JPH0822956B2 - Polyimide resin composition - Google Patents

Description

The present invention relates to a resin composition for molding. For more details,
The present invention relates to a polyimide-based molding resin composition having excellent heat resistance, chemical resistance, mechanical strength, and the like, and excellent molding processability.

[Conventional technology]

Conventionally, polyimide obtained by the reaction of tetracarboxylic dianhydride and diamine has high mechanical strength, dimensional stability, flame retardancy, and electrical insulation in addition to its high heat resistance. , Aerospace equipment, transportation equipment, etc., and is expected to be widely used in the fields where co-heat resistance is required in the future.

Various polyimides having excellent characteristics have been developed so far.

However, even if it is excellent in heat resistance, it does not have a clear glass transition temperature, so when it is used as a molding material, it must be processed using a method such as sintering molding. In addition, it has a low glass transition temperature, is soluble in halogenated hydrocarbons, is not satisfactory in terms of heat resistance and solvent resistance, and has advantages and disadvantages in performance.

[Problems to be solved by the invention]

An object of the present invention is to obtain a polyimide resin composition having excellent molding properties in addition to the excellent properties inherent to polyimide.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have found that a polyimide-based resin composition consisting of a novel polyimide and a specific amount of aromatic polysulfone is particularly effective for the above purpose. Completed the invention.

The present inventor has previously shown that polyimide having excellent mechanical properties, thermal properties, electrical properties, solvent resistance, etc. (In the formula, 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-bonded group in which aromatic groups are directly or cross-linked with each other. A resin having a repeating unit represented by the formula (4) represents a tetravalent group selected from the group consisting of condensed polycyclic aromatic groups.
(See JP-A-62-50372).

The above polyimide is a novel heat resistant resin having many good physical properties peculiar to polyimide. However, compared with ordinary engineering plastics represented by polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, polyphenylene sulfide, etc., the above-mentioned polyimide is much superior in heat resistance and other characteristics, but has a large molecular weight. If so, melt flowability is lowered, and moldability is still inferior to those resins.

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

That is, the present invention is (In the formula, R is Represents at least one tetravalent group selected from the group consisting of: ) A resin composition comprising 99.9 to 50% by weight of a polyimide having a repeating unit represented by: and 0.1 to 50% by weight of an aromatic polysulfone.

The polyimide used in the present invention has a formula as a diamine component. An ether diamine represented by, namely, 1,4-bis [4
-(3-Aminophenoxy) benzoyl] benzene and / or 1,3-bis [4- (3-aminophenoxy)
Benzoyl] benzene is used, which is obtained by imidizing a polyamic acid obtained by reacting this with one or more tetracarboxylic dianhydrides in an organic solvent.

The tetracarboxylic dianhydride used at this time has the formula (Wherein R is the same as described above).

That is, the tetracarboxylic dianhydride used is ethylene tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride Product, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane Dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-phenylenedioxy) diphthalate Acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride Anhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride , 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and these tetracarboxylic dianhydrides are independent. There may be used a mixture of two or more.

The polyimide used in the composition of the present invention is a polyimide used as a raw material for the ether diamine, but a polyimide obtained by mixing and using another diamine within a range that does not impair the good physical properties of the polyimide. Can also be used in the compositions of the present invention.

Examples of the diamine that can be used as a mixture include m-phenylenediamine, o-phenylenediamine,
p-phenylenediamine, m-aminobenzylamine,
p-aminobenzylamine, bis (3-aminophenyl) ether, (3-aminophenyl) (4-aminophenyl) ether, bis (4-aminophenyl) ether, bis (3-aminophenyl) sulfide, (3- Aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-aminophenyl)
(4-aminophenyl) sulfoxide, bis (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3 , 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, bis [4- (3-aminophenoxy) phenyl] methane,
Bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4
-Aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane,
2,2-bis [4- (4-aminophenoxy) phenyl]
Propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene ,
1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [ 4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4
-Aminophenoxy) phenyl] sulfide, bis [4
-(3-aminophenoxy) phenyl] sulfoxide,
Bis [4- (4-aminophenoxy) phenyl] sulfoxide, Bis [4- (3-aminophenoxy) phenyl] sulfone, Bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [4- (3-amino) Examples thereof include phenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether.

The aromatic polysulfone used as a fluidization accelerator in the present invention is A polysulfone having a repeating unit such as "VICTREX PE from the UK
Polyethersulfone commercially available under the trademark "S" and / or a general formula "UDEL POLY" from Union Carbide
Mention may be made of the polysulfones marketed under the trademark "SULFONE".

As these aromatic polysulfones, those having various degrees of polymerization can be freely produced, and those having a melt viscosity characteristic suitable for a target blend can be arbitrarily selected.

The molding resin composition of the present invention is the polyimide 99.9 to 50
%, Aromatic polysulfone is adjusted to be in the range of 0.1 to 50% by weight.

The polyimide / aromatic polysulfone composite resin system of the present invention exhibits remarkably low melt viscosity in a high temperature range such as 350 ° C. or higher. The good fluidizing effect of the aromatic polysulfone is recognized even in a small amount, and the lower limit of the composition ratio is 0.1% by weight, but preferably 0.5% by weight or more.

The mechanical strength of aromatic polysulfone at high temperature belongs to the excellent class of heat-resistant resins, but
In particular, since the Izod impact strength is inferior to that of polyimide, if the amount of aromatic polysulfone in the composition is too large, the mechanical strength inherent to polyimide cannot be maintained, which is not preferable. Therefore, the composition ratio of the aromatic polysulfone has an upper limit and is preferably 50% by weight or less.

