JPS6228982B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a novel resin composition, and more specifically, a novel resin composition having excellent moldability, chemical properties, mechanical properties, and heat resistance, which is made by blending polyether amide and polyarylene polyether. The present invention relates to a thermoplastic resin composition. A polyether amide produced from an aromatic dibasic acid or a functional derivative thereof and a diamine containing an ether bond or a functional derivative thereof is known from, for example, JP-A-52-23198. Such polyetheramides have various properties such as mechanical strength, electrical properties such as arc resistance and dielectric loss factor, as well as chemical resistance, flame retardance, abrasion resistance, fatigue resistance and dimensional stability. Excellent. However, molding this resin requires high temperatures of around 350°C, which is close to its decomposition temperature, and one of its weaknesses is that the allowable working temperature range is narrow. On the other hand, polyarylene polyether has excellent properties such as dimensional stability, heat resistance, and flame retardancy, but its application fields are limited due to insufficient water resistance and fatigue resistance. Ta. Therefore, the inventors of the present invention have made repeated studies to improve these problems, and have completed the present invention. An object of the present invention is to provide a novel resin composition having excellent properties and improved moldability. That is, the present invention provides [A] General formula () (In the general formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other.
R ₁ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. Ar represents a P-phenylene group, a m-phenylene group, an oxydiphenylene group, a sulfonyldiphenylene group, a biphenylene group, or a naphthylene group) and [B ] General formula () [-O-E-O-E']- () (In the general formula (), E is a residue of divalent phenol, and E' is ortho or para to the valence bond. is a residue of a benzenoid compound having an inert electron-withdrawing group in at least one position, and both residues are bonded to an ether oxygen via an aromatic carbon atom). This is a thermoplastic resin composition containing 95 to 5% by weight of polyarylene polyether. The polyether amide having a repeating unit represented by the general formula () used in the present invention is
Aromatic dibasic acids or their functional derivatives and general formula () (In the general formula (), R ₁ to _{R 6} mean the same as those in the general formula ()) and are obtained by a polycondensation reaction. Aromatic dibasic acids and their functional derivatives used here include terephthalic acid, isophthalic acid, oxydibenzoic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, their dichlorides, their dibromides, etc. , their alkyl esters, their aryl esters, etc. Further, as specific examples of diamines represented by the general formula (), 2,2-bis[4-(4-
aminophenoxy)phenyl]propane, 2,2
-Bis[3-methyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-(4-aminophenoxy)phenyl]
Propane, 2,2-bis[3-bromo-4-(4
-aminophenoxy)phenyl]propane, 2,
2-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-
Propyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-butyl-4-(4-aminophenoxy) ) Phenyl]propane, 2,2-
Bis[3-sec-butyl-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3
-Methoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-ethoxy-
4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dimethyl-4-(4
-aminophenoxy)phenyl]propane, 2,
2-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[ 3,5
-dimethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-
4-(4-aminophenoxy)-5-methylphenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-methyl-4-(4-aminophenoxy)phenyl] Ethane, 1,1-bis[3-chloro-4
-(4-aminophenoxy)phenyl]ethane,
1,1-bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3
-Ethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-propyl-4-
(4-aminophenoxy)phenyl]ethane,
1,1-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-butyl-4-(4-aminophenoxy)
Phenyl]ethane, 1,1-bis[3-sec-butyl-4-(4-aminophenoxy)phenyl]
Ethane, 1,1-bis[3-methoxy-4-(4
-aminophenoxy)phenyl]ethane, 1,1
-Bis[3-ethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5
-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dichloro-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3,5-dibromo-4 -(4
-aminophenoxy)phenyl]ethane, 1,1
-Bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[3-chloro-4-(4-aminophenoxy)phenyl-5-methylphenyl]ethane, bis[4
-(4-aminophenoxy)phenyl]ethane,
Bis[3-methyl-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro-4-
(4-aminophenoxy)phenyl]methane, bis[3-bromo-4-(4-aminophenoxy)
phenyl]methane, bis[3-ethyl-4-(4
-aminophenoxy)phenyl]methane, bis[3-propyl-4-(4-aminophenoxy)
phenyl]methane, bis[3-isopropyl-4
-(4-aminophenoxy)phenyl]methane,
Bis[3-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-sec-butyl-4-(4-aminophenoxy)phenyl]methane, bis[3-methoxy-4-(4-aminophenoxy)phenyl] ] Methine, bis[3-ethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]methane, bis[3,5-
Dichloro-4-(4-aminophenoxy)phenyl]methane, bis[3,5-dibromo-4-(4
-aminophenoxy)phenyl]methane, bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]methane, bis[3-chloro-4
-(4-aminophenoxy)-5-methylphenyl]methane, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1 ,3,
3,3-hexachloro-2,2-bis[4-(4
-aminophenoxy)phenyl]propane, 3,
3-bis[4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,1,1,
3,3,3-hexafluoro-2,2-bis(3,5-dimethyl-4-(4-aminophenoxy)phenyl)propane, 1,1,1,3,3,
3-hexachloro-2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]
Propane, 3,3-bis[3,5-dimethyl-4
-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-dimethyl-4-(4
-aminophenoxy)phenyl]propane, 1,
1,1,3,3,3-hexafluoro-2,2-
Bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 1,1,1,3,
3,3-hexachloro-2,2-bis[3,5-
Dibromo-4-(4-aminophenoxy)phenyl]propane, 3,3-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]pentane, 1,1-bis[3,5-dibromo-4-
(4-aminophenoxy)phenyl]propane,
2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3-methyl-4
-(4-aminophenoxy)phenyl]butane,
2,2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]butane, 2,2-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]butane, 1,1, 1, 3, 3,
Examples include 3-hexafluoro-2,2-bis[3-methyl-4-(4-aminophenoxy)phenyl]propane. Among these, 2,2-bis[4-(4-aminophenoxy)phenyl]propane is a representative example. If necessary, two or more of the above diamines can be used in combination, or other known aromatic diamines or aliphatic diamines can also be used in combination. Therefore, the polyether amide of component [A] may contain repeating units other than the repeating units represented by the general formula (). Here, examples of other aromatic diamines include m
-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylpropane-2,2,4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene , 4,4'-diaminodiphenylethane, m-tolylene diamide, p-tolylene diamine,
3,4'-diaminobenzanilide, 1,4-diaminonaphthalene, 3,3'-dichloro-4,4'-diaminodiphenyl, benzidine, 4,4'-diaminodiphenylamine, 4,4'-diamino Diphenyl-N-methylamine, 4,4'-diaminodiphenyl-N-phenylamine, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyldiethylsilane, 4,4'-diaminodiphenyl Examples include silane, 4,4'-di(p-aminophenoxy)diphenylsulfone, and 4,4'-di(m-aminophenoxy)diphenylsulfone, and at least one of these is used. These are preferably used in an amount of 50 mol % or less in the aromatic diamine. If it exceeds 50 mol%, there is a risk that molding processability will deteriorate. Further, known aliphatic diamines include, for example, piperazine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine,
nonamethylene diamine, decamethylene diamine,
p-xylylene diamine, m-xylylene diamine, tetramethylene diamine, dodecamethylene diamine, 4,4-dimethylheptamethylene diamine, 3-methylheptamethylene diamine, 2,11
-Diaminododecane, 1,12-diaminooctadecane, etc. These are preferably 30 mol% or less, particularly preferably 10% by mole, based on the total diamine component.
