JPH01165662A - Aromatic polyamide-imide resin composition - Google Patents

Abstract

PURPOSE:To provide an arom. polyamide-imide resin compsn. improved in molding processability and reduced in water absorptivity, by blending an arom. polyamide-imide with a specific amt. of a specific polyimide. CONSTITUTION:100 pts.wt. arom. polyamide-imide (A) (e.g., a polymer having recurring units of formula I) is mixed with 1-100 pts.wt. polyimide having recurring units of formula II (wherein X is a direct bond, a 1-10C divalent hydrocarbon group, hexafluoroisopropylidene, carbonyl, thio, or sulfonyl; Y1-Y4 are each H, lower alkyl, lower alkoxy, chlorine, or bromine; and R is a tetravalent group selected from among at least 2C aliph. groups, arom, groups, etc.) to prepare an arom, polyamide-imide resin compsn. The resin compsn. is suitably used in electric appliances, electronic appliances, etc. The component B is prepd. by reacting an ether-diamine of formula III with a tetracarboxylic acid dianhydride of formula IV and imidating the resulting polyamic acid.

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 an aromatic polyamide-imide molding resin composition that has excellent heat resistance, chemical resistance, mechanical strength, etc., good moldability, and low water absorption.

[Conventional technology]

Aromatic polyamide-imide has traditionally been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment due to its excellent heat resistance, mechanical strength, dimensional stability, flame retardance, and electrical insulation properties. It is expected that it will continue to be widely used in the future.

However, aromatic polyamide-imide has a high melt viscosity, and when kept at a high temperature in a cylinder for a long time, the melt viscosity further increases, making it difficult to mold. Furthermore, because of its high water absorption rate, its application in the electrical and electronic fields has been limited by its usage conditions and usage environment.

[Problem that the invention seeks to solve]

An object of the present invention is to provide an aromatic polyamide-imide resin composition that has excellent processability and low water absorption, in addition to the excellent properties inherent to aromatic polyamide-imide.

[Means for solving problems]

The present inventors conducted intensive research to solve the above-mentioned problems and found that an aromatic polyamide-imide resin composition composed of an aromatic polyamide-imide and a specific polyimide is particularly effective for the above-mentioned purpose. , completed the invention.

That is, the present invention comprises 100 parts by weight of an aromatic polyamideimide and a compound having the formula (wherein X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, a thio group, or represents a group selected from the group consisting of sulfonyl groups, Y, Y2+ y:+ and Y4 each represent a group selected from the group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine, 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.

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 ^r is a trivalent aromatic compound containing at least one benzene ring). Z represents a divalent organic group).

Particularly preferred aromatic polyamideimides in the present invention are of the formula and formula.

It is an aromatic polyamideimide having a repeating unit represented by:

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

The polyimide used in the present invention was previously discovered by the present inventor as a polyimide that has excellent mechanical, thermal, electrical properties, and solvent resistance, and has good moldability. (Unexamined Japanese Patent Publication No. 61-143478.62-68817.6
2-86021.62-235381 and patent application Sho 6l
-274206).

This polyimide has the formula (wherein X, Y,
, Y, , Y, and Y4 are the same as above) It is obtained by imidizing a polyamic acid obtained by reacting an ether diamine represented by the following with one or more types of tetracarboxylic dianhydride in an organic solvent.

Diamines used in this method include bis(4-(
3-aminophenoxy)phenylcomethane, 1.1-bisC4-(3-aminophenoxy)phenyl]ethane,
1.2-bis[4-(3-aminophenoxy)phenyl]ethane, 2.2-bis(4-(3-aminophenoxy)phenyl)propane, 2-(4-(3-aminophenoxy)phenyl) - 2-[4-(3-aminophenoxy)-3-methylphenyl]propane, 2.2-bis[4-(3-aminophenoxy)-3-methylphenyl]propane, 2-(4-(3-amino phenoxy)phenyl) -2-[4-(3-aminophenoenoxy)
-3゜5-dimethylphenyl]propane, 2,2-bix
(4-(3-aminophenoxy)-3,5-dimethylphenyl)propane, 2,2-bis[4-(3-aminophenoxy)phenylcobutane, 2,2-bis(4-
(3-aminophenoxy)phenyl) -1,1,1,
3,3,3-hexafluoropropane, 4.4'-bis(3-aminophenoxy)biphenyl, 4.4'-bis(3-7minophenoxy)-3-methylbiphenyl, 4
．． 4″-bis(3-aminophenoxy)-3,3′-dimethylbiphenyl, 4,4′-bis(3-aminophenoxy)-3,5-dimethylbiphenyl, 4,4″-bis(3-aminophenoxy) )-3,3°, 5.5′-tetramethylbiphenyl, 4,4′-bis(3-aminophenoxy)-3,3′-dichlorobiphenyl, 4.4′
-bis(3-aminophenoxy)-3,5-dichlorobiphenyl, 4,4'-bis(3-aminophenoxy)-
3,3',5.5'-tetrachlorobiphenyl, 4,4
゛-bis(3-aminophenoxy)-3,3'-dibromobiphenyl, 4.4'-bis(3-aminophenoxy)-3゜3',5.5'-tetrabromobiphenyl, bis(4-( 3-aminophenoxy) phenylkoketone,
Bis[4-(3-aminophenoxy)phenyl]sulfide, bis(4-(3-aminophenoxy)-3-methoxyphenyl)sulfide, (4-(3-aminophenoxy)phenyl) (4-(3-amino phenoxy)
-3,5-dimethoxyphenyl]sulfide, bis(4-(3-7minophenoxy)-3,5-dimethoxyphenyl)sulfide, and bis(4-(3-aminophenoxy)phenylcosulfone). may be used alone or in combination of two or more.

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'
-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)propanihydride
-dicarboxyphenyl)ether dianhydride, bis(3
, 4-dicarboxyphenyl)sulfone dianhydride, 1.
l-Bis(2,3-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4.4 '-(p-phenylenedioxy)cyphthalic dianhydride, 4.4'-(tophenylenedioxy)
cyphthalic dianhydride, 213.6.7-naphthalenetetracarboxylic dianhydride, 114.5.8-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, l.

2.7.8-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone or in a mixture 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-(4-aminophenoxy)phenylcomethane), 1. 1-bis[4-(4-aminophenoxy)
phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 2,2-bisC4-(4
-aminophenoxy)phenyl]propane, 2,2-bis(4-(4-aminophenoxy)phenylcobutane),
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(4-aminophenoxy)biphenyl, bisC4-C4
-aminophenoxy)phenylkoketone, bis(4-(
4-aminophenoxy)phenyl] sulfide, bis[
4-(4-aminophenoxy)phenyl]sulfoxide, bis(4-(4-aminophenoxy)phenyl)sulfone, bisC4-(3-aminophenoxy)phenylphether, bisC4-(4-aminophenoxy)phenylphether ter, ■, 3-bisC4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis(4-(3
-aminophenoxy)benzoyl]benzene and the like.

The molding resin composition of the present invention contains 100 parts by weight of the aromatic polyamide-imide and 100 parts by weight or more of the polyimide.
Consisting of less than parts by weight.

In the aromatic polyamide-imide resin composition of the present invention, the effect of improving processability and reducing water absorption by the polyimide used in the present invention can be observed even in small amounts, and the lower limit of the composition ratio is 1 part by weight, but it is preferable. is 5 parts by weight or more.

In addition, in order to maintain the mechanical properties and heat resistance characteristic of aromatic polyamide-imide, there is an upper limit to the composition ratio of polyimide, which is less than 100 parts by weight per 100 parts by weight of aromatic polyamide-imide.

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

(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, the solvent is removed to form a powder. .

(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 normally used imidization After chemical imidization using a solvent, 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.

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 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.

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. 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.

The resin composition of the present invention may be added with antioxidants, mature fixers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, and colorants within the limits that do 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 3.68 kg (10 mol) of 4,4''-bis(3-aminophenoxy)biphenyl and N,N-dimethylacetamide were placed in a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. 52.15 kg of pyromellitic dianhydride (9
, 7 mol) was added while being careful not to increase the solution temperature, and the mixture was subsequently 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 to obtain pale yellow polyimide powder.

This polyimide powder was sludged with methanol, separated, and dried under reduced pressure at 150° C. for 8 hours to obtain a 5.36-pale yellow polyimide powder. This powder had a glass transition temperature of 235° C. as determined by SC measurement, and a 5% thermal decomposition temperature of 560° C. as determined by DTA-TG measurement.

Further, the logarithmic viscosity of this polyimide powder was 0.50d17g. Here, the logarithmic viscosity is 0.5g of polyimide powder.
- Mixed solvent of chlorophenol and phenol (p-chlorophenol:phenol = 90:10 weight ratio) 100
This is the value measured after heating and dissolving in n+1 and cooling to 35°C.

Examples-1 to 4 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, 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 injection 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 to create a test piece. The physical, thermal properties, and water absorption rate of the test pieces were measured.

The results are shown in Table 1.

The minimum injection molding pressure is also listed in each table.

Is the tensile strength in the table AST? l D-638, flexural strength and flexural modulus are according to STM D-790, glass transition temperature is according to TIIA needle method, and heat distortion temperature is according to ASTM D-648. The water absorption rate was expressed as the rate of increase in ffl amount after 200 hours of immersion in 80°C warm water.

Comparative Examples 1 to 2 Using compositions outside the scope of the present invention, the results of measuring the physical, thermal properties, and water absorption of molded products obtained by the same operations as Examples 1 to 4 are combined. The results are shown in Table 1 as Comparative Examples 1 and 2.

Synthesis Examples 2 to 6 Various polyimide powders were obtained by combining various diamines and various tetracarboxylic dianhydrides in the same manner as in Synthesis Example 1. Table 2 shows the polyimide synthesis conditions and the resulting polyimide powders. The logarithmic viscosity and glass transition temperature of

Examples-5 to 13 and Comparative Examples-3 to 7 Synthesis Examples-2 to 6
Using the polyimide powder obtained in , homogeneous compound pellets were obtained in the same manner as in Examples 1 to 4, and then injection molded in the same manner as above, and the physical and thermal properties and water absorption of the molded products were measured.

The results of compositions within the scope of the present invention are shown in Examples-5 to 18.
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, in addition to the excellent properties originally possessed by aromatic polyamideimide, moldability is significantly good,
An aromatic polyamide-imide resin composition with low water absorption is provided.

Claims (1)

[Claims] 100 parts by weight of aromatic polyamideimide and the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, Y_1, Y_2, Y_3 and Y_4 each represent a group consisting of hydrogen, lower alkyl group, lower alkoxy group, chlorine or bromine; R represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, or an aromatic group directly or by a bridge member. Represents a tetravalent group selected from the group consisting of interconnected non-fused polycyclic aromatic groups. Polyamide-imide resin composition.