JPH0686566B2 - Polyphenylene ether resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyphenylene ether resin composition having improved impact resistance and moldability. For more details,
The present invention relates to a polyphenylene ether resin composition containing a radial tereblock copolymer composed of a vinyl aromatic compound, a conjugated diene rubber and a coupling agent as an elastomer component and having improved impact strength and moldability.

[Conventional technology]

Polyphenylene ether resin is US Pat. No. 3306874, 3
It is a known resin disclosed in various known documents such as 306875, 3257357, 3257358 and 4011200, or JP-A-50-126800.

Polyphenylene ether resin is a resin having excellent heat resistance, but it requires extrusion and molding at high temperatures. Extrusion and molding processing at high temperature cause deterioration of the polyphenylene ether resin, and as a result, the excellent performance originally possessed by the polyphenylene ether resin is impaired. Further, the impact resistance of the polyphenylene ether resin is small and it is insufficient to use it as it is. US Pat. No. 3,383,435 discloses a resin composition containing a polyphenylene ether and a vinyl aromatic resin as a method for simultaneously improving such drawbacks of the polyphenylene ether resin. By blending vinyl aromatic resin and polyphenylene ether, it is possible to lower the temperature required for extrusion and molding. Further, when a rubber-modified polystyrene resin is used as the vinyl aromatic resin, the impact resistance strength of the resin composition is also improved. Since the rubber content in the composition increases with an increase in the proportion of the rubber-modified polystyrene, the degree of improvement in impact strength also increases, but the improvement in impact strength is still insufficient. Furthermore, the heat resistance is markedly reduced as the rubber-modified polystyrene increases.

Various resin compositions have been proposed as means for improving impact strength. For example, US Pat. No. 3660531 discloses a resin composition containing polyphenylene oxide, polystyrene and rubber, and US Pat. No. 3994856 discloses a polyphenylene oxide, polystyrene and AB-.
A resin composition containing an A'type block copolymer, U.S. Pat. No. 4,128,602, contains polyphenylene oxide, polystyrene and rubber, and has a maximum mean diameter of rubber particles dispersed in the resin composition. A resin composition having a diameter of 2 μm, U.S. Pat. No. 4,128,603 describes elastomer gel particles containing polyphenylene oxide and high impact polystyrene, the high impact polystyrene being 22 to 80% by weight. Resin compositions that appear to contain, and Japanese Patent Publication No. 57-8139 discloses polyphenylene ether, polystyrene and acrylic resin modified ABS.
Resin compositions each containing are disclosed.

[Problems to be solved by the invention]

However, it is hard to say that the above-mentioned known compositions have the drawbacks of the polyphenylene ether-based resin improved without impairing the original characteristics of the resin. Therefore, by using an impact resistance imparting component different from the above composition, the impact resistance was improved, and the moldability was improved without significantly lowering the heat resistance of the polyphenylene ether resin. Development of a polyphenylene ether resin composition is desired.

[Means for solving problems]

As a result of diligent studies by the present inventors to satisfy the above-mentioned demand,
A poly (phenylene ether) resin composition having improved impact resistance and moldability is obtained by blending a radial tereblock copolymer and an organic phosphate ester compound into a polyphenylene ether resin and melt-mixing them. The inventors have found what is obtained and have reached the present invention.

That is, the present invention contains (a) a polyphenylene ether resin, (b) a vinyl aromatic compound, a radial tereblock copolymer composed of a conjugated diene rubber and a coupling agent, and (c) an organic phosphate compound. A polyphenylene ether resin composition having improved impact resistance and moldability.

The polyphenylene ether resin used as the component (a) of the present invention is a monocyclic phenol represented by the general formula (I). (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and
R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) Is a polyphenylene ether obtained by oxidative polycondensation of one or more of The polyphenylene ether may be a homopolymer or a copolymer.

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-ethylphenol, 2,6-dimethyl-3-
Examples include propylphenol and the like. And, as the polyphenylene ether obtained by polycondensation of one or more of these monocyclic phenols, for example, poly (2,6-
Dimethyl-1,4-phenylene) ether, 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 Examples include polymers and 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymers. Particularly, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferable as the polyphenylene ether resin used in the present invention. is there.

