JPH06192572A - Polyimide resin composition - Google Patents

Abstract

(57) [Summary] [Configuration] The following formula (1) A polyimide resin composition obtained by mixing 0.5 part by weight or more and less than 100 parts by weight of an aromatic polyimide oligomer with 100 parts by weight of the polyimide resin shown in. [Effect] By adding the aromatic polyimide oligomer, it was possible to significantly reduce the viscosity of the resin when melted and improve the molding processability.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyimide resin composition having excellent moldability.

[0002]

2. Description of the Related Art Thermoplastic polyimide resins represented by Ultem (registered trademark of GE) are superior to general-purpose engineering plastics in terms of heat resistance and mechanical strength, and are called super engineering plastics. It has been widely studied in applications such as electronic devices, machines, and automobiles.

Recently, with the progress of technology, development of a novel thermoplastic polyimide resin having heat resistance and mechanical properties higher than that of Ultem is required.

For example, a method for producing a polyimide resin obtained by reacting ether diamine and tetracarboxylic dianhydride is disclosed in US Pat. No. 4,847,349.
A method for producing a polyimide resin obtained by reacting 3,3′-diaminobenzophenone and tetracarboxylic dianhydride has also been submitted by JP-A-2-018419. All of them provide a novel polyimide resin having heat resistance and mechanical properties which are not available in the past.

[0005]

However, polyethylene terephthalate, polybutylene terephthalate,
Compared to ordinary engineering plastics represented by polyether sulfone, polysulfone, polyphenylene sulfide, etc., although the above-mentioned polyimide is far superior in heat resistance and other characteristics, when the molecular weight increases, melt flowability decreases, Moldability still falls short of those resins. Further, it was found that the addition of bisimide, which is the minimum unit of polyimide, increases the melt fluidity, and filed an application earlier (Japanese Patent Application No. 03-28).
7660). However, in this case, the mechanical properties and heat resistance inherent to the polyimide resin may be impaired.

An object of the present invention is to provide a polyimide resin composition for molding which is extremely excellent in terms of fluidity when melted, without impairing the inherent properties of polyimide.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors found that a polyimide resin composition comprising a specific polyimide and a specific polyimide oligomer has the above-mentioned object. The inventors have found that it is effective and completed the present invention. That is, the present invention is basically represented by the following formula (1)

[0008]

[Chemical 3]

[Wherein, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group,
Represents a group selected from the group consisting of a carbonyl group, a thio group and a sulfonyl group, Y _{1 to} Y ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, which may be the same or different. Good. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ] A polyimide resin composition obtained by mixing 0.5 part by weight or more and less than 100 parts by weight of an aromatic polyimide oligomer with 100 parts by weight of a polyimide resin represented by the following repeating unit, wherein the aromatic polyimide has the following formula (2). (Chemical formula 4)

[0010]

[Chemical 4]

[Wherein X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group,
Represents a group selected from the group consisting of a carbonyl group, a thio group and a sulfonyl group, Y _{1 to} Y ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, which may be the same or different. Good. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ] The polyimide resin composition shown by the repeating unit.

The logarithmic viscosity of the polyimide resin powder represented by the above formula (1) is usually 0.40 to 1.50 dl / g, preferably 0.40 to 1.20 dl / g. 0.
If it is less than 40, it is difficult to obtain desired mechanical properties, and if it is more than 1.50, the melt viscosity becomes high and the moldability becomes poor.

The logarithmic viscosity of the aromatic polyimide oligomer represented by the above formula (2) is usually 0.10 to 0.3.
It is in the range of 8 dl / g, preferably 0.20 to 0.30 dl / g. If it is less than 0.10, it is difficult to maintain the mechanical properties and heat resistance, and if it is more than 0.38, the improvement of the melt fluidity is not observed, and the improvement of the moldability, which is the object of the present invention, is not recognized. More preferably, if the difference between the logarithmic viscosity of the polyimide resin powder represented by the formula (1) and the logarithmic viscosity of the aromatic polyimide oligomer represented by the formula (2) is 0.20 or more, the effect of the present invention is further enhanced. Become. The logarithmic viscosity shown here is a value measured by heating and dissolving the solvent in a mixed solvent of parachlorophenol / phenol (weight ratio 90/10) at a concentration of 0.5 g / 100 ml, followed by cooling to 35 ° C. The polyimide resin represented by the above formula (1) has the following formula (3)

[0014]

[Chemical 5]

[Wherein X, Y _{1 to} Y ₄ and R are the same as before. ] And the following formula (4)
(Chemical formula 6)

[0016]

[Chemical 6]

Wherein R is the same as before. ] It is a polyimide synthesize | combined by dehydrating cyclization of the polyamic acid obtained by making it react with 1 or more types of tetracarboxylic dianhydride shown by these.

Specifically, JP-A-61-143478, 6
2-68817, 62-205124, JP-A-1-11
It can be easily adjusted by the method disclosed by 0530 and the like.

As the diamine represented by the above formula (3), bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2 , 2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,
5-dimethylphenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) -3-methylbiphenyl, 4,4'-bis (3-aminophenoxy)- 3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,5-Dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy)
-3,3'-dichlorobiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,5-dichlorobiphenyl,
4,4'-bis (3-aminophenoxy) -3,3 ',
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3
-Aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- ( 3-aminophenoxy) phenyl] sulfone and the like can be mentioned, and these can be used alone or in admixture of two or more.

Examples of the tetracarboxylic acid dianhydride of the formula (4) used in this method include ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride and pyromellitic acid. Acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid Acid dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-
Biphenyl tetracarboxylic dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (2,2
3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
(4,4'-p-phenylenedioxy) diphthalic dianhydride, 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

In the production of the polyimide resin represented by the formula (1) of the present invention, a range that does not impair the good properties of the polyimide resin of the present invention, for example, 50% by weight or less, preferably 30% by weight of the amount of the diamine is preferable. Other diamines can be used in place of the weight% or less.

Further, in the production of the polyimide resin represented by the above formula (1), it is preferable to carry out the reaction in the presence of a dicarboxylic acid anhydride or a monoamine in order to improve the thermal stability. is there.

The aromatic polyimide oligomer used as a fluidization accelerator in the present invention is represented by the above formula (2) and has the following formulas (5) and (7).

[0024]

[Chemical 7]

[Wherein X, Y _{1 to} Y ₄ and R are the same as before. ] And the following formula (6)
(Chemical formula 8)

[0026]

[Chemical 8]

Wherein R is the same as before. ] It is an aromatic polyimide oligomer synthesize | combined by dehydrating cyclization of the polyamic acid obtained by making it react with 1 or more types of tetracarboxylic dianhydride shown by these.

Specifically, JP-A-61-143478, 6
2-68817, 62-205124, JP-A-1-11
It can be easily adjusted by the method disclosed by 0530 and the like.

The diamine represented by the above formula (5) includes bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 2, 2-bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2 , 2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3,
5-dimethylphenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3
-Hexafluoropropane, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) -3-methylbiphenyl, 4,4'-bis (3-aminophenoxy)- 3,3'-dimethylbiphenyl, 4,4'-bis (3-aminophenoxy)-
3,5-Dimethylbiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetramethylbiphenyl, 4,4'-bis (3-aminophenoxy)
-3,3'-dichlorobiphenyl, 4,4'-bis (3
-Aminophenoxy) -3,5-dichlorobiphenyl,
4,4'-bis (3-aminophenoxy) -3,3 ',
5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3'-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,
5-dibromobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrabromobiphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3
-Aminophenoxy) phenyl] [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfide, bis [4- ( 3-aminophenoxy) phenyl] sulfone and the like can be mentioned, and these can be used alone or in admixture of two or more.

Examples of the tetracarboxylic acid dianhydride of the formula (6) used in this method include ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride and pyromellitic acid. Acid dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride,
2,2-bis (3,4-dicarboxyphenyl) -1,
1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl)-
1,1,1,3,3,3-hexafluoropropane dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid Acid dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-
Biphenyl tetracarboxylic dianhydride, bis (3,4-
Dicarboxyphenyl) ether dianhydride, bis (2,2
3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride,
(4,4'-p-phenylenedioxy) diphthalic dianhydride, 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride , 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

In the production of the aromatic polyimide oligomer represented by the formula (2) of the present invention, a range which does not impair the good properties of the aromatic polyimide oligomer of the present invention, for example, usually 50% by weight or less based on the amount of the diamine. Other diamines may be used as substitutes, preferably within the range of 30% by weight or less.

In the production of the aromatic polyimide oligomer represented by the above formula (2), it is preferable to carry out the reaction in the presence of dicarboxylic acid anhydride or monoamine in order to improve the thermal stability. Is the way.

The molding resin composition of the present invention has the above formula (1).
0.5 part by weight or more of the aromatic polyimide oligomer represented by the formula (2) per 100 parts by weight of the polyimide of
It is used in the range of less than 00 parts by weight. The effect of the aromatic polyimide oligomer as a fluidization accelerator is recognized even in a relatively small amount, and the lower limit thereof is 0.5 parts by weight with respect to 100 parts by weight of polyimide, but preferably 1 part by weight or more and 20 parts by weight or more.
Parts by weight. However, when 100 parts by weight or more of the aromatic polyimide oligomer is used, the mechanical strength of the obtained polyimide resin composition is impaired, so there is an upper limit to the amount used, and it is preferable to use less than 100 parts by weight. .

In preparing the polyimide resin composition according to the present invention, it can be produced by a generally known method. For example, the following method is a preferable method.

1. The polyimide resin powder and the aromatic polyimide oligomer are pre-kneaded into a powder form using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender and the like.

2. The polyimide resin powder is dissolved or suspended in an organic solvent in advance, and the aromatic polyimide oligomer is added to this solution or suspension to uniformly disperse or dissolve, and then the solvent is removed to obtain a powder.

3. In an organic solvent solution of a polyamic acid that is a precursor of polyimide, an aromatic polyimide oligomer and / or an aromatic polyamic acid oligomer that is a precursor thereof is dissolved or suspended, and then heat-treated at 100 to 400 ° C., Alternatively, after chemically imidizing using a commonly used imidizing agent, the solvent is removed to obtain a powder.

The powdery resin composition thus obtained is directly used for various molding applications, such as injection molding, compression molding, transfer molding, extrusion molding, etc., but it is further used after melt blending. This is the preferred method.

For the melt-blending, the equipment used for melt-blending ordinary rubber or plastics, for example, hot roll, Banbury mixer, Brabender, extruder or the like can be used. The melting temperature is set above the melting temperature of the compounding system and below the temperature at which the compounding system begins to thermally decompose, but the temperature is usually 280 to 420.
C., preferably 300 to 400.degree.

The molding method of the resin composition of the present invention includes:
Extrusion molding or injection molding, which is a molding method that forms a homogeneous melt blend and has high productivity, is suitable, but other transfer molding, compression molding, sinter molding, extrusion film molding and the like are also applied. Further, in the production of a prepreg for a composite material, the uniformly adjusted resin composition can be melt-impregnated into carbon fiber, glass fiber or the like, or a polyimide resin or an aromatic polyimide oligomer can be uniformly dispersed or A method of impregnating various fibers with the dissolved liquid and then removing the solvent can also be adopted.

One or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead monoxide and lead powder can be added to the resin composition of the present invention. It is also possible to add one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide, silicon carbide fiber, potassium titanate fiber and glass beads.

With respect to the resin composition of the present invention, an antioxidant, a heat stabilizer,
One or more ordinary additives such as an ultraviolet absorber, a flame retardant, a flame retardant aid, an antistatic agent, a lubricant and a coloring agent can be added.

[0043]

EXAMPLES The present invention will be described in more detail with reference to synthesis examples, examples and comparative examples. Synthesis Example 1 Synthesis of Polyimide Based on JP-A-1-110530, 4,4′-bis (3
-Aminophenoxy) biphenyl and pyromellitic dianhydride and phthalic acid have a logarithmic viscosity of 0.50 dl / g [where the logarithmic viscosity is parachlorophenol: phenol (weight ratio 9
It is a value measured after dissolving with heating at a concentration of 0.5 g / 100 ml using a mixed solvent of 0:10) and then cooling to 35 ° C. ] The polyimide powder of was obtained. This polyimide had a glass transition temperature of 250 ° C. and a melting point of 390 ° C. (by DSC).

Synthesis Example 2 Synthesis of Polyimide Polyimide powder was obtained in the same manner as in Synthesis Example 1, except that the type of diamine was changed. Table 1 collectively shows the physical properties of the raw materials and the produced polyimide. Table 1 also shows the results of Synthesis Example 1.

[0045]

[Table 1]

Synthesis Example 3 Synthesis of aromatic polyimide oligomer 368.4 g (1.0 mol) of 4,4'-bis (3-aminophenoxy) biphenyl was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. , Phthalic anhydride 59.
24 g (0.4 mol), pyromellitic dianhydride 174.5
g (0.8 mol) and m-cresol (2,172 g) were charged, the mixture was heated to 200 ° C. under stirring, and kept at 200 ° C. for 6 hours. Then, toluene was charged to the reaction solution, the precipitate was filtered off, and further washed with toluene several times,
It was dried at 250 ° C. for 6 hours in a nitrogen atmosphere to obtain a polyimide oligomer powder having a logarithmic viscosity of 0.21 dl / g.
This polyimide has a glass transition temperature of 210 ° C. and a melting point of 3
It was 85 ° C (by DSC).

Synthesis Example 4 Synthesis of Aromatic Polyimide Oligomer An aromatic polyimide oligomer powder was obtained in the same manner as in Synthesis Example 3, except that the type of diamine was changed. Raw materials in Table 2,
The physical properties of the resulting aromatic polyimide oligomer are summarized below. The results of Synthesis Example 3 are also shown in Table 2.

[0048]

[Table 2]

Examples 1 to 3 and Comparative Example 1 The polyimide obtained in Synthesis Example 1 and the aromatic polyimide oligomer obtained in Synthesis Example 3 were dry blended in the proportions shown in Table 3. The obtained resin composition was used with a Koka type flow tester (CFT-500 manufactured by Shimadzu Corporation) to have a diameter of 0.1c.
Using an orifice of m and 1 cm in length, the temperature was kept at 420 ° C. for 5 minutes and then extruded under a load of 100 kg to measure the melt viscosity. The results are shown in Table 3. Further, the obtained resin composition was extruded at 400 ° C. using a twin-screw melt extruder and granulated. The obtained pellets are subjected to injection molding at a molding temperature of 400 ° C. and a mold temperature of 150 ° C. by using an ordinary injection molding machine,
The heat distortion temperature (HDT) of the molded product was measured. The results are shown in Table 3.
Shown in. In the table, the heat distortion temperature is according to ASTM D-648.

Comparative Examples 2 to 4 Polyimide obtained in Synthesis Example 1 and Japanese Patent Application No. 03-004
According to 963, bisimide synthesized from 4,4′-bis (3-aminophenoxy) biphenyl and phthalic anhydride was dry-blended in the ratio shown in Table 3. Melt viscosity and heat distortion temperature were measured in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Examples 4 to 6 and Comparative Example 5 The polyimide obtained in Synthesis Example 2 and the aromatic polyimide oligomer obtained in Synthesis Example 4 were dry blended in the proportions shown in Table 3. In measuring the melt viscosity, the melt viscosity and the heat distortion temperature were measured in the same manner as in Example 1 except that the temperature was kept at 400 ° C. for 5 minutes, and the results shown in Table 3 were obtained.

Comparative Examples 6 to 8 The polyimide obtained in Synthesis Example 2 and Japanese Patent Application No. 03-004.
In accordance with 963, bis [4- (3-aminophenoxy)
Bisimide synthesized from phenyl] sulfide and phthalic anhydride was dry blended at the ratio shown in Table 3. Melt viscosity and heat distortion temperature were measured in the same manner as in Example 4, and the results shown in Table 3 were obtained.

[0053]

[Table 3]

[0054]

EFFECT OF THE INVENTION By adding an aromatic polyimide oligomer, it is possible to significantly reduce the viscosity of the resin before melting without significantly reducing the heat resistance of the polyimide resin and improve the molding processability. It was

Claims (4)

[Claims] 1. The following formula (1) (formula 1) [Wherein, X represents a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ] Polyimide resin 100 represented by repeating unit
A polyimide resin composition comprising 0.5 part by weight or more and less than 100 parts by weight of an aromatic polyimide oligomer with respect to parts by weight. 2. A mixed solvent having a logarithmic viscosity [parachlorophenol: phenol (weight ratio 90:10) of the polyimide resin represented by the above formula (1), and a concentration of 0.5 g / 10.
It was heated and dissolved in 0 ml solvent, cooled and measured at 35 ° C] was 0.4
The polyimide resin composition according to claim 1, which is 0 to 1.50 dl / g. 3. The aromatic polyimide oligomer has the following formula (2) (formula 2): [Wherein, X represents a group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group or a sulfonyl group, and Y _{1 to} Y ₄ represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different. R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic groups are directly or crosslinked with each other. Represents a tetravalent group selected from the group consisting of formula aromatic groups. ] The polyimide resin composition of Claim 1 shown by the repeating unit. 4. The logarithmic viscosity of the aromatic polyimide oligomer represented by the above formula (2) is 0.10 to 0.38 dl / g.
The polyimide resin composition according to claim 1, which is