JPH0676552B2 - Polyimide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a molding resin composition. More specifically, it 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 comprising a novel polyimide and a specific amount of aromatic polysulfone is particularly effective for the above purpose. Completed the invention.

The inventor has previously described mechanical properties, thermal properties, electrical properties,
Formulated as a polyimide with excellent solvent resistance and heat resistance (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member. . The present invention has found a resin having a repeating unit represented by the formula (Japanese Patent Application No. 62-076095).

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 has much better heat resistance and other properties, 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 A polyimide having a repeating unit represented by the formula (wherein R is the same as above) 99.9 to 50
The resin composition is composed of 0.1% by weight and 0.1 to 50% by weight of aromatic polysulfone.

The polyimide used in the present invention has a formula as a diamine component. Ether diamine represented by bis [4- {3-
(4-aminophenoxy) benzoyl} phenyl] ether is used, and it is obtained by imidizing a polyamic acid obtained by reacting this with one or more tetracarboxylic dianhydrides.

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

That is, as the tetracarboxylic dianhydride used,
Ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid anhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4 '
-Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'
-Biphenyltetracarboxylic dianhydride, 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 dianhydride, 4,4 '-(m-phenylenedioxy)
Diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,
3,6,7-anthracene tetracarboxylic dianhydride, 1,2,
7,8-phenanthrenetetracarboxylic dianhydride and the like, and these tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Incidentally, the polyimide used in the composition of the present invention is a polyimide used as a raw material of the above ether diamine, polyimide obtained by mixing and using other diamine within the range not impairing good physical properties of this polyimide Can also be used in the compositions of the present invention.

Examples of diamines that can be mixed and used include m-phenylenediamine, o-phenylenediamine, and 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-hexafluoro Propane, 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 (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,
Examples thereof include bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether.

The aromatic polysulfone used as the fluidization accelerator in the present invention is A polysulfone having a repeating unit such as "VICTREX PES" from ICI Corp., UK
Polyethersulfone marketed under the trademark and / or the general formula "UDELPOLYSU from Union Carbide Company of the United States.
Mention may be made of the polysulfones marketed under the trademark "LFONE".

As these aromatic polysulfones, those having various degrees of polymerization can be freely produced, and those having appropriate melt viscosity characteristics for the intended blend can be arbitrarily selected.

The molding resin composition of the present invention is adjusted so that the polyimide is in the range of 99.9 to 50% by weight and the aromatic polysulfone is 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.

Further, the mechanical strength of aromatic polysulfone at high temperature belongs to an excellent class among heat-resistant resins, but the mechanical strength is inferior to that of polyimide, so if the amount of aromatic polysulfone in the composition is too large. However, 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.

When the composition according to the present invention is mixed and adjusted, it 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 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 melt blending, the equipment used to melt blend ordinary rubbers or plastics, such as hot rolls,
A Banbury mixer, Brabender, extruder, etc. can be used. The melting temperature is set to a temperature above which the compounding system can be melted, and below the temperature at which the compounding system begins to thermally decompose.
It is 00 ° C.

As the molding method of the resin composition of the present invention, injection molding or extrusion molding, which is a molding method of molding a homogeneous melt blend and having high productivity, is preferable, but other transfer molding, compression molding, or sintering molding is performed. Shape, extrusion film molding, etc. can be applied without any problem.

One or more solid lubricants such as molybdenum disulfide, graphite, boric acid 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 fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, potassium titanate fibers, and glass beads.

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 A reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube was charged with 5.92 kg (10 mol) of bis [4- {3- (4-aminophenoxy) benzoyl} phenyl] ether and N,
Charge 18.8 kg of N, -dimethylacetamide, and under a nitrogen atmosphere at room temperature, 2.14 kg (9.8 mol) of pyromellitic dianhydride.
Was added while paying attention to the rise of the solution temperature, and the mixture was stirred at room temperature for about 24 hours to obtain a polyamic acid solution.

Add N, N-dimethylacetamide 5.3 to this polyamic acid solution.
Add 7 kg and stir at room temperature in a nitrogen atmosphere at 4.08 k
g (40 mol) triethylamine and 6.03 kg (60 mol) acetic anhydride were added dropwise. After stirring for about 24 hours at room temperature, the solution was discharged into 250 l of water with vigorous stirring. The resulting precipitate was filtered off, washed with methanol, and then dried under reduced pressure at 150 ° C for 24 hours to obtain 7.47 kg (yield 97.0
%) Light yellow polyimide powder was obtained.

The polyimide powder had an inherent viscosity of 0.86 dl / g. Here, the logarithmic viscosity is 0.5 g of polyimide powder and p-chlorophenol and phenol mixed solvent (p-chlorophenol:
(Phenol = 90:10 weight ratio) It is a value measured by heating and dissolving in 100 g and cooling to 35 ° C.

The glass transition temperature of this powder measured by DSC was 235 ° C.

Examples-1 to 3 Polyimide powder obtained in Synthesis Example-1 and aromatic polysulfone powder, which are commercially available UDEL POLYSULFO
NE P-1700 (Trademark of Union Carbide, USA) is shown in Table-1.
After dry blending with various compositions as described above, the mixture was extruded at 360 to 390 ° C. and granulated using a twin-screw melt extruder.

The obtained pellets were applied to an injection molding machine and injection-molded at a cylinder temperature of 360 to 390 ° C and a mold temperature of 170 ° 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 an index of moldability, is also shown.

In the table, tensile strength and elongation at break are ASTM D-638, bending strength and flexural modulus are ASTM D-790, and Izod impact value is ASTM D-2.
56, glass transition temperature is TMA penetration method, heat distortion temperature is ASTM D-
According to 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 By combining various diamines and various tetracarboxylic dianhydrides, the same procedure as in Synthesis Example-1 was performed to obtain various polyimide powders.

Table 2 shows the polyimide resin synthesis conditions, and the logarithmic viscosity and glass transition temperature of the produced polyimide powder. Examples 4-1
1. Comparative Examples-2 to 5 Polyimide powders obtained in Synthesis Examples-2 to 5 and aromatic polysulfone, which are commercially available UDELPOLYSULFONE P-
1700 (trademark of Union Carbide Corporation, USA) or VICTRE
X-PES 3600P (trademark of IC eye company)
With the above composition, an operation of extruding while melt-kneading with an extruder was performed to obtain a uniform blended pellet.

Next, the uniformly compounded pellets obtained above were used in Example-1 to
Injection molding was carried out under the same conditions as in 3, and the physical and thermal properties were measured.

The results of compositions within the scope of the present invention are shown in Examples -4- In Table 11, compositions outside the range are shown in Tables 3 to 4 as Comparative Examples 2 to 5.

[Effects of the Invention] According to the method of the present invention, a polyimide-based resin composition having excellent molding processability in addition to the excellent properties inherent to polyimide is provided.

Claims (3)

[Claims] 1. A formula (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group in which aromatic groups are connected to each other directly or by a bridging member. . ) Polyimide having repeating unit represented by
A resin composition comprising 1% by weight and 0.1 to 50% by weight of aromatic polysulfone. 2. The aromatic polysulfone has the following formula: The resin composition according to claim 1, which is a polysulfone having a repeating unit represented by: 3. The aromatic polysulfone has the following formula: The resin composition according to claim 1, which is a polysulfone having a repeating unit represented by: