JPH0253855A - Polyamide-imide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide-imide resin composition having excellent properties of characteristic polyimide and excellent processing properties and/or low water absorption by blending a polyamide-imide with a specific amount of a specific polyimide. CONSTITUTION:(A) 100 pts.wt. aromatic polyamide-imide containing a repeating unit shown by formula I (Ar is trifunctional aromatic group containing one or more benzene rings; Z is bifunctional organic group), preferably one containing repeating units shown by formula II and formula III is blended with (B) >=1 pt.wt. -<100 pts.wt., preferably <=5 pts.wt. - <100 pts.wt. polyimide which is prepared by imidating a polyamic acid, a reaction product of an ether diamine shown by formula IV and a tetracarboxylic acid dianhydride and contains a repeating unit shown by formula V (R is tetrafunctional group such as >=2C aliphatic group, alicyclic group or monocyclic aromatic group), mixed in a dry state and kneaded in a molten state to give a composition.

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 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 electrical and electronic equipment, aerospace equipment, transportation equipment, etc. due to its high heat resistance, excellent mechanical strength, dimensional stability, flame retardancy, and electrical insulation properties. It is expected to be widely used in fields where high 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 problems such as high melt viscosity and difficulty in molding process, such as the melt viscosity further increasing when kept at high temperature in a cylinder for a long time. Ta. In addition, because of its high water absorption, its application in the electrical and electronic fields has been limited by its use 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]

The present inventors have conducted intensive research to solve the above-mentioned problems, and have 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-mentioned purpose. The present invention was completed based on this discovery.

That is, the present invention provides a compound of the formula (1) (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic group) based on 100 parts by weight of aromatic polyamideimide. Represents a tetravalent group selected from the group consisting of an aromatic group and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member.) A polyimide having a repeating unit represented by It is a polyamide-imide resin composition consisting of 1 part by weight or more and less than 100 parts by weight.

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:

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

In the present invention, the polyimide resin used in combination for the purpose of improving molding processability and/or reducing water absorption of aromatic polyamide-imide is represented by the following formula (1) and the formula (in which R is the same as before). It is a polyimide having a repeating unit of
The present inventors first discovered a polyimide with excellent thermal properties, electrical properties, solvent resistance, etc., and good moldability. (Patent application 1986-163940.62163941)
It uses ether diamine represented by the formula as a diamine component, that is, bis(1-(4-(4-aminophenoxy)phenoxy)phenyl)sulfone, and this and one or more tetracarboxylic acid diamines. It is obtained by imidizing polyamic acid obtained by reacting it with an anhydride.

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, cyclopenkune tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3°, 4.4'
-Henzophenonetetracarboxylic 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(213-
dicarboxyphenyl)propanihydride, bis(3,
4-dicarboxyphenyl)ether diamine, bis(
3,4-dicarboxyphenyl)sulfone 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, 4,4''=(m)unilenedioxy)cyphthalic dianhydride, 23.6.7-naphthalenetetracarboxylic dianhydride, 1°4,5. 8-Naphthalenetetracarboxylic dianhydride, 1゜2.5.6-naphthalenetetracarboxylic dianhydride, 1゜2,3.4-benzenetetracarboxylic dianhydride, 3,4゜9.10- These include perylenetetracarboxylic dianhydride, 2.36.7-anthracenetetracarboxylic dianhydride, 12.7.8-phenanthrenetetracarboxylic dianhydride, and these tetracarboxylic dianhydrides may be used alone or in combination with two or more. It is used by mixing more than one species.

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-aminohensylamine, p
-aminohensylamine, 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-amidiphenyl)(4-
aminophenyl) sulfoxide, bis(4-aminophenyl) sulfoxide, bis(3-aminophenyl) sulfone, (3-aminophenyl)(4-aminophenyl)
Sulfone, bis(4-aminophenyl)sulfone, 3.
[ 4-(3-aminophenoxy)phenylcomethane, bisC4-<4-aminophenoxy)phenylcomethane,
1.1-bis(4-(3-aminophenoxy)phenyl)ethane, 1,1-bis[4(4-aminophenoxy)
phenyl]ethane, 1,2-his(4-(3-aminophenoxy)phenyl)ethane, 1,2-bis(4-(4
-aminophenoxy)phenyl]ethane, 2.2-bis(4-(3aminophenoxy)phenyl)propane, 2
．． 2-bis(4-(4-aminophenoxy)phenyl)
Prohane, 2,2-his(4-(3-aminophenoxy)phenyl]butane, 2,2-bis[:4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4(
3-aminophenoxy)phenyl 3-1. C13, 3,
3-hexafluoropropane, 2,2-bis(4(4-
aminophenoxy)phenyl) -LLl, 33.3-
Hexafluoropropane, 1,3-bis(3-aminophenoxy)henzen, 1,3-bis(4-aminophenoxy)henzen, 1,4-bis(3-aminophenoxy)henzen, 1,4-bis( 4-aminophenoxy)henzen, 4.4°-bis(3-aminophenoxy)biphenyl, 4,4″-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)ketone, Bis[4-(4-aminophenoxy)phenylkoketone, bis(4-(3-aminophenoxy)phenyl]sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-amino) phenoxy)phenyl] sulfoxide, bis[4(4-aminophenoxy)phenyl]sulfoxide, bis(4-(
3-aminophenoxy)phenyl]sulfone, bisC4
-(4-aminophenoxy)phenyl]sulfone, bis(1-(3-aminophenoxy)phenyl ether,
Bis[4(4-aminophenoxy)phenyl ether, 1,4-his(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°-bisC4
-C4-amino-α α-dimethylbenzyl)phenoxifbenzophenone, 4.4bis(4-(4-amino-
Examples include α,α-dimethylhensyl)phenoxy]diphenylsulfone.

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.

Furthermore, although the polyimide used in the present invention has excellent mechanical properties and heat resistance, they are not as good as those of aromatic polyamide-imide, and if the amount of polyimide is too large, It becomes impossible to maintain physical properties and heat resistance. Therefore, there is an upper limit to the composition ratio of polyimide, and aromatic polyamide-imide 10
The amount is preferably less than 100 parts by weight compared to 0 parts by weight.

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) Polyimide powder and aromatic polyamide-imide powder are pre-kneaded into powder using a mortar, Henschel mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc.

(2) Polyimide powder is dissolved or suspended in an organic medium in advance, aromatic polyamide-imide is added to this solution or suspension, and after uniformly dispersing or dissolving, the solvent is removed and powdered do.

(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 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 while melt-blending it. It's a method. In particular, when mixing and preparing the composition,
Mixing and melting powders, pellets, or powders and pellets is also a simple and effective method.

Melt blending involves equipment used to melt blend conventional rubbers or plastics, such as hot rolls,
A Banbury mixer, Brabender, extruder, 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 440°C, preferably 300 to 420°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, boric acid 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 fibers, 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 , etc. can be added.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. The polyimide resin used in the present invention is disclosed in Japanese Patent Application No. 62-163940 and No. 6216394.
The elemental analysis values and basic physical properties are summarized in Table 1.

Examples 1 to 13 The polyimide powder obtained in Production Examples 3 to 5 was added to commercially available TORLON 4203L (trademark of Amoco, Inc., USA), which is an aromatic polyamideimide powder, as shown in Tables 2 to 3. After tri-blending various compositions, 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 base (Arburg All Round A220 manufactured by Arburg) at a barrel temperature of 380-400'C and a 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 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 ASTM D-790, Izod impact value is ASTM D-256, glass transition temperature is TMA needle corporation deformation temperature is ASTM D- According to 648.

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

Comparative Examples 1 to 6 Tables 2 to 3 summarize the results of measuring the physical and thermal properties of molded products obtained by the same operations as Examples 1 to 13 using compositions outside the scope of the present invention. Shown.

〔Effect of the invention〕

According to the method of the present invention, in addition to the excellent properties inherently possessed by polyamide-imide, a polyamide-imide resin composition that is moldable and/or has low water absorption properties is provided.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd. λ1

Claims (1)

[Claims] For 100 parts by weight of polyamideimide, the following formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a It represents a tetravalent group selected from the group consisting of a cyclic 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: