JPH01158071A - Polyimide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent heat-resistance, chemical resistance, mechanical strength, etc., as well as moldability, by compounding a specific polyimide with a specific amount of an aromatic polyamide imide. CONSTITUTION:The objective composition can be produced by compounding (A) 99.9-50wt.% of a polyimide having the recurring unit of formula I (X is carbonyl, etc.; R is tetravalent group selected from non-condensed polycyclic aromatic group having >=2C aliphatic group or cyclic aliphatic group, etc., bonded with each other directly or via a crosslinking group) and (B) 0.1-50wt.% of an aromatic polyamide imide having the recurring unit of formula II (Ar is trivalent aromatic group containing one or more benzene rings; Z is bivalent organic group).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition. More specifically, the present invention relates to a polyimide-based molding resin composition that has excellent heat resistance, chemical resistance, mechanical strength, etc., and excellent moldability.

[Conventional technology]

Polyimide has traditionally been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment due to its high heat resistance, excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. It is expected that it will continue to be widely used in fields where heat resistance is required.

Various polyimides have been developed that exhibit superior properties.

However, even though it has excellent 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 methods such as sintering. .

Or, while it has excellent processability, it has a low glass transition temperature, is soluble in halogenated hydrocarbons, and is unsatisfactory in terms of heat resistance and solvent resistance.
There were pros and cons to performance.

[Problem that the invention seeks to solve]

An object of the present invention is to obtain a polyimide resin composition that has improved heat resistance and/or mechanical strength in addition to the excellent properties inherently possessed by polyimide.

[Means for solving problems]

The present inventors conducted extensive research to solve the above-mentioned problems, and found that a polyimide-based resin composition consisting of polyimide and a specific amount of aromatic polyamide-imide is particularly effective for the above-mentioned purpose. Completed the invention.

The inventor first described mechanical properties, thermal properties, electrical properties,
As a polyimide having excellent solvent resistance and heat resistance, the formula (wherein X represents a carbonyl group or a sulfonyl group, R
is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic pentacyclic aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. We have found a resin having a repeating unit represented by ), which represents a tetravalent group selected from the group consisting of group groups. (
JP-A-62-53388).

The above polyimide is a heat-resistant resin that has many good physical properties unique to polyimide.

An object of the present invention is to provide a polyimide resin composition that has improved heat resistance and mechanical strength without impairing the mechanical, thermal and electrical properties and solvent resistance inherent to these polyimides. There is a particular thing.

That is, the present invention provides polyimide 99.9 having a repeating unit represented by the formula (wherein R is the same as before)
It is a resin composition consisting of ~50% by weight and 0.1 to 50% by weight of aromatic polyamideimide.

The polyimide used in the present invention is an ether diamine represented by the formula % as a diamine component, that is, 4.4"-
Bis(4-(4-amino-α,α-dimethylbenzyl)
phenoxy]benzophenone or bis[4-(4-(
4-amino-α,α-dimethylbenzyl)phenoxy)
It uses phenyl]sulfone and is obtained by reacting this with one or more tetracarboxylic dianhydrides in an organic solvent and imidizing the resulting polyamic acid.

The tetracarboxylic dianhydride used at this time has the formula (R in the formula is the same as before) It is a tetracarboxylic dianhydride represented by

That is, the tetracarboxylic dianhydride used is:
Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobenkune tetracarboxylic dianhydride, pyromellitic dianhydride, 3.3", 4.4'
-benzophenonetetracarboxylic dianhydride, 2.2'
, 3.3'-benzophenonetetracarboxylic dianhydride, 3.3',4.4'-biphenyltetracarboxylic dianhydride, 2.2' 3.3°-biphenylte!・
Carboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanijLk'lh, 2,2-bis(2,3-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl) carboxyphenyl) ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl) ecunnihydride, bis(2,3-dicarboxyphenyl) Methani dianhydride, bis(334-dicarboxyphenyl)methanidianhydride, 4.4'-(p-phenylenedioxy)cyphthalic dianhydride, 4.4'-(tophenylenedioxy)cyphthalic 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-phenanthrenetetracarboxylic dianhydride, etc. Anhydrides may be used alone or in combination of two or more.

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

Examples of diamines that can be used in combination include m-phenylenediamine, 0-phenylenediamine, and p-phenylenediamine.
-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,)phenylcomethane, bis (4-(4-aminophenoxy)phenylcomethane, 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)phenylcobutane, 2,2-bis(
4-(4-aminophenoxy)phenylcobutane, 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,
l, 3-bis(4-aminophenoxy)benzene, l,
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)phenylkoketone, bis(4-
(4-aminophenoxy)phenylkoketone, bis(4
-(3-aminophenoxy) phenyl fusulfide, bis(4-(4-aminophenoxy) phenyl fusulfide, bis[4-(3-aminophenoxy) phenyl] sulfoxide, bis(4-(4-aminophenoxy) phenyl) ] Sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, bisC4-<3-aminophenoxy)phenyl ether, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(4-aminophenoxy)phenyl)sulfone, -Aminophenoxy)phenyl]-thyl, and the like.

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

A particularly preferred aromatic polyamide-imide in the present invention is an aromatic polyamide-imide having a repeating unit represented by the formula and the formula 〇U.

These aromatic polyamide-imides are commercially available, for example, from Amoco Corporation in the United States under the trade name TORLON, and from Toshisha Co., Ltd. under the trade name Tl-1000 series or Tl-5000 series of aromatic polyamide-imides. There is.

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

In the polyimide/aromatic polyamide-imide composite resin system of the present invention, the effect of improving heat resistance and/or mechanical strength by the aromatic polyamide-imide is also observed in the green mold,
The lower limit of the composition ratio is 0.1% by weight, but preferably 0.5% by weight or more.

In addition, since aromatic polyamide-imide has a much higher melt viscosity than ordinary thermoplastic resins, it is necessary to increase the amount of aromatic polyamide-imide in the composition (this will maintain the excellent moldability of polyimide). Moreover, the elongation at break also decreases, which is undesirable.Therefore, there is an upper limit to the composition ratio of the aromatic polyamideimide, and it is preferably 50% by weight or less.

The composition according to the present invention can be mixed and prepared by commonly known methods, but the following methods are preferred, for example.

(1) Preliminarily kneading polyimide powder and aromatic polyamide-imide powder using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill ribbon blender, etc. to form a powder.

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

(3) After dissolving or suspending aromatic polyamide-imide in an organic solvent solution of polyamic acid, which is a precursor of the polyimide of the present invention, heat treatment is performed at 100 to 400'C, or a commonly used imide is dissolved or suspended. After chemical imidization using a curing agent, the solvent is removed to form a powder.

The powdered polyimide resin composition thus obtained can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, and extrusion molding.
A more preferred method is to use the mixture after melt blending. In particular, when preparing the composition by mixing, it is a simple and effective method to mix and melt powders, pellets, or powders and pellets.

For melt blending, equipment commonly used for melt blending rubbers or plastics, such as hot rolls, Banbury mixers, Brabenders, extruders, etc., can be used. The melting temperature is set above the temperature at which the blended system can be melted and below the temperature at which the blended system begins to thermally decompose, and the temperature is usually 280 to 420°C, preferably 300 to 400°C.

As a molding method for the resin composition of the present invention, injection molding or extrusion molding, which forms a homogeneous melt blend and has high productivity, is suitable, but other methods such as transfer molding, compression molding, and sinter molding are suitable. There is no problem in applying shapes etc.

Note that one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, -lead oxide, and lead powder may be added to the resin composition of the present invention. Further, one or more types of reinforcing agents such as glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, potassium titanate fibers, and glass peas can be added.

In addition, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, and colorants may be added to the resin composition of the present invention within a range that does not impair the purpose of the present invention. One or more conventional additives such as can be added.

〔Example〕

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

Synthesis Example-1 Bis(4-(4-(4-amino-α) was added to a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.

6.68 kg (10 moles) of α-dimethylbenzyl)phenoxy)phenyl]sulfone and 50.0 kg of N,N-dimethylacetamide were charged, and 2.06 kg of pyromellitic dianhydride (2.06 kg of pyromellitic dianhydride ( 9,45
mol) was added while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours.

To the thus obtained polyamic acid solution, 2.02 kg (20 mol) of triethylamine and 2.55 kg (25 mol) of acetic anhydride were added dropwise under a nitrogen atmosphere at room temperature. After stirring at room temperature for about 20 hours, a yellow slurry was obtained. This slurry was filtered, further sludged with methanol, separated, and dried under reduced pressure at 180"C for 8 hours.
0 kg (97.6% yield) of pale yellow polyimide powder was obtained. The glass transition temperature of this powder was determined by DSC measurement to be 280"C, and the glass transition temperature was determined by DTA-TG method to be 5%
The weight loss hot water temperature was 545°C.

Further, the logarithmic viscosity of this polyimide material was 0.48 a/g. Here, the logarithmic viscosity is p-
Mixed solvent of chlorophenol and phenol (p-chlorophenol:phenol = 90:10 weight ratio) 100m
This value was measured after heating and dissolving in A and cooling to 35°C.

Examples-1 to 3 The polyimide powder obtained in Synthesis Example-1 and the aromatic polyamide-imide powder, Torlon 4, which is commercially available.
After tri-blending 203L (TORLON 4203L; trademark of Amoco, Inc., USA) with various compositions as shown in Table 1, an extrusion operation was performed while melt-kneading to obtain uniformly blended pellets.

Next, the uniformly mixed pellets obtained above were molded using an injection molding machine (Arburg All Round A-220, manufactured by Arburg Co., Ltd.) at a barrel temperature of 380-400"C1 mold temperature of 220°C.
The specimens were injection molded to create test pieces, and the physical and thermal properties of the test pieces were measured.

The results are shown in Table 1.

In the table, tensile strength and elongation at break are ASTM D-638, flexural strength and flexural modulus are ^STM D-790, Izod impact value is A37M Rho 256, and heat distortion temperature is A37.
Based on M Law 648.

The table also shows the minimum injection molding pressure, which is a measure of melt fluidity.

Comparative Examples 1 to 2 Using compositions outside the scope of the present invention, the physical and thermal properties of molded products obtained in the same manner as in Examples 1 to 3 are measured. The results are also shown in Table 1. These are shown as Comparative Examples-1 and 2.

Synthesis Examples 2 to 6 Various polyimide powders were obtained in the same manner as in Synthesis Example 1 using combinations of various diamines and various tetracarboxylic dianhydrides. Table 2 shows the polyimide synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Examples-4 to 14 and Comparative Examples-3 to 7 Synthesis Examples-2 to 6
Using the polyimide powder obtained in the above, uniformly blended pellets were obtained in the same manner as in Examples 1 to 3, and then injection molded in the same manner as above, and the physical and thermal properties of the molded products were measured.

The results of compositions within the scope of the present invention are shown in Examples-4 to 14.
Compositions outside the range are shown in Table 3 as Comparative Examples 3 to 7.
- Shown in 4.

〔Effect of the invention〕

According to the method of the present invention, a polyimide-based resin composition is provided which has significantly improved heat resistance and/or mechanical strength in addition to the excellent properties inherently possessed by polyimide.

Claims (1)

[Claims] Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a carbonyl group or a sulfonyl group, and R
is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused polycyclic group in which aromatic groups are interconnected directly or through a bridge member. Represents a tetravalent group selected from the group consisting of aromatic groups. ) Polyimide having a repeating unit represented by 99.9~
A resin composition comprising 50% by weight of aromatic polyamideimide and 0.1 to 50% by weight of aromatic polyamideimide.