JPH0681803B2 - 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, 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. Represents a divalent non-fused polycyclic aromatic group.) This polyetherimide is a well-known engineering plastics, for example, Takekoshi et al .: Po
lymen Preprint 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 the following repeating unit 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 (JP-A-62-50372) is not only excellent in mechanical properties, heat resistance, solvent resistance and electrical properties,
It 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, 1,4-bis [4-
(3-aminophenoxy) benzoyl] benzene and /
Or) 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene is used, and polyamic acid obtained by reacting these with one or more tetracarboxylic dianhydrides is imidized. can get.

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

That is, as the tetracarboxylic dianhydride that does not contain two or more ether bonds used, for example,
Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic 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'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid 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-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetra Examples thereof include carboxylic dianhydrides, and these tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Incidentally, the thermoplastic polyimide used in the composition of the present invention is a polyimide used as a raw material of the above-mentioned ether diamine, but by mixing and using other diamine within the range that does not impair the good physical properties of this polyimide. The resulting polyimide can also be used in the composition of the present invention.

Examples of the diamine that can be mixed and used include, for example,
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 4,4'-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-amino) Phenoxy)
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] Examples thereof include ether and bis [4- (4-aminophenoxy) phenyl] ether.

The aromatic polyetherimide-based resin composition of the present invention is adjusted 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) The aromatic polyetherimide powder and the thermoplastic polyimide powder are pre-kneaded into a powder form by 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 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 form. And

(3) Aromatic polyetherimide is dissolved or suspended in an organic solvent solution of a polyamic acid which is a precursor of the thermoplastic polyimide of the present invention, and then heat treated at 100 to 400 ° C, or usually 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 coloring agents 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 1,3-bis [4- (3-aminophenoxy) benzoyl] was added to a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
5 kg of benzene (10 mol) and N, N-dimethylacetamide 4
0.5 kg was charged, the mixture was cooled to around 0 ° C., and 2.147 kg (9.85 mol) of pyromellitic dianhydride was added in 5 portions in a nitrogen atmosphere while stirring the solution temperature, and the mixture was stirred for about 2 hours. Then, the above solution was returned to room temperature and subsequently stirred under a nitrogen atmosphere for about 20 hours.

2.02 kg (20 mol) of triethylamine and 2.55 were added to the polyamic acid solution thus obtained at room temperature under a nitrogen atmosphere.
kg (25 mol) acetic anhydride was added dropwise. This slurry was filtered to obtain polyimide powder. The polyimide powder was sludged with methanol, filtered off, 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 0.5 g of polyimide powder dissolved by heating in 100 ml of a mixed solvent of p-chlorophenol and phenol (p-chlorophenol: phenol = 90:10 weight ratio).
It is a value measured by cooling to 5 ° 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 12 and Comparative Examples-1 to 4 Aromatic polyether imide (manufactured by GEE, Inc .; trade name Ultem 1000) and the thermoplastic polyimide powders obtained in Synthesis Examples 1 to 5 are shown in Table- 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 2-3 as Examples-1-12. The table also shows the minimum injection molding pressure, which is an index of moldability. 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 and cannot be used.

Further, using the composition outside the scope of the present invention, the physical properties of the molded articles obtained by the same operation as in Examples-1 to 12 were measured, and Tables 2-3
In addition, it is described as Comparative Examples 1 to 4.

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. Representing a divalent non-condensed polycyclic aromatic group) 100 parts by weight of an aromatic polyetherimide having a repeating unit represented by (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 part by weight or more of a thermoplastic polyimide having a repeating unit represented by 100)
An aromatic polyetherimide resin composition containing less than 1 part by weight.