Used in mole % or less. When reacting the above diamine with an aromatic dibasic acid or its functional derivative, the method already used for the reaction between a publicly known amine and an acid can be directly adopted, and there are no particular limitations on the conditions. isn't it. For example, this can be achieved by an interfacial polycondensation method or a solution polycondensation method. When aromatic dicarboxylic acid dihalides are used, known water-soluble neutralizing agents described below are used in the interfacial polycondensation reaction, and known tertiary amines such as triethylamine, pyridine, tributylamine, and pyridine are used in the solution polymerization method. A neutralizing agent consisting of: A reaction solvent is used in the interfacial polycondensation method and the solution polycondensation method, and this solvent is a diamine whose main component is an aromatic diamine, an aromatic dibasic acid, or a functional derivative thereof (preferably an aromatic dicarboxylic acid dihalide). Of these,
It must be capable of dissolving at least one, preferably both. A representative example of a particularly effective reaction solvent for use in the present invention is cyclohexanone. Some examples of other solvents that can be used include methylene chloride, trichlene,
Berkrene, ethane dichloride, nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone,
Acetophenone, p-methylacetophenone,
N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, pyridine,
Examples include dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, dimethyltetramethylenesulfone, and the like. Two or more reaction solvents may be used in combination, if necessary, to facilitate the dissolution operation. Furthermore, in order to obtain a product with as high a molecular weight as possible, it is preferable to use a highly dehydrated solvent for dissolving the aromatic carboxylic acid dihalide. In particular, N, N
- When carrying out solution polycondensation using a polar solvent such as dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone, use 5 to 10% by weight of lithium chloride, calcium chloride, calcium rhodan, etc. as a co-solvent. It is advantageous to synthesize the compound by adding it, as it significantly increases the solubility. In addition to this co-solvent, all other known co-solvents as described below are effective. Further, according to research conducted by the present inventors, the following effective reaction method was discovered. That is, unlike the usual interfacial polycondensation method in which diamines are dissolved in an alkaline aqueous solution, the diamine is dispersed in an alkaline aqueous solution, and a solution of an aromatic dicarboxylic acid dihalide dissolved in an organic solvent is added thereto. This is a method of causing a reaction. By polymerizing in this method, the generated halogenated aqueous solution is neutralized with a neutralizing agent and becomes water and a metal halide, which dissolves in water.If the polymer is precipitated from the organic phase, the hydrochloric acid of the polymer Since no residue remains, this gives favorable results to various properties of the polymer. In this case, the amount of alkali used is at least 1.3 equivalents relative to the aromatic dicarboxylic acid halide, preferably from 1.0 to 1.1 equivalents. Examples of the neutralizing agent used here include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc. that are soluble in water. Further, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, using more than that will not affect the reaction. Further, the reaction temperature is in a state where water is a liquid, that is, in the range of 0 to 100°C, preferably 5 to 60°C. The above polycondensation method can be carried out, for example, by the following procedure. First, a neutralizing agent is dissolved in an appropriate amount of water, and an aromatic diamine is added thereto. Furthermore, a solution of aromatic dicarboxylic acid halide dissolved in an organic solvent is added and reacted. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline aqueous solution by stirring. Next, only the organic phase is separated and placed in an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By filtering this, an aromatic polyetheramide resin is obtained. In the present invention, the aforementioned various aromatic diamines and aliphatic diamines can be used as neutralizing agents. In this case, the amount may be increased at a rate of 1 equivalent or less (an amount not involved in the reaction). In addition, a known polyamide-forming reaction between an amide-forming derivative other than aromatic dicarboxylic acid dihalide and a diamine whose main component is an aromatic diamine represented by the general formula (), such as high-temperature polycondensation or transesterification using a phosphorus catalyst. An aromatic polyetheramide resin having a repeating unit represented by the general formula () can also be obtained by a method such as the following method. The polyarylene polyether used in the present invention is a linear thermoplastic polymer having repeating units represented by the above general formula (). In the general formula (), E is preferably the following general formula
This is a dinuclear phenol residue (residue with aromatic hydroxyl group removed) having the structure (A). In formula (A), Ar is an aromatic group, preferably a phenylene group, and Y and Y' are an alkyl group having 1 to 4 carbon atoms or an inert substituent such as a halogen atom, and are the same and may also be different.
r and s are 0 or an integer from 1 to 4, and R represents a bond between aromatic carbon atoms as in dihydroxydiphenyl or CO, O, S, -S
-S-, an inorganic group such as _SO2 , an alkylene group, an alkylidene group, a cycloaliphatic group, an alkylene group substituted with a halogen, an alkyl group, an aryl group, or a similar group thereof, an alkylidene group similarly substituted, Similarly substituted cycloaliphatic groups, alkyl-substituted alicyclic groups, alkaline groups, aromatic groups,
Represents a divalent group such as a divalent organic hydrocarbon group such as a ring fused to an Ar group. Examples of specific divalent polynuclear phenols include, among others, bis-(hydroxyphenyl)alkanes such as 2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane, Bis(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane, bis-
(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane, 1,1-bis-(4-hydroxyphenyl)-ethane, 1,2-bis-
(4-hydroxyphenyl)ethane, 1,1-bis-(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)propane, 1,3-bis -(3-
methyl-4-hydroxyphenyl)propane,
1,3-bis-(3-methyl-4-hydroxyphenyl)propane, 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane, 2,2
-bis-(3-isopropyl-4-hydroxyphenyl)propane, 2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane,
2,2-bis-(4-hydroxynaphthyl)propane, 2,2-bis-(4-hydroxyphenyl)pentane, 3,3-bis-(4-hydroxyphenyl)pentane, 2,2-bis- (4-hydroxyphenyl)heptane, bis-(4-hydroxyphenyl)phenylmethane, 2,2-bis-
(4-hydroxyphenyl)-1-phenylpropane, 2,2-bis-(4-hydroxyphenyl)1,1,1,3,3,3-hexafluoropropane, etc.; di(hydroxyphenyl) ) Sulfones such as bis-(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone,
5'-chloro-2,4'-dihydroxydiphenylsulfone, 5'-chloro-4,4'-dihydroxydiphenylsulfone, etc.; di(hydroxyphenyl) ether such as bis-(4-hydroxyphenyl)
ether, 4,3'-,4,2'-,2,2'-,2,
3'-dihydroxydiphenyl ether, 4,4'-
Dihydroxy-2,6-dimethyl diphenyl ether, bis-(4-hydroxy-3-isobutylphenyl) ether, bis-(4-hydroxy-
3-isopropylphenyl) ether, bis-
(4-hydroxy-3-chlorophenyl) ether, bis-(4-hydroxy-3-fluorophenyl) ether, bis-(4-hydroxy-3-
promphenyl) ether, bis-(4-hydroxynaphthyl) ether, bis-(4-hydroxy-3-chlornaphthyl) ether, bis-(2
-Hydroxy phether, 4,4'-dihydroxy-3,6-dimethoxydiphenyl ether, 4,
4'-dihydroxy-2,5-diethoxydiphenyl ether and similar. In the present invention, mixtures of two or more different dihydric phenols can also be used to achieve the same objectives as above. Thus, in the above description, when there is an --E- group in the polymer structure, it may actually be the same or different aromatic residue. Next, E′ is a residue of a dihalobenzenoid compound (excluding the halogen atom) that has two halogen atoms bonded to the benzene nucleus and an electron-withdrawing group in at least one position that is ortho or para to the nuclear halogen atom. (residue). Dihalobenzenoid compounds can be mononuclear in which halogens are bonded to the same benzenoid nucleus, or polynuclear in which halogens are bonded to different benzenoid nuclei, as long as there is an electron-withdrawing group in the ortho or para position of the benzenoid nucleus. It may be hot. Therefore, E' may mean the same residue as E. Examples of electron-withdrawing groups are classified into the following two types. A Monovalent group activating one or more halogens on the same ring, such as the nitro group, phenylsulfone or alkylsulfone, cyano, trifluoromethyl, nitroso and heteronitrogen such as in pyridine B Sulfone group

