JPH0218450A - Polyamide imide resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat-resistance, chemical resistance, etc., good moldability and low water-absorption by compounding an aromatic polamide imide with a specific amount of a specific polyimide. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.wt. of an aromatic polyamide imide having the recurring unit of formula I (Ar is trivalent aromatic group containing one or more benzene rings; Z is bivalent organic group) with (B) 1-100pts.wt. of a polyimide having a recurring unit of formula II (R is tetravalent group selected from >=2C aliphatic group, cycloaliphatic group, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resin composition for molding. More specifically, the present invention relates to a polyamide-imide resin composition that has excellent heat resistance, chemical resistance, etc., good moldability, and low water absorption.

[Conventional technology]

Polyamide-imide 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 be widely used in fields where heat resistance is required in the future.

Various polyamideimides have been developed that exhibit superior properties.

However, even though it has excellent heat resistance and mechanical properties, it has a high melt viscosity, and if the temperature is kept in a cylinder for a long time, the melt viscosity increases further, making it difficult to form. Ta.

In addition, because of its high water absorption rate, its application in the electrical and electronic fields has been limited by its usage conditions and environment.

[Problem that the invention seeks to solve]

An object of the present invention is to obtain a polyamide-imide resin composition that has excellent processability and/or low water absorption in addition to the excellent properties inherent to polyamide-imide.

[Means for solving problems]

As a result of intensive research to solve the above problems, the present inventors found that a polyamide-imide resin composition consisting of an aromatic polyamide-imide and a specific amount of a new polyimide is particularly effective for the above purpose. discover that it is a thing,
The invention has been completed.

That is, in the present invention, based on 100 parts by weight of aromatic polyamideimide, formula (1) (wherein 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 fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member. . ) A polyamide-imide resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyimide having a repeating unit represented by:

The aromatic polyamideimide used in the present invention has imide and amide bonds in the repeating unit of the main chain, and has the following bond (where Ar is a trivalent aromatic compound containing at least one benzene ring). It is an aromatic polyamide-imide having a repeating unit represented by a group (Z represents a divalent group).

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

These aromatic polyamideimides are commercially available, for example, from Amoco, USA under the trade name TORLON.

The polyimide resin used in combination in the present invention for the purpose of improving the moldability and/or reducing water absorption of aromatic polyamide-imide is represented by the following formula ('I) (wherein R is the same as before): A polyimide having a repeating unit of The diamine component is an ether diamine represented by the formula, i.e., bis[4-(
3-(4-aminophenoxy)benzoyl)phenyl]
It mainly uses ether and is obtained by imidizing polyamic acid obtained by reacting this with one or more tetracarboxylic dianhydrides.

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

That is, the tetracarboxylic dianhydride used is:
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic acid, cyclopenkunetetracarboxylic 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′-biphenyltetracarboxylic dianhydride, 2.2-bis(3,4-dicarboxyphenyl)propanihydride 2,2-bis(2,3-dicarboxyphenyl)propanihydride, bis(3,4-
dicarboxyphenyl)ether diamine, bis(3,
4-dicarboxyphenyl)sulfonic anhydride, 1.1
-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4.4'-(P -phenylenedioxy)cyphthalic dianhydride, 414'-(mphenylenedioxy)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-perylenetetra carboxylic dianhydride, 2.3.6.7-anthracenetetracarboxylic dianhydride, 1,2,7.8-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone. Alternatively, two or more types may be used as a mixture.

The polyimide used in the composition of the present invention is a polyimide using the above-mentioned ether diamine as a raw material, but polyimides obtained by mixing other diamines within a range that does not impair the good physical properties of this polyimide may also be used. can also be used in the compositions of the 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-(:)-aminophenoxy)phenyl]propane, 2,2-bisC4-C4-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, 13-bis(4-aminophenoxy)benzene, 14-bis(3-
aminophenoxy)benzene, 14-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)getone, bis(4-(3-aminophenoxy)phenyl fusulfide, bis(4-(4-aminophenoxy)phenyl fusulfide), Bis(4-(
4-aminophenoxy)phenyl]sulfoxide, bis(4-(3-aminophenoxy)phenyl)sulfone,
Examples include bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)ether, and bis(4-(4-aminophenoxy)phenyl)ether.

In the aromatic polyamide-imide/polyimide composite resin system of the present invention, the effect of improving processability and/or water absorption resistance by polyimide is recognized even in small amounts, and the lower limit of the composition ratio is 1 part by weight, but preferably 5 parts by weight. That's all.

