JPH07116353B2 - Polyphenylene ether resin composition having excellent thermal stability - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent thermal stability. More specifically, the copper content is 10pp
The present invention relates to a polyphenylene ether resin composition having excellent thermal stability, which contains a good solvent-non-solvent polyphenylene ether resin having a sulfur content of 250 ppm or less and a vinyl aromatic resin.

Polyphenylene ether resin is a US patent 3306874.
No. 3,306875, 3257357, 3257358 and 4011200, or various known documents such as JP-A No. 50-126800. A polyphenylene ether resin having a molecular weight above a certain level has a high softening point and is useful for applications requiring heat resistance. However, since it has a high softening point, a resin composition containing a polyphenylene ether resin is used for a long time at a relatively high temperature unlike other general-purpose resins. There are many. By the way, as is well known, the polyphenylene ether resin composition is relatively unstable with respect to heating in an atmosphere in which oxygen is present, and long-term use under heating requires polyphenylene ether. This causes deterioration of the physical properties of the ether resin composition. Such a decrease in physical properties limits the wide range of use of the polyphenylene ether resin composition, and improvement of this defect is desired.

By the way, various methods for stabilizing a resin composition containing a polyphenylene ether-based resin have been already proposed, and specifically, a method of capping a hydroxyl group existing at the terminal of a polyphenylene ether molecule by acylation or the like. Alternatively, stabilization is attempted by a method of adding various stabilizers.

As stabilizers effective for stabilizing polyphenylene ether, benzoates are disclosed in U.S. Pat.No. 3,379,875, U.S. Pat.Nos. 3,414,536, 3420792, 3249850, 346506.
2,3472814, 3482371, 3792121 and 3816562, the hexaalkylphosphoric trioctamide or the combination of this phosphoric triamide with other compounds is disclosed in U.S. Pat. Alkylpyrophosphamide or combinations of this pyroosphloamide with other compounds are described in US Pat.
3563934 and 3956423 for amines, U.S. Pat.No. 3,633,334 for phosphite and hydrazines, U.S. Pat.No. 3,761,541 for alkanolamines, U.S. Pat. The aryl phosphine onycdiamides are described in US Pat.
According to US Pat. No. 54719, sterically hindered phenols having a triazine ring or an isocyanuric ring are described in US Pat.
The dicarboxylic acid dihydrazides substituted by 904, the high molecular weight phosphite or the combination of the high molecular weight phosphite and other compounds according to U.S. Pat.No. 3,952,072 is disclosed in JP-B-44-29748. As a result, amides are classified into Japanese Patent Publication No. 19395/45 and Japanese Patent Publication No.
According to Japanese Patent Publication No. 352, a metal salt of dithiocarbamic acid, a carboxylic acid anhydride according to Japanese Patent Publication No. 44-29750, a phosphite according to Japanese Patent Publication No. 44-29751, Japanese Patent Publication No. 46-43473, Japanese Patent Publication No. 46-42029, Japanese Patent Publication No. 46-4203
No. 0, JP-B-46-42031, JP-B-46-42032 and JP-B-46-42033 disclose that a sterically hindered phenol or a combination of a sterically hindered phenol and another compound is disclosed in JP-B-46-24782. According to the publication, a sterically hindered phenol having one amide bond in the molecule is disclosed in Japanese Patent Publication No. 48-
According to JP 38623, a sterically hindered phenol having one ester bond in the molecule has a high molecular weight according to JP 49-23846, JP 49-31755 and JP 50-40476. JP-A-49-129750 discloses a combination of phosphite amides and a boron compound, respectively. In spite of the fact that many stabilizers are provided as described above, the fact is that no resin composition containing a polyphenylene ether having a sufficiently stable thermal stability for practical use has been found yet. Is.

The present inventors, unlike the solution polymerization method which uses only a good solvent for polyphenylene ether that is usually performed for the production of polyphenylene ether, is a mixed solvent of a good solvent and a non-solvent for polyphenylene ether. Developed a polymerization method to carry out oxidative polycondensation reaction of phenols in
Polyphenylene ether resin composition using a polyphenylene ether resin obtained by this method (in the present specification, this resin is abbreviated as “good solvent-nonsolvent method polyphenylene ether resin”) As a result of the detailed examination of the good solvent-nonsolvent method polyphenylene ether resin content of impurities in the good solvent-nonsolvent method polyphenylene ether resin resin composition containing heat stability The present invention has been completed by finding that it has a correlation with the thermal stability during long-term use under high temperature, especially high temperature.

That is, the present invention is a polyphenylene ether resin composition containing a good solvent having a copper content of 10 ppm or less and sulfur 250 ppm or less-nonsolvent method polyphenylene ether resin and vinyl aromatic resin. In addition, the resin composition exhibits excellent thermal stability.

The good solvent-nonsolvent method polyphenylene ether-based resin in the present invention is one or more of the monocyclic phenols represented by the general formula (I), (Here, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R ₃ are hydrogen atoms or a lower alkyl group having 1 to 3 carbon atoms, and at least one ortho position of the hydroxyl group must be a lower alkyl group. Substituent must be present.) A polymer obtained by oxidative polycondensation reaction in the presence of a catalyst using a mixture of a good solvent and a non-solvent for the resulting polyphenylene ether resin as a solvent. Includes both polymers and copolymers.

Examples of the monocyclic phenol represented by the general formula (I) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2-methyl-6-ethylphenol and 2 -Methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-
Cresol, 2,3-dimethylphenol, 2,3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol , 2-ethyl-3-propylphenol, 2-propyl-3-methylphenol, 2-propyl-3-ethylphenol, 2,3,6-trimethylphenol, 2,3,6-triethylphenol, 2,3, 6-tripropylphenol, 2,6-dimethyl-3-ethyl-phenol, 2,6-dimethyl-3
-Propylphenol and the like. Examples of the polyphenylene ether obtained by polycondensation of one or more of these phenols include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,6-diethyl-1,4). -Phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-)
6-ethyl-1,4-phenylene) ether, poly (2-
Methyl-6-propyl-1,4-phenylene) ether,
Poly (2-ethyl-6-propyl-1,4-phenylene)
Ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,
6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-
Examples thereof include dipropylphenol / 2,3,6-trimethylphenol copolymer and the like. In particular, poly (2,6-dimethyl-
1,4-phenylene) ether, 2,6-dimethylphenol
The / 2,3,6-trimethylphenol copolymer is preferred as the polyphenylene ether resin used in the present invention.

The method for producing the good solvent-nonsolvent method polyphenylene ether-based resin will be described in detail. An aromatic hydrocarbon that is a good solvent for the polyphenylene ether to be produced and an aliphatic hydrocarbon that is a nonsolvent are prescribed. Oxidative polycondensation of at least one monocyclic phenol represented by formula (I) in the presence of a catalyst consisting of a cuprous salt and a primary amine or secondary amine in a mixed solvent mixed at a ratio of By doing so, the desired polymer is produced. Examples of the good solvent used here include aromatic hydrocarbons exemplified by benzene, toluene, xylene, ethylbenzene and the like, and halogenated aromatic hydrocarbons represented by chlorobenzene, and toluene is particularly preferable. Examples of the non-solvent include linear aliphatic hydrocarbons such as n-hexane, n-pentane, n-heptane, and n-octane, and n-heptane is particularly preferable. The mixing ratio of a good solvent and a non-solvent is an important requirement, keeping the reaction rate of the oxidative polymerization of monocyclic phenols in a practical range, and obtaining an intrinsic viscosity of the polyphenylene ether of 0.47 dl / g ( In order to obtain the target polyphenylene ether in chloroform at a temperature of 30 ° C.) or higher and with a high yield, a good solvent is a non-solvent to a good solvent in a weight ratio.
It is preferable to use a mixture of both solvents in the range of 0.9 to 1.1. Examples of the cuprous salt used as a catalyst include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous thiocyanate, cuprous sulfate and cuprous acetate. Can be mentioned. Among them, cuprous iodide, cuprous cyanide or cuprous thiocyanide is preferably used, and cuprous iodide is particularly preferable. Furthermore, the following compounds are mentioned as a primary amine or a secondary amine used as a catalyst. Examples of the primary amine include monoamines such as ethylamine, propylamine, isopropylamine, n-butylamine, amylamine and laurylamine; monocycloalkylamines represented by cyclohexylamine; benzylamine and β-phenyl. Examples thereof include monoaralkylamines exemplified by ethylamine and the like,
Examples of secondary amines include dialkylamines represented by dimethylamine, diethylamine, dipropylamine and dibutylamine.

The operation itself of oxidative polycondensation of monocyclic phenols in a reaction system using a catalyst composed of the above-mentioned cuprous salt and a primary amine or secondary amine using a mixed solvent having the above-mentioned specific ratio is known per se. The operation may be the same as the above, and the oxidative polymerization reaction is performed while passing oxygen or a gas containing oxygen through the reaction system. The polymerization reaction may be normally carried out by appropriately selecting from a temperature in the range of 20 to 100 ° C, and air is industrially used as the oxygen-containing gas blown into the reaction system, but is not particularly limited to this. Not a thing.

In the above polymerization operation, when the molecular weight of the polyphenylene ether resin reaches a certain value determined by the ratio of the good solvent and the non-solvent, the dissolution of the polymer reaches the limit and the polyphenylene ether resin precipitates. Is deposited as. If the resin deposited as a precipitate is left as it is, the molecular weight changes, so it is desirable to add a reaction terminator to prevent the molecular weight from changing. As the reaction terminator, a chelating agent such as a tetrasodium salt of ethylenediaminetetraacetic acid (EDTA) or a similar substance alone, or a combination of these chelating agents with hydrosulfite or catechol is desirable. The precipitated resin is recovered by filtration, but impurities are present in the recovered resin. When a chelating agent alone or a combination of a chelating agent and catechol is used as a terminating agent, copper and nitrogen which are catalyst residues are present as main impurities, and when a combination of a chelating agent and hydrosulfite is used. The main impurities are copper and nitrogen, which are catalyst residues, and sulfur, which is a residue of hydrosulfite. The amount of copper and sulfur will depend on the amount of quencher used and the degree of washing of the recovered resin due to excess.

The good solvent-nonsolvent method polyphenylene ether-based resin obtained by the above method has an intrinsic viscosity of 0.47 to 0.70 dl / g measured in chloroform at 30 ° C., which is the same polymer obtained by a conventionally known method. It has a glass transition point higher than 5 ° C. at least as compared with the skeleton polyphenylene ether, and it is understood that it has excellent heat resistance. Such a feature is that, compared to polyphenylene ether obtained by a known method using only a good solvent for polyphenylene ether, when viewed at the same intrinsic viscosity, the molecular weight of the low molecular weight and high molecular weight substances is small. It is understood that it is due to having a distribution. Incidentally, the glass transition point is a value measured at a temperature rising rate of 8 ° C./min in a nitrogen atmosphere by using a differential scanning calorimeter (abbreviated as DSC).

In the resin composition of the present invention, the content of copper as an impurity in the good solvent-nonsolvent method polyphenylene ether resin obtained by the above method is 10 ppm or less, preferably 7 pp.
A resin that is less than or equal to m must be used. Further, when hydrosulfite is used as the reaction terminator as described above, the resulting resin contains sulfur as an impurity. Therefore, when using a good solvent-nonsolvent method polyphenylene ether-based resin obtained by this method in the resin composition of the present invention, in addition to the copper content, an ion content of 250 ppm or less resin It is desirable to use.

The vinyl aromatic resin in the present invention has the following general formula (I
The monomer structural unit shown in I) is (Here, R ₄ represents a hydrogen atom or a lower alkyl group, Z represents a halogen atom or a lower alkyl group, and p represents 0 or 1 to 1.
It is a positive integer of 3. ) A resin having at least 25% by weight or more in the combination, such as polystyrene, rubber-modified polystyrene (impact-resistant polystyrene), poly-p-methylstyrene, rubber-modified poly-p-methylstyrene, styrene-butadiene copolymer, styrene- Butadiene-acrylonitrile copolymer, styrene-acrylic rubber-acrylonitrile copolymer, styrene-α-methylstyrene copolymer,
Styrene butadiene block copolymers and the like,
You may use these in mixture of 2 or more types.

Good solvent constituting the polyphenylene ether resin composition of the present invention-mixing ratio of non-solvent method polyphenylene ether resin and vinyl aromatic resin is 95/5 to 5/95, preferably
90/10 to 10/90.

An elastomer component can be blended with the resin composition of the present invention in addition to the above resin components. Here, the elastomer component is an elastomer in a general sense,
For example, AV Tobolsky's “Properties and Structures of
Polymers "(John Wiley & Sons, Inc., 1960) 71-78
The definition adopted on the page can be quoted, and an elastomer has a Young's modulus at room temperature of 10 ⁵ to 10 ⁹ dynes / cm ² (0.1 to 1020
kg / cm ² ) means a polymer. Specific examples of the elastomer include A-B-A 'type elastomeric block copolymers and A in which the double bond of the polybutadiene portion is hydrogenated.
-BA 'type elastomeric block copolymer, polybutadiene, polyisoprene, copolymer of diene compound and vinyl aromatic compound, nitrile rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer ( EPDM), thiocol rubber, polysulfide rubber, acrylate rubber, polyurethane rubber, grafted product of butyl rubber and polyethylene, polyester elastomer and the like. Above all, an AB-A 'type elastomeric block copolymer is preferable. The terminal blocks A and A'of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, B is a polymerized conjugated diene block, and the molecular weight of B block is the combination of A and A'blocks. It is desirable that the molecular weight is larger than the molecular weight. The end blocks A and A'may be the same or different and the blocks are thermoplastic homopolymers or copolymers derived from vinyl aromatic compounds whose aromatic moieties may be monocyclic or polycyclic. Examples of such vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,3-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene and mixtures thereof. The molecular weight of each end block A and A'is preferably in the range of about 2,000 to about 100,000, while the molecular weight of the central block B is preferably about.
It ranges from 25,000 to about 1,000,000.

The resin composition of the present invention is a polyphenylene ether resin,
When an elastomer is contained as a resin component in addition to the vinyl aromatic resin, the proportion of the polyphenylene ether resin in the resin component varies depending on the purpose of producing the resin composition, but is usually 5% by weight. That is all.

Various additives or fillers may be added to the resin composition of the present invention in addition to the above resin components. Above all, flame retardants and stabilizers are important. Examples of flame retardants include phosphorus-containing compounds and halogen-containing compounds. Phosphate compounds are generally used as phosphorus-containing compounds, but even phosphonate compounds and phosphine oxide compounds,
As long as flame retardancy is imparted to the resin composition, it can be used. The phosphate compound includes an aromatic phosphate compound and an aliphatic phosphate compound. In general, the former is preferable because it has excellent heat resistance, but it does not prevent the latter from being used. As aromatic phosphite compounds, triphenyl phosphonate, tricresyl phosphonate, cresyl diphenyl phosphonate, phosphonate produced from a mixture of isopropyl phenol and phenol, cresyl diphenyl phosphate dimer Specific examples include the body. Chlorine compounds and bromine compounds are generally used as halogen-containing compounds, but bromine compounds are preferred. However, it does not prevent the former use. As the bromine compound, decabromobiphenyl,
Specific examples thereof include a polycarbonate oligomer produced using decabromobiphenyl ether, pentabromotoluene, brominated bisphenol A, brominated polystyrene, brominated bisphenol A, and brominated polyphenylene ether oligomer.