[Formula] Carbonyl group

[Formula] Vinyl group

[Formula] Sulfoxide base

[Formula] Azo group -N=N-, saturated fluorocarbon group -CF ₂ CF ₂ -, organic oxidized phosphine group

[Formula] [In the above formula, R is a hydrocarbon group], ethylidene group

The displacement of the halogen can be activated on two different rings such as [Formula X is hydrogen or halogen] or difluorobenzoquinone, 1,4- or 1,5
- or a divalent group capable of activating a halogen on the same ring, as in 1,8-difluoroanthraquinone.Of course, E' can also mean a mixed residue of two or more dihalobenzenoid compounds. be. The following formula (B) is a typical polyarylene polyether represented by the general formula () used in the present invention. A polymer commonly called "borisulfone" having a repeating unit represented by the following formula (C) A polymer commonly called "polyether sulfone" having a repeating unit represented by the following formula:
(D) There are polymers having repeating units represented by: As the polyarylene polyether of the present invention, for example, those disclosed in Japanese Patent Publication No. 7799/1984 can be used. Such polyarylene polyether can be produced by the method disclosed in the publication. In the present invention, the blending ratio of polyether amide (a) and polyarylene polyether (b) can be freely selected within the range of (a)/(b) from 95/5 to 5/95 by weight. However, the range of 80/20 to 20/80 is more preferable. When (A)/(B) exceeds 95/5, the improvement in formability is small, and when it is less than 5/95, fatigue resistance tends to decrease. The method of mixing aromatic polyether amide and polyamide when producing the resin composition of the present invention is not limited at all as long as both can be substantially uniformly dispersed. Good and
Melt mixing may also be used. Incomplete or non-uniform dispersion of both components is not preferred because the mechanical performance of the molded article will be impaired. Furthermore, the resin composition of the present invention can contain a thermal decomposition inhibitor, an antioxidant, or an ultraviolet absorber in order to improve its heat resistance and weather resistance. In addition, plasticizers, pigments, lubricants, etc. may be added. The resin composition of the present invention is prepared into powder, chips, or other shapes, and is made into a resin composition that is more relaxed than aromatic polyether amide by a commonly known plastic molding method such as press molding, injection molding, or extrusion molding. Shaped according to conditions. The molded article is flame retardant with excellent impact strength, tensile strength, bending strength, abrasion resistance, and electrical properties. Therefore, this resin composition is useful as an engineering plastic, and is used in the manufacture of various products that require high performance, such as gears, bearings, and electrical component containers. Next, the present invention will be specifically explained with reference to Examples. Example 1 (A) Production of aromatic polyether amide In a reactor equipped with a stirrer, thermometer and dropping funnel, 154.8 g of sodium hydroxide was added to 800 ml of water.
Dissolve and prepare. Next, 2,2-bis [4-
(4-aminophenoxy)phenyl]propane
656 g was dissolved in 3.4 Kg of cyclohexanone, added to the reactor, and cooled to -2°C. On the other hand, a solution prepared by dissolving 164 g of terephthalic acid dichloride and 164 g of isophthalic acid dichloride in 2.4 kg of cyclohexanone is added dropwise while maintaining the temperature of the liquid in the vessel not to exceed 10°C. 3 hours after the start of dropping, add 16.9g of benzoyl chloride to cyclohexanone.
Dissolve in 500g and add. After another 2 hours, the reaction solution is poured into methanol to separate the polymer. (B) Add Udel P-1700 (manufactured by Union Carbide, USA, commonly known as polysulfone) to the aromatic polyetheramide pellets obtained in (A) above.
were mixed in the weight ratio shown in Table 1 and granulated using a 40 mmφ extruder at a die temperature of 300°C. In addition,
The polysulfone has the following repeating unit. 4.5 ounces of pellets of this resin composition were molded using an in-line screw type injection molding machine.
Characteristic tests were conducted by molding into specified test pieces. The results obtained are shown in Table 1. Note that the injection molding pressure was 1100 Kg/cm ² .

[Table] All of the above compositions had good fatigue resistance. Example 2 (A) Method for producing aromatic polyetheramide copolymer 10 Separable flasks were equipped with a stirring bar, a thermometer,
Set the dropping funnel and add 171.8 g of NaOH to 800 g of water.
ml and put it in a flask. Next, 2,2
-Bis-[4-(4-aminophenoxy)phenyl]propane 594g and 4,4'-diaminodiphenyl ether 66g cyclohexanone 3.4g
Kg and pour it into the flask above, −
Cool to 2°C. On the other hand, 182 g of terephthalic acid dichloride and 182 g of isophthalic acid dichloride
Dissolve g in 2.4 kg of dichlorohexanone. Pour this acid chloride solution through the dropping funnel, making sure that the reaction temperature does not exceed 10°C. 8 hours after the start of dropping, benzoyl chloride
Dissolve 18.9g in 500g of cyclohexanone and add. After another 2 hours, the reaction solution is poured into methanol to isolate the polymer. (B) Add Victrex 200P to the aromatic polyetheramide pellets obtained in (A) above.
(manufactured by Imperial Chemical Co., Ltd., commonly known as polyether sulfone) were mixed at the weight ratio shown in Table 2, and property tests were conducted in the same manner as in Example 1. In addition, the said polyether sulfone has the following repeating unit.

[Table] Example 3 (A) Production of aromatic polyetheramide Using the raw materials with the following composition, the above Example 1 (A)
Aromatic polyetheramide powder was obtained in the same manner as above.

[Table] (B) Production of polyarylene polyether In a flask equipped with a stirrer, a thermometer, a water-cooled condenser, and a moisture trap filled with benzene, 100.2 g of (4,4'-dihydroxydiphenyl)methane ( 0.5 mol), 42.8% caustic potash solution
131 g (1 mole KOH), 500 ml of dimethyl sulfoxide, and 60 ml of benzene are charged and the system is purged with nitrogen to maintain the reaction mixture in an inert atmosphere. The mixture is refluxed for 3-4 hours, the water contained in the reaction mixture as an azeotrope of benzene is continuously removed, and the benzene is thoroughly distilled off to bring the reflux mixture to 130-135°C. The reflux mixture consists of the dipotassium salt of (4,4′-dihydroxydiphenyl)methane and dimethyl sulfoxide and is essentially water-free, cooling the mixture;
4,4'-dichlorodiphenyl sulfone 143.5
g (0.5 mol) and then 400 ml of anhydrous dimethyl sulfoxide. All of this is done under nitrogen pressure. The mixture is at 130℃
130-135 for 7 hours with good stirring.
The viscous orange solution, kept at
Pour into 300 ml, the finely divided white polymer is filtered and then dried in a vacuum oven at 110° C. for 16 hours. The polyarylene polyether thus obtained has the following repeating units. (C) After uniformly mixing the aromatic polyether amide powder obtained in the above (A) and the polyarylene polyether powder obtained in the above (B) using a super mixer, using a 40 mmφ extruder, It was granulated at a die temperature of 300°C. The obtained composition was injection molded to prepare test pieces, and physical property tests were conducted. The results obtained in the third
Shown in the table.

[Table] In the above, the creep characteristics were determined by measuring the change in deformation over time when a constant bending stress (support spacing 80 mm) was applied at a constant temperature using a Shimadzu creep tester. In the evaluation, the case where the time was shorter than that of the polyether sulfone alone in Example 2 was evaluated as good. In addition, fatigue resistance is measured by measuring the number of times it takes to break when a certain tensile stress is repeatedly applied (one swing) using a fatigue resistance testing machine manufactured by Shimadzu Corporation. The tensile stress, which is considered to break only after ¹⁰⁷ repetitions, was calculated by interpolation. The evaluation was rated as good when the interpolated tensile stress was greater than that of the polyarylene polyether alone in Examples 1 and 3. As is clear from the above, the resin composition according to the present invention exhibits excellent moldability and fatigue resistance,
Other properties are also excellent.

Claims (1)

[Claims] 1 [A] General formula () (In the general formula (), R ₁ to _{R 4} represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine, or bromine, and may be the same or different from each other.
R ₅ and R ₆ are hydrogen, a methyl group, an ethyl group, a trifluoromethyl group or a trichloromethyl group, and may be the same or different.
Ar represents a P-phenylene group, a m-phenylene group, an oxydiphenylene group, a sulfonyldiphenylene group, a biphenylene group, or a naphthylene group) and [B ] General formula () [-O-E-O-E']- () (In the general formula (), E is a residue of divalent phenol, and E' is ortho or para to the valence bond. is a residue of a benzenoid compound having an inert electron-withdrawing group in at least one position, and both residues are bonded to an ether oxygen via an aromatic carbon atom). A thermoplastic resin composition containing 95 to 5% by weight of polyarylene polyether.