimide precursor composition comprising 4,4′-diaminobenzoanilide and paraphenylenediamine.

Moreover, it is a polyimide precursor composition whose 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride is 20 mol% or more and 80 mol% or less of the aromatic tetracarboxylic dianhydride component.

Moreover, it is the photosensitive polyimide precursor composition formed by containing the photosensitive agent in the polyimide precursor composition mentioned above.

Moreover, it is an electronic component provided with the polyimide resin film formed by imide conversion of the polyimide precursor composition or photosensitive polyimide precursor composition mentioned above.

In the present invention, the photosensitive polyimide precursor composition as described above can be applied to electronic parts and the like as raw materials for coverlay films and the like. For example, if a photosensitive polyimide precursor composition is applied and dried on a conductor circuit pattern and the coating film is developed with an inorganic alkaline aqueous solution, the polyimide precursor in the coating film is converted to an imide, and a polyimide coverlay film is formed. Can be produced.

The polyimide precursor composition or photosensitive polyimide precursor composition of the present invention has properties such as heat resistance, electrical properties, mechanical properties and nonflammability inherently possessed by polyimide resins, and is excellent in adhesion and flexibility. A coverlay film having a small warp during molding can be formed, and a coverlay excellent in resistance to processes such as alkali degreasing and washing can be formed.

The polyimide precursor composition or photosensitive polyimide precursor composition of the present invention is a polyimide precursor obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, and the aromatic tetracarboxylic dianhydride is At least one aromatic tetracarboxylic dianhydride having 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride as an essential component, 4,4′-oxydianiline, paraphenylenediamine, It is obtained by polymerizing 4,4′-diaminobenzoanilide, 1,3-bis- (3-aminophenoxy) benzene, and methylene dianiline with at least two kinds of aromatic diamines.

In the present invention, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride is preferably in a proportion of 20 mol% to 80 mol% of the aromatic tetracarboxylic dianhydride component. If the ratio is less than the above ratio, the alkali resistance of the resulting polyimide film is lowered, which is not preferable. If the ratio is higher than the above ratio, the flexibility of the obtained polyimide film is impaired, which is not preferable.

In the present invention, it is preferable that 4,4′-diaminobenzoanilide is in a proportion of 20 mol% or more and 80 mol% or less of the aromatic diamine component. When the ratio is less than the above ratio, the amount of warpage of the obtained polyimide film increases, which is not preferable. When the ratio exceeds the ratio, the mechanical strength of the obtained polyimide film decreases, which is not preferable.

Moreover, in this invention, it is preferable that paraphenylenediamine is 20 mol% or more and 80 mol% or less of an aromatic diamine component. When the ratio is less than the above ratio, the alkali resistance of the obtained polyimide film is deteriorated, which is not preferable. When the ratio is higher than the above ratio, the flexibility of the obtained polyimide film is deteriorated, which is not preferable.

In the present invention, 4,4'-oxydianiline is preferably in a proportion of 40 mol% to 80 mol% of the aromatic diamine component. If the ratio is less than the above ratio, the flexibility of the resulting polyimide film is impaired, which is not preferable. If the ratio is greater than the above ratio, the resulting polyimide film has a large linear expansion coefficient and is used as a cover layer for electronic components such as FPC. In such a case, problems such as warpage occur in the molded product obtained, which is not preferable.

As a solvent for polymerizing the polyimide precursor composition or photosensitive polyimide precursor composition of the present invention, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl- 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphoric triamide, 1,2-dimethoxyethane, diglyme, triglyme, tetrahydrofuran, 1,4-dioxane, γ-butyrolactone Dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, diethoxyethane, dimethyl sulfoxide, sulfolane and the like. A preferred solvent is N, N-dimethylacetamide. These solvents can be used alone or as a mixture. These solvents can be used by mixing with other solvents such as aromatic hydrocarbons such as toluene and xylene and alcohols such as methanol and ethanol.

The polyimide precursor composition or photosensitive polyimide precursor composition according to the present invention preferably has a polystyrene-equivalent weight average molecular weight of 100,000 g / mol or more and 200,000 g / mol or less. When the weight average molecular weight in terms of polystyrene is lower than 100,000 g / mol, mechanical properties such as bendability and resistance to end tearing of the substrate are insufficient when used as a cover layer for electronic parts such as flexible substrates. In the case where it is higher than 200,000 g / mol, the solution viscosity becomes high and the molding process becomes difficult.

The polyimide precursor composition or the photosensitive polyimide precursor composition can be adjusted by changing the mixing ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine. In the present invention, the mixing ratio for obtaining a preferable molecular weight is 80: 100 to 99: 100. In addition, as for this mixing ratio, any of aromatic tetracarboxylic dianhydride and aromatic diamine may be large.

In the present invention, as the photosensitive polyimide precursor composition, any one of 1,2-naphthoquinonediazide-4-sulfonic acid ester compound and 1,2-naphthoquinonediazide-5-sulfonic acid ester compound, or these It is preferable to blend a photosensitive agent that is a mixture. This photosensitive agent has an absorption wavelength centered at 405 nm.
In such a case, the 1,2-naphthoquinonediazide-4-sulfonic acid ester compound is preferably an ester compound of 1,2-naphthoquinonediazide-4-sulfonic acid and hydroxybenzophenone, and 1,2-naphthoquinonediazide The -5-sulfonic acid ester compound is preferably an ester compound of 1,2-naphthoquinonediazide-5-sulfonic acid and hydroxybenzophenone. Also, 1,2-naphthoquinonediazide-5-sulfonic acid is preferably 1,2-naphthoquinone- (2) -diazide-5-sulfonic acid, and hydroxybenzophenone is 2,3,4-trihydroxybenzophenone. Is preferred.

Furthermore, it is preferable that the photosensitive agent is blended in an amount of 20 to 80 parts by weight with respect to 100 parts by weight of the solid content of the polyimide precursor.

Moreover, a rust preventive agent can be added to the polyimide precursor composition or photosensitive polyimide precursor composition of the present invention in order to prevent oxidation of the copper wiring circuit. For example, benzotriazole or a derivative thereof can be used as a rust inhibitor. The rust inhibitor is preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive polyimide precursor composition.

In addition, an antifoaming agent or a leveling agent can be added to the polyimide precursor composition or the photosensitive polyimide precursor composition of the present invention in order to improve the smoothness after screen printing. Examples of the antifoaming agent or leveling agent include organopolysiloxane, polyacrylic acid ester, and polyvinyl ether. Of these antifoaming agents or leveling agents, the solubility parameter δ is 7.3 cal / cm ³ or more and 9.4 cal / cm ³ or less, and the surface tension γ is 0.020 N / cm or more and 0.035 N / cm. The following are particularly preferable. These antifoaming agents or leveling agents may be used alone or in combination. The antifoaming agent or leveling agent is preferably added in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of the solid content of the photosensitive polyimide precursor composition. And when an antifoamer and a leveling agent are added to the photosensitive polyimide precursor composition, after screen printing, the coating film is dried at a solvent volatilization rate of 20 mg / min to 70 mg / min for 10 minutes or more, and then The coating is preferably imide converted. If it does in this way, the smoothness of the coating film after screen printing can be improved.

Moreover, such a polyimide precursor composition or a photosensitive polyimide precursor composition can be applied to an electronic component or the like as a raw material for a coverlay film or the like. For example, the photosensitive polyimide precursor composition is applied on a conductor circuit pattern formed using CCL at a thickness in the range of 10 to 100 μm, dried at a temperature of about 100 ° C., and then coated on the coating film. After putting the mask putter and exposing the coating film with near ultraviolet light having a wavelength of around 400 nm, the coating film is developed with an inorganic alkaline aqueous solution to open holes and windows at predetermined positions. If the polyimide precursor is imide converted at a temperature of 200 to 250 ° C., a polyimide coverlay can be formed.

In addition, the polyimide precursor composition and photosensitive polyimide precursor composition of the present invention include the resulting polyimide film, polyimide cover lay, heat resistance, electrical insulation, folding characteristics, alkali resistance, mechanical resistance of the photosensitive polyimide cover lay. Additives such as rust preventives, adhesion aids, surface smoothing agents, organic and inorganic fillers, etc. may be added to the extent that properties such as mechanical strength are not impaired.

The post-baking temperature is preferably low in order to prevent oxidation of electrical circuits such as copper. For this reason, 3-hydroxypyridine, 3-hydroxybenzoic acid, benzimidazole, 1-methylimidazole, 2-hydroxybenzoic acid, 3-hydroxyphenylacetic acid, 3-phenolsulfonic acid, 4 are previously added to the photosensitive polyimide precursor composition. -It is preferable to mix an imidizing agent such as hydroxypyridine.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited to these Examples.

(1) Preparation of polyimide precursor composition A synthesis vessel was assembled by attaching stirring blades to a 500 mL three-necked flask. In the synthesis container, 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as “BPDA”) 44 manufactured by Wako Pure Chemical Industries, Ltd. so that the solid content is 17% by mass. .04 g (0.1498 mol) and 29.93 g of N-methylpyrrolidone (hereinafter referred to as “NMP”) manufactured by Mitsubishi Gas Chemical Co., Ltd. were added, and the contents of the synthesis container were heated to 60 ° C. The mixture was stirred for 2 hours to obtain a BPDA solution. Thereafter, 14.98 g (0.0749 mol) of 4,4′-diaminodiphenyl ether (hereinafter referred to as “ODA”) manufactured by Wako Pure Chemical Industries, Ltd. and paraphenylenediamine (hereinafter referred to as “PPD”) were added to the BPDA solution. 8.09 g (0.0749 mol) was added, and the content was further stirred at 60 ° C. for 1 hour to obtain a polyamic acid solution. The viscosity of this polyimide precursor composition was 160 poise.

(2) Evaluation of physical properties After a polyimide precursor composition was screen-printed on a copper-clad laminate Espanex M (manufactured by Nippon Steel Chemical Co., Ltd.), the coating film was dried at a temperature of 80 ° C. for 10 minutes for primary imidization. A film was formed. At this time, the thickness of the primary imidized film was 15 μm. Then, after placing a photomask pattern on the primary imidized film, the primary imidized film was irradiated with near-ultraviolet rays of 400 nm for 30 minutes. Next, this primary imidized film was developed with a 0.5 wt% sodium carbonate aqueous solution and then heated at 120 ° C. for 30 minutes and further at 200 ° C. for 30 minutes for host baking.

(A) Evaluation of flexibility The specific location of the coverlay film produced as described above was repeatedly bent, and the number of times of bending when the coverlay film was broken was measured. The results are shown in Table 1. In addition, when the number of times of bending is 20 times or more, the symbol “◎” is attached, when it is 2 or more and less than 20 times, the symbol “◯” is attached, and when it is 2 times or less, the symbol “x” is attached. .

(B) Evaluation of adhesiveness Evaluation of adhesiveness was performed according to JIS K-5400 cross cut method. Specifically, the coverlay film produced as described above was cut into 6 vertical and horizontal cuts at intervals of 2 mm with a cutter or other tool to form a total of 25 2 mm square resin pieces (hereinafter, this part is After applying cellophane adhesive tape to the grid area, press the cellophane adhesive tape firmly with your finger to bring the cellophane adhesive tape into close contact with the grid area. Thereafter, the cellophane adhesive tape is peeled upward, and the number of peeled film pieces is counted. The results are shown in Table 1. When the peeled film piece was 5 or less, the symbol “◎” was given, when it was 5-20, the symbol “◯” was given, and when it was more than 20, the symbol “x” was given.

(C) Evaluation of curling property The coverlay film produced as described above was cut into 40 mm × 40 mm, and the curl degree was measured with a steel rule. The results are shown in Table 1. When the degree of curl is less than 5 mm, the symbol “◎” is given, when it is 5-20 mm, the symbol “◯” is given, and when it is larger than 20 mm, the symbol “x” is given.

(D) Alkali resistance The coverlay film produced as described above was cut into 20 mm × 20 mm, immersed in a 10% sodium hydroxide solution for 10 minutes, and the dissolved film thickness was measured with a dial gauge. The results are shown in Table 1. The symbol “場合” was assigned when the dissolution amount was less than 1 μm, the symbol “◯” was assigned when it was 1 to 3 μm, and the symbol “x” was assigned when it was larger than 3 μm.

  44.04 g of BPDA was replaced with 22.02 g (0.0749 mol) of BPDA and 16.33 g (0.0749 mol) of pyromellitic dianhydride (hereinafter referred to as “PMDA”), and 295.93 g of NMP was replaced with 268.14 g. Except for the above, a polyimide precursor composition was prepared in the same manner as in Example 1 (see Table 1). Table 1 shows the results of various evaluations.

  44.04 g of BPDA was replaced with 22.02 g (0.0749 mol) of BPDA and 16.33 g (0.0749 mol) of PMDA, 295.93 g of NMP was replaced with 311.66 g, and 8.09 g of PPD was replaced with 4,4′-diaminobenzanilide A polyimide precursor composition was prepared in the same manner as in Example 1 except that the amount was changed to 17.00 g (0.0749 mol) (referred to as “DABA”) (see Table 1). Table 1 shows the results of various evaluations.

  44.04 g of BPDA was replaced with 22.02 g (0.0749 mol) of BPDA and 24.12 g (0.0749 mol) of BTDA, 295.93 g of NMP was replaced with 373.46 g, and 8.09 g of PPD was replaced with 1,3-bis- (3-amino A polyimide precursor composition was prepared in the same manner as in Example 1 except that 21.87 g (0.0749 mol) of phenoxy) benzene (hereinafter referred to as “APB”) was used (see Table 1). Table 1 shows the results of various evaluations.

  NMP295 was replaced by replacing 44.04 g of BPDA with 22.02 g (0.0749 mol) of BPDA and 33.26 g (0.0749 mol) of 4,4 ′-(hexafluoroisopropyl) phthalic dianhydride (hereinafter referred to as “6FDA”). Polyimide in the same manner as in Example 1 except that .93 g was replaced with 383.70 g and PPD 8.09 g was replaced with 14.4 g (0.0749 mol) of 4,4′-diaminodiphenylmethane (hereinafter referred to as “MDA”). A precursor composition was prepared (see Table 1). Table 1 shows the results of various evaluations.

  44.04 g of BPDA is replaced with 22.02 g (0.0749 mol) of BPDA and 16.33 g (0.0749 mol) of PMDA, 295.93 g of NMP is replaced with 278.02 g, and 14.98 g of ODA is 4,4′-diaminobenzanilide (hereinafter referred to as “4DA”). A polyimide precursor composition was prepared in the same manner as in Example 1 except that the amount was changed to 17.00 g (0.0749 mol) (referred to as “DABA”) (see Table 1). Table 1 shows the results of various evaluations.

  A polyimide precursor composition was prepared in the same manner as in Example 1 except that 44.04 g of BPDA was replaced with 35.22 g (0.1198 mol) of BPDA and 6.54 g (0.0300 mol) of PMDA, and 295.93 g of NMP was replaced with 284.80 g. Things were adjusted (see Table 1). Table 1 shows the results of various evaluations.

  The polyimide precursor composition was the same as in Example 1 except that 44.04 g of BPDA was replaced with 8.82 g (0.0300 mol) of BPDA and 26.112 g (0.1198 mol) of PMDA, and 295.93 g of NMP was replaced with 251.48 g. Things were adjusted (see Table 1). Table 1 shows the results of various evaluations.

  44.04 g of BPDA is replaced with 22.02 g (0.0749 mol) of BPDA and 16.33 g (0.0749 mol) of PMDA, 295.93 g of NMP is replaced with 288.31 g, and 14.98 g of ODA is replaced with 23.96 g (0.1198 mol). A polyimide precursor composition was prepared in the same manner as in Example 1 except that 8.09 g of PPD was replaced with 3.24 g (0.0300 mol) (see Table 1). Table 1 shows the results of various evaluations.

