JPH0676553B2 - 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 has been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment because it has excellent mechanical strength, dimensional stability, flame resistance, and electrical insulation in addition to its high heat resistance. Therefore, it 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 halocarbons, and is not satisfactory in terms of heat resistance and solvent resistance.

[Problems to be solved by the invention]

An object of the present invention is to obtain a polyimide resin composition having improved heat resistance and / or mechanical strength 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 polyimide and a specific amount of aromatic polyamideimide 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 (JP-A-62-076095).

An object of the present invention is to provide a polyimide-based resin composition having improved mechanical resistance, mechanical strength, thermal resistance, electrical resistance and solvent resistance of these polyimides, and further improved heat resistance and mechanical strength. Especially.

That is, the present invention is (Wherein R is the same as the above), a resin composition comprising 99.9 to 50% by weight of a polyimide having a repeating unit and 0.1 to 50% by weight of an aromatic polyamideimide.

The polyimide used in the present invention has a formula as a diamine component. An ether diamine represented by, that is, bis [4- {3
-(4-aminophenoxy) benzoyl} phenyl] ether is used, which 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.

The thermoplastic polyimide used in the composition of the present invention is a polyimide used as a raw material for the above ether diamine, but is obtained by mixing and using another diamine within a range that does not impair the good physical properties of this polyimide. The resulting polyimides can also be used in the composition 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 (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-aminophenoxy) phenyl] ether, Bis [4- (4-amino) Phenoxy) phenyl] ether and the like.

The aromatic polyamide-imide used in the present invention has an imide-amide bond in the repeating unit of the main chain, and has the following general formula: (In the formula, Ar represents a trivalent aromatic group containing at least one benzene ring, and Z represents a divalent organic group), and the aromatic polyamideimide has a repeating unit.

Particularly preferred aromatic polyamideimide in the present invention has the formula: And the expression, It is an aromatic polyamideimide having a repeating unit represented by:

These aromatic polyamide imides are, for example, under the trade name of TORLON from Amoco, Inc. of the United States, and TI-1000 series or TI- of aromatic polyamide imides from Toray.
It is marketed under the trade name of 5000 series.

The molding resin composition of the present invention is adjusted such that the polyimide is in the range of 99.9 to 50% by weight and the aromatic polyamideimide is in the range of 0.1 to 50% by weight, and the total thereof is 100% by weight.

In the polyimide / aromatic polyamideimide composite resin system of the present invention, the effect of improving the heat resistance and / or mechanical strength by the aromatic polyamideimide is recognized even in a small amount, and the lower limit of the composition ratio is 0.1% by weight, but preferably ,
It is 0.5% by weight or more.

Further, since the aromatic polyamideimide has a very high melt viscosity as compared with the usual thermoplastic resin, if the amount of the aromatic polyamideimide in the composition is too large, the excellent moldability of the polyimide cannot be maintained. Also, the elongation at break is lowered, which is not preferable. Therefore, the composition ratio of the aromatic polyamideimide has an upper limit, and is preferably 50% by weight or less.

When the composition according to the present invention is mixed and prepared, 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 polyamideimide 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 previously dissolved or suspended in an organic solvent, and aromatic polyamideimide is added to this solution or suspension to uniformly disperse or dissolve,
Remove the solvent to give a powder.

(3) After dissolving or suspending an aromatic polyamideimide in an organic solvent solution of a polyamic acid that is a precursor of the polyimide of the present invention, heat treatment at 100 to 400 ° C. or a commonly used imidization After chemical imidization using an agent, the solvent is removed to obtain 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, 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 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 polyamidoimidic acid solution.

N, N-dimethylacetamide was added to this polyamic acid solution.
Add 5.37 kg and stir at room temperature in a nitrogen atmosphere 4.
08 kg (40 mol) of triethylamine and 6.03 kg (60 mol) of 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 dried under reduced pressure at 150 ° C. for 24 hours to give 7.47 kg (yield 97.
0%) of pale yellow polyimide powder was obtained.

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

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

Examples-1 to 4 The polyimide powder obtained in Synthesis Example-1 and an aromatic polyamideimide powder, which are commercially available Torlon 42
03L (TORLON 4203L; trademark of Amoco, USA) was dry-blended with various compositions as shown in Table 1, and then extruded while melt-kneading to obtain uniformly mixed pellets.

Next, the homogeneously mixed pellets obtained above are injection-molded at a barrel temperature of 380 to 400 ° C and a mold temperature of 200 ° C by using an injection molding machine (Argburg All Round A-220 manufactured by Arburg Co., Ltd.) to prepare a test piece. Then, the physical and thermal properties of the test piece were measured.

The results are shown in Table-1.

The minimum injection molding pressure is also shown in each table.

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 ASTM D-
256, heat distortion temperature according to ASTM D-648.

Comparative Examples 1-2 The results of measuring the physical and thermal properties of the moldings obtained by the same operation as in Examples 1 to 4 using the composition outside the scope of the present invention are also shown in Table-1. Are shown as Comparative Examples-1 and 2.

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 synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Examples-5 to 14 and Comparative Examples-3 to 6 Using the polyimide powders obtained in Synthesis Examples-2 to 5, homogeneously compounded pellets were obtained in the same manner as in Examples-1 to 4, and then similarly injection-molded. The physical and thermal properties of the molded product were measured.

The results of the compositions within the scope of the present invention are shown as Examples-5 to 14, and the compositions outside the ranges are shown as Comparative Examples-3 to 6, and Tables 3 to
4 shows.

[Effects of the Invention] According to the method of the present invention, a polyimide resin composition is provided which has not only the excellent properties inherent to polyimide but also significantly improved heat resistance and / or mechanical strength.

Claims (1)

[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 polyamideimide.