JPH0611862B2 - Aromatic polyetherimide 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, the present invention relates to an aromatic polyetherimide-based molding resin composition which is excellent in heat resistance, chemical resistance, mechanical strength, and the like and has excellent moldability.

[Conventional technology]

Aromatic polyether imides are well known as engineering plastics having relatively good heat resistance.
Aromatic polyetherimide has a low heat distortion temperature of around 200 ° C., and since it has fluidity at a temperature of 350 ° C. or higher, it can be melt-molded and is an excellent resin that can be injection-molded and extrusion-molded. However, this resin has a low glass transition temperature, is soluble in halogenated hydrocarbons, and has heat resistance,
It is not a satisfactory resin in terms of solvent resistance.

Therefore, it is desired to improve the heat resistance of the molded article, especially the heat distortion temperature, and the mechanical strength, especially the impact strength and the solvent resistance.

[Problems to be solved by the invention]

An object of the present invention is to obtain an aromatic polyetherimide resin composition having improved heat resistance, chemical resistance, and mechanical strength in addition to the excellent processability inherent in aromatic polyetherimide.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors found that an aromatic polyetherimide resin composition comprising an aromatic polyetherimide and a specific thermoplastic polyimide is particularly effective for the above purpose. The present invention has been completed and the present invention has been completed.

That is, the present invention, 100 parts by weight of aromatic polyether imide, the following 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. It does not contain more than one ether bond. ) An aromatic polyetherimide resin composition comprising 1 part by weight or more and less than 100 parts by weight of a thermoplastic polyimide having a repeating unit represented by

Aromatic polyetherimide used in the method of the present invention is a polymer composed of an ether bond and an imide bond as two essential bond units, and it is considered that the repeating unit is composed of diamine and tetracarboxylic dianhydride. In this case, the tetracarboxylic acid dianhydride side has two or more ether bonds, and the following general formula The repeating unit represented by is the main unit.

(In the formula, Z is a trivalent aromatic group, two groups are bonded to two adjacent carbons, and Ar and Y are each a divalent monocyclic aromatic group or a bridging member. This represents a divalent non-fused polycyclic aromatic group.) This polyetherimide is a well-known engineering plastic, and is described in, for example, Takekoshi et al .: P.
olymen Prerint 24 (2) 312-313 (1983).

Examples of the aromatic polyetherimide used in the present invention include aromatic polyetherimides having the following repeating units.

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. In particular Polyetherimide consisting of repeating units is widely used as Ultem-1000.

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.

The polyimide used in the present invention has the following formula (In the formula, R is the same as before) and is a polyimide having a repeating unit.

Polyimide is known as a resin having excellent heat resistance, chemical resistance, and mechanical strength. However, in general, polyimide is a resin that does not exhibit a glass transition temperature or has poor fluidity at high temperatures and is difficult to process.

However, the polyimide used in the present invention disclosed by the present inventors (Japanese Patent Application No. 62-76095) has mechanical properties, heat resistance,
Not only has excellent solvent resistance and electrical properties, but also has excellent fluidity at high temperatures and is thermoplastic.

Therefore, it becomes possible to satisfactorily melt-knead with the aromatic polyether imide, without impairing the moldability of the aromatic polyether imide, and further, the heat resistance, solvent resistance and mechanical strength of the aromatic polyether imide are remarkably increased. An improved resin composition could be obtained.

The thermoplastic 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, and it is obtained by imidizing a polyamic acid obtained by reacting these with one or more tetracarboxylic acid dianhydrides.

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

That is, examples of the tetracarboxylic dianhydride that does not contain two or more ether bonds used include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic acid. Dianhydride, pyromellitic 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′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone 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-
Perylene tetracarboxylic acid dianhydride, 2,3,6,7-anthracene tetracarboxylic acid dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, etc., these tetracarboxylic acid dianhydrides Are used alone or in admixture of two or more.

Incidentally, the thermoplastic polyimide used in the composition of the present invention is a polyimide which can be used as a raw material of the ether diamine, but by mixing and using other diamine within a range not impairing good physical properties of this polyimide. The resulting polyimide 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-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] su Rufoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4 -Aminophenoxy) phenyl] ether and the like.

The aromatic polyetherimide-based resin composition of the present invention is prepared so as to be in the range of 1 part by weight or more and less than 100 parts by weight of the thermoplastic polyimide with respect to 100 parts by weight of the aromatic polyetherimide.

In the aromatic polyetherimide / thermoplastic polyimide composite resin system of the present invention, the effect of improving the heat resistance, solvent resistance and mechanical strength by the thermoplastic polyimide is recognized even in a small amount, and the lower limit of the composition ratio of the thermoplastic polyimide is It is 1 part by weight, but preferably 5 parts by weight or more.

Further, the thermoplastic polyimide is inferior in melt flowability to the aromatic polyetherimide, so that if the amount of the thermoplastic polyimide in the composition is too large, the original fluidity of the aromatic polyetherimide is maintained. become unable. Therefore, the composition ratio of the thermoplastic polyimide has an upper limit,
Less than 100 parts by weight is preferable with respect to 100 parts by weight of aromatic polyetherimide.

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) Aromatic polyetherimide powder and thermoplastic polyimide powder are pre-kneaded into a powder form using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender and the like.

(2) Thermoplastic polyimide powder is dissolved or suspended in an organic solvent in advance, aromatic polyetherimide is added to this solution or suspension, and after uniformly dispersing or dissolving, the solvent is removed and powdered And

(3) In the organic solvent solution of the polyamic acid that is the precursor of the thermoplastic polyimide of the present invention, after dissolving or suspending the aromatic polyetherimide, heat treatment at 100 to 400 ° C, or normally used After chemically imidizing using the imidizing agent, the solvent is removed to obtain a powder.

The powdery aromatic polyetherimide resin composition thus obtained is directly used for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding, etc. Is a more preferable method.

In particular, in mixing and preparing the composition, powder comrades,
It is a simple and effective method to mix pellets with each other or to mix powder and pellets.

For melt blending, the equipment used for melt blending conventional rubbers or plastics, such as hot rolls, Banbury mixers, Brabenders, extruders and the like can be utilized. The melting temperature is set above the melting temperature of the blending system and below the temperature at which the blending system begins to thermally decompose, but the temperature is usually 280 to 420 ° C., preferably 30.
It is 0 to 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. 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. 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.

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,
One or more conventional additives such as flame retardants, flame retardant aids, antistatic agents, lubricants and colorants 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-aminofinoxy) benzoyl} phenyl] ether and N, Charge 18.8 kg of N-dimethylacetamide, add 2.14 kg (9.8 mol) of pyromellitic dianhydride in a nitrogen atmosphere at room temperature while paying attention to the rise in solution temperature, and stir at room temperature for about 24 hours to prepare a polyamic acid solution Got

In this polyamic acid solution, N, N-dimethylacetamide 5.
Add 37 kg and stir at room temperature in a nitrogen atmosphere at 4.08
kg (40 mol) triethylamine and 6.03 kg (60 mol) acetic anhydride were added dropwise. After stirring at room temperature for about 24 hours, the solution was discharged into 250 of vigorously stirred water. 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 about 9%).
7.0% of pale yellow polyimide powder was obtained.

The logarithmic viscosity of this polyimide powder was 0.86 d / g.
Here, the logarithmic viscosity is a value measured by dissolving 0.5 g of polyimide powder in 100 m 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 measured by the powder DSC was 235 ° C.

Synthesis Examples-2 to 5 Various diamines and various tetracarboxylic dianhydrides were combined and the same procedure as in Synthesis Example-1 was performed to obtain various polyimide powders. Table 1 shows the polyimide resin synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Examples-1 to 11 and Comparative Examples-1 to 6 Tables showing aromatic polyetherimide (manufactured by GE, Inc .; trade name Ultem 1000) and the thermoplastic polyimide powders obtained in Synthesis Examples-1 to 5 After dry-mixing in the proportions shown in 2-3, it is extruded at 370-400 ° C using a twin-screw extruder to granulate, and the resulting pellets are injected into an injection molding machine (cylinder temperature).
Then, the test piece was molded, and the physical and thermal properties and chemical resistance of the molded product were measured.

The results are shown in Tables 2 to 3 as Examples-1 to 11. In addition,
The minimum injection molding pressure, which is an index of moldability, is also shown in each table. The minimum injection molding pressure is lower as the melt viscosity is lower.

In the table, tensile strength is ASTM D-638, bending strength is ASTM D-790,
Izod impact value is ASTM D-256, heat distortion temperature is ASTM D-6
According to 48.

Regarding the chemical resistance, the test piece was immersed in each chemical for 20 minutes and the change in appearance was observed. In the table, ○ indicates no change, Δ indicates a little change, and X indicates a large change that cannot be used.

Further, using a composition outside the scope of the present invention, Examples -1 to 11
The physical properties of the molded product obtained by the same operation as in
In addition to 3, the results will be described as Comparative Examples 1 to 6.

EFFECTS OF THE INVENTION The present invention provides an aromatic polyetherimide resin composition having improved heat resistance, chemical resistance, and mechanical strength in addition to the excellent processability inherent in aromatic polyetherimide. It

Claims (1)

[Claims] 1. The following general formula (In the formula, Z is a trivalent aromatic group, two groups are bonded to two adjacent carbons, and Ar and Y are each a divalent monocyclic aromatic group or a bridging member. A divalent non-condensed polycyclic aromatic group), and 100 parts by weight of an aromatic polyetherimide having a repeating unit represented by
The following 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. It does not contain more than one ether bond. ) 1 to 10 parts by weight or more of a thermoplastic polyimide having a repeating unit represented by
An aromatic polyetherimide resin composition containing less than 0 part by weight.