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

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

(2) Polyimide powder is dissolved or suspended in an organic solvent in advance, and aromatic polysulfone is added to this solution or suspension to uniformly disperse or dissolve, and then the solvent is removed to obtain a powder.

(3) An aromatic polysulfone is dissolved or suspended in a solution of a polyamic acid, which is a precursor of the polyimide of the present invention, in an organic solvent, followed by heat treatment at 100 to 400 ° C, or a commonly used imidizing agent. After chemical imidization using
Remove the solvent to give a powder.

The powdery polyimide resin composition thus obtained is directly used for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use it after melt blending. Is. Particularly, in mixing and preparing the composition, it is a simple and effective method to mix powders, mix pellets, or mix powders and pellets.

For the melt blending, devices used for melt-blending ordinary rubber or plastics, for example, a hot roll, a Banbury mixer, a Brabender, an extruder and the like can be used. The melting temperature is set to a temperature higher than the melting temperature of the blending system and lower than the temperature at which the blending system starts to thermally decompose, and the temperature is usually 280 to 420 ° C., preferably 30 ° C.
0-400 ° C.

As a molding method of the resin composition of the present invention, injection molding or extrusion molding, which is a molding method of forming a homogeneous melt blend and having high productivity, is preferable, but other transfer molding, compression molding, or sintering molding is performed. There is no problem even if shape or extrusion film molding is applied.

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. Further, one or more reinforcing agents such as glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, potassium titanate fiber, and glass beads can be added.

In addition, with respect to the resin composition of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, an antistatic agent, a lubricant, and a coloring material, within a range that does not impair the object of the present invention. One or more usual additives such as can be added.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples.

Synthesis Example-1 5 kg (10 mol) of 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene and N, N-dimethylacetamide 40.5 were placed in a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube. Into a nitrogen atmosphere, 2.147 kg (9.85 mol) of pyromellitic dianhydride was added in 5 portions under a nitrogen atmosphere while stirring, and the mixture was stirred for about 2 hours. Next, the above solution was returned to room temperature and subsequently stirred under a nitrogen atmosphere for about 20 hours.

To the polyamic acid solution thus obtained, 2.02 kg (20 mol) of triethylamine and 2. under a nitrogen atmosphere at room temperature.
55 kg (25 mol) of acetic anhydride was added dropwise. The mixture was stirred at room temperature for about 20 hours to give a yellow slurry. This slurry was filtered to obtain polyimide powder. The polyimide powder was sludged with methanol, separated, and dried under reduced pressure at 150 ° C. for 8 hours to obtain 6.6 kg of a pale yellow polyimide powder. DSC of this powder
The measured glass transition temperature was 235 ° C.

The logarithmic viscosity of this polyimide powder was 0.86 dl / g. The logarithmic viscosity here is that 35 g of polyimide powder is dissolved by heating in a mixed solvent of p-chlorophenol and phenol (p-chlorophenol: phenol = 90: 10 weight ratio).
It is a value measured by cooling to ℃.

FIG. 1 shows an infrared absorption spectrum of the obtained polyimide powder.

In this spectrum, the characteristic absorption band of imide is 17
Absorption near 1240 cm ^-1 is 80 cm ^-1 and around 1720 cm ^-1 and near the characteristic absorption band of ether linkage was clearly observed.

Examples-1 to 3 Polyimide powders obtained in Synthesis Example-1 and aromatic polysulfone powders, which are commercially available UDEL POLYSU
LFONE P-1700 (trademark of Union Carbide Co., USA) was dry blended with various compositions as shown in Table 1 and then extruded at 300 to 330 ° C. using a twin-screw extruder to granulate.

The obtained pellets were applied to an injection molding machine and injection-molded at a cylinder temperature of 330 to 360 ° C. and a mold temperature of 150 ° C., and the physical and thermal properties of the molded product were measured.

The results are shown in Table 1 as Examples-1 to 3. In the table, the minimum injection molding pressure which is a measure of moldability is also shown.

In the table, tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ASTM D-790, and Izod impact value is AST.
MD-256, glass transition temperature is TMA penetration method, heat distortion temperature is A
Based on STM D-648.

Comparative Example-1 Using the composition outside the scope of the present invention, the physical and thermal properties of the molded articles obtained by the same operation as in Examples-1 to 3 were measured, and the results are compared in Table 1. This is shown as Example-1.

Synthesis Examples-2 to 5 Various polyimides were obtained in the same manner as in Synthesis Example-1 by combining various diamines and various tetracarboxylic dianhydrides.

Table 2 shows the polyimide resin synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Examples-4 to 11 and Comparative Examples-2 to 5 Polyimide powders obtained in Synthesis Examples-2 to 5 and aromatic polysulfones, which are commercially available UDEL POLYSULFON
EP-1700 (trademark of Union Carbide, USA) or VICTREX PES 3600P (trademark of ICC Ltd.) having the composition shown in Tables 3 to 5 is extruded while being melt-kneaded by an extruder to obtain a uniform blend pellet Obtained.

Next, the uniformly compounded pellets obtained above were used in Example-1.
When injection molding was carried out under the same conditions as described in Nos. 1 to 3 and physical and thermal properties were measured, the results shown in Tables 3 to 5 were obtained.

[Effect of the Invention] According to the method of the present invention, a polyimide resin composition is provided which has not only excellent properties inherent to polyimide but also excellent moldability.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of an example of polyimide used in the polyimide resin composition of the present invention.

Claims (1)

[Claims] 1. A formula (In the formula, R is Represents at least one tetravalent group selected from the group consisting of ) Polyimide having repeating unit represented by 99.9
~ 50% by weight A polyimide resin composition comprising 0.1 to 50% by weight of an aromatic polysulfone comprising at least one repeating unit selected from the group consisting of: