JPS638139B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition comprising polyphenylene oxide, polyamide, and a compound having a specific structure. Polyphenylene oxide resin is a resin with excellent thermal, mechanical, and electrical properties, and commercially, it is blended with polystyrene resin and manufactured and sold as Noryl resin by General Electric Company. There is. The disadvantage of polyphenylene oxide resin and its modified product, noryl resin, is that it has poor solvent resistance, and although it has other excellent properties, it is difficult to use it for certain applications. Currently, its use is limited, and its improvement is strongly desired. As a result of intensive research into the development of a resin with excellent solvent resistance without significantly impairing the various properties of polyphenylene oxide resin, the inventor first discovered that polyphenylene oxide and polyamide were mixed in a specific ratio. They discovered that a material with excellent tolerability could be provided by melt-kneading, and filed a patent application. Although the resin composition produced by this method exhibits excellent solvent resistance without phase separation during molding, it is still insufficient in terms of impact resistance. In order to improve this point, we continued our research and found that a product obtained by adding a compound with a specific structure to polyphenylene oxide and polyamide and melt-kneading it was compared to a melt-kneaded product of only polyphenylene oxide and polyamide. It was discovered that a material with excellent mechanical strength such as impact resistance can be obtained. Although it is not clear why the composition obtained according to the present invention has better mechanical strength than a melt-kneaded product of only polyphenylene oxide and polyamide, it is clear from the electron micrographs of both of them that It is presumed that in the composition of the present invention, a graft reaction occurs between polyphenylene oxide and polyamide. That is, compared to a product obtained by melt-kneading only polyphenylene oxide and polyamide, the product obtained by the method according to the present invention has a significantly finer distribution of polyphenylene oxide and polyamide parts. is recognized. In the present invention, a compound having a specific structure, that is, a compound having an oxirane ring in the molecule and/or a condensed polymer of dihydric phenol and epichlorohydrin is added to polyphenylene oxide and polyamide. This invention relates to a resin composition having excellent mechanical strength such as impact resistance, which can be obtained by melt-kneading. The polyphenylene oxide resin in the present invention has the general formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are selected from hydrogen, halogen atoms, hydrocarbon groups, or substituted hydrocarbon groups, and one of them is necessarily a hydrogen atom. It is a polymer obtained by oxidative polymerization of the phenol compound shown in Specific examples of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ in the above general formula include hydrogen, chlorine, fluorine, bromine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, bidroxymethyl, carboxyethyl,
Examples include methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, and ethylphenyl. Specific examples of the above general formula include phenol,
0,m or p-cresol, 2,6-,2,5
-, 2,4- or 3,5-dimethylphenol,
2-methyl-6-phenyl-phenol, 2,6
-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol,
2,3,5-, 2,3,6- and 2,4,6-
Examples include trimethylphenol. Two or more types of these phenol compounds may be used. The oxidative coupling catalyst used in oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having polymerization ability may be used. For example, typical examples include catalysts consisting of cuprous salts and tertiary amines, such as cuprous chloride-trimethylamine, cuprous acetate-triethylamine, cuprous chloride-pyridine, etc. - Pyridine - Secondary compounds such as potassium hydroxide
Copper salts - catalysts consisting of tertiary amines and alkali metal hydroxides, manganese chloride - catalysts consisting of manganese salts and primary amines such as ethanolamine, manganese acetate - ethylenediamide, manganese chloride - sodium methylate, chloride manganese-
Examples include catalysts consisting of manganese salts such as sodium phenolate and alcoholates or phenolates, and catalysts consisting of a combination of cobalt salts and tertiary amines. The polyamide used in the present invention has a

[Formula] Anything is possible as long as it has a bond and can be melted by heating. Typical examples include 4-nylon, 6-nylon,
-Nylon, 6,6-nylon, 12-nylon,
6,10-nylon, polyamides from terephthalic acid and trimethylhexamethylene diamine, polyamides from adipic acid and metaxylylene diamine, polyamides from adipic acid, azelaic acid and 2,2-bis(p-aminocyclohexyl)-propane. , polyamides made from terephthalic acid and 4,4'-diaminocyclohexylmethane, and the like. A suitable mixing ratio of polyphenylene oxide and polyamide is 5 to 95 wt% of polyphenylene oxide and 95 to 5 wt% of polyamide. polyamide
If the polyamide content is less than 5 wt%, the effect of improving solvent resistance is small, and if the polyamide content exceeds 95 wt%, thermal properties such as heat distortion temperature tend to be poor, which is not preferable. Specific examples of the compound having an oxirane ring in the present invention include compounds obtained by condensing polyhydric phenols and epichlorohydrin in various proportions, such as bisphenol A.
and epichlorohydrin (products include, for example, Sumiepoxy from Sumitomo Chemical Co., Ltd.)
ELA-115, ELA-127, ELA-128, ELA-
134, ESA-011, ESA-014, ESA-017, ESA
-019, etc.), condensates of resorcinol and epichlorohydrin, condensates of hydroquinone and epichlorohydrin, condensates of tetrabromobisphenol A and epichlorohydrin, phenol novolak or cresol novolak with chrycidyl ether (for example, Sumiepoxy ESCN-220 series by Sumitomo Chemical Co., Ltd.). Condensation products of polyhydric alcohols and epichlorohydrin. Typical examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolethane, trimethylolpropane, and bentaerythritol. Examples include. Glycidyl ethers of monohydric phenols or monohydric alcohols, such as phenyl glycidyl ether, butyl glycidyl ether, cresyl glycidyl ether, and the like. Glycidylated amine compounds (for example, Sumiepoxy ELN-125, which is a diclycidylated aniline commercially available from Sumitomo Chemical Co., Ltd.), epoxidized products of higher olefins,
Examples include epoxidized products of cycloalkenes. The most commonly available product of the condensed polymer of dihydric phenol and epichlorohydrin used in the present invention is called phenoxy resin. It is also possible to use two or more kinds of specific compounds in the present invention. The amount of the specific compound added in the present invention is as follows:
There is no particular limitation on the method for producing the composition of the present invention based on 100 parts by weight of the mixture of polyphenylene oxide and polyamide, and any conventional known method may be employed. Generally, a method of melting and kneading is preferred. There are no particular limitations on the temperature and time for melt-kneading. Although the temperature varies slightly depending on the composition ratio of polyphenylene oxide and polyamide, it is generally in the range of 150 to 350°C. The apparatus for melt-kneading may be any method as long as it can handle a molten viscous material, and either a batch method or a continuous method can be used.
Specific examples include an extruder, a Banbury mixer, a roll, a kneader, and the like. In carrying out the present invention, it is also possible to add other polymers, fillers such as glass fiber, carbon fiber, carbon black, silica, _TiO2 , plasticizers, flame retardants, pigments, etc. In particular, it is desirable to add a rubbery polymer, a rubber-modified styrenic resin, and a styrenic polymer to further improve processability in order to improve impact strength. Specific examples of rubbery polymers include polybutadiene, butadiene-styrene copolymer, ethylene-propylene copolymer, and ethylene-propylene copolymer.
Diene copolymer, polyisoprene, polyisobutylene, polyacrylate, polyester,
Examples include polyurethane and various modified polymers thereof. Specific examples of rubber-modified styrene resins include butadiene-based rubber-modified polystyrene, butadiene-based rubber-modified styrene-acrylonitrile copolymer, acrylic rubber-modified polystyrene, acrylic rubber-modified styrene-acrylonitrile copolymer, and ethylene-propylene copolymer. Examples include polymer-modified polystyrene and ethylene-methyl methacrylate copolymer-modified polystyrene. Hereinafter, the method of the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto. Examples 1 to 7 Poly(2,6-dimethyl-
1,4-phenylene oxide) (intrinsic viscosity measured in chloroform: 0.55 d/g) and nylon-6,6 (manufactured by Toray Industries, Inc.), the specific compounds listed in Table 1 were added, and the The mixture was kneaded for 5 minutes at a temperature range of .degree. A Brabender Plastograph was used as a kneading device. The Izod impact value was measured to indicate mechanical strength, and the heat distortion temperature (HDT) was measured to indicate heat resistance. The results are shown in Table 1. Comparative Example 1 The results of melt-kneading the polyphenylene oxide and polyamide used in Example 1 without adding any specific compound are shown in Table 1 as Comparative Example 1.

[Table] As can be seen from the results in Table 1, it is clear that the products to which the specific compound according to the present invention was added have improved impact resistance compared to the comparative example. Examples 8 to 11 50 parts by weight of poly(2,6-dimethyl-1,4-phenylene oxide) used in Example-1, 50 parts by weight of various impact-resistant nylons, and 1283 parts by weight of Sumiepoxy ELA-1 After dry blending, PCM-30 type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.)
The mixture was kneaded at about 270°C. Izod impact test pieces were prepared from the obtained pellets and impact values were measured. Also, as a comparative example, Sumiepoxy ELA-128
The same treatment was carried out without the addition of , and the impact value was measured. This is referred to as Comparative Example-2. The results are shown in Table-2.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are hydrogen, halogen atoms, hydrocarbons or substituted hydrocarbon groups, and at least one is always hydrogen.) A compound having an oxirane ring in the molecule and/or dihydric phenol and epichlorohydride per 100 parts by weight of a resin consisting of 5 to 95 wt% of a polymer obtained by oxidative polymerization of one or more types and 95 to 5 wt% of polyamide. A resin composition containing 0.1 to 20 parts by weight of a condensed polymer with phosphorus.