JPH0657128A - Resin composition excellent in low-temperature impact resistance - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in the balance between low- temperature impact resistance and rigidity and also in chemical resistance by mixing a polyphenylene ether resin with a polyolefin resin, a specified copolymer and a specified partially hydrogenated high impact-resistant PS resin. CONSTITUTION:The resin composition excellent in low-temperature impact resistance is obtained by mixing 40-94 pts.wt. polyphenylene ether resin or mixture thereof with a polystyrene resin with 2-20 pts.wt. polyolefin resin, 4-40 pts.wt. vinylaromatic compound/conjugated diene compound copolymer and/or its hydrogenation product and 1-50 pts.wt. partially hydrogenated high impact- resistant polystyrene resin of a mean rubber particle diameter of 1.5mum or above. This composition is excellent in the balance between low-temperature impact resistance and rigidity and also in chemical resistance and can be used in electrical and electronic fields, automobile field and industrial material field.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in impact resistance, particularly in low temperature impact resistance and rigidity, and also excellent in chemical resistance, and can be used in the fields of electric and electronic fields, automobile fields and various industrial materials fields. The present invention relates to a resin composition suitable for applications such as automobile outer panels and wheel caps, which require impact resistance.

[0002]

2. Description of the Related Art Polyphenylene ether has excellent mechanical properties, electrical properties, heat resistance, low water absorption and excellent dimensional stability, but has the disadvantage of poor moldability and impact resistance. By improving the processability and impact resistance by blending with high-impact polystyrene, for example, industrial parts, electric / electronic parts,
Office equipment housing Widely used as resin moldings for automobile parts and precision parts. However, although the classical polyphenylene ether resin composition composed of this polyphenylene ether and high-impact polystyrene has improved impact resistance, it has the drawback of being inferior in chemical resistance. A technique for blending polyolefins to improve the chemical resistance of polyphenylene ether is Japanese Patent Publication No.
Although it is disclosed in No. 69, the fact is that it cannot be put into practical use due to defects such as delamination of the layer and weak impact strength because no compatibilizer is added.

Several techniques have been disclosed for improving impact resistance, chemical resistance, and compatibility of polyphenylene ether resin and polyolefin. JP-A-53-71158 discloses impact resistance improvement by blending a premixture of a hydrogenated product of a polyolefin and a vinyl aromatic compound-conjugated diene compound copolymer with a polyphenylene ether resin. In JP-A-54-88960,
Impact resistance improvement is disclosed with hydrogenated products of polyphenylene ether resin, polyolefin, vinyl aromatic compound-conjugated diene compound block copolymer or vinyl aromatic compound-conjugated diene compound block copolymer.

Japanese Unexamined Patent Publication No. 56-51356 discloses the improvement of adhesion between a polyphenylene ether resin and a polyolefin resin with a hydrogenated product of a polyphenylene ether resin, a polyolefin and a vinyl aromatic compound-conjugated diene compound block copolymer. . JP-A-59-10015
No. 9 discloses impact resistance improvement with a hydrogenated product of a polyphenylene ether resin, a polyolefin resin, and a vinyl aromatic compound-conjugated diene compound diblock copolymer. JP-A-62-179561 discloses improvement of fluidity, glossiness and impact resistance with a composition comprising a polyphenylene ether resin, a polyethylene resin having a density of 0.94 or less and rubber. In JP-A-63-218748, JP-A-63-245453, JP-A-1-13936, JP-A-1-40556, and JP-A-2-92957,
It is disclosed that a polyphenylene ether resin, a polystyrene resin, a premixed polyolefin and a vinyl aromatic compound-conjugated diene compound block copolymer are blended to improve stress crack resistance and impact resistance. JP-A-2-225563 discloses that the dispersion of hydrogenated polyphenylene ether resin, polyolefin and a specific vinyl aromatic compound-conjugated diene compound block copolymer is 0.3 μm or less, and improvement in chemical resistance is disclosed. There is. JP-A-3-157451 discloses chemical resistance, impact resistance, and delamination improvement by blending a polyphenylene ether resin, a polyolefin, and two specific types of vinyl aromatic compound-conjugated diene compound block copolymers. .

In Japanese Patent Application Laid-Open No. 58-103557, a polyolefin resin is used as a matrix and a polyphenylene ether resin and a specific vinyl aromatic compound-conjugated diene compound block copolymer or vinyl aromatic compound-conjugated diene compound block copolymer are used. Fluidity with hydrogenates,
Improved brittleness is disclosed. Japanese Patent Laid-Open No. 60-76547
In the publication, a polyolefin resin is used as a matrix, and a polyphenylene ether resin and a specific vinyl aromatic compound-
Hydrogenated blends of conjugated diene compound block copolymers or vinyl aromatic compound-conjugated diene compound block copolymers are disclosed. JP-A-63-831
No. 49 discloses a blend of a polyolefin resin, a polyphenylene ether resin, and a hydrogenated product of a specific vinyl aromatic compound-conjugated diene compound block copolymer. JP-A-63-225642 discloses a blend of a hydrogenated product of a polyolefin resin, a polyphenylene ether resin, and a specific vinyl aromatic compound-conjugated diene compound block copolymer.

Further, Japanese Unexamined Patent Publication No. 64-90208 and Japanese Unexamined Patent Publication No. 3-143953 disclose techniques for blending partially hydrogenated rubber-modified polystyrene with a polyphenylene ether resin.

[0007]

However, in these techniques, there is a problem that the impact resistance is lowered as the amount of the polyphenylene ether resin and the polystyrene resin is a matrix and the amount of the polyphenylene ether resin is reduced. . As a solution to this problem, if a large amount of impact-resistant polystyrene resin is added, the rigidity decreases, and the rigidity and impact resistance cannot be balanced. Further, when a large amount of a polyolefin resin and a vinyl aromatic compound-conjugated diene compound block copolymer and / or a hydrogenated product thereof is added, the rigidity decreases and the rigidity and impact resistance cannot be balanced. In applications such as automobile outer panels and wheel caps, impact resistance at low temperatures is particularly required, but the technology disclosed in the past cannot solve the problem.

An object of the present invention is to obtain a resin composition which is excellent in impact resistance, particularly low temperature impact resistance and rigidity, and is also excellent in chemical resistance.

[0009]

Means for Solving the Problems As a result of intensive studies in view of this point, the present inventors have found that polyphenylene ether resin containing polyphenylene ether resin or polystyrene resin, polyolefin resin, vinyl aromatic compound-conjugated diene By adding a partially hydrogenated high impact polystyrene resin having a specific rubber particle size to a resin composition comprising a hydrogenated product of a compound block copolymer and / or a vinyl aromatic compound-conjugated diene compound block copolymer Excellent impact resistance, especially low temperature impact resistance and rigidity,
Moreover, they have found that they have excellent chemical resistance and have reached the present invention. The present invention specifically includes (A) a polyphenylene ether resin containing a polyphenylene ether resin or a polystyrene resin 40 to 94 parts by weight (B) a polyolefin resin 2 to 20 parts by weight (C) a vinyl aromatic compound-conjugated diene compound copolymer and Or hydrogenated product of vinyl aromatic compound-conjugated diene compound copolymer 4 to 40 parts by weight (D) 1-50 parts by weight of partially hydrogenated impact-resistant polystyrene resin having an average rubber particle size of 1.5 μm or more A resin composition characterized by the above can be provided.

The present invention will be described in detail below. (A) component polyphenylene ether resin (hereinafter simply referred to as P
Abbreviated as PE) is a bonding unit

[0011]

[Chemical 1]

The reduced viscosity (0.5 / deciliter, chloroform solution, measured at 30 ° C.) is 0.30 to 0.
It is a homopolymer and / or copolymer in the range of 70, more preferably in the range of 0.40 to 0.65. This P
Specific examples of PE include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-). 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and further, 2,6-dimethylphenol and other phenols (for example, 2,3). , 6-trimethylphenol and 2-methyl-6-butylphenol) are preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,3. A copolymer with 6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable.

The PPE is not particularly limited as long as it is obtained by a known method, and for example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst, For example 2,
It can be easily produced by oxidative polymerization of 6-xylenol. In addition, US Pat. No. 3,306,875
US Pat. No. 3,257,357, US Pat. No. 325
It can be easily produced by the method described in Japanese Patent No. 7358 and Japanese Patent Publication No. 52-18880.

The PPE used in the present invention is the above-mentioned PPE.
In addition to PE, the PPE and α, β-unsaturated carboxylic acid or a derivative thereof in the presence or absence of a radical generator in a molten state, a dissolved state or a slurry state of 80-
Modified PPE obtained by reacting at a temperature of 350 ° C (0.01 to 10% by weight is grafted or added)
The above PPE and the modified PPE
May be a mixture in any ratio.

Further, the polystyrene resin in the component (A) may be a homopolymer of a vinyl aromatic compound or a resin containing a monomer copolymerizable with the vinyl aromatic compound. Examples of the vinyl aromatic compound include styrene, α-methylstyrene, α-ethylstyrene, α-
Nuclear alkyl-substituted styrenes such as methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, di-styrene. Examples thereof include nuclear halogenated styrenes such as chlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene, and among them, styrene and α-methylstyrene are preferable.

Examples of the monomer copolymerizable with the vinyl aromatic compound include vinyl cyanide such as acrylonitrile, methacrylonitrile, fumaronitrile and maleonitrile, methyl methacrylate, methyl acrylate and methacrylic acid. Acrylic acid, maleic anhydride and the like can be mentioned, of which acrylonitrile is preferred. In the present invention, the amount of component (A) is in the range of 40 to 94 parts by weight, preferably 55 to 91 parts by weight.
The polystyrene resin is in the range of 5 to 95 parts by weight, preferably 10 to 9 parts by weight, relative to 100 parts by weight of the component (A).
0 parts by weight.

Next, the component (B) polyolefin of the present invention has a number average molecular weight of 3 which is used as a usual molding material.
50,000 or more polyolefins, for example, high density polyethylene, ultra high molecular weight high density polyethylene, low density polyethylene, linear low density polyethylene, density 0.9
Ultra low density polyethylene less than 0, isotactic polypropylene, and a copolymer of two or more compounds selected from ethylene, propylene, other α-olefins, unsaturated carboxylic acids or their derivatives, for example, ethylene / butene. -1 copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, propylene / ethylene (random, block) copolymer, propylene / 1-hexene copolymer, Propylene / 4-methyl-1-pentene copolymer, and poly (4
-Methyl-1-pentene), polybutene-1 and the like. These can be used alone or in combination of two or more. Of these polyolefins, polyethylene is preferable, ethylene / propylene copolymer,
Low density polyethylene, linear low density polyethylene, and high density polyethylene are preferred. In the present invention, the component (B) is in the range of 2 to 20 parts by weight, preferably 3-1.
5 parts by weight.

Next, the vinyl aromatic compound-conjugated diene compound copolymer and the hydrogenated product of the vinyl aromatic compound-conjugated diene compound copolymer (hereinafter, compatibilizer) of the component (C) of the present invention are vinyl. Hydrogenated product of copolymer obtained by copolymerizing aromatic compound and conjugated diene compound, copolymer obtained by copolymerizing vinyl aromatic compound and conjugated diene compound (olefin based on copolymerized conjugated diene compound) At least 50% or more, preferably 80% or more of the sex double bonds are hydrogenated), and at least one of these is used and may be used in combination. Examples of the copolymerization form of this compatibilizer include a random copolymer, a block copolymer, a graft copolymer and a combination thereof, and among them, the block copolymer is preferable.

As the vinyl aromatic compound constituting the compatibilizer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like are selected. Of these, styrene is preferred. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable.

Examples of such a compatibilizer include a styrene-butadiene copolymer obtained by anionic polymerization and a hydrogenated product of this styrene-butadiene copolymer. No. 1,130,770, U.S. Pat. No. 3,281,38
3 and 3,639,51, British Patent 1,020,720, U.S. Pat. No. 3,33.
It can be easily produced by the method described in 3,024 and 4,501,857.

As this compatibilizer, for example,
Asahi Kasei Kogyo Co., Ltd. “Toughprene”, “Sorprene”, “Tuffden”, “Asaprene”, “Tuftec”
What is marketed by the brand name can be used. Further, if necessary, even if the unsaturated portion of the structure (for example, butadiene portion) such as styrene-butadiene copolymer is saturated by hydrogenation by a known method, α, β-unsaturated Saturated carboxylic acid or its derivative in the presence or absence of a radical generator in a molten state, a dissolved state or a slurry state at 80 to 300 ° C.
It may be a modified elastomer obtained by reacting under the temperature of, or may be a mixture of the above elastomer with the hydrogenated elastomer and the modified elastomer. In the present invention, the component (B) is 4
To 40 parts by weight, preferably 6 to 30 parts by weight.

Next, the partially hydrogenated impact-resistant polystyrene resin as the component (D) of the present invention is a vinyl aromatic compound or its vinyl aromatic compound and other vinyl compounds in the presence of the conjugated diene rubber after the partial hydrogenation. It is a resin obtained by polymerizing an aromatic compound and a copolymerizable monomer. The amount of conjugated diene rubber is in the range of 3 to 30% by weight, preferably 4
~ 12% by weight. The impact-resistant polystyrene resin has a rubber average particle size of 1.5 μm or more, preferably 2.5 μm.
That is all. The partially hydrogenated conjugated diene rubber is obtained by partially hydrogenating a conjugated diene rubber by a known method. The conjugated diene rubber generally includes all rubbers used for producing impact-resistant polystyrene resin.
For example, polybutadiene (low cis polybutadiene, high cis polybutadiene), styrene-butadiene copolymer (SBR), polyisoprene, butadiene-isoprene copolymer, natural rubber and the like, particularly butadiene polymer, styrene-butadiene copolymer Can be mentioned as a preferable example.

Taking butadiene rubber as an example of the conjugated diene rubber, the preferable amount of 1,2-vinyl bonds in the total double bonds of butadiene rubber is generally 5% by weight or more. Is desirable. In the partially hydrogenated conjugated diene rubber, 5 to 70 wt% of all double bonds are hydrogenated, and the remaining 1,2-vinyl bond amount and 1,4-bond amount are each 3 wt% or less. And 30% by weight or more. The vinyl aromatic compound used here is the same as the vinyl aromatic compound contained in the component (A). Preferred vinyl aromatic compounds include styrene and copolymers of styrene and acrylonitonil. The average particle size of the rubber-like polymer particles in the partially hydrogenated impact-resistant polystyrene-based resin is determined by a method well known to those skilled in the art, for example, a phase contrast microscope, a transmission electron microscope, a centrifugal sedimentation method, a call counter method, or the like. It can be measured by the method. The method used in the present invention is a call counter method, and the average particle size is volume average. The component (D) is a substantially continuous phase, but the rubber particles are present in the dispersed phase. When the components (A), (B), (C) and (D) are melt-kneaded, a photograph is taken with a transmission electron microscope to measure the volume average particle diameter of the rubber component. In the present invention, the component (D) is 1 to 5
It is in the range of 0 parts by weight, preferably 3 to 30 parts by weight.

The resin composition of the present invention is obtained by melt-kneading the above-mentioned component (A), component (B), component (C) and component (D), and is obtained by various molding methods shown below. An example of the melt-kneading method is a method of melt-kneading using an extruder or the like, but it is not particularly limited as long as it is a generally-used kneading method. As a feeding method, a method of charging the materials all at once, a method of side-feeding a part of the materials, or a method of feeding the pre-kneaded material can be considered, but any method may be used. The kneading temperature is the glass transition point of PPE (about 210
℃) or more, but preferably 220 ℃ ~ 350
C., more preferably in the range of 230.degree. C. to 320.degree. In the obtained resin composition, the continuous phase was composed of (A) and (D), and the dispersed phase was (B) and (C).

In the present invention, in addition to the above-mentioned components, if necessary, other additional components such as an antioxidant, a weather resistance improver, and a polyolefin composition may be used as long as the characteristics and effects of the present invention are not impaired. Nucleating agents, slip agents, inorganic or organic fillers and reinforcing materials (glass fiber, carbon fiber, whiskers,
Mica, talc, calcium carbonate, potassium titanate,
(Wollastonite, etc.), flame retardants (halogen flame retardants, red phosphorus, phosphorus compound flame retardants such as triphenyl phosphate), flame retardant aids, plasticizers, various colorants, antistatic agents, release agents, etc. You may add it.

The resin composition of the present invention may be molded by any commonly used molding method such as injection molding, extrusion molding, compression molding, blow molding, etc., and the shape of the resulting resin composition may be any. It is not limited and is not restricted by the molding method.

[0027]

【Example】

[Reference Example: Preparation of PPE] The inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor and having a cooling coil and stirring blades inside was thoroughly replaced with nitrogen, and then 53.6 g of cupric bromide. , Di-n-butylamine 1110 g, toluene 20 liters, n-butanol 16 liters,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 4 liters of methanol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring to carry out polymerization for 180 minutes. In addition, in order to maintain the internal temperature at 30 ° C., water was circulated through the cooling coil during the polymerization. After completion of the polymerization, the precipitated polymer was separated by filtration, a methanol / hydrochloric acid mixture was added to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and dried to give a pale yellowish white powder PPE (reduction A viscosity of 0.54) was obtained. [Reference Example: Preparation of Partially Hydrogenated Impact-Resistant Polystyrene] Partially hydrogenated polybutadiene used in the examples was prepared by the following representative examples. Using a jacketed autoclave with a stirrer and an internal volume of 10 liters as a reactor, butadiene / n
-Hexane mixture (butadiene concentration 20%) at 20 liters / hr and n-butyllithium / n-hexane solution (concentration 5%) at 70 ml / hr were introduced to continuously polymerize butadiene at a polymerization concentration of 110 ° C. did. The obtained active polymer was deactivated with methanol, and 8 liters of the polymer solution was transferred to another reactor having a jacket with a stirrer and an inner volume of 10 liters, and at a temperature of 80 ° C., di-p-tolylbis ( 0-250 ml of 1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1.2 mmol / l) and 50 ml of n-butyllithium solution (concentration 6 mmol / l)
℃, add a mixture under a hydrogen pressure of 2kg / cm ² ,
The reaction was carried out at a hydrogen partial pressure of 3 kg / cm ^{2 for} 60 minutes. The resulting partially hydrogenated polymer solution was used as an antioxidant in 2,6-
Ditert-butyl hydroxytoluene was added at 0.5 parts per polymer to remove the solvent. Table 1. No. 1
Of polybutadiene was obtained.

The partially hydrogenated high impact polystyrene resin used in the examples was produced by a bulk polymerization method. A typical example will be described below. Polybutadiene (10 parts) was dissolved in styrene (90 parts) and ethylbenzene (8 parts).
05 parts benzoyl peroxide and 0.10 parts α-
Add methyl styrene dimer and stir at 80 ° C for 4 hours.
Polymerization was carried out under stirring at 0 ° C. for 4 hours and at 150 ° C. for 4 hours. Further heat treatment at around 230 ℃ for 30 minutes,
Then, unreacted styrene and ethylbenzene were removed in vacuum to obtain a high impact polystyrene resin.

The content of polybutadiene in the resulting partially impact-resistant polystyrene-based resin was 11%, and the average particle diameter of polybutadiene in the state of containing dispersed polystyrene particles was 2.5 μm. Next, a method for measuring and evaluating physical properties of the resin composition will be described. (0) Preparation of test piece Injection molding machine (FANUC CORPORATION MODEL 50D
A test piece was prepared at a cylinder temperature of 280 ° C. and a molding cycle of 1 minute). (1) Izod impact strength ASTM D258, notch: Yes 23 ° C, -30 ° C (2) Flexural modulus ASTM D790 (3) Chemical resistance Chemical resistance evaluation by creep rupture tester (100 mm
Put resin in a mold of × 100mm × thickness of 2mm and set it to 250
Width of 4m for sample molded at ℃, preheat 3 minutes, press 2 minutes
Adjusted to m x length 70 mm x thickness 2 mm, 80 ° C x 48
Anneal for hours. One end of this sample was attached to a creep rupture machine manufactured by Seiwa Riko, a load of 1 kg was set on the other end, and 0.2 g of salad oil (manufactured by Nisshin Oil Co., Ltd.) was applied to 20 mm from the load setting end, and the time until rupture. To measure.
(The measurement room is a constant temperature room at 23 ° C and 50% humidity)

[0030]

Example 1 21 parts by weight of polyphenylene ether having a reduced viscosity of 0.54, 48 parts by weight of polystyrene (685; manufactured by Asahi Kasei Kogyo Co., Ltd.), 7 parts by weight of low density polyethylene (Suntech LD-M1804; manufactured by Asahi Kasei Kogyo Co., Ltd.) Department,
Styrene-butadiene copolymer (Asaflex 80
5: Asahi Chemical Industry Co., Ltd. 7 parts by weight, styrene-butadiene copolymer (Sorprene T406 Nippon Elastomer Co., Ltd.) 7 parts by weight, Table 1. No. 1 part hydrogenated high impact polystyrene 10 parts, as a stabilizer Irga. 0.2 parts of Knox 3114 (made by Ciba Geigy) and 0.6 parts of PEP36 (made by Asahi Denka) are blended with a Henschel mixer,
Twin-screw co-direction extruder (ZSK-25; Werner & Pf
Cylinder temperature of 280
Melt kneading at 0 ° C. to obtain extruded strands as pellets. The pellets obtained here were supplied to an injection molding machine set at 280 ° C., and a test piece was injection molded under the condition of a mold temperature of 80 ° C. The results are shown in Table 2.

As compared with Comparative Example 3, the rigidity is not changed, the impact resistance and the chemical resistance can be greatly improved, and the physical properties are balanced.

[0032]

Comparative Example 1 21 parts by weight of polyphenylene ether of Example 1, 48 parts by weight of polystyrene, No. Example 1 was repeated with 35 parts by weight of polyphenylene ether and 44 parts by weight of polystyrene blended in place of 10 parts by weight of 1 impact polystyrene. The results are shown in Table 2.

[0033]

Comparative Example 2 Example 1 was repeated by blending 30 parts by weight of polyphenylene ether and 48 parts by weight of polystyrene in place of 35 parts by weight of polyphenylene ether and 44 parts by weight of polystyrene of Comparative Example 1. The results are shown in Table 2.

[0034]

Comparative Example 3 Example 1 was repeated except that 21 parts by weight of polyphenylene ether and 58 parts by weight of polystyrene were blended instead of 35 parts by weight of polyphenylene ether and 44 parts by weight of polystyrene of Comparative Example 1. As can be seen from Comparative Examples 1 to 3, the smaller the PPE content, the lower the Izod impact strength.

[0035]

Comparative Example 4 No. 1 of the first embodiment. No. 1 instead of 10 parts by weight of partially hydrogenated high impact polystyrene. Example 1 was repeated with 10 parts by weight of non-partially hydrogenated high impact polystyrene having an average rubber particle size of 2.5 μm of No. 2 blended. The results are shown in Table 2.
It was shown to. When the rubber component of the impact-resistant polystyrene is non-hydrogenated, the low-temperature impact is lower than in Example 1.

[0036]

[Comparative example 5] No. 1 instead of 10 parts by weight of partially hydrogenated high impact polystyrene. Example 1 was repeated with 10 parts by weight of partially hydrogenated high impact polystyrene having an average rubber particle size of 0.7 .mu.m blended. The results are shown in Table 2. When the rubber average particle size is 0.7 μ, the ratio I to that in Example 1
The zod impact strength is significantly reduced.

[0037]

Second Embodiment No. 1 of the first embodiment. In place of 10 parts by weight of the partially hydrogenated impact resistant polysulene of No. 1, No. 1 Example 4 was repeated by blending 10 parts by weight of partially hydrogenated high impact polystyrene having an average rubber particle size of 1.5 μm. The results are shown in Table 2. When the average rubber particle size is 1.5 μm, the physical property balance is better than in Comparative Example 3.

[0038]

COMPARATIVE EXAMPLE 6 28 parts by weight of the polystyrene of Comparative Example 5 are used in Table 1. No. Example 3 was repeated with 3 parts impact polystyrene changed to 30 parts by weight and blended. The results are shown in Table 2. The rigidity is significantly reduced as compared with the first embodiment.

[0039]

Example 3 69 parts by weight of polyphenylene ether having a reduced viscosity of 0.54, low density polyethylene (Suntech LD-
M1804; Asahi Kasei Kogyo Co., Ltd. 7 parts by weight, styrene-butadiene copolymer (Asaflex 805; Asahi Kasei Kogyo KK) 7 parts by weight, styrene-butadiene copolymer (Sorprene T406; Nippon Elastomer Co., Ltd.) Made)
7 parts by weight, Table 1. No. 1 part hydrogenated high impact polystyrene 10 parts, flame retardant triphenyl phosphate (TPP; made by Daihachi Chemical Co., Ltd.) 15 parts, stabilizer Irganox 3114 (made by Ciba Geigy) 0.2 parts, PEP
0.6 part of 36 (manufactured by Asahi Denka Co., Ltd.) was blended with a Henschel mixer, and a twin-screw co-direction extruder (ZSK-25; Werne) was used.
r & Pfleiderer) was melt-kneaded at a cylinder temperature of 280 ° C. to obtain extruded strands as pellets. The pellets obtained here were supplied to an injection molding machine set at 280 ° C., and a test piece was injection molded under the condition of a mold temperature of 80 ° C. The results are shown in Table 2.

[0040]

COMPARATIVE EXAMPLE 7 No. 4 of Example 4. Instead of 10 parts by weight of 1-part hydrogenated high-impact polystyrene, no. Example 4 was repeated, blending 10 parts of high impact polystyrene of 2.
The results are shown in Table 2.

[0041]

[Comparative Example 8] Instead of 10 parts by weight of 1-part hydrogenated high-impact polystyrene, no. Example 4 was repeated, blending 10 parts of 3 high impact polystyrene.
The results are shown in Table 3.

[0042]

Example 4 Example 1 was repeated by adding 7 parts by weight of high-density polyethylene (Suntech B-871; manufactured by Asahi Chemical Industry Co., Ltd.) in place of the low-density polyethylene of Example 1. The results are shown in Table 3. Similar to Example 1, the balance of physical properties is excellent.

[0043]

Example 5 Example 1 was repeated except that 7 parts by weight of polypropylene (Suntec E-1100; manufactured by Asahi Chemical Industry Co., Ltd.) was added in place of the low density polyethylene of Example 1. The results are shown in Table 3. Similar to Example 1, the balance of physical properties is excellent.

[0044]

Example 6 Example 1 was repeated except that 7 parts by weight of linear low density polyethylene (Suntec LF2408; manufactured by Asahi Chemical Industry Co., Ltd.) was added in place of the low density polyethylene of Example 1. The results are shown in Table 3. Similar to Example 1, the balance of physical properties is excellent.

[0045]

Example 7 7 parts by weight of the styrene-butadiene copolymer (Asaflex 805; manufactured by Asahi Kasei Kogyo KK) of Example 1 and a styrene-butadiene copolymer (Sorprene T40).
6; 14 parts of hydrogenated styrene-butadiene block copolymer (Tuftec H-1051: Asahi Kasei Co., Ltd.) was added in place of 7 parts by weight of Nippon Elastomer Co., Ltd.,
Example 1 was repeated. The results are shown in Table 3.

[0046]

[Comparative example 9] No. 1 in place of the partially hydrogenated high impact polystyrene. Average rubber particle size of 3 is 0.7μ
Example 1 was repeated with the addition of 10 parts by weight of partially hydrogenated high impact polystyrene of m. The results are shown in Table 3.

[0047]

COMPARATIVE EXAMPLE 10 JP-A-64-90208, JP-A-3-
Comparison with the technology of 143953. 21 parts by weight of polyphenylene ether having a reduced viscosity of 0.54, polystyrene (68
5; Asahi Kasei Kogyo KK) 69 parts by weight, Table 1. No. 1
10 parts by weight of high impact polystyrene and 0.2 part of Irganox 3114 (made by Ciba-Geigy) as a stabilizer, PEP
0.6 part of 36 (manufactured by Asahi Denka Co., Ltd.) was blended with a Henschel mixer, and a twin-screw co-direction extruder (ZSK-25; Werne) was used.
r & Pfleiderer) was melt-kneaded at a cylinder temperature of 280 ° C. to obtain extruded strands as pellets. The pellets obtained here were supplied to an injection molding machine set at 280 ° C., and a test piece was injection molded under the condition of a mold temperature of 80 ° C. Example 1 was repeated. The results are shown in Table 3.

Impact resistance and chemical resistance are significantly inferior to those of Example 1.

[0049]

Comparative Example 11 21 parts by weight of polyphenylene ether having a reduced viscosity of 0.54, 55 parts by weight of polystyrene (685; manufactured by Asahi Chemical Industry Co., Ltd.), styrene-butadiene copolymer (Asaflex 805; manufactured by Asahi Chemical Industry Co., Ltd.) 7 parts by weight, styrene-butadiene copolymer (Sorprene T40
6; 7 parts by weight of Nippon Elastomer Co., Ltd., Table 1. N
o. 1 high-impact polystyrene 10 parts by weight and 0.2 parts of Irganox 3114 (made by Ciba-Geigy) as a stabilizer,
0.6 part of PEP36 (manufactured by Asahi Denka Co., Ltd.) was blended with a Henschel mixer, and a twin-screw co-direction extruder (ZSK-25; We
rner & Pfleiderer) was melt-kneaded at a cylinder temperature of 280 ° C. to obtain extruded strands as pellets. The pellets obtained here were supplied to an injection molding machine set at 280 ° C., and a test piece was injection molded under the condition of a mold temperature of 80 ° C. Example 1 was repeated.
The results are shown in Table 3.

The chemical resistance is significantly inferior to that of Example 1.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

Industrial Applicability According to the present invention, it is possible to provide a resin composition having excellent impact resistance, particularly low temperature impact resistance and rigidity, and excellent chemical resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 55/02 LMF 7142-4J

Claims (1)

[Claims] 1. A polyphenylene ether resin containing (A) a polyphenylene ether resin or a polystyrene resin 40 to 94 parts by weight (B) a polyolefin resin 2 to 20 parts by weight (C) a vinyl aromatic compound-conjugated diene compound copolymerization Hydrogenated product of polymer and / or vinyl aromatic compound-conjugated diene compound copolymer 4 to 40 parts by weight (D) Partially hydrogenated impact-resistant polystyrene resin having an average rubber particle size of 1.5 μm or more 1 to 50 parts by weight A resin composition having excellent impact resistance at low temperature, characterized by comprising: