JP2003035950A - Photosensitive polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive polyimide resin composition which has excellent positive photosensitive characteristics and good resolution in pattern formation, is less liable to warp because of relieved thermal stress, and is easily worked. SOLUTION: The photosensitive polyimide resin composition contains 5-200 pts.wt. elastomer and 1-50 pts.wt. photosensitive agent, based on 100 pts.wt. solid component of a solvent-soluble polyimide resin having a weight average molecular weight of 20,000-300,000 obtained by reacting at least one compound selected from diamines with at least one compound selected from acid dianhydrides in an organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide resin composition, and more particularly to a polyimide resin and a photosensitive resin which are excellent in positive-type photosensitive characteristics and can suppress warpage when compounded (laminated) with another substrate. -Related polyimide resin composition.

[0002]

2. Description of the Related Art Since polyimide resins have excellent heat resistance, electrical insulation properties and mechanical properties, many studies have been conducted for application to wiring interlayer insulation coatings, solder resists and the like. Furthermore, recently, it is expected that the polyimide resin will be used as a constituent material of a photoresist layer that can be used as an insulating coating after pattern formation by imparting photosensitivity to the polyimide resin.

Conventionally, as a polyimide resin suitable for this use, for example, Japanese Patent Application Laid-Open No. 10-158397 discloses:
A polyamic acid is produced by reacting a diamine and an acid dianhydride, an imide ring is closed by subjecting the polyamic acid to a chemical treatment or a heat treatment, and a resin having an addition polymerizable group introduced is proposed. Mechanical strength after heat curing,
It is said to have excellent heat resistance and expandability.

[0004]

However, since the photosensitivity of the above-mentioned polyimide resin is a negative solvent-insoluble type, which is based on the curing of polyamic acid by irradiation with light, the cured film swells during development, resulting in a pattern. There is a problem that the resolution at the time of formation is lowered.

Although a solvent-soluble polyimide resin is also known, a conventional insulating film formed of this kind of polyimide resin has a relatively large linear expansion coefficient, so that it is applied to a plate base material such as copper, aluminum or stainless steel and dried. And then compounded,
There is a problem that warpage occurs.

The present invention has been made to solve the above-mentioned problems of the prior art, and is a photosensitive polyimide having excellent positive type photosensitive characteristics and capable of suppressing the occurrence of warpage when compounded with another substrate. The purpose is to provide a resin composition.

[0007]

In order to achieve the above object, the present invention comprises reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent. And the average molecular weight is 20,
5 to 20 parts of the elastomer is added to 100 parts by weight of the solid content of the solvent-soluble polyimide resin of 000 to 300,000.
Provided is a photosensitive polyimide resin composition containing 0 part by weight and 1 to 50 parts by weight of a photosensitizer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a diamine as a raw material of a solvent-soluble polyimide resin has a chemical formula

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

[Chemical 41] as well as

[Chemical 42] At least one selected from the compounds represented by

As the acid dianhydride,

[Chemical 43]

[Chemical 44]

[Chemical formula 45]

[Chemical formula 46]

[Chemical 47] as well as

[Chemical 48] At least one selected from the compounds represented by

In the present invention, the chemical formulas (1) and (2)
One or both of the diamines of Chemical formula (18) to (23) are used as an essential component, and the dianhydrides of chemical formulas (18) to (23) and, if necessary, the diamine of chemical formulas (3) to (17) are used as reaction components. By doing so, it is possible to produce a solvent-soluble polyimide resin having excellent photosensitivity, by further adding an elastomer component to this polyimide resin, it is possible to reduce the elasticity of the resin layer and to reduce the thermal stress that causes warpage. Can be relaxed.

The solvent-soluble polyimide resin of the present invention is obtained by dissolving a diamine and an acid dianhydride in an organic solvent to directly imidize them, and by dissolving and reacting the diamine and the acid dianhydride in an organic solvent. Then, it can synthesize | combine by adding at least 1 side of a diamine and an acid dianhydride, and imidating. The mixing ratio of the diamine and the acid dianhydride is preferably 0.95 to 1.05 mol% of the total amount of the diamine with respect to 1 mol% of the total amount of the acid dianhydride.

Examples of the organic solvent include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, sulfolane, anisole, dioxolane, butylcellosolve acetate and lactone series, which can be used alone. You may mix and use 2 or more types. Examples of the lactone type include γ-caprolactone, γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-phthalide acid, and γ-coumarin, and the lactone type and pyridine, quinoline, N
Mixtures with basic compounds such as methylmorpholine can also be used.

In the present invention, the weight average molecular weight of the solvent-soluble polyimide must be in the range of 20,000 to 300,000. If it is less than 20,000, the heat resistance is insufficient and the film is formed in a varnish state. Becomes difficult,
If it exceeds 300,000, gelation tends to occur in a varnish state, so that storage stability becomes poor and film formation becomes difficult.

Elastomers to be blended with the polyimide resin include chlorinated polyethylene rubber, ethylene propylene rubber, silicone rubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer, acrylonitrile butadiene rubber, hydrogenated acrylonitrile butadiene rubber. And the like, and these are used alone or in combination of two or more kinds. The elastomer is 5 to 2 with respect to 100 parts by weight of the polyimide resin.
It is necessary to mix it in an amount of 00 parts by weight, preferably 10 to 100 parts by weight. If it is less than 5 parts by weight, there is no effect of suppressing the warp, and if it exceeds 200 parts by weight, it becomes difficult to form a coating film.

As the photosensitizer, diazonaphthoquine compounds such as diazonaphthoquinone sulfonate are suitable. The photosensitizer is 1 per 100 parts by weight of the polyimide resin.
It is necessary to mix in the range of 50 to 50 parts by weight, preferably 10 to 30 parts by weight. If it is less than 1 part by weight, sufficient photosensitivity cannot be obtained, and if it exceeds 50 parts by weight, the original properties of the polyimide resin are impaired. Become.

The photosensitive polyimide resin composition of the present invention is
Demonstrates excellent poly-type photosensitivity and low warpage, on substrates such as copper, aluminum, stainless steel, and polyimide films,
Alternatively, it can be applied to a semiconductor substrate and dried before use.

[0017]

EXAMPLES Examples of the present invention will be described below together with comparative examples.

Example 1 [Step 1a] A 1000 ml separable three-necked flask equipped with a stirrer was fitted with a ball cooling tube equipped with a trap with a silicon cock. Bicyclo (2,2,2)
Octo-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCD, chemical formula (18)) 21.3 g, 4,
4'-diaminodiphenyl ether (p-DADE, chemical formula (8)) 40.0 g, γ-caprolactone 1.2
g, 1.9 g of pyridine, 300.0 g of N-methyl-2-pyrrolidone (NMP), and 60.0 g of toluene,
After stirring at room temperature under a nitrogen atmosphere for 10 minutes, the content in the reaction vessel was heated to 180 ° C. and the stirrer was rotated at 180 rpm.
The reaction time was set to m and stirred for 1 hour. [Step 1b] Next, this reaction solution was air-cooled, and
58.4 g, 3,3'- 3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA, chemical formula (21))
Dihydroxybenzidine (HOAB, chemical formula (2)) 2
0.0g, NMP220.0g, and toluene 44.0g were added, the content in the reaction vessel was heated to 180 ° C., and the mixture was stirred for 5 minutes.
Stir for a reaction to react. The rotation speed of the stirrer is 180 rp
It was set to m and was appropriately lowered as the reaction decreased. Then, vacuum drying was performed to obtain a reaction liquid (varnish). Water generated during the reaction was removed from the silicon cock at appropriate times. [Step 2] By pouring the varnish obtained in [Step 1b] into methanol, the generated precipitate is separated, pulverized,
A polyimide resin powder was obtained by the steps of filtering, washing and drying under reduced pressure. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1.
And characteristic absorption of the imide ring was observed at 1785 cm ^-1 .
The infrared absorption spectrum is MF manufactured by JASCO Corporation.
Using T-2000, the solder resist applied on the copper foil was measured by the reflection method. [Step 3] After that, 4.0 g of polyimide resin powder was dissolved in 20.0 g of NMP, and diazonaphthoquinone sulfonate (NT-200: manufactured by Toyo Gosei Co., Ltd.) was used as a photosensitizer.
Was blended for 15 phr and acrylonitrile butadiene rubber was dispersed for 5 phr to obtain a photosensitive polyimide resin composition.

Example 2 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] 50 p of acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that the dispersion was carried out for hr.

Example 3 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] 100 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that phr was dispersed.

Example 4 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] 200 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that phr was dispersed.

(Example 5) [Step 1a], [Step 1b] Except that the reaction time of [Step 1a] of Example 1 was 0.5 hours and the reaction time of [Step 1b] was 0.5 hours. Example 1
A varnish was obtained in the same manner as in [Step 1a] and [Step 1b]. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Example 5, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

Example 6 [Step 1a], [Step 1b] The reaction time of [Step 1a] of Example 1 was 1 hour, and [Step 1]
A varnish was obtained in the same manner as in [Step 1a] and [Step 1b] of Example 1 except that the reaction time of [b] was 8 hours. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Example 6, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

(Example 7) [Step 1a], [Step 1b] In Example 1, except that the reaction time of [Step 1a] of Example 1 was 1 hour and the reaction time of [Step 1b] was 9 hours. A varnish was obtained in the same manner as in [Step 1a] and [Step 1b]. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Example 7, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

(Example 8) [Step 1a] 49.62 g of BCD, 21.62 of HOAB
g, γ-caprolactone 1.2 g, pyridine 1.9 g,
A reaction liquid was obtained in the same manner as in [Step 1a] of Example 1 except that 100.0 g of NMP and 20.0 g of toluene were used. [Step 1b] BPDA 29.42 g, bis {4- (4-
Aminophenoxy) benzene} (m-BAPS, chemical formula (13)) 21.63 g, hexamethylenediamine (H
MDA, chemical formula (14)) 17.43 g, NMP45
A varnish was obtained in the same manner as in [Step 1b] of Example 1 except that 8.8 g and toluene 46.2 g were used. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Example 8, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

Example 9 [Step 1a] BCD 49.62 g, 3,5-diaminobenzoic acid (DABz, chemical formula (1)) 30.44 g, γ-
Valerolactone 1.2g, pyridine 1.9g, NMP1
A reaction solution was obtained in the same manner as in [Step 1a] of Example 1 except that 00.0 g and toluene 20.0 g were used. [Step 1b] BPDA 29.42 g, m-BAPS2
1.63 g, HMDA 17.43 g, NMP458.8
g and toluene 46.2 g were used, and a varnish was obtained in the same manner as in [Step 1b] of Example 1. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Example 9, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

Example 10 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 5 phr of hydrogenated acrylonitrile butadiene rubber was dispersed. (Example 11) [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 50 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.

(Example 12) [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] [Step 3] of Example 1 except that 100 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.
A photosensitive polyimide resin composition was obtained in the same manner as.

Example 13 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] [Step 3] of Example 1 except that 200 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.
A photosensitive polyimide resin composition was obtained in the same manner as.

(Example 14) [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 50 phr of chlorinated polyethylene rubber was dispersed.

(Example 15) [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 50 phr of ethylene-propylene rubber was dispersed.

Example 16 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 50 phr of the silicone elastomer was dispersed.

(Example 17) [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 50 phr of polystyrene elastomer was dispersed.

Example 18 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] 50 phr of polyolefin elastomer
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that the photosensitive polyimide resin composition was dispersed.

Table 1 shows the measurement results of the weight average molecular weight of the polyimide resins of Examples 1 to 18 and the photosensitive resolution and warpage of the coating film made of the photosensitive polyimide resin composition. The weight average molecular weight, manufactured by Tosoh Corporation TSKgel GMH _HR -
It calculated | required by polystyrene conversion using a M-type gel column and a UV-8020 type | mold detector. The photosensitive resolution is
Using a vacuum ultraviolet exposure apparatus manufactured by Oak Co., Ltd., a polyimide photosensitive pattern produced by irradiation with 1000 mJ / cm ² through a predetermined mask and development (35 ° C.) using a 75% aminoethanol aqueous solution was performed with an optical microscope. It was observed and measured. The warp is 100 mm × 100 mm, and the photosensitive polyimide resin composition is applied on an electrolytic copper foil having a thickness of 25 μm.
It was pre-dried at 30 ° C. for 30 minutes and then dried at 280 ° C. for 30 minutes to form a coating film having a thickness of 25 μm, and the distance from the bottom surface to the highest point of the substrate was measured on a smooth glass plate.

[0036]

[Table 1]

Example 2, Example 11, Examples 14-18
Table 2 shows the tensile strength of the coating film formed of the photosensitive polyimide resin composition. Tensile strength is obtained by applying a polyimide resin composition on a glass plate, predrying it at 110 ° C. for 30 minutes, and then drying it at 280 ° C. for 30 minutes to produce a film having a thickness of 30 μm. Trim,
This test piece is manufactured by ORIENTEC Tensilon Universal Testing Machine RTC-1310 and data processor MPW-300S.
Was measured at a crosshead speed of 50.00 mm / min under a temperature of 25 ° C. and a humidity of 50%.

[0038]

[Table 2]

Comparative Example 1 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] 2.5 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that phr was dispersed.

Comparative Example 2 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] 250 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that phr was dispersed.

Comparative Example 3 [Step 1a], [Step 1b] Except that the reaction time of [Step 1a] of Example 1 was 0.3 hours and the reaction time of [Step 1b] was 0.3 hours. Example 1
A varnish was obtained in the same manner as in [Step 1a] and [Step 1b]. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Comparative Example 3, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

(Comparative Example 4) [Step 1a], [Step 1b] The reaction time of [Step 1a] of Example 1 was 1 hour, and [Step 1]
A varnish was obtained in the same manner as in [Step 1a] and [Step 1b] of Example 1 except that the reaction time of [b] was changed to 10 hours. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 1. The infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 17
Characteristic absorption of the imide ring was observed at 85 cm ^-1 . [Step 3] Using the polyimide resin powder obtained in [Step 2] of Comparative Example 3, 5 acrylonitrile-butadiene rubber was used.
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 1 except that 0 phr was dispersed.

Comparative Example 5 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] [Step 3] of Example 1 except that 2.5 phr of the hydrogenated acrylonitrile-butadiene rubber was dispersed.
A photosensitive polyimide resin composition was obtained in the same manner as.

Comparative Example 6 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 1. . [Step 3] [Step 3] of Example 1 except that 250 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.
A photosensitive polyimide resin composition was obtained in the same manner as.

Comparative Example 7 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 8. . [Step 3] After that, 4.0 g of polyimide resin powder was dissolved in 20.0 g of NMP, and diazonaphthoquinone sulfonate (NT-200: manufactured by Toyo Gosei Co., Ltd.) was used as a photosensitizer.
Was blended for 15 phr to obtain a photosensitive polyimide resin composition.

Comparative Example 8 [Step 1a], [Step 1b], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1a], [Step 1b] and [Step 2] of Example 9. . [Step 3] After that, 4.0 g of polyimide resin powder was dissolved in 20.0 g of NMP, and diazonaphthoquinone sulfonate (NT-200: manufactured by Toyo Gosei Co., Ltd.) was used as a photosensitizer.
Was blended for 15 phr to obtain a photosensitive polyimide resin composition.

Table 3 shows the measurement results of the weight average molecular weights of the polyimide resins of Comparative Examples 1 to 8 and the photosensitive resolution and warpage of the coating film made of the photosensitive polyimide resin composition.

[0048]

[Table 3]

(Example 19) [Step 1] 21.3 g of BCD, p-DADE 40.0
g, BPDA 58.4 g, HOAB 20.0 g, γ-caprolactone 1.2 g, pyridine 1.9 g, NMP52
After adding 0.0 g and 104.0 g of toluene and stirring at room temperature under a nitrogen atmosphere for 10 minutes, the content of the reaction vessel was 180
The temperature was raised to 0 ° C., and the mixture was stirred for 5 hours for reaction. The number of revolutions of the stirrer was set to 180 rpm, and was appropriately lowered as the reaction was lowered. Then, vacuum drying was performed to obtain a reaction liquid (varnish). Water generated during the reaction was removed from the silicon cock at appropriate times. [Step 2] The varnish obtained in [Step 1] was put into methanol to separate the generated precipitate, and the polyimide resin powder was obtained by the steps of crushing, filtering, washing and drying under reduced pressure. When the infrared absorption spectrum of this polyimide resin powder was measured, characteristic absorption of the imide ring was observed at 1715 cm ^-1 and 1785 cm ^-1 . [Step 3] After that, 4.0 g of polyimide resin powder was dissolved in 20.0 g of NMP, and diazonaphthoquinone sulfonate (NT-200: manufactured by Toyo Gosei Co., Ltd.) was used as a photosensitizer.
Was blended for 15 phr and acrylonitrile butadiene rubber was dispersed for 5 phr to obtain a photosensitive polyimide resin composition.

Example 20 [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 19. [Step 3] 50 p of acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that the dispersion was carried out for hr.

(Example 21) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 19. [Step 3] 100 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that phr was dispersed.

Example 22 [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 19. [Step 3] 200 acrylonitrile butadiene rubber
A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that phr was dispersed.

(Example 23) [Step 1] A varnish was obtained in the same manner as in [Step 1] of Example 1 except that the reaction time in [Step 1] of Example 19 was 1 hour. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 19. Infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 1
Characteristic absorption of the imide ring was observed at 785 cm ^-1 . [Step 3] [Step 3] of Example 19 except that the polyimide resin powder obtained in [Step 2] of Example 23 was used and 50 phr of acrylonitrile butadiene rubber was dispersed therein.
A photosensitive polyimide resin composition was obtained in the same manner as.

Example 24 [Step 1] A varnish was obtained in the same manner as in [Step 1] of Example 1 except that the reaction time in [Step 1] of Example 19 was 8 hours. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 19. Infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 1
Characteristic absorption of the imide ring was observed at 785 cm ^-1 . [Step 3] [Step 3] of Example 19 except that the polyimide resin powder obtained in [Step 2] of Example 24 was used and 50 phr of acrylonitrile butadiene rubber was dispersed therein.
A photosensitive polyimide resin composition was obtained in the same manner as.

Example 25 [Step 1] A varnish was obtained in the same manner as in [Step 1] of Example 1 except that the reaction time in [Step 1] of Example 19 was changed to 9 hours. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 19. Infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 1
Characteristic absorption of the imide ring was observed at 785 cm ^-1 . [Step 3] [Step 3] of Example 19 except that the polyimide resin powder obtained in [Step 2] of Example 25 was used and 50 phr of acrylonitrile butadiene rubber was dispersed therein.
A photosensitive polyimide resin composition was obtained in the same manner as.

Example 26 [Step 1] BCD 49.62 g, HOAB 21.62
g, BPDA 29.42 g, m-BAPS 21.63
g, HMDA 17.43 g, γ-caprolactone 1.2
g, 1.9 g of pyridine, 558.8 g of NMP, and 66.2 g of toluene were used to obtain a reaction liquid in the same manner as in [Step 1] of Example 1. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 19. Infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 1
Characteristic absorption of the imide ring was observed at 785 cm ^-1 . [Step 3] [Step 3] of Example 19 except that the polyimide resin powder obtained in [Step 2] of Example 26 was used and 50 phr of acrylonitrile butadiene rubber was dispersed therein.
A photosensitive polyimide resin composition was obtained in the same manner as.

Example 27 [Step 1] 49.62 g of BCD, DABz 30.44
g, BPDA 29.42 g, m-BAPS 21.63
g, HMDA 17.43 g, γ-valerolactone 1.2
g, 1.9 g of pyridine, 558.8 g of NMP, and 66.2 g of toluene were used, and a reaction liquid was obtained in the same manner as in [Step 1] of Example 19. [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 2] of Example 19. Infrared absorption spectrum of this polyimide resin powder was measured and found to be 1715 cm ^-1 and 1
Characteristic absorption of the imide ring was observed at 785 cm ^-1 . [Step 3] [Step 3] of Example 19 except that the polyimide resin powder obtained in [Step 2] of Example 27 was used and 50 phr of acrylonitrile butadiene rubber was dispersed therein.
A photosensitive polyimide resin composition was obtained in the same manner as.

(Example 28) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 5 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.

(Example 29) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] [Step 3] of Example 19 except that 50 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.
A photosensitive polyimide resin composition was obtained in the same manner as.

(Example 30) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 100 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.

(Example 31) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 200 phr of hydrogenated acrylonitrile butadiene rubber was dispersed.

(Example 32) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 50 phr of chlorinated polyethylene rubber was dispersed.

Example 33 [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 50 phr of ethylene-propylene rubber was dispersed.

(Example 34) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 50 phr of the silicone elastomer was dispersed.

Example 35 [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] A photosensitive polyimide resin composition was obtained in the same manner as in [Step 3] of Example 19 except that 50 phr of the polystyrene elastomer was dispersed.

(Example 36) [Step 1], [Step 2] A polyimide resin powder was obtained in the same manner as in [Step 1] and [Step 2] of Example 27. [Step 3] 50 phr of polyolefin elastomer
A photosensitive polyimide resin composition was obtained in the same manner as in [Process 3] of Example 19 except that the photosensitive polyimide resin composition was dispersed.

Table 4 shows the measurement results of the weight average molecular weight of the polyimide resins of Examples 19 to 36 and the photosensitive resolution and warpage of the coating film made of the photosensitive polyimide resin composition.

[0068]

[Table 4]

[0069]

The photosensitive polyimide resin composition of the present invention contains 5 to 200 parts by weight of an elastomer and 100 parts by weight of a solid content of a solvent-soluble polyimide resin having a weight average molecular weight of 20,000 to 300,000. 5 to photosensitizer
Since it contains 50 parts by weight, it becomes possible to form a coating layer having excellent positive type photosensitive characteristics and capable of suppressing the occurrence of warpage when compounded with another substrate.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 G03F 7/004 501 G03F 7/004 501 7/022 7/022 H01L 21 / 027 H01L 21/30 502R (72) Inventor Seiji Kamimura 5-1-1 Hidaka-cho, Hitachi-shi, Ibaraki Hitachi Cable, Ltd. Research Institute of Technology (72) Inventor Yoshiyuki Ando 5 Hidaka-cho, Hitachi-shi, Ibaraki 1-1-1, Hitachi Cable Co., Ltd., Comprehensive Research Laboratory (72) Inventor Kenji Asano 5-1-1, Hidakacho, Hitachi City, Ibaraki Hitachi Cable, Co., Ltd. (72) Inventor, Yuzo Ito Ibaraki Prefecture 5-1-1, Hidaka-cho, Hitachi City F-term in the Research Institute of Hitachi Cable, Ltd. (reference) 2H025 AA02 AB15 AB17 AD03 BE01 CB25 CC05 CC20 FA03 FA15 4J002 AC07X AC11X BB01X BB15X BB24X BC02X CM04W CP03X EV236 FD146 GQ01 GQ05 4J043 PA02 PA15 PA19 PC016 PC116 PC146 QB26 QB31 RA35 RA42 RA52 SA72 SB01 TA47 TB01 UA121 UA122 UA132 UA141 UA151 UA341 UA461 UA621 UA692 UA761 UA771 UB011 UB012 UB021 UB121 UB122 UB152 UB301 VA011 VA021 VA022 VA031 VA051 VA052 VA062 ZA31 ZA46 ZB50

Claims (5)

[Claims] 1. A compound obtained by reacting at least one compound selected from diamines and at least one compound selected from acid dianhydrides in an organic solvent and having a weight average molecular weight of 2
An elastomer is added to 5 parts by weight with respect to 100 parts by weight of the solid content of the solvent-soluble polyimide resin of 30,000 to 300,000.
A photosensitive polyimide resin composition comprising 200 parts by weight and 1 to 50 parts by weight of a photosensitizer. 2. The solvent-soluble polyimide resin is represented by the chemical formula: Or [Chemical 2] The photosensitive polyimide resin composition according to claim 1, wherein at least one compound represented by the formula (1) is subjected to the reaction. 3. The solvent-soluble polyimide resin is represented by the chemical formula: Or [Chemical 4] At least one compound represented by: and [Chemical 6] [Chemical 7] [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] [Chemical 17] [Chemical 18] And [Chemical 19] The photosensitive polyimide resin composition according to claim 1, wherein at least one selected from the compounds represented by: is subjected to the reaction. 4. The solvent-soluble polyimide resin is as an acid dianhydride. [Chemical 21] [Chemical formula 22] [Chemical formula 23] [Chemical formula 24] And [Chemical 25] The photosensitive polyimide resin composition according to claim 1, wherein at least one selected from the group is subjected to the reaction. 5. The elastomer is selected from chlorinated polyethylene rubber, ethylene propylene rubber, silicone rubber, styrene thermoplastic elastomer, olefin thermoplastic elastomer, acrylonitrile butadiene rubber and hydrogenated acrylonitrile butadiene rubber. The photosensitive polyimide resin composition according to claim 1, which is at least one kind.