JPH0788466B2 - Polyphenylene ether heat-resistant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a polyphenylene ether-based heat resistant resin composition having excellent thermal stability. More specifically, it relates to a polyphenylene ether heat-resistant resin composition that does not cause a defective appearance "silver" during high temperature molding.

<Prior art> Polyphenylene ether resin is a resin with excellent heat resistance and impact resistance, but since it is difficult to mold by itself, it is a workability that consists of polyphenylene ether resin and styrene resin. Many improved resin compositions have been proposed, and some of them have already been put into practical use. (Japanese Patent Publication 43-17812, Japanese Publication 47-43174, Japanese Publication 51-28659, USP3
383435, USP4360618) A resin composition composed of a polyphenylene ether resin and a styrene resin is generally molded at a set temperature of about 290 ° C., but due to the increase in size of plastic molded products and the complicated design in recent years, more Excellent workability is required.

The workability is improved by increasing the blending amount of the styrene resin, but the heat resistance is remarkably lowered.

Further, when the molding processing temperature is raised, the apparent workability is improved, but the thermal stability is reduced, and silver streaks (hereinafter referred to as silver) are generated on the surface of the molded product. The silver generation portion does not disappear even after the secondary processing (painting, etc.), and if the molding temperature is lowered, the workability deteriorates and the problem of insufficient filling in the mold occurs.

It is generally known that the more the volatile component contained in the resin, the more remarkable the generation of silver, and measures such as strengthening the drying conditions before molding are taken. However, the cause of silver generation is not only the volatile components contained in the resin before molding, but there are other unknown causes as well, so even if the drying conditions are strengthened, the occurrence of silver has not been completely eliminated. Is the reality. Further, it is not improved by the addition of a general antioxidant.

<Means for Solving Problems> The inventors of the present invention have conducted extensive studies in view of the above problems, and as a result,
By adding a small amount of a specific compound to a resin composition composed of a polyphenylene ether resin and a styrene resin, it is possible to significantly reduce silver generation during high temperature molding, and it is possible to mold at higher temperatures. The present invention has been accomplished by finding an ether heat-resistant resin composition.

That is, the present invention relates to 100 parts by weight of a resin composition (A) composed of a polyphenylene ether resin (hereinafter referred to as PPE) and a styrene resin, and a metal deactivator represented by a specific structural formula ( B) Poor appearance "silver" during high temperature molding, characterized by containing 0.001 to 5.0 parts by weight
The present invention provides a polyphenylene ether-based heat-resistant resin composition that does not generate heat.

Hereinafter, the present invention will be described in detail.

PPE The PPE used in the present invention is a polymer obtained by oxidatively polymerizing one or more monocyclic phenols represented by the following general formula in the presence of an oxidative coupling catalyst and oxygen or an oxygen-containing gas.

(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. ) PPE may be a homopolymer or a copolymer of the monocyclic phenol represented by the above general formula.

Examples of the monocyclic phenol represented by the above general formula 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-propylphenol and the like can be mentioned.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include a cuprous chloride-triethylamine, a cuprous chloride-pyridine catalyst such as cupric chloride and a tertiary amine, and cupric chloride-pyridine-potassium hydroxide. Cupric salt-Amine-catalyst consisting of alkali metal hydroxide, manganese chloride-ethanolamine, manganese acetate such as manganese acetate-ethylenediamine and a catalyst consisting of primary amines, manganese chloride-sodium methylate, manganese chloride- Examples thereof include a catalyst composed of a manganese salt such as sodium phenolate and an alcoholate or a phenolate, and a catalyst composed of a combination of a cobalt salt and a tertiary amine.

Examples of the polyphenylene ether obtained by polycondensation of one or more monocyclic phenols include, 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 copolymerization Combined, 2,6-dimethylphenol /
2,3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer, 2,
6-dipropylphenol / 2,3,6-trimethylphenol copolymer and the like can be mentioned. Particularly, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferable.

Styrenic Resin The styrene resin in the present invention is a polymer containing an aromatic vinyl compound such as styrene, α-methylstyrene, p-methylstyrene, chlorostyrene as an essential component, and a homopolymer of an aromatic vinyl compound. , A copolymer of an aromatic vinyl compound and another copolymerizable compound, or a grafted polymer obtained by polymerizing the aromatic vinyl compound alone or together with another copolymerizable compound in the presence of a rubbery polymer. It also means a combination, and further a mixture of those styrene polymers (homopolymers, copolymers, graft polymers).

Examples of the other copolymerizable compound constituting the above-mentioned copolymer or graft polymer include unsaturated nitrile compounds (i) such as acrylonitrile and methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate,
Unsaturated carboxylic acid alkyl ester such as butyl (meth) acrylate (ii), unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic anhydride or unsaturated dicarboxylic acid anhydride (ii
i), maleimide compounds (iv) such as maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide, and O-chloro-N-phenylmaleimide.

Specific examples of the copolymer include the following various copolymers. Styrene-acrylonitrile copolymer,
α-methylstyrene-acrylonitrile copolymer, styrene-methylmethacrylate copolymer, α-methylstyrene-acrylonitrile-methylmethacrylate copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-maleic anhydride copolymer Polymer, styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer.

Further, as the rubbery polymer constituting the graft polymer,
Polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and other diene polymer (i), ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene (ethylidene norbornene, dicyclopentadiene, etc.) copolymerization Acrylic rubber typified by ethylene-propylene polymer (ii) such as polymer, chlorinated polyethylene (iii), and polybutyl acrylate (i
v), ethylene-vinyl acetate copolymer (v) and the like.

Specific examples of the graft polymer include the following various graft polymers. Acrylonitrile-diene rubber-styrene polymer, methylmethacrylate-diene rubber-styrene polymer, acrylonitrile-ethylene-propylene rubber-styrene polymer, acrylonitrile-acrylic rubber-styrene polymer, acrylonitrile-chlorinated polyethylene- Styrene polymer, styrene-diene rubber-maleic anhydride polymer.

The styrene resin can be obtained by a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or a combination of these polymerization methods.

Resin composition (A) The resin composition (A) is composed of PPE and a styrene resin, and there is no limitation on the composition ratio thereof. However, from the viewpoint of the balance between heat resistance and processability, it is particularly preferable that PPE is 10 to 90% by weight and styrene resin is 90 to 10% by weight.

Metal deactivator (B) The metal deactivator (B) used in the present invention is
It is a compound represented by the following structural formulas 1 to 2 and may be used alone or in combination of two or more.

Metal deactivators (B) represented by the above structural formulas
Is used in an amount of 0.001 to 5.0 parts by weight based on 100 parts by weight of the resin composition (A). If it is less than 0.001 part by weight, there is no silver preventing effect at the time of high-temperature molding, while if it exceeds 5.0 parts by weight, there is a silver preventing effect, but the heat resistance and rigidity of the final composition decrease, which is not preferable. Particularly preferably
0.05 to 1.0 parts by weight.

In the polyphenylene ether heat-resistant resin composition of the present invention, there is no limitation on the compounding method of the resin composition (A) and the metal deactivator (B), and a Banbury mixer, a single screw extruder, a twin screw extruder. It can be performed by a known mixing / kneading device such as.

In addition, it is possible to mix known additives such as a colorant, an inorganic filler, an antioxidant, a plasticizer, an antistatic agent, an ultraviolet absorber, a flame retardant, a foaming agent, and a lubricant when mixing and kneading. .

Hereinafter, the resin composition of the present invention will be specifically described with reference to Examples and Comparative Examples. In the following description, parts and percentages (%) are expressed on a weight basis unless otherwise specified.

Further, the embodiments are merely illustrative and do not limit the present invention.

Example PPE 2,6-Dimethylphenol, di-n-butylamine, cupric bromide and toluene were used, while oxygen was blown into them.
After polymerizing at ℃, purified by detouching, polyphenylene ether having an intrinsic viscosity of 0.50 dl / g (25 ℃, chloroform) was obtained.

Styrene-based resin (i) Polystyrene (PS) Polystyrene "Esbright 4" manufactured by Nippon Polystyrene Co., Ltd. (ii) High-impact polystyrene (HIPS) High-impact polystyrene manufactured by Japan Polystyrene Co., Ltd. "Esbright 400" (iii) Acrylonitrile-styrene copolymer (AS) Consists of 27% by weight of acrylonitrile and 73% by weight of styrene, and the intrinsic viscosity in dimethylformamide solution at 30 ℃
A commercial copolymer that is 0.62.

(Iv) Acrylonitrile-diene rubber-styrene polymer (ABS) 100 parts by weight of polybutadiene rubber latex (solid content 50% by weight) having a weight average particle size of 0.43 µ and a gel content of 85% by a known emulsion polymerization method. Then, 35 parts by weight of styrene and 15 parts by weight of acrylonitrile were graft-polymerized to obtain a polymer having a rubber content of about 50% by weight.

(V) Acrylonitrile-ethylene-propylene rubber-styrene polymer (AES) Ethylene-propylene-ethylidene norbornene having 43% by weight of propylene and an iodine value of 13 by a known solution polymerization method.
100 parts by weight, styrene 400 parts by weight and acrylonitrile
170 parts by weight was graft-polymerized to obtain a polymer having a rubber content of about 15% by weight.

Metal deactivator (B-1 to B-8) Colorant Sumitomo Chemical Co., Ltd. Phthalocyanine Blue "Sumitone Cyanine Blue GH" Antioxidant (i) Nippon Ciba-Geigy n-Octadecyl-3-
(4'-Hydroxy-3 ', 5'-di-tert-butylphenyl) propionate "Irganox 1076" (ii) 1,3,5-trimethyl-2,4,6 manufactured by Ciba-Geigy Japan
-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene "Irganox 1330" (iii) Phenyl β-naphthylamine PPE, styrene resin, metal deactivator, colorant and antioxidant After batch mixing with a Banbury mixer,
The mixture was kneaded and granulated with an extruder.

After drying the obtained pellets at 110 ° C. for 4 hours, a test piece of 150 mm × 70 mm × 3 mm was prepared under the following molding conditions, and the state of silver generation was visually observed and judged.

-Judgment criteria- -Molding conditions-3.5 ounce injection molding machine FS-75 manufactured by Nissei Plastic Co., Ltd. Resin temperature: 310 ° C (set temperature 300 ° C) Residence time: 5 minutes, 10 minutes Back pressure: 5kg / cm ² Injection speed: 8/10 screw rotation : 100 rpm Mold temperature: 80 ° C Molding cycle: 8 seconds (injection) -15 seconds (cooling) -5 seconds (takeout) Table 1 shows the composition of each composition and the evaluation results.

In addition, various test pieces were prepared from each composition, evaluated, and the heat distortion temperature (1/4) of the composition of the present invention containing the metal deactivator and the composition containing no metal deactivator. ″, 264PS
i, no annealing), workability (250 ℃, 30kg / cm ² ) and notched Izod impact strength (1/4 ″, 23 ℃),
It was confirmed that there was no great difference between the two compositions.

<Effects of the Invention> The present invention enables high temperature molding (without silver generation) without sacrificing the original characteristics of the resin composition comprising PPE and a styrene resin.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-50-56383 (JP, A) JP-A-50-3086 (JP, A) JP-A-49-112868 (JP, A) JP-A-50- 74653 (JP, A) JP 60-245667 (JP, A) JP 60-248773 (JP, A)

Claims (3)

[Claims] 1. A resin composition (A) comprising a polyphenylene ether resin and a styrene resin, relative to 100 parts by weight,
The metal deactivator (B) represented by the following structural formulas (B) 0.
A polyphenylene ether-based heat-resistant resin composition, characterized by containing 001 to 5.0 parts by weight. 2. The resin composition (A) comprises 10 to 90% by weight of polyphenylene ether resin and 90 to 10% by weight of styrene resin.
The composition according to claim 1, which is a composition comprising 3. The resin according to claim 1, wherein the styrene resin is a resin obtained by polymerizing an aromatic vinyl compound and another copolymerizable compound in the presence or absence of a rubbery polymer. The composition according to the item.