  44.04 g of BPDA is replaced with 22.02 g (0.0749 mol) of BPDA and 16.33 g (0.0749 mol) of PMDA, 295.93 g of NMP is replaced with 261.40 g, and 14.98 g of ODA is replaced with 11.98 g (0.0599 mol). A polyimide precursor composition was prepared in the same manner as in Example 1 except that 8.09 g of PPD was replaced with 9.71 g (0.0899 mol) (see Table 1). Table 1 shows the results of various evaluations.

  Example 1 except that NMP295.93g was replaced with 322.84g, ODA14.98g was replaced with 26.96g (0.1348mol), and PPD8.09g was replaced with 1.62g (0.0150mol). A polyimide precursor composition was prepared (see Table 1). Table 1 shows the results of various evaluations.

  Except that NMP295.93g was replaced with 269.03g, ODA14.98g was replaced with 3.00g (0.0150mol), and PPD8.09g was replaced with 14.56g (0.1348mol), the same as Example 1. A polyimide precursor composition was prepared (see Table 1). Table 1 shows the results of various evaluations.

(Comparative Example 1)
44.04 g of BPDA is replaced with 39.63 g (0.1348 mol) of BPDA and 3.27 g (0.0150 mol) of PMDA, 295.93 g of NMP is replaced with 324.01 g, and 14.98 g of ODA and 8.09 g of PPD are 29.96 g (0. A polyimide precursor composition was prepared in the same manner as in Example 1 except that 1498 mol) was used (see Table 1). Table 1 shows the results of various evaluations.

(Comparative Example 2)
44.04 g of BPDA is replaced with 4.41 g (0.0150 mol) of BPDA and 29.39 g (0.1348 mol) of PMDA, 295.93 g of NMP is replaced with 279.56 g, and 14.98 g of ODA and 8.09 g of PPD are converted to ODAg (0.1498 mol). A polyimide precursor composition was prepared in the same manner as in Example 1 except for changing to (see Table 1). Table 1 shows the results of various evaluations.

(Comparative Example 3)
A polyimide precursor composition was prepared in the same manner as in Example 1 except that 44.04 g of BPDA was replaced with 32.66 g (0.1498 mol) of PMDA and 240.35 g of NMP was replaced with 240.35 g (see Table 1). Table 1 shows the results of various evaluations.

  The polyimide precursor composition or photosensitive polyimide precursor composition of the present invention can be used for heat-resistant electronic parts. For example, it is particularly suitable for an overcoat agent for screen printing, an interlayer insulating film, a protective film (coverlay) and the like. In addition, it can be used as an adhesive or heat-resistant paste.

Claims (6)

A polyimide precursor obtained from an aromatic tetracarboxylic dianhydride and an aromatic diamine, wherein the aromatic tetracarboxylic dianhydride is 3,4,3 ′, 4′-biphenyltetracarboxylic dianhydride It consists of at least one aromatic tetracarboxylic dianhydride as an essential component, and the aromatic diamine is 4,4′-oxydianiline, paraphenylenediamine, 4,4′-diaminobenzoanilide, 1,3-bis. A polyimide precursor composition comprising at least two aromatic diamines among-(3-aminophenoxy) benzene and methylenedianiline. Among the aromatic diamines, 4,4′-diaminobenzoanilide is an essential component, and 4,4′-oxydianiline, paraphenylenediamine, 1,3-bis- (3-aminophenoxy) benzene, and methylenedianiline. The polyimide precursor composition according to claim 1, comprising at least one aromatic diamine. The polyimide precursor composition according to claim 1, wherein the aromatic diamine comprises 4,4′-diaminobenzoanilide and paraphenylenediamine. The said 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride is 20 mol% or more and 80 mol% or less of an aromatic tetracarboxylic dianhydride component. Polyimide precursor composition. The photosensitive polyimide precursor composition formed by containing the photosensitive agent in the said polyimide precursor composition in any one of Claims 1-4. An electronic component comprising a polyimide resin film formed by imide conversion of the polyimide precursor composition or the photosensitive polyimide precursor composition according to claim 1.