JPH05320446A - Polyphenylene ether resin composition and molded article prepared therefrom - Google Patents

Abstract

PURPOSE:To provide the subject compsn. which gives a lightweight molded article excellent in mechanical strengths, heat resistance, solvent resistance, and dimensional stability and which overcomes the problem with distortion of a molded member caused by the difference in linear thermal expansion when used in combination with a metal part. CONSTITUTION:This compsn. is prepd. by compounding 10-90 pts.wt. acid- modified olefin polymer having carboxyl groups or/and acid anhydride groups, 90-10 pts.wt. polyphenylene ether resin having, if necessary, carboxyl groups or/and acid anhydride groups, 2-60 pts.wt. arom. vinyl-conjugated diene block copolymer or/and hydrogenation product thereof having, if necessary, carboxyl groups or/and acid anhydride groups, and 2-60 pts.wt. polystyrene resin having oxazoline rings.

Description

Detailed Description of the Invention

[0001]

The present invention relates to dimensional stability, mechanical properties,
The present invention relates to a resin composition having excellent heat resistance and chemical resistance, and a molded product obtained by melt molding the resin composition.

[0002]

2. Description of the Related Art In recent years, in the field of automobiles and the like, in order to reduce the weight and shorten the processing steps, there is an increasing number of cases in which large plastic moldings are used for bumpers, fascias and the like. Among them, the resin composition containing a crystalline polyolefin resin such as polypropylene as a main component is a relatively inexpensive polyolefin resin, and further, heat resistance, rigidity, moldability,
It is one of the most widely used resin compositions in the automobile field because of its excellent chemical resistance. Such a polyolefin resin composition is disclosed, for example, in JP-A-61-1.
No. 2,742, JP-A No. 61-72039 and the like disclose a resin composition containing a propylene homopolymer or copolymer, an olefin elastomer and an inorganic filler. Such a resin composition improves the low impact resistance, which is a defect of polypropylene, by adding an elastomer, and increases the rigidity by using an inorganic filler such as talc together, and at the same time, has a molding shrinkage ratio and a linear expansion coefficient. Is effectively reduced to improve dimensional stability.

However, the linear expansion coefficient of the above resin composition is 7.8 to 9.0 × 10 according to the disclosure of the publication.
It is in the range of ^-5 m / m ° C. Considering the combination with metal in response to the recent increase in the size of plastic parts for automobiles,
It is hard to say that it still has sufficient dimensional stability.

On the other hand, in recent years, polypropylene and EP
In a resin composition comprising R (ethylene / propylene copolymer rubber), a resin composition that achieves low linear expansion (8 × 10 ⁻⁵ m / m ° C.) by optimizing the characteristics and addition ratio of EPR Is disclosed. However, the decrease in rigidity and the decrease in heat resistance due to the addition of EPR have not been suppressed, and the mechanical strength, heat resistance, and dimensional stability are not satisfied at a sufficient level.

On the other hand, polyolefin-based resins include, for example,
It is also known that dimensional stability is improved by adding an amorphous resin having a high Tg (glass transition temperature) such as polyphenylene ether as an organic filler (Japanese Patent Publication No. 42-7069). This method can also improve the dimensional stability and also improve the heat resistance by adding a high Tg polymer. However, polyphenylene ether has poor compatibility with polyolefins, and even if they are simply kneaded, they show a coarse phase-separated structure, and there is a problem that mechanical strength, particularly impact strength, is reduced. In this composition, in order to improve compatibility and improve impact resistance,
A method of adding a block copolymer of an alkenyl aromatic compound and a conjugated diene or a hydride thereof to a composition of polypropylene and polyphenylene ether has also been disclosed (JP-A-59-140257, JP-A-59-140257). 5
No. 9-100159), but the dimensional stability is not at a sufficient level, and the compatibilizing effect is insufficient, so that the heat resistance and mechanical strength have not been sufficiently improved.

On the other hand, Japanese Patent Laid-Open No. 63-277273 discloses a polyphenylene ether, an aromatic vinyl copolymer,
An olefin polymer having an oxazoline ring and a composition containing a polyolefin are disclosed. A molded article obtained from the composition has solvent crack resistance (solvent resistance), impact resistance, rigidity, heat resistance, and moldability at sufficient levels. However, in this publication, no attempt is made to improve the dimensional stability which is lowered by containing a polyolefin, and a resin molded product having both the above-mentioned characteristics and dimensional stability is still strong in the automobile field and the like. Is desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition having a good balance of heat resistance, mechanical properties, moldability and chemical resistance, and particularly improved dimensional stability represented by low linear expansion. The object is to provide an article and a molded article obtained from the article.

[0008]

Thus, according to the present invention, (i) 10 to 90 parts by weight of an acid-modified olefin polymer component containing a carboxyl group or / and an acid anhydride structure,
(Ii) 90 to 10 parts by weight of a polyphenylene ether resin component containing a carboxyl group and / or an acid anhydride structure as necessary, (iii) an aromatic containing a carboxyl group and / or an acid anhydride structure as necessary Group vinyl
2 to 60 parts by weight of a conjugated diene block copolymer or / and its hydrogenated product, and (iv) 2 to 60 parts by weight of a polystyrene resin component having an oxazoline ring, a polyphenylene ether resin. A composition is provided, which is a molded article obtained by melt-molding the above polyphenylene ether resin composition,
The component (i) forms a matrix phase, and the components (ii) and (ii
i) and (iv) each independently form a dispersed phase, or a structural structure in which a mixture of at least two kinds selected from components (ii), (iii) and (iv) forms a dispersed phase There is provided a molded article characterized by having:

The structure of the present invention will be described in detail below, but more preferable embodiments and advantages based on them will become apparent.

(I) Acid-modified olefin polymer: The modified olefin polymer used in the present invention is an unmodified olein polymer having a carboxyl group or an acid anhydride structure or both introduced therein. As a method, for example,
Unmodified olefin polymer with unsaturated carboxylic acid or /
And a method of introducing an unsaturated carboxylic acid anhydride unit by a graft copolymerization technique.

Specific examples of the unsaturated carboxylic acid and unsaturated carboxylic acid anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, 2-norbornene-5,6-dicarboxylic acid and the like. Examples thereof include saturated carboxylic acids, unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and 2-norbornene-5,6-dicarboxylic acid anhydride.
Of these, acrylic acid and maleic anhydride are preferable.

As a graft copolymerization method for introducing such an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride into an olefin polymer, an olefin polymer and the above unsaturated carboxylic acid or unsaturated carboxylic acid anhydride are used. In the presence or absence of a radical reaction initiator, it is also possible to adopt a method of melt-kneading under heated conditions, or,
A method of reacting the olefin polymer and the above unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in a solvent in the presence or absence of a radical reaction initiator under heated conditions can also be adopted. The temperature during the grafting reaction is 50 to 330 ° C, preferably 60 to 300 ° C. As the radical reaction initiator, any of peroxide type and azo type initiators can be used, and specifically, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, azobisisobutyro Examples thereof include nitrile, and dicumyl peroxide and di-t-butyl peroxide are particularly preferable.

The olefin polymer constituting the modified olefin polymer (ii) is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Α-olefins such as octadecene and 1-eicosene,
It is preferably an olefin polymer mainly containing an α-olefin component having 2 to 20 carbon atoms, and may be crystalline, low crystalline or non-crystalline. In addition to these α-olefin components, small amounts of butadiene, isoprene, 1,
A diene component such as 4-hexadiene, 5-ethylidene-2-norbornene or 5-vinyl-2-norbornene may be copolymerized.

Of these olefin polymers, specific examples of the crystalline olefin polymer include polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and 90 mol of any olefin component. % Olefin copolymer present, for example, ethylene-propylene copolymer, ethylene / 1-butene copolymer, ethylene-4-methyl-1-pentene copolymer,
An ethylene / 1-hexene copolymer etc. can be illustrated.

The amorphous or low crystalline olefin copolymer is a copolymer in which any one of the olefin components is present in an amount of 10 to 90 mol%, and more specifically, eletin-propylene random copolymer, ethylene. In addition to 1-butene random copolymer, ethylene / 1-hexene random copolymer, etc., EPDM such as ethylene / propylene / dicyclopentadiene copolymer and ethylene / propylene / 5-ethylidene-2-norbornene copolymer Can be illustrated. The intrinsic viscosity of these olefin polymers is preferably 0. 0 when measured in decalin at 135 ° C.
01 to 30 dl / g, more preferably 0.05 to 25
dl / g. The modification amount is not particularly limited, but is usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight in terms of carboxyl group. The acid anhydride structure is calculated assuming that there are two carboxyl groups.

(Ii) Polyphenylene ether-based resin The polyphenylene ether-based resin used in the present invention has the general formula [I]

[Chemical 1] (In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, a nitro group, an amino group and a phenoxy group. Group or a sulfo group.) Is a homopolymer or copolymer of the monomer represented by

Specific examples of such a polyphenylene ether resin include 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-
Isopropyl-1,4-phenylene ether, poly-
2,6-dichloromethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, poly-2,6-dicyano-1,4-phenylene ether, poly-2,6- Dichloro-1,4-phenylene ether, poly-2,5-dimethyl-1,4-phenylene ether, poly-2,3,6-trimethyl-1,4
-Phenylene ether and copolymers of the monomers constituting these homopolymers with each other. Of these, poly-
Suitable are 2,6-dimethyl-1,4-phenylene ether and copolymers of 2,6-dimethyl-phenol and 2,3,6-trimethyl-phenol.

These polyphenylene ether resins are
It may contain a carboxyl group and / or an acid anhydride structure. By containing these, the composition of the present invention has excellent mechanical strength, particularly impact resistance. Examples of the method of incorporating a carboxyl group and an acid anhydride structure include a method of graft modification with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof. Specific examples of the unsaturated carboxylic acid and the unsaturated carboxylic acid anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, 2-norbornene-
Examples thereof include unsaturated carboxylic acids such as 5,6-dicarboxylic acid and anhydrides of these unsaturated carboxylic acids. Of these, acrylic acid and maleic anhydride are preferable.

As a method of graft-modifying the polyphenylene ether resin, the polyphenylene ether resin and the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride or a mixture thereof are added in the presence or absence of a radical reaction initiator. , A kneader-type kneader, an extruder or the like is preferably used, and a grafting method in which the mixture is melt-kneaded under heated conditions, and the polyphenylene ether resin and the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride or a mixture thereof are preferable. It is also possible to employ a method in which the graft reaction is carried out in a solvent in the presence or absence of a radical reaction initiator under heated conditions.

Specific examples of the radical reaction initiator include benzoyl peroxide, dicumyl peroxide and di-t.
-Butyl peroxide, azobisisobutyronitrile, and particularly dicumyl peroxide, di-t-
Butyl peroxide is preferred.

The temperature for the graft modification is 250 to 350 ° C. when the melt-kneading method is adopted, and 40 to 300 ° C., preferably 60 when the reaction in a solvent is adopted.
~ 200 ° C. The degree of graft modification is not particularly limited, but the content of the carboxyl group and / or the acid anhydride structure is preferably 0.01% by weight to 15% by weight,
It is more preferably 0.1 to 3% by weight. Again,
The acid anhydride structure is calculated assuming that there are two carboxyl groups. When the amount of graft is within the above range, the mechanical strength of the composition of the present invention, particularly impact resistance is appropriate, and three-dimensional crosslinking reaction or the like does not occur in the graft reaction, so molding of the composition of the present invention is performed. Workability does not decrease.

The intrinsic viscosity [η] of these polyphenylene ether resins is usually 0.01 to 5 dl / g, particularly 0.1 to 3 dl / g (however, measured in chloroform at 30 ° C.).

(Iii) Aromatic vinyl-conjugated diene block
Copolymer and hydrogenated product of the copolymer The aromatic vinyl-conjugated diene block copolymer used in the present invention comprises a block A in which vinyl aromatic is polymerized and a block B in which a conjugated diene compound is polymerized. Composed,
It is a block copolymer having rubber elasticity exemplified by A-B-A type or A-B type. The hydrogenated product of the block copolymer is a block copolymer in which some or all of the double bonds of the block B are hydrogenated.

Specific examples of the vinyl aromatic constituting the block A include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof, which are the polyphenylene ether resin component ( Preferred from the viewpoint of compatibility with ii). Of these, styrene and α-methylstyrene are particularly preferable because of their high price and high compatibility with the polyphenylene ether resin. Further, as an example of the conjugated diene compound that constitutes the block B,
Mention may be made of butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene and mixtures thereof. Considering the availability and the effect of imparting impact resistance, butadiene and isoprene are preferable. The content ratio of the block A and the block B is not particularly limited, but the block A enhances the compatibility with the polyphenylene ether, while the block B, which is a rubber elastic body, is effective in impact resistance. Therefore, A: B = The ratio is 2: 8 to 8: 2, preferably 3: 7 to 7: 3 (molar ratio). The molecular weight of such an aromatic vinyl-conjugated diene block copolymer (and hydrogenated product of the copolymer) is not particularly limited, but preferably 1000 to 2000 in terms of weight average molecular weight.
00.

Specific examples of such aromatic vinyl-conjugated diene block copolymers include styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS). Also, so-called SEBS in which SBS is hydrogenated as a hydrogenated product, and hydrogenated SIS in which SIS is hydrogenated, that is, so-called SEPS
Etc. Such an aromatic vinyl-conjugated diene block copolymer or its hydrogenated product may contain a carboxyl group and / or an acid anhydride group. In order to introduce a carboxyl group and / or an acid anhydride structure, an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride can be introduced by a graft reaction technique. Specifically, the method described for the component (i) can be applied including the preferred embodiment. The content of the carboxyl group and / or the acid anhydride structure is not particularly limited, but is usually 0.01 to 15% by weight, particularly 0.1 to 10% by weight.
Is preferred.

(Iv) Polystyrene having an oxazoline ring
Polystyrene resin having an oxazoline ring used in the down-based resin The present invention can be a styrene monomer and a vinyl oxazoline random copolymer, obtained by graft copolymerization of a vinyl oxazoline block copolymer or polystyrene resin. Here, the styrenic monomer is a component
The aromatic vinyl described in (iii) can be applied. Of these, styrene, α-methylstyrene and vinyltoluene are preferable. In addition to the components described above, acrylonitrile, maleic anhydride, and the like can be contained in appropriate amounts as components constituting the component (iv).

As a method of copolymerizing a styrene-based monomer and an oxazoline ring, a method of bulk polymerization, solution polymerization or suspension polymerization of vinyloxazoline together with the above-mentioned monomer in the presence or absence of a radical reaction initiator, Polymerize polystyrene resin in advance,
Examples thereof include a method of graft-polymerizing vinyl oxazoline to the obtained polymer in the presence or absence of a radical reaction initiator. The content of the oxazoline component in the component (iv) is not particularly limited, but is preferably 0.1 to 20% by weight, and more preferably 0.5 to 10% by weight in terms of vinyloxazoline.

Mixing ratio of each component The above components (i) to (iv) are mixed in the following ratios. Component (i) 10 to 90 parts by weight Component (ii) 90 to 10 parts by weight Component (iii) 2 to 60 parts by weight Component (iv) 2 to 60 parts by weight

When each component deviates from the above range, for example, when the component (i) is less than the range and the component (ii) is more than the range, the heat resistance is improved, but the molding processability is deteriorated, and the resistance is high. Solvent properties are also reduced. On the contrary, when the amount of the component (i) is larger than the range and the amount of the component (ii) is smaller than the range, the moldability and the solvent resistance are improved, but the heat resistance is lowered. Further, if the amount of the component (iii) is less than this range, the impact resistance is poor, and if it is more than this range, the heat resistance is significantly lowered. On the other hand, when the amount of the component (iv) is less than the above range, the compatibility between the polyphenylene ether-based resin and the polyolefin-based resin decreases, and problems such as a composition in which heat resistance and impact resistance are difficult to be compatible occur.

As described above, in the composition of the present invention, if the content ratio deviates from the above range, a resin composition having well-balanced molding processability, heat resistance, mechanical properties and solvent resistance cannot be obtained. If desired, additives such as inorganic oxides, inorganic fibers, organic fibers, granular organic substances, antioxidants, flame retardants and the like can be added to the polyphenylene ether resin composition of the present invention. Examples of such additives include inorganic oxides, talc, mica, calcium carbonate, glass fibers and carbon fibers as the inorganic fibers, and examples of organic fibers and granular organic substances include aramid fibers and aromatics. Examples thereof include polyester fibers and phenol resin beads. Examples of the antioxidant include hindered phenol-based or phosphorus-based organic compounds, and examples of the flame retardant include halogenated organic compounds and antimony-based compounds. These may be contained in any amount as long as they do not impair the object of the present invention.

Method for Preparing the Composition of the Present Invention The method for preparing the composition of the present invention is not particularly limited, and any conventional melt kneading method may be used. For example, a method of mixing each component with a Henschel mixer and then melt-kneading with a twin-screw extruder, a single-screw extruder, a kneader-type kneader, a Brabender, or the like may be appropriately selected and used. In this case, the kneading temperature is usually 100 to 350 ° C,
The temperature is preferably 150 to 300 ° C., and the residence time (kneading time) is usually 15 seconds to 30 minutes, preferably 30.
Seconds to 10 minutes.

Molded Article By subjecting the resin composition described in detail above to melt molding such as injection molding, extrusion molding and blow molding, a molded article having well-balanced heat resistance, mechanical properties and solvent resistance can be obtained. .. According to the research conducted by the present inventors, in the texture structure of the molded article, the component (i) forms a matrix phase and the component (i)
i), (iii) and (iv) each independently form a dispersed phase, or a mixture of at least two components selected from components (ii), (iii) and (iv) forms a dispersed phase. It has been found to be preferable.

Also, injection molding is adopted as the melt molding method, and the aspect ratio of the dispersed phase is 4 or more, particularly 5.
0 to 15.0, the major axis of which is oriented substantially parallel to the resin flow direction, and the minor axis of the dispersed phase has an average diameter of 5 μm or less, particularly 0.1 to 1 .0
It has been found that μm is particularly preferred.
By satisfying these conditions, the balance of heat resistance, mechanical properties and solvent resistance is excellent and the linear expansion coefficient is lowered.

The molded product in such a dispersed state has a barrel temperature of 150 to 380 ° C., an injection pressure of 20 kg / cm ² G or more, an injection speed of 5% or more, and a mold temperature of 40 to 150 ° C. It can be obtained by injection molding the resin composition.

Although the reason why the molded article of the present invention has the above-mentioned dispersed form and the linear expansion coefficient is particularly lowered is not clear, it is considered as follows. The other components, which become the dispersed phase and are mixed with the polyphenylene ether-based resin, form the dispersed phase during melt molding and are highly oriented, so that residual stress is generated in the major axis direction. As a result, it is considered that when the molded product expands as the temperature rises, this stress is relieved and the function of suppressing the volume expansion occurs. Such a structure is achieved by melt-molding the resin composition of the present invention.

[0036]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples. In these examples, the physical properties of the resin composition were measured by the following methods. (1) Heat distortion temperature The load was set to 4.6 kgf / cm ² according to ASTM D-648. (2) Izod impact strength According to ASTM D-256, test pieces with a thickness of ⅛ inch were used with notch at 23 ° C. (3) Flexural Modulus According to ASTM D-790, a 1/8 inch thick test piece was used. (4) Solvent resistance A test piece having a thickness of 1/8 inch was immersed in toluene for 1 hour, and then the surface of the test piece was observed and evaluated as follows. ○ Almost no change is observed. × Clearly, surface erosion is observed. (5) Intrinsic viscosity of polyphenylene ether It was measured at 30 ° C in chloroform. (6) Evaluation of Dimensional Stability Based on ASTM D696-79, -30 ° C to 30 ° C
The linear expansion coefficient in the range was measured. (7) Measurement of Shape and Size of Dispersed Particles According to ASTM D-790, a test piece having a thickness of 1/8 inch was frozen in liquid nitrogen, and then, a direction parallel to a flow direction of a resin and a right angle were obtained. The impact test (with a notch) was performed in the direction. The obtained sample was immersed in carbon tetrachloride for 6 hours to selectively etch only the dispersed phase, and then the fracture surface was observed by SEM (accelerating voltage 25 kV, magnification 1000 times and 3000 times). The dispersed particle size and the spectral ratio were measured from the obtained SEM photograph.

Reference Example 1 Preparation of Maleic Anhydride Modified Polypropylene (Component (i))
Manufacturing: Polypropylene (SH152, Tokuyama Soda Co., Ltd.)
2 kg, 60 g of maleic anhydride and 15 g of dicumyl peroxide were thoroughly mixed with a Henschel mixer,
Using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35B), melt kneading was performed under the conditions of 220 ° C. and 200 rpm.

15 g of the pellets obtained were mixed with 15 parts of hot xylene.
After dissolving in 0 g and reprecipitating with hexane, the precipitate was filtered. This operation was repeated 3 times to remove unreacted maleic anhydride. The obtained maleic anhydride-modified polypropylene was pressed into a film and then subjected to IR measurement to quantify the grafted amount of maleic anhydride based on a calibration curve prepared in advance. As a result, the grafted amount of maleic anhydride was 1.40% by weight.

(Reference Example 2) Production of polyphenylene ether; 10 g of anhydrous copper chloride, 2 liters of nitrobenzene and 0.7 liter of pyridine were charged into a polymerization tank, and oxygen gas was blown at 350 ml / min for 30 minutes. Add 3 liters of a solution of 6-dimethylphenol in nitrobenzene, and add 30 to 3
Oxidation polymerization was carried out at a temperature of 5 ° C. with stirring while blowing oxygen into this mixed solution. After the polymerization, the reaction solution was diluted with 2 liters of chloroform, and the polymer was precipitated in hydrochloric acid-methanol. The precipitated polymer was reprecipitated again with chloroform / methanol system, filtered, washed, and dried to obtain polyphenylene ether. The intrinsic viscosity of the obtained polyphenylene ether is [η] = 0.45dl
/ G.

Reference Example 3 Maleic anhydride-modified polyphenylene ether (component (i
Production of i)); 1.2 kg of the polyphenylene ether obtained in Reference Example 2, 24 g of maleic anhydride and 6 g of dicumyl peroxide were thoroughly mixed with a Henschel mixer, and then a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.). , TEM35B) at 320 ° C. and 250 rpm.

15 g of the obtained pellet was added to chloroform 2
After being dissolved in 00 g and reprecipitated with THF (tetrahydrofuran), the precipitate was filtered. This operation was repeated 3 times in total to remove unreacted maleic anhydride to obtain maleic anhydride-modified polyphenylene ether. The obtained maleic anhydride modified polyphenylene ether was titrated with a CH ₃ ONa toluene solution using thymol blue as an indicator to quantify the amount of modified maleic anhydride. The modification amount was 0.97% by weight.

Reference Example 4 Preparation of Maleic Anhydride Modified Polypropylene (Component (i))
Production; Reference Example 1 except that the amounts of maleic anhydride and dicumyl peroxide added were 20 g and 5 g, respectively.
A maleic anhydride-modified polypropylene was obtained by the same method as described above. The modification amount was 0.45% by weight.

Example 1 850 g of maleic anhydride-modified polyphenylene ether obtained in Reference Example 3, Reference Example 1
Maleic anhydride-modified polypropylene 850 obtained in
g, SEBS (Asahi Kasei Corp., Tuftec H105
1) 300 g and oxazoline ring-containing polystyrene (manufactured by Nippon Shokubai Co., Ltd., RPS1005, oxazoline content 5% by weight) were uniformly mixed with a Henschel mixer, and then twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM3).
5B) was melt-kneaded under the conditions of 280 ° C. and 400 rpm. The obtained pellets were sufficiently dried and then subjected to injection molding to obtain test pieces for measuring various physical properties. Table 1 shows the results of measurement of physical properties.

(Example 2) 850 g of maleic anhydride-modified polyphenylene ether obtained by repeating Reference Example 3 and maleic anhydride-modified polypropylene 8 obtained in Reference Example 4
Melt kneading and injection molding were carried out in the same manner as in Example 1 except that 50 g and 300 g of oxazoline ring-containing polystyrene (manufactured by Nippon Shokubai Co., Ltd., RPS1001, oxazoline content 1% by weight) were used. Table 1 shows the physical properties of the injection molded products.

Example 3 As a modified polyolefin resin (component (i)), acrylic acid modified polypropylene (manufactured by Dainippon Ink and Chemicals, PB1001, modified amount 6%)
300 g and unmodified polypropylene (SH152) 8
Using the raw materials shown in Table 1 except that 50 g of the mixture was used, the raw materials and the method similar to those in Example 1 were melt-kneaded and injection-molded. Table 1 shows the physical properties of the injection molded products.

(Examples 4 to 6) Maleic anhydride-modified polyphenylene ether obtained by the same method as Reference Examples 2 and 3, maleic anhydride-modified polypropylene obtained by the same method as Reference Example 4, SEBS (Asahi Kasei) Co., Ltd., Tuftec H1051) and oxazoline-containing polystyrene (manufactured by Nippon Shokubai Co., Ltd., RPS1005, oxazoline content 5% by weight) were used in the proportions shown in Table 1, except that
Melt kneading and injection molding were carried out in the same manner as in Example 1. Table 1 shows the physical properties of the injection molded products.

Example 7 As component (iii), maleic anhydride-modified SEBS (Tuftec M19 manufactured by Asahi Kasei Corporation) was used.
The melt-kneading and injection molding were carried out in the same manner as in Example 1 except that 53 and a modification amount of 1.8% by weight) were used in the proportions shown in Table 1. Table 1 shows the physical properties of the injection molded products.

(Example 8) SEBS was used as the component (iii).
Melt kneading and injection molding were carried out in the same manner as in Example 1 except that (Clayton TRKX65S manufactured by Shell Chemical Co., Ltd.) was used. Table 1 shows the physical properties of the injection molded products.

Example 9 As component (iii), maleic anhydride modified SEBS (M1953 manufactured by Asahi Kasei Co., Ltd.) and unmodified SEBS (H1051 manufactured by Asahi Kasei Co., Ltd.) are shown in Table 1.
A kneading experiment was conducted in the same manner as in Example 1 except that the ratio was used. Table 1 shows the physical properties of the injection molded products.

Comparative Examples 1, 5, 6 and 7 Without using oxazoline-containing polystyrene (component (iv)), as a polyphenylene ether resin (component (i)) and polypropylene resin (component (ii)) Unmodified polypropylene (SH152 manufactured by Tokuyama Soda Co., Ltd.) and
Using unmodified polyphenylene ether (synthesized in the same manner as in Reference Example 1), the components were melt-kneaded in the proportions shown in Table 1 and injection-molded. The results are shown in Table 1.
Shown in.

(Comparative Examples 2, 3 and 4) The same kneading experiment as in Example 1 was carried out, except that the mixing ratios of the respective components were as shown in Table 1. Table 1 shows the physical properties of the injection molded products.

(Comparative Example 8) (Composition similar to JP-A-63-277273) Polypropylene (SH152, Tokuyama Soda Co., Ltd.)
2 kg, 60 g of vinyl oxazoline, and 15 g of dicumyl peroxide were sufficiently mixed with a Henschel mixer, and then melted under the conditions of 220 ° C. and 200 rpm using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35B). Kneading was performed to obtain polypropylene containing an oxazoline ring. 850 g of the obtained oxazoline ring-containing polypropylene, 850 g of unmodified polyphenylene ether obtained by the same method as in Reference Example 2 and SEBS (H1 manufactured by Asahi Kasei Corporation)
051) 300 g was uniformly mixed with a Henschel mixer, and then twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35B)
Was melt-kneaded under the conditions of 280 ° C. and 400 rpm. The pellets thus obtained were sufficiently dried and then injection-molded to obtain test pieces for measuring various physical properties. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

1) MAH-: Indicates maleic anhydride modification. 2) Polypropylene SH152 manufactured by Tokuyama Soda Co., Ltd.
(MI = 15) 3) Hydrogenated product of styrene-butadiene-styrene block copolymer Tuftec H1051 manufactured by Asahi Kasei Co., Ltd. 4) Oxazoline-containing polystyrene Nippon Shokubai Co., Ltd. RPS1005 (modified amount 5% by weight) 5) Oxazoline-containing polystyrene Nippon Shokubai Co., Ltd. RPS1001 (Modification amount 1% by weight) 6) Acrylic acid modified polypropylene PB1001 (Modification amount 6% by weight) 7) Maleic anhydride modified SEBS Asahi Kasei Co., Ltd. Tuftec M1953 (modified) Quantity 1.
8% by weight) 8) SEBS Shell Chemical Co., Ltd. Clayton TRK
In the X65S table, "-" in the blending ratio means that no addition was made, and "-" in the physical properties means unmeasured.

As can be seen from Table 1, the polyphenylene ether compositions obtained in the Examples have higher impact resistance, heat resistance, bending rigidity and dimensional stability than the polyphenylene ether structures of Comparative Examples. It had balanced characteristics. The results are shown in comparison with FIGS.

When the compounding ratio of the present invention is deviated (Comparative Examples 3 and 4), heat resistance, flexural rigidity, or
The result was inferior in solvent resistance and contained defects as compared with the composition of the present invention.

1 and 2 show the microstructure and the microstructure in the direction perpendicular to the flow direction of the injection-molded article of Example 1, respectively. The aspect ratio of the dispersed phase is 9. 1. The average minor axis diameter was 1.2 μm. On the other hand, FIGS. 3 and 4 show similar structure structures to Comparative Example 1, respectively, but the aspect ratio of the dispersed phase was 3.9, and the average minor axis diameter was 0.8 μm. In FIGS. 1 to 4, the black portion is the dispersed phase and the white portion is the matrix phase.
From these figures, it can be seen that the molded product of Example 1 contains the dispersed particles highly mixed in the flow direction of the molded product as compared with Comparative Example 1.

[0060]

EFFECTS OF THE INVENTION A molded product obtained by melt molding from the resin composition of the present invention is lightweight, has excellent mechanical strength, heat resistance, solvent resistance and dimensional stability, and can be used in combination with metal parts. The problem of member deformation due to the difference in linear expansion is also reduced.

Therefore, the plastic molded article of the present invention is
It can be preferably used for automobile parts, particularly exterior parts such as bumpers, fascias, bumper covers, fenders, radiator grills, balance panels, front panels, door members, and interior parts such as installation panels.
Further, it is possible to obtain a molded product that is also useful in the field of home electric appliance parts other than automobile members.

[Brief description of drawings]

FIG. 1 is a drawing-substituting photograph showing a particle structure of a molded product.

FIG. 2 is a drawing-substituting photograph showing the particle structure of a molded product.

FIG. 3 is a drawing-substituting photograph showing a particle structure of a molded product.

FIG. 4 is a drawing-substituting photograph showing a particle structure of a molded product.

FIG. 5 is a graph comparing the physical properties of compositions.

FIG. 6 is a graph comparing the physical properties of compositions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08J 5/00 CEZ 9267-4F C08L 25/08 LDS 9166-4J LDW 9166-4J LDX 9166-4J LED 9166-4J 51/06 LLE 7142-4J 51/08 LLQ 7142-4J 53/00 LLY 7142-4J LLZ 7142-4J 53/02 71/12 LQP 9167-4J

Claims (4)

[Claims] 1. An (i) acid-modified olefin polymer component 10 containing a carboxyl group and / or an acid anhydride structure.
90 parts by weight, (ii) 90 to 10 parts by weight of a polyphenylene ether resin component containing a carboxyl group or / and an acid anhydride structure as required, (iii) a carboxyl group or / and an acid anhydride structure as required 2 to 60 parts by weight of an aromatic vinyl-conjugated diene block copolymer or / and a hydrogenated product thereof, and (iv) 2 to 60 parts by weight of a polystyrene resin component having an oxazoline ring. A characteristic polyphenylene ether resin composition. 2. A molded article obtained by melt-molding the polyphenylene ether resin composition according to claim 1, wherein the component (i) forms a matrix phase, and the components (ii) and (iii
) And (iv) each independently form a dispersed phase, or a structure in which a mixture of at least two kinds selected from components (ii), (iii) and (iv) forms a dispersed phase. A molded article characterized by having. 3. The molded article is an injection molded molded article,
The molded article according to claim 2, wherein the dispersed phase has an aspect ratio of 4 or more, and its major axis is oriented substantially parallel to the resin flow direction. 4. The molded article according to claim 3, wherein the average diameter of the minor axis of the dispersed phase is 5 μm or less.