In addition, although the polyimide used in the present invention has excellent mechanical properties and heat resistance, they are not sufficient compared to aromatic polyamide-imide, and if the amount of polyimide is increased too much, the excellent mechanical properties and heat resistance of polyamide-imide may be Mechanical properties and heat resistance cannot be maintained. Therefore, there is an upper limit to the composition ratio of polyimide, and aromatic polyamide-imide 1
The amount is preferably less than 100 parts by weight compared to 00 parts by weight.

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

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

(2) Polyimide powder is dissolved or suspended in an organic solvent in advance, aromatic polyamide-imide is added to this solution or suspension, and after uniformly dispersing or dissolving it,
Remove the solvent and form a powder.

(3) After melting 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 polyamide-imide resin composition thus obtained can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, extrusion molding, etc., but it is more preferable to use it after melt blending. It's a method. In particular, in mixing and adjusting the composition, it is a simple and effective method to mix and melt powders, pellets, or powders and pellets.

Melt blending involves equipment used to melt blend conventional rubbers or plastics, such as hot rolls,
A Banbury mixer, plying machine, extruder, etc. can be used. The melting temperature is set above the temperature at which the mixed system can be melted and below the temperature at which the compounded system starts to 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, extrusion film molding, etc.

In addition, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead oxide, lead powder, etc. can be added to the resin composition of the present invention. It is also possible to add one or more types of reinforcing agents such as glass fibers, carbon fibers, aromatic polyamide resins, silicon carbide fibers, potassium titanate fibers, and glass peas.

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 synthetic agents, Examples, and Comparative Examples.

Synthesis Example 1 5.92 kg (10 mol) of bis(4-(3-(4-aminophenoxy)benzoyl)phenyl)ether and N,N- Charge 18.8 kg of dimethylacetamide, and add 2 pyromellitic dianhydrides at room temperature under a nitrogen atmosphere.
．． 14 kg (9.8 mol) was added while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 24 hours to obtain a polyamic acid solution.

To this polyamic acid solution, 5.37 kg of N,N-dimethylacetamide was added, and 4.08 kg (40 mol) of triethylamine and 6.03 kg (60 mol) of acetic anhydride were added dropwise while stirring at room temperature under a nitrogen atmosphere.

After approximately 24 hours of additional stirring at room temperature, the solution was drained into 2501 of vigorously stirred water. The resulting precipitate was filtered, washed with methanol and then incubated at tSO°C for 2
Drying under reduced pressure for 4 hours yielded 7.47 kg (yield approximately 97.0%)
) was obtained as pale yellow polyimide powder.

The logarithmic viscosity of this polyimide powder was 0.86 dl/g. Here, the logarithmic viscosity is P-
Mixed solvent of chlorophenol and phenol cP-chlorophenol:phenol=90:1011k ratio)
It was heated and dissolved in 100 g, cooled to 35°C, and measured (directly).

Furthermore, the glass transition temperature of this powder according to DSC measurement is 2.
The temperature was 35°C.

Synthesis Examples 2 to 6 Various diamines and various tetracarboxylic dianhydrides were combined and carried out in the same manner as in Synthesis Example 1 to obtain various polyimide powders.

Table 1 shows the polyimide resin synthesis conditions and the logarithmic viscosity of the produced polyimide powder.

Example 1 Aromatic polyamide-imide powder, commercially available TORLON 4203L (TORLON 4230L)
After tri-blending the polyimide powders obtained in Synthesis Examples 1 to 5 with various compositions as shown in Tables 2 to 3, the mixture was extruded 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) at a barrel temperature of 380 to 400°C and a mold temperature of 220°C.
A test piece was prepared by injection molding using C, and 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 listed in each table.

In the table, tensile strength and elongation at break are ASTM D-638,
Bending strength and flexural modulus are determined by ASTM D-790, Izod impact value is determined by ASTM D-256, glass transition temperature is determined by the TMA needle method, and heat distortion temperature is determined by ASTM D-648.

The water absorption rate is the weight increase rate after 200 hours of immersion in 80°C warm water.

Comparative Examples 1 to 6 Tables 2 to 3 show the results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 14 using compositions outside the scope of the present invention. Also shown.

〔Effect of the invention〕

According to the method of the present invention, in addition to the excellent properties inherent to polyimide, a polyimide-based resin composition that has extremely good moldability and/or low water absorption is provided.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) For 100 parts by weight of polyamideimide, the following formula (
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group,
Represents a tetravalent group selected from the group consisting of a monocyclic 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. . ) A polyamide-imide resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyimide having a repeating unit represented by: