JPH0759664B2 - 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, polyamide 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 improved molding processability 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 found that a polyimide resin composition comprising a novel polyimide and a specific amount of aromatic polyetherimide is particularly effective for the above purpose. The present invention has been completed.

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. . ] A polyimide having a repeating unit represented by the following formula was found (JP-A 1-9226, JP-A 1-9227).

The above polyimide is a novel heat resistant resin having many good physical properties peculiar to polyimide.

It is an object of the present invention 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 these polyimides.

That is, the present invention is A resin composition comprising 99.9 to 50% by weight of a polyimide having a repeating unit represented by the following formula and X and R being 0.1 to 50% by weight of an aromatic polyetherimide having a specific repeating unit. is there.

The aromatic polyetherimide having a specific repeating unit is at least one aromatic polyetherimide selected from the following (1) to (8).

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

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

That is, as the tetracarboxylic dianhydride used,
Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic 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, 3,3'-
Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 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-amino) Phenoxy) 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-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [ 4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4
-(3-aminophenoxy) benzoyl] benzene, 4,
4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,
4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4
Examples include-(4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone.

The aromatic polyimide used as the fluidization accelerator in the present invention is a polymer having both an ether bond and an imide bond as essential bond units, and has a general formula The repeating unit represented by is the main unit.

Here, Z is a trifunctional aromatic residue in which a difunctional group of the trifunctional groups is bonded to adjacent carbons, Ar is a divalent aromatic residue, and Y is
Is a divalent aromatic diamine residue. Then, the following can be cited as a specific example. That is, Etc. as a base skeleton.

These aromatic polyetherimides are commercially available from G.E., Inc. of Ultem-1000, Ultem-4000, Ultem-
It is marketed under the name such as 6000.

As these aromatic polyetherimides, 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.

Molding resin composition of the present invention, the polyimide 99.9-50
% By weight, aromatic polyether imide 0.1 to 50% by weight.

The polyimide / aromatic polyetherimide composite resin system of the present invention is remarkably low in a high temperature range, particularly at 350 ° C. or higher, as compared with the case of using polyimide alone. This effect is recognized even with a small amount of aromatic polyetherimide, and the lower limit of the effect is 0.1% by weight, but preferably 0.5% by weight or more.

Further, the mechanical strength of aromatic polyetherimide at high temperature belongs to the excellent class among heat-resistant resins, but the mechanical strength, especially Izod impact strength, is inferior to that of polyimide. If the amount of the group polyether imide is too large, the mechanical strength inherent to the polyimide cannot be maintained, which is not preferable.

Further, since aromatic polyether imides are easily dissolved in halogenated hydrocarbons such as methylene chloride and chloroform, amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, aromatic polyether imides in the composition If the amount of imide is too large, the chemical resistance inherent to polyimide cannot be maintained, which is not preferable.

For the above reasons, the composition ratio of the aromatic polyetherimide 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 polyetherimide 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 polyetherimide is added to this solution or suspension to uniformly disperse or dissolve, and then the solvent is removed to obtain a powder. .

(3) Aromatic polyether imide is dissolved or suspended in an organic solvent solution of polyamic acid, which is a precursor of polyimide, and then heated at 100 to 400 ° C., or a commonly used imidizing agent is used. After chemical imidization using it, 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, but the temperature is usually 280 to 420 ° C., preferably 300 to 4
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.

Note that one or more solid lubricants such as molybdenum disulfide, graphide, 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.

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

The polyimide resin used in the present invention was produced by the method described in Japanese Patent Application Nos. 62-163940 and 62-163941.

〔Example〕

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

The polyimide resin used in the present invention is disclosed in
It was produced by the method described in 62-163940 and 62-163941, and its elemental analysis values and basic physical properties are summarized in Table-1.

Examples-1 to 12 Polyimide powders obtained in Production Examples 1 to 5 shown in Table 1 and aromatic polyetherimide (manufactured by GE, USA;
Ulutem 1000) (trade name) was dry blended with the compositions shown in Tables 2 to 3 and then extruded while melt-kneading to obtain pellets having a uniform composition.

Next, the homogeneously mixed pellets obtained above are injection-molded at a barrel temperature of 380 to 400 ° C and a mold temperature of 170 ° 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 Tables 2-3.

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

In the table, tensile strength and elongation at break are ASTM-D638, bending strength and flexural modulus are ASTM D-790, Izod impact Impact value is based on ASTM D-256, glass transition temperature is based on TMA penetration method, and heat distortion temperature is based on ASTM D-648.

Comparative Examples-1 to 5 The results obtained by measuring the physical and thermal properties of the molded articles obtained by the same operation as in Examples 1 to 12 using the compositions outside the scope of the present invention are shown in Tables 2-3. Are also shown.

〔The invention's effect〕

The method of the present invention provides a polyimide-based resin composition having excellent melt flowability in addition to the excellent properties inherent to polyimide.

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. . ) A thermoplastic polyimide 9 having a repeating unit represented by
Polyimide resin composition comprising 9.9 to 50% by weight and 0.1 to 50% by weight of at least one aromatic polyetherimide selected from those having repeating units represented by the following formulas (1) to (8) object.