Examples of the stabilizer include sterically hindered phenols, organic phosphaites, phosphonites, phosphonas acids, cyclic phosphonites, hydrazine derivatives, amine derivatives, carbamate derivatives, thioethers, phosphorite triamides, benzimidazole derivatives, and metal sulfides. These may be used as a mixture.

Other additives include benzotriazole derivatives,
UV absorbers such as benzophenone derivatives, salicylate derivatives, sterically hindered amines, oxalic acid diamide derivatives and organic nickel complexes; olefin wax as a lubricant represented by polyethylene wax, polypropylene wax; titanium oxide, zinc oxide , Pigments represented by carbon black, etc .; inorganic fillers represented by glass fiber, glass beads, asbestos, wollastonite, mica, talc, clay, calcium carbonate, silica; carbon fiber, aromatic polyamide fiber, heat resistant Examples thereof include organic fillers represented by phenol resin fibers and the like. The amount of these additives added is appropriately selected according to the type of compound used or the purpose of addition.

Hereinafter, the resin composition of the present invention will be specifically described with reference to Examples and Comparative Examples, but the parts and percentages of the respective constituents of the resin composition are expressed on a weight basis unless otherwise specified. .

Reference Example 1 600 parts of toluene and 588 parts of n-heptane were added to a reactor equipped with a stirrer, a reflux condenser and an air blowing tube.
Next, 1.0 part of cuprous iodide was added to n-butylamine 134.
Add the catalyst prepared by dissolving in
Warmed to ° C. To this solution was added 2,6-dimethylphenol 18
A monomer solution prepared by dissolving 8.9 parts and 11.3 parts of 2,3,6-trimethylphenol in a mixed solvent of 400 parts of toluene and 392 parts of n-heptane was supplied by a metering pump to start the reaction. The supply of the monomer solution was completed in 65 minutes. A polymer precipitate was formed as the polymerization reaction proceeded. 120 minutes after starting the reaction, tetrasodium salt of ethylenediaminetetraacetic acid (EDTA) 5.
An aqueous solution containing 9 parts and 2.7 parts of hydrosulfite was added, and stirring was continued for a while. Then, the polymer was separated from the reaction solution and washed with the above toluene-n-heptane mixed solution. The obtained good solvent-nonsolvent method polyphenylene ether copolymer was dried and then the intrinsic viscosity was measured to be 0.
It was 52 dl / g (30 ° C., in chloroform). Copper content and sulfur content in the polymer are 3 ppm and 20 pp, respectively.
It was m. Further, the glass transition point measured by DSC was 231 ° C. The good solvent-nonsolvent polyphenylene ether copolymer obtained here is referred to as "resin A".

Reference Example 2 In Reference Example 1, the degree of washing of the polymer obtained after the polymerization operation was changed, and the good solvent and non-solvent polyphenylene ether copolymers shown in Table 1 having different contents of five kinds of copper and ions were used. Polymers (“resins B, C, D, E and F”) were prepared.

Reference Example 3 In Reference Example 1, except that the amounts of EDTA and hydrosulfite used were changed, Reference Example 1 was repeated to synthesize a good solvent-nonsolvent polyphenylene ether copolymer, which was obtained separately after the polymerization operation. The degree of washing of the polymer was changed and Table 1
Although the copper content described in parallel exceeds 10 ppm, the sulfur content is a copolymer of 250 ppm or less, the copper content is 10 ppm or less, the sulfur content is a copolymer of more than 250 ppm, the copper content is Copolymers (resins a, b, c, d and e) above 10 ppm and also above 250 ppm sulfur were prepared.

Example 1 and Comparative Example 1 60 parts of good solvent-non-solvent method 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer (“resin A”) obtained in Reference Example 1, impact resistance Polystyrene [matrix intrinsic viscosity 0.89 dl / g (25 ° C, in chloroform), gel content 16.5 wt% (analyzed with methyl ethyl ketone solvent)] 37 parts,
Polystyrene-polybutadiene-polystyrene block copolymer (the weight ratio of polystyrene part and polybutadiene part is 30/70, and 25% by a Brookfield model RVT viscometer of a 20% toluene solution of the copolymer).
Viscosity at 1500 cps) 2 parts, ethylene-propylene copolymer (concentration 0.1 g / 100 ml with decalin as solvent, temperature 13
Reduced specific viscosity 2.0 measured at 5 ° C; glass transition temperature -49
1 part), triphenylphosphonate 6 parts, titanium oxide (having a rutile type crystal structure, particle size 0.3 to 0.5 μ) 7
Parts, hydrogenated bisphenol A phosphite resin 0.4 parts and 2,2'-methylene-bis (4-methyl-6-tert.
-Butylphenol) 0.6 part was mixed using a Hensiel mixer. The obtained mixture was extruded into a pellet by an AS-30 type twin-screw extruder (manufactured by Nakatani Kikai Seisakusho) in which the maximum temperature of the cylinder was set to 290 ° C, and then pelletized, and then the maximum temperature of the cylinder was set to 280 ° C. Using a −35B type injection molding machine (manufactured by each machine manufacturing company), a test piece for measuring Izod impact strength having a shape of 1/8 ″ × 1/2 ″ × 5/2 ″ was molded. The notched Izod impact strength was measured, this test piece was hot air aged for 20 days in a hot air circulation oven maintained at 115 ° C., and the notched Izod impact strength of the test piece was measured. Evaluated by the retention rate after heat aging,
The results are shown in Table 2. Table 2 also shows the results obtained with the same formulation as above for the five types of "resins B to F" obtained in Reference Example 2. The retention rate was calculated according to the following formula (Example 1).

2,6-Dimethylphenol / 2,3,6 obtained in Reference Example 3
The same operation as above was repeated using a trimethylphenol copolymer, and the notched Izod impact strength before hot air aging and after hot air aging was measured. The results are also shown in Table 2 as a retention rate (Comparative Example 1).

It should be noted that the larger the retention value, the better the thermal stability.

Example 2 and Comparative Example 2 The copper content obtained in Reference Example 2 was 7 ppm and the sulfur content was
Same formulation as in Example 1 but with 20 ppm polymer and no hydrogenated bisphenol A phosphite resin and 2,2'-methylene-bis (4-methyl-6-tert-butylphenol). The operation was repeated (Example 2).

Example 2 was repeated using the polymer obtained in Reference Example 3 with a copper content of 12 ppm and a sulfur content of 50 ppm (Comparative Example 2).

The results are as follows.

Izod impact strength retention rate (%) Example 2: 33 Comparative Example 2: 25 Example 3 and Comparative Example 3 Copper content 7 ppm and sulfur content 20 obtained in Reference Example 2
60 parts by ppm of polyphenylene ether copolymer, Example 1
40 parts of high-impact polystyrene used in Example 6, 6 parts of triphenylphosphite, and titanium oxide 7 used in Example 1
Parts, 0.4 parts of tris (nonylphenyl) phosphite and 0.6 parts of 2,6-di-tert-butyl-p-cresol were used, and other operations were repeated as in Example 1 (Example 3).

Copper content 12 ppm and sulfur content 5 obtained in Reference Example 3
Example 3 was repeated with 0 ppm of polymer (Comparative Example 3).

The results are as follows.

Izod impact strength retention rate (%) Example 3: 47 Comparative Example 3: 30 Example 4 and Comparative Example 4 Good solvent having a copper content of 8 ppm and a sulfur content of 20 ppm obtained in the same manner as in Reference Example 1-non 42 parts of solvent-processed polyphenylene ether copolymer, 53.5 parts of high impact polystyrene used in Example 1, 3.5 parts of polystyrene-polybutadiene-polystyrene block copolymer used in Example 1,
Ethylene-propylene copolymer 1 used in Example 1
Parts, 7 parts of titanium oxide used in Example 1, 0.4 parts of hydrogenated bisphenol A phosphite resin and 0.6 parts of 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), and others. The same procedure as in Example 1 was repeated (see Example 4).

Copper content 12 ppm and sulfur content 5 obtained in Reference Example 3
Example 4 was repeated with 0 ppm of polyphenylene ether copolymer (Comparative Example 4).

The results are as follows.

Izod impact strength retention rate (%) Example 4: 41 Comparative Example 4: 28 Example 5 and Comparative Example 5 Copper content obtained by the same operation as in Reference Example 1 except that hydrosulfite was not used in Reference Example 1. A good solvent with an intrinsic viscosity of 0.51dl / g (30 ℃, in chloroform) at an amount of 8ppm-
Example 1 was repeated using a non-solvent method polyphenylene ether copolymer (Example 5).

A polyphenylene ether copolymer having a copper content of 11 ppm and an intrinsic viscosity of 0.51 dl / g (at 30 ° C. in chloroform) obtained by the same operation as in Reference Example 3 except that hydrosulfite was not used. Example 1 was repeated using (Comparative Example 5).

The results are as follows.

Izod impact strength retention rate (%) Example 5: 42 Comparative Example 5: 31 Example 6 and Comparative Example 6 Copper content 6 ppm produced in the same manner as in Reference Example 1 using 2,6-dimethylphenol alone. And sulfur content 20
Intrinsic viscosity of 0.53dl / g in ppm (30 ℃, in chloroform)
68 parts of 2,6-dimethyl-1,4-phenylene ether, 32 parts of high impact polystyrene used in Example 1, 14 parts of triphenylphosphonate, titanium oxide 7 used in Example 1
Parts, hydrogenated bisphenol A phosphite resin 0.4 parts and 2,2'-methylene-bis (4-methyl-6-tert.
-Butylphenol) 0.6 part was mixed using a Hensiel mixer. In the other operations, Example 1 was repeated except that the maximum temperature of the cylinder of the injection molding machine was 265 ° C and the temperature of the hot air circulation oven was 100 ° C (Example 6).

A 2,6-dimethyl-1,4-phenylene ether having a copper content of 13 ppm and a sulfur content of 35 ppm and an intrinsic viscosity of 0.53 dl / g (at 30 ° C. in chloroform) produced by the same method as in Reference Example 3 was used. Example 6 was repeated except that it was used (Comparative Example 6).

Comparative Example 7 The 2,6-dimethyl-1,4-phenylene ether used in Example 6 was prepared by a homogeneous solution method using 2,6-dimethylphenol alone, and the copper content was 6 ppm and the sulfur content was 20.
Intrinsic viscosity of 0.53dl / g in ppm (30 ℃, in chloroform)
Example 6 was repeated except that 2,6-dimethyl-1,4-phenylene ether was used.

The results are as follows.

 Izod impact strength retention (%) Example 6: 65 Comparative example 6: 42 Comparative example 7: 52

 ─────────────────────────────────────────────────── --Continued from the front page Judgment panel for referees Akiko Hanaoka Judge Judge Seiichiro Numabe Judge Kawahide Mihide (56) References JP51-37998 (JP, A) JP53-94598 (JP, A) ) JP-A-47-4887 (JP, A) JP-A-51-122196 (JP, A)

Claims (1)

[Claims] 1. A good solvent-nonsolvent polyphenylene ether resin 5 to 95 parts by weight treated with a chelating agent and hydrosulfite, having a copper content of 10 ppm or less and a sulfur content of 250 ppm or less, and vinyl. Aromatic resin 95
To 5 parts by weight of polyphenylene ether resin composition having excellent thermal stability