Next, the radial tereblock copolymer used as the component (b) of the present invention is an elastomeric branched polymer composed of a vinyl aromatic compound polymer block, a conjugated diene rubber block and a coupling agent. More particularly, two or more chains of conjugated diene rubber extend from the coupling agent, with the opposite end of each chain from the coupling agent being attached to the vinyl aromatic polymer chain. Radial tereblock copolymers are known in the art, for example, conjugated diene compounds and vinyl aromatic compounds are polymerized in the presence of an organometallic polymerization initiator to give lithium-like activity at one end of various polymer chains. It can be prepared by preparing a copolymer containing metal atoms and then reacting the copolymer with a coupling agent having at least two active groups capable of substituting active metal atoms. As a result, a polymer having a branch of a polymer chain extending radially around the coupling agent as a nucleus is obtained. Such a radial teleblock copolymer is commercially available from Asahi Kasei Kogyo Co., Ltd. under the trade name of "Sorprene T-411".
It is sold under the trade name of "Sorprene T-414",
It is commercially available.

The vinyl aromatic compound in the component (b) is a compound represented by the following general formula (II).

(In the formula, R ₄ is a hydrogen atom or a lower alkyl group, Z is a halogen atom or a lower alkyl group, and p is 0 or 1
Is a positive integer of ˜3. ) Specifically, styrene, p-methylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, bromostyrene, chlorostyrene and the like can be mentioned. The conjugated diene rubber in the component (b) is a polymer obtained by polymerizing a conjugated diene compound, and the conjugated diene compound is 1,
Examples thereof include 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. Also,
The coupling agent in the component (b) is polyepoxide, polyisocyanate, polyamine, polyaldehyde, polyketone, polyanhydride, polyester, polyhalide or the like. These compounds may be used in combination.

The ratio of the vinyl aromatic compound to the conjugated diene rubber in the component (b) is 1/99 to 45/55 (weight ratio). Also,
The molecular weight ranges from about 50,000 to about 350,000. Furthermore,
The amount of coupling agent in component (b) is generally 0.02 to 1 part by weight per 100 parts by weight of component (b).

The ratio (weight) of the component (a) and the component (b) in the resin composition of the present invention is 99/1 to 50/50, preferably 95/5 to 70 /.
30. When the amount of the component (a) is large, the effect of the component (b) is not recognized, and when the amount of the component (b) is too large, the performance of the resin composition is rather impaired.

The organophosphate compound (c) in the present invention is a compound represented by the general formula (III).

(In the formula, R ₅ , R ₆ and R ₇ may be the same or different, an alkyl group, a haloalkyl group, a cycloalkyl group,
It represents an aryl group, a haloaryl group, an alkyl-substituted aryl group, a haloalkyl-substituted aryl group, an aryl-substituted alkyl group, a haloaryl-substituted alkyl group or a hydrogen atom, and R _{5 to} R ₇ are not all hydrogen atoms.

Specifically, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tricresyl phosphate, tris (isopropylphenyl) phosphate, triphenyl phosphate, triethyl phosphate, dibutyl phenyl phosphate, diethyl Phenyl phosphate, isooctyl diphenyl phosphate, tributyl phosphate, isodecyl diphenyl phosphate, isodecyl dicresyl phosphate, didecyl resilyl phosphate, tri-m-hexyl phosphate, di-n-octyl Examples include phenyl phosphate and mixtures thereof. Particularly preferred are aromatic phosphates represented by triphenyl phosphate.

The addition amount of the organophosphate compound in the present invention is 30 parts by weight or less, preferably 1 to 20 parts by weight, relative to 100 parts by weight of the resin component. If the amount is less than the lower limit, the effect of the organophosphate compound will not be recognized, and if it is more than the upper limit, the heat resistance of the resin composition will be significantly lowered.

The resin composition of the present invention, various additives, depending on the purpose,
It is possible to mix other components such as a filler. For example, stabilizers such as sterically hindered phenol, organic phosphite, phosphonite, phosphononic acid, cyclic phosphononite, hydrazine derivative, amine derivative, carbamate derivative, thioether, phosphorite triamide, benzoxazole derivative, and metal sulfide; benzotriazole. UV absorbers such as derivatives, benzophenone derivatives, salicylate derivatives, sterically hindered amines, oxalic acid diamide derivatives, organic nickel complexes; olefin wax as a lubricant represented by polyethylene wax or polypropylene wax; titanium oxide, oxidation Pigments represented by lead, carbon black, etc .; represented by glass fiber, glass beads, asbestos, wollastonite, mica, talc, clay, calcium carbonate, silica, etc. Machine filler: Metal flakes typified by flakes of copper, nickel, aluminum, lead, etc .; Metal fibers typified by aluminum fibers, aluminum alloy fibers, brass fibers, stainless fibers; typified by carbonic acid fibers and aromatic polyamide fibers Examples of the organic fillers include:
The addition amount of these other components may be appropriately selected depending on the type of compound used or the purpose of addition.

In preparing the polyphenylene ether resin composition of the present invention, conventionally known methods can be adopted. For example, a method of mixing the components with a blender such as a turnbull mixer or a Henschel mixer and then kneading with an extruder, a Banbury mixer, a roll, or the like is appropriately selected.

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. .

〔Example〕

Examples 1 to 4 2,6-intrinsic viscosity of 0.52 dl / g (at 25 ° C. in chloroform)
Dimethylphenol / 2,3,6-trimethylphenol copolymer (the latter ratio is 5 mol%; abbreviated as "PPE"), radial tereblock copolymer of styrene and butadiene (manufactured by Asahi Chemical Industry Co., Ltd., Product name "Sorprene T-411"; styrene content 30%, butadiene content
70%; abbreviated as "RTB". ) And triphenyl phosphate (abbreviated as TPP)) were mixed in a ratio as shown in Table 1 using a Hensiel mixer. The resulting mixture was extruded into pellets with an AS-30 type twin-screw extruder (Nakaya Machinery Co., Ltd.) in which the maximum temperature of the cylinder was set to 300 ° C, and then SJ in which the maximum temperature of the cylinder was set to 305 ° C. A test piece was molded under the conditions of an injection pressure of 1310 Kg / cm ² using a −35B type injection molding machine (Meiki Seisakusho). The results of measurement of physical properties are shown in Table 1. The heat distortion temperature was adopted as a measure of moldability. If the moldability improves,
The heat distortion temperature decreases.

Comparative Examples 1 to 4 The operation according to Example 1 was repeated using the PPE used alone in Example 1, or using PPE, the radial tereblock copolymer and TPP in the proportions shown in Table 1, respectively.
The results are also shown in Table 1 as in the case of the examples.

In Table 1, the following is clear when the results of Examples and Comparative Examples are compared.

i) The use of radial tereblock copolymer and TPP improves the Izod impact strength and moldability as compared with PPE.

ii) Even if the ratio of PPE and radial teleblock copolymer is the same, the presence of TPP increases the izot impact strength and tensile impact strength. Therefore, TP
P and the radial teleblock copolymer have a synergistic effect in improving the impact strength.

Example 5 The procedure of Example 2 was repeated except that the amount of TPP used was changed to 15 parts. The performance measurement results are shown below.

Heat distortion temperature: 122 ° C. Izod impact strength (with notch): 27.4 Kg · cm / cm Tensile impact strength: 396 Kg · cm / cm ² [Effect of the invention] As apparent from the above examples, the resin composition of the present invention In addition to improving the moldability of the product, the combined use of an organic phosphate compound and a radial tereblock copolymer,
Impact strength is improved based on these synergistic effects.

Claims (1)

[Claims] 1. A polyphenylene ether-based resin (a),
(B) A radial tereblock copolymer comprising a vinyl aromatic compound, a conjugated diene rubber and a coupling agent, and (c) a ratio of a polyphenylene ether resin and a radial tereblock copolymer containing an organic phosphate compound. Polyphenylene ether resin composition having improved impact resistance and moldability (weight) of 99/1 to 50/50