JP2797015B2 - Resin molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is excellent in delamination resistance, weld strength retention, heat resistance, impact resistance, chemical resistance, electric / electronic field, automobile field, various The present invention relates to a resin molded body that can be used in the field of industrial materials.

[Conventional technology]

Polyphenylene ether is excellent in transparency, mechanical properties, electrical properties, heat resistance, low water absorption and excellent in dimensional stability, but has drawbacks of poor moldability and impact resistance, so polystyrene, high impact polystyrene By improving the processability and impact resistance by blending with resin, it has been widely used as resin molded products such as industrial parts, electric / electronic parts, office equipment housings, automobile parts, precision parts, and the like. However, the classic polyphenylene ether resin composition comprising polyphenylene ether and high-impact polystyrene (disclosed in U.S. Pat. No. 3,383,435) has the disadvantage that, although the impact resistance is improved, the chemical resistance is poor. doing.

For this reason, for example, U.S. Pat.
No. 7069 proposes to improve the solvent resistance and impact resistance by blending polyphenylene ether with a polyolefin, but at present, the delamination phenomenon is remarkably unpractical. Also, U.S. Pat.
No. 4,145,377 describes improvement in impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and a styrene resin with a hydrogenated block copolymer. Impact resistance and solvent resistance by blending with polyphenylene ether and styrene resin and polyolefin / hydrogenated block copolymer = 20-80 parts by weight / 80-20 parts by weight of premix and hydrogenated block copolymer And U.S. Pat.Nos. 4,416,055, 4,396,733 and 4,242,263.
The publication describes the improvement of impact resistance by blending polyphenylene ether with a block copolymer or hydrogenated block copolymer and a polyolefin. U.S. Pat. No. 4,383,082, EP 115712 and German Patent 7410861 describe improving the impact resistance by blending polyphenylene ether with a polyolefin and a hydrogenated block copolymer.

Also, U.S. Pat.No. 4,863,997 and JP-A-63-113058
No. 63-225642, No. 64-98647, No. 64-204939 and No. 64-221444, a specific hydrogenated block copolymer for modifying a resin composition comprising a polyolefin resin and a polyphenylene ether resin. There has been proposed a resin composition which incorporates a coalescence and has excellent chemical resistance and workability.

On the other hand, the present applicant has disclosed Japanese Patent Application Laid-Open Nos. 63-218748 and 63-2454.
No. 53 and No. 64-40556 propose a resin composition excellent in chemical resistance and processability by melt-kneading a pre-compound of a specific block copolymer and polyolefin with polyphenylene ether.

[Problems to be solved by the invention]

However, the prior art relating to resin compositions in which these polyphenylene ether polyolefins are blended has a solvent resistance and impact resistance which are lower than those of classic polyphenylene ether resin compositions (compositions composed of polyphenylene ether and styrene resin). Although the effect of improving the above is recognized, its performance is insufficient. In particular, a resin composition composed of substantially 50% by weight or more of polyphenylene ether and 20% by weight or less of polyolefin is prepared by these prior arts. In the molded product which has undergone delamination, the molded product having a weld line portion has a remarkable decrease in weld strength (tensile strength), and cannot meet the performance requirements of plastics, which are becoming increasingly sophisticated as various industrial materials every year. The problem remains.

It is an object of the present invention to provide a resin molded product in which the molded product containing a polyphenylene ether and a polyolefin, which cannot be achieved by the above-mentioned prior art, has been improved in layer delamination and weld strength of a molded product having a weld line.

[Means for solving the problem]

The present inventors, in view of such current situation, as a result of intensive studies on a resin molded body composed of polyphenylene ether, polyolefin and a compatibilizer,
By controlling the polyolefin and compatibilizer that form the dispersed phase to a specific dispersion state, in addition to significantly improving the weld strength of the resin molded body having the weld line, the delamination is also improved at the same time. The present inventors have found that a resin molded article having excellent impact resistance and chemical resistance under stress can be obtained, and arrived at the present invention.

That is, the present invention provides a resin molded article comprising: (a) a continuous phase: polyphenylene ether; (b) a dispersed phase: a vinyl aromatic compound-conjugated diene compound in a polyolefin outer layer substantially dispersed with a minor axis diameter of 0.5 μm or less. At least one copolymer selected from a copolymer and a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer is aggregated, and the copolymer is substantially 0.3 μm in minor axis diameter alone. The present invention provides a resin molded product characterized by being dispersed below.

Here, the fact that the minor axis diameter is 0.5 μm or less is calculated by measuring the maximum minor axis diameter based on a 40,000 × photograph (18 cm × 25 cm) taken by a transmission electron microscope, and calculating 90% of the maximum value. The above is 0.
It means that the particles are dispersed with a minor axis diameter of 5 μm or less. Similarly, the meaning that the particles are dispersed with a minor axis diameter of 0.3 μm or less is also defined in the same manner as described above.

The polyphenylene ether (hereinafter simply abbreviated as PPE) that forms the continuous phase of the resin molded article of the present invention has a bonding unit: (Where R ₁ , R ₂ , R ₃ , and R ₄ are each hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group A hydrocarbon oxy group or a halohydrocarbon oxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, which may be the same or different from each other) And reduced viscosity (0.5g
/ dl, chloroform solution, measured at 30 ° C) is a homopolymer and / or copolymer having a range of 0.15 to 0.70, more preferably a range of 0.20 to 0.60. Specific examples of the PPE include, for example, poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-
Phenylene ether), poly (2,6-diphenyl-1,4-)
Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.
-Dimethylphenol and other phenols (for example, 2,
Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether) is preferred.

The method for producing such a PPE is not particularly limited as long as it can be obtained by a known method.For example, a complex of a cuprous salt and an amine according to Hay described in U.S. Pat. , 6-xylenol can be easily produced by oxidative polymerization, and in addition, U.S. Patent Nos. 3,306,875, 3,257,357 and 3,257.
No. 35, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628 can be easily produced.

Further, the PPE used in the present invention, in addition to the PPE described above,
It is obtained by reacting the PPE with an α, β-unsaturated carboxylic acid or a derivative thereof in the presence, absence or presence of a radical generator in a molten state, a dissolved state, or a slurry state at a temperature of 80 to 350 ° C. It may be a known modified (the α, β-unsaturated carboxylic acid or its derivative is grafted or added by 0.01 to 10% by weight) PPE, and further a mixture of the above-mentioned PPE and the modified PPE in any ratio. It doesn't matter.

Further, 9,10-dihydro-9-oxa-10-phosphaphenanthrene is used in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of PPE.
A phosphorus compound-treated PPE that has been added by weight and melt-kneaded can also be provided as PPE having excellent color tone.

Next, the polyolefin forming the dispersed phase of the resin molded article of the present invention is a polyolefin having a number average molecular weight of 30,000 or more used as a normal molding material, for example, high-density polyethylene, ultra-high-molecular-weight highest-density polyethylene, low-density polyethylene. Polyethylene, linear low density polyethylene, density 0.90
Less than low-density polyethylene, isotactic polypropylene, a copolymer of two or more compounds selected from ethylene, propylene, other α-olefins, unsaturated carboxylic acids or derivatives thereof, 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, poly (4-methyl-1-pentene), polybutene-1, and the like can be mentioned, and not only one kind but also two or more kinds can be used in combination. Of these polyolefins, polyethylene is preferred, and low density polyethylene, linear low density polyethylene, and high density polyethylene are preferred.

Next, a vinyl aromatic compound-conjugated diene compound copolymer and a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer which form a dispersed phase of the resin molded article of the present invention (hereinafter, abbreviated as a compatibilityizer) Is a hydrogenated product of a copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound, and a copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound (copolymerized conjugated diene compound). At least 50 of olefinic double bonds based on
% Or more, preferably 80% or more is hydrogenated), and at least one of them is used.

Examples of the copolymerization form of the compatibilizer include a random copolymer, a block copolymer, a graft copolymer, and a combination thereof. Among them, a block copolymer is preferable.

As the vinyl aromatic compound constituting the compatibilizer, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like can be selected. Styrene is preferred. As the conjugated diene compound, for example, butadiene, isoprene, 1,3-
One or more kinds are selected from pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferred.

Examples of such a compatibilizer include a styrene-butadiene copolymer obtained by anionic polymerization, and a hydrogenated product of the styrene-butadiene copolymer.These include, for example, British Patent No. 1,130,
No. 770 and U.S. Pat.Nos. 3,281,383 and 3,639,51
No. 7,020,720 and U.S. Pat. Nos. 3,333,024 and 4,501,857.

Of these compatibilizers, the Young's modulus is 15
A hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer of at least 00 kg / cm ^{2 and} a vinyl aromatic compound-conjugated diene compound block copolymer of a Young's modulus of at least 1500 kg / cm ² is preferred. As the compatibilizer, for example, those marketed by Asahi Kasei Kogyo Co., Ltd. under the trade names "Tuffrene", "Solprene", "Tuffden", "Asaprene", and "Toughtec" can be used.

As described above, the present invention is a resin molded article having the following characteristics.

(A) continuous phase: formed polyphenylene ether; (b) dispersed phase: a vinyl aromatic compound-conjugated diene compound copolymer and a vinyl aromatic compound-conjugated in a polyolefin outer layer substantially dispersed with a minor axis diameter of 0.5 μm or less. At least one copolymer selected from hydrogenated diene compound copolymers is agglomerated, and the copolymer is substantially a minor axis diameter of 0.3 μm or less, more preferably 0.1 μm or less.
The following is characterized by having a dispersed structure.

By showing such a special morphology,
Although the molded article achieves the above-mentioned excellent effects, the quantitative ratio of each component of the molded article is preferably selected as follows (but is not limited to this). Less than 20% by weight of at least one copolymer selected from a vinyl aromatic compound-conjugated diene compound copolymer and a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer.
It is a resin molded product containing 50 to 95% by weight of polyphenylene ether, and in particular, 5 to 15% by weight of polyolefin.
% By weight, 10 to 35% by weight of at least one copolymer selected from a vinyl aromatic compound-conjugated diene compound copolymer and a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer, and polyphenylene ether, When the content is 90 to 50% by weight, a resin molded article having excellent chemical resistance, heat resistance, impact resistance, and weld strength can be obtained.

As described above, the resin molded article of the present invention has two types of dispersed phases (the above and). Among such features, the vinyl aromatic compound-conjugated diene compound copolymer which is a compatibilizer is included. At least one selected from a hydrogenated product of a copolymer and a vinyl aromatic compound-conjugated diene compound copolymer is used alone in PPE forming a matrix, and substantially has a minor axis diameter of 0.3 μm or less, preferably 0.1 μm or less.
By dispersing in the following, a very good result is obtained for the weld strength of the resin molded body having a weld line.

However, the short axis diameter dispersion of such polyolefins substantially exceeds 0.5 μm, or the short axis diameter dispersion of a compatibilizer that is dispersed alone is substantially 0.3 μm.
In the resin molded product exceeding the above, delamination is remarkably observed, and a decrease in weld strength of the resin molded product having a weld line is remarkably observed.

The dispersion state of the polyolefin and the compatibilizer forming a dispersed phase in polyphenylene ether can usually be easily confirmed by an electron micrograph, and these dispersed phases are (major axis diameter / minor axis diameter) ≧ In particular, when the major axis diameter is equal to the minor axis diameter, the dispersion form is circular, and when (major axis diameter / minor axis diameter)> 1, the dispersion form has a lamella structure or a fibril structure. In a dispersed form.

In addition, the state of the compatibilizer which is substantially agglomerated in the polyolefin outer layer dispersed with a minor axis diameter of 0.5 μm or less can also be easily confirmed by an electron microscope photograph.

Aggregation in the present invention specifically means a dispersion form in which the compatibilizer surrounds the dispersed polyolefin in fine particles, and a dispersion form in which the compatibilizer surrounds the polyolefin outer layer in a layered manner. In addition to these forms, the compatibilizer may be melted into the polyolefin.

The resin molded article of the present invention is characterized by comprising one or more of the above-mentioned dispersion forms which can be confirmed by an electron microscope.

Hereinafter, the method for producing the resin molded article of the present invention will be described.

In order to be able to become the resin molded article of the present invention, it is, of course, important to select the polyphenylene ether species, polyolefin species, and compatibilizer species to be provided, the selection of the quantitative ratio relationship of each material to be provided, and the selection of melt mixing conditions. However, in order to significantly improve the delamination of the resin molded product obtained and the weld strength of the resin molded product having a weld line, the polyolefin and the compatibilizer, which are the disperse phase of the resin molded product, have the specific fine dispersion described above. It must have a structure.

The method for obtaining the dispersion state of the resin molded article of the present invention is as follows.
A melt kneader for melt kneading the above components,
It is a multi-screw extruder having two or more screws capable of incorporating a kneading block at an arbitrary position of a screw, wherein all kneading blocks of a screw to be used are substantially (L / D ≧ 1.5, more preferably (L / D ≧ 5) [where L
Represents the length of the kneading block, and D represents the maximum outer diameter of the kneading block].
D · N / h) ≧ 50 [where, π; 3.14, D: screw outer diameter corresponding to the metering zone, N: screw rotation speed (rotations / second), h: groove depth of the metering zone] Filling, and further, each of the above components are simultaneously fed to an extruder,
In addition, it is necessary to set the barrel setting temperature of the extruder corresponding to the position where the kneading block portion is incorporated into the glass transition temperature (about 210 ° C.) of the PPE or less, and perform melt-kneading.

These, in addition, compounding a Tiby riser, at least a Young's modulus 1500 kg / cm ² or more vinyl aromatic compound - conjugated diene compound copolymer, and at least a Young's modulus 1500 kg / cm ² or more vinyl aromatic compound - conjugated diene By selecting at least one copolymer selected from hydrogenated compounds of the compound copolymer, the resin molded article of the present invention can be desirably obtained.

The resin molded article of the present invention manufactured under such conditions,
The weld strength of a resin molding having delamination and a weld line is greatly improved.

In the present invention, in addition to the above-mentioned components, other additional components as necessary within a range that does not impair the features and effects of the present invention,
For example, polystyrene resins (polystyrene, high impact polystyrene, etc.), antioxidants, weather resistance improvers, nucleating agents for polyolefins, slip agents, inorganic or organic fillers and reinforcing agents (glass fiber, carbon fiber, whisker) , Mica, talc, calcium carbonate, potassium titanate, wollastonite, etc.), flame retardants, plasticizers (phosphorus compounds such as triphenyl phosphate, etc.), various colorants, antistatic agents, release agents, etc. It doesn't matter.

The resin molded article of the present invention may be a resin molded article obtained by any molding method, as long as the polyolefin dispersed in polyphenylene ether and the compatibilizer show the specific finely dispersed acid state described above. For example, pellets can be obtained as resin molded articles of various parts by using the pellets, for example, by compression molding, injection molding, extrusion molding, or hollow molding.

These various parts include, for example, automobile parts, and specifically, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, and instrument panels. It is suitable for interior parts such as console boxes, trims, etc., and can also be suitably used as interior and exterior parts of electric equipment, and specifically, cabinets for OA equipment, televisions, videos, video games, various disc players, etc. Suitable for parts such as refrigerators.

〔The invention's effect〕

The resin molded article of the present invention comprises a polyolefin dispersed in polyphenylene ether and at least one selected from a hydrogenated product of a vinyl aromatic compound-conjugated diene compound copolymer and a vinyl aromatic compound-conjugated diene compound copolymer. Has a specific finely dispersed structure, so that delamination and weld strength are greatly improved.

〔Example〕

The present invention will be described in more detail by way of examples.
It is not limited by these examples.

Example 1 70 parts by weight of polyphenylene ether having a reduced viscosity of 0.56, 10 parts by weight of low-density polyethylene (Suntech LD-M1804, manufactured by Asahi Kasei Corporation), styrene-butadiene copolymer (Asaflex 810; Young's modulus 4600 kg / cm ²⁾ Asahi Kasei Kogyo Co., Ltd.) 10 parts by weight, styrene-butadiene copolymer (Sorprene T406; Young's modulus 2100 kg / cm ² , Nippon Elastomer Co., Ltd.) 10 parts by weight, 9,10-dihydro-9-oxa-
1.5 parts by weight of 10-phosphaphenanthrene and 7 parts by weight of triphenyl phosphate were blended with a Henschel mixer, and the kneading block portion of the screw was mixed with 190 parts.
° C and the other part was set to 270 ° C using a co-rotating twin-screw extruder (PCM-30; manufactured by Ikegai Iron Works Co., Ltd.). D.N / h) = 157, and the extruded strands were obtained as pellets. The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. Perform a tensile test (ASTM D-638) using this test piece,
When the presence or absence of delamination of the molded article was confirmed from the fractured surface, no delamination was observed.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain a weld strength (the tensile strength of a test piece having a weld line divided by a weld strength). The tensile strength of a test piece without a line × 100%) was determined to be 97%.

The test piece having a weld line means a test piece for a tensile test of an ASTM Type I dumbbell piece (thickness: 1/8 inch) having a weld line in the center. The same applies to the following.

On the other hand, when a section of another test piece for tensile test stained with osmic acid (OsO ₄ ) was photographed with a transmission electron microscope, low-density polyethylene was substantially dispersed with a minor axis diameter of 0.5 μm or less, and styrene was removed. A structure in which the butadiene copolymer is substantially dispersed in polyphenylene ether with a minor axis diameter of 0.1 μm or less, and the styrene-butadiene copolymer is aggregated in the form of fine particles in the outer layer of the low-density polyethylene of the dispersed phase. Met.

Comparative Example 1 The extruder used was a different-direction rotating twin-screw extruder (30 mm diameter; manufactured by Nakatani Machinery Co., Ltd.)
Example 1 except that D = 0 (the screw of this extruder cannot substantially incorporate a kneading block), (π · D · N / h) = 36.2, and the set temperature was 240 to 270 ° C. The composition was melt-kneaded with the same composition as in Example 1, and injection molding was performed under the same conditions as in Example 1. Example 1 using the obtained tensile test piece
A tensile test was carried out under the same conditions as in Example 1. As a result, remarkable delamination was observed at the surface portion of the fractured surface of the test piece.

The weld strength retention of the test piece having a weld line was determined to be 64%.

Furthermore, when another test piece was photographed using a transmission electron microscope under the same conditions as in Example 1, the low-density polyethylene was dispersed with a short axis diameter of 0.4 to 1.7 μm, and was substantially dispersed.
The minor axis diameter exceeded 0.5 μm. Further, the styrene-butadiene copolymer is dispersed in the polyphenylene ether with a short axis diameter of 0.5 to 1.8 μm, has a short axis diameter substantially exceeding 0.3 μm, and the styrene-butadiene copolymer is a dispersed phase. The structure was such that the low-density polystyrene was aggregated in the outer layer.

Examples 2-3, Comparative Examples 2-3 76 parts by weight of polyphenylene ether having a reduced viscosity of 0.49, 8 parts by weight of high-density polyethylene (Suntech HD-J240; manufactured by Asahi Kasei Corporation), hydrogen of styrene-butadiene block copolymer Additives (hydrogenation rate of polybutadiene part 9
8 parts by weight of 9.9%, Young's modulus 3200 kg / cm ² ) and 8 parts by weight of hydrogenated styrene-butadiene block copolymer (hydrogenation rate of polybutadiene 99.9%, Young's modulus 5300 kg / cm ² ) by Henschel mixer Then, using a co-rotating twin-screw extruder (PCM-30; Ikegai Iron Works Co., Ltd.) with the set temperature corresponding to the kneading block part of the screw set to 200 ° C and the other part set to 270 ° C , L / D of all kneading blocks = 4.1, (π · D · N / h) = 94.2 (Example 2), L / D of all kneading blocks = 14, (π · D
D · N / h) = 62.9 (Example 3), L / D of all kneading blocks = 2.0, (π · D · N / h) = 37.7 (Comparative Example 2),
L / D = 0 for all kneading blocks, (π · D · N / h) =
The extruded strands were obtained as pellets by melt-kneading under the conditions of 62.9 (Comparative Example 3). 28 pellets obtained here
The test piece was supplied to a screw in-line type injection molding machine set at 0 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. A tensile test (ASTM D-638) was performed using this test piece, and the presence or absence of delamination of the molded article was confirmed from the fracture surface. As a result, no delamination was observed in the test pieces obtained in Examples 2 and 3. I couldn't. However, in the test pieces obtained in Comparative Examples 2 and 3, which were compositions having the same composition, a remarkable delamination phenomenon was observed.

Further, the weld strength retention of the test piece having a weld line was determined.
Is 84%, and Comparative Examples 2 and 3 are 71% and 63%, respectively.
Met.

Examples 2-3, a test piece of each of Comparative Examples 2-3 were stained with ruthenium acid (RuO _4), was photographed using a transmission electron microscope, Examples 2-3 are in the polyphenylene ether The high-density polyethylene that is dispersed in the dispersion is substantially dispersed with a minor axis diameter of 0.5 μm or less.
High-density polyethylene is dispersed with a short axis diameter of m to 1.0 μm,
The minor axis diameter substantially exceeded 0.5 μm. Comparative Example 3
The high-density polyethylene was dispersed with a short axis diameter of 0.5 μm to 2.3 μm, and the short axis diameter substantially exceeded 0.5 μm. Also, the hydrogenated product of the styrene-butadiene block copolymer of the compatibilizer aggregated in the outer layer of the high-density polyethylene, and the compatibilizer alone dispersed in PPE was substantially equivalent to that of Examples 2-3. Short shaft diameter 0.1μ
m, but in Comparative Examples 2-3, 0.1 μm
It was dispersed with a short axis diameter of 0.9 μm, and had a short axis diameter substantially exceeding 0.3 μm.

Comparative Example 4 Preparation of a composition according to US Pat. No. 4,145,377.

Of the compositions shown in Table 1, (c ¹⁾ and low density polyethylene component (c ²⁾ component of the styrene - a hydrogenated product of butadiene block copolymers, co-rotating twin screw extruder (PCM-30;
Pre-compound (C) was prepared by melting and kneading at a set temperature of 200 to 240 ° C. using Ikegai Iron Works Co., Ltd.). Further, the pre-compound obtained here and the remaining components were melt-kneaded using a co-rotating twin-screw extruder under the conditions of a set temperature of 230 to 280 ° C. and a screw rotation of 200 rpm, and an extruded strand was obtained as a pellet.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
Remarkable delamination was observed in the surface layer portion of the fracture surface of the test piece.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). The tensile strength of the test piece without the line x 100%) was 66%. On the other hand, when a section of another test piece for tensile test stained with ruthenic acid (RuO ₄ ) was photographed with a transmission electron microscope, it was found that the low-density polyethylene had a content of 0.
It was dispersed with a minor axis diameter of 8 to 2.9 μm, and the minor axis diameter substantially exceeded 0.5 μm. Further, the styrene-butadiene copolymer is dispersed in polyphenylene ether with a short axis diameter of 0.9 to 2.1 μm, has a short axis diameter substantially exceeding 0.3 μm, and the styrene-butadiene copolymer is a dispersed phase. The low-density polyethylene had a structure agglomerated in the outer layer.

Comparative Examples 5 to 7 U.S. Pat.
Preparation of a composition according to No. 263.

The composition shown in Table 2 was melt-kneaded using a co-rotating twin-screw extruder (PCM-30; Ikegai Iron Works Co., Ltd.) at a set temperature of 230 to 280 ° C. and a screw rotation of 200 rpm, and the extruded strand was pelletized. As obtained.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
Remarkable delamination was observed in the surface layer portion of the fracture surface of the test piece (Comparative Examples 5 to 7).

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). The tensile strength of a test piece without a line × 100%) was determined, and the results were 59% for Comparative Example 5, 68% for Comparative Example 6, and 51% for Comparative Example 7.
%Met. On the other hand, when a section of another test piece for tensile test stained with ruthenic acid (RuO ₄ ) or osmate (OsO ₄ ) was photographed with a transmission electron microscope, Comparative Example 5 showed that the low-density polyethylene was 1.1 to 2.2. The particles were dispersed with a short axis diameter of μm, and had a short axis diameter substantially exceeding 0.5 μm. Hydrogenated styrene-butadiene copolymer is 0.7-2.3μ
m having a minor axis diameter of greater than 0.3 μm, and having a minor axis diameter of greater than 0.3 μm.
The structure was such that the hydrogenated butadiene copolymer was aggregated in the outer layer of the low-density polyethylene in the dispersed phase. In Comparative Example 6, the low-density polyethylene was dispersed with a minor axis diameter of 0.8 to 2.5 μm, and the minor axis diameter substantially exceeded 0.5 μm. The styrene-butadiene copolymer is dispersed in the polyphenylene ether with a short axis diameter of 0.5 to 2.4 μm, has a short axis diameter substantially exceeding 0.3 μm, and the styrene-butadiene copolymer has a low axis of the dispersed phase. The structure was agglomerated in the outer layer of high density polyethylene. Comparative Example 7 had a low density polyethylene of 1.3
It was dispersed with a minor axis diameter of 〜2.6 μm, and had a minor axis diameter substantially exceeding 0.5 μm. A styrene-butadiene copolymer and a hydrogenated product thereof are dispersed in polyphenylene ether with a short axis diameter of 1.1 to 2.8 μm, have a short axis diameter substantially exceeding 0.3 μm, and a styrene-butadiene copolymer and The structure was such that the hydrogenated product was agglomerated in the outer layer of the low-density polyethylene of the dispersed phase.

Comparative Example 8 JP-A-63-218748, JP-A-63-245453 and JP-A-64-40
Preparation of a composition according to No. 556.

Of the composition shown in Table 3, (c ¹⁾ and low density polyethylene component (c ²⁾ component of the styrene - butadiene radial teleblock copolymer, co-rotating twin screw extruder (PCM-30;
Pre-compound (C) was prepared by melting and kneading at a set temperature of 200 to 240 ° C. using Ikegai Iron Works Co., Ltd.). Further, the pre-compound obtained here and the remaining components were melt-kneaded using a co-rotating twin-screw extruder under the conditions of a set temperature of 230 to 280 ° C. and a screw rotation of 200 rpm, and an extruded strand was obtained as a pellet.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
No delamination was observed.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). The tensile strength of a test piece without a line × 100%) was determined to be 72%. On the other hand, when a section of another test piece for tensile test stained with osmic acid (OsO ₄ ) was photographed with a transmission electron microscope, it was found that the low-density polyethylene had a content of 0.
The particles were dispersed with a minor axis diameter of 3 to 1.1 μm, and the minor axis diameter substantially exceeded 0.5 μm. Styrene-butadiene radial teleblock is a structure in which the styrene-butadiene radial teleblock copolymer is layered and aggregated in the outer layer of the low-density polyethylene of the disperse phase, and is substantially dispersed in polyphenylene ether at substantially 0.3 μm or less. No copolymer was found.

Examples 4 to 6 The components shown in Table 4 were melt-kneaded and extruded under the same extruder conditions using the same co-rotating twin-screw extruder (PCM-30; Ikegai Iron Works, Ltd.) as in Example 1. The strand was obtained as a pellet.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
No delamination was observed in any of the test pieces of Examples 4 to 6.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). When the tensile strength of a test piece without a line × 100%) was determined, all of Examples 4 to 6 were 100%.

On the other hand, another tensile test piece ruthenium (Ru
When the sections stained with O ₄ ) were photographed with a transmission electron microscope, the high-density polyethylene was dispersed with a minor axis diameter of substantially 0.5 μm or less in all of the test pieces of Examples 4 to 6, and a styrene-butadiene block was obtained. The structure is such that the hydrogenated product of the copolymer is layered and agglomerated in the outer layer of the high-density polyethylene of the dispersed phase, and the hydrogenated product of the styrene-butadiene block copolymer dispersed alone in polyphenylene ether is substantially Was 0.1 μm or less.

Examples 7 to 9 The components shown in Table 5 were melt-kneaded and extruded under the same extruder conditions using the same co-rotating twin-screw extruder (PCM-30; Ikegai Iron Works, Ltd.) as in Example 1. The strand was obtained as a pellet.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
No delamination was observed in any of the test pieces of Examples 7 to 9.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). When the tensile strength of a test piece without a line × 100%) was determined, all of Examples 7 to 9 were 100%.

On the other hand, another tensile test piece ruthenium (Ru
The sections stained with O ₄ ) were photographed with a transmission electron microscope. As a result, in all of the test pieces of Examples 7 to 9, polypropylene was substantially dispersed with a short axis diameter of 0.5 μm or less, and the styrene-butadiene block copolymer was dispersed. The combined hydrogenated product has a structure in which the hydrogenated product of the styrene-butadiene block copolymer dispersed alone in polyphenylene ether is substantially 0.1 μm or less. there were.

Examples 10 to 12 The components shown in Table 6 were melt-kneaded using the same co-rotating twin-screw extruder (PCM-30; Ikegai Iron Works, Japan) as in Example 1 under the same extruder conditions. The extruded strand was obtained as a pellet.

The pellets obtained here were supplied to a screw in-line type injection molding machine set at 280 to 300 ° C, and a test piece for a tensile test was injection-molded at a mold temperature of 80 ° C. When a tensile test (ASTM D-638) was performed using this test piece and the presence or absence of layer delamination of the molded body was confirmed from the fracture surface,
No delamination was observed in any of the test pieces of Examples 10 to 12.

Furthermore, a test piece for a tensile test is injection-molded using a mold capable of forming a weld line, and a tensile test (ASTM D-638) is performed to maintain the weld strength (the tensile strength of the test piece with a weld line divided by the weld strength). When the tensile strength of a test piece without a line × 100%) was determined, all of Examples 10 to 12 were 100%.

On the other hand, another tensile test piece ruthenium (Ru
The sections stained with O ₄ ) were photographed by transmission electron microscopy, showing that polypropylene and low-density polyethylene were substantially 0.5% in all of the test pieces of Examples 10 to 12.
Styrene-butadiene dispersed in a polyphenylene ether by itself, in which the hydrogenated styrene-butadiene block copolymer is dispersed in a layered form in the outer layer of polypropylene of the dispersed phase, and is dispersed with a minor axis diameter of not more than μm. The hydrogenated product of the block copolymer was substantially 0.1 μm or less.

Example 13 65 parts by weight of a polyphenylene ether having a reduced viscosity of 0.54, 15 parts by weight of a linear low-density polyethylene (Suntech LL-LM7625; manufactured by Asahi Kasei Corporation), and a hydrogenated product of a styrene-butadiene copolymer (Young's modulus 4800 kg / cm ² , hydrogenation rate 99.9
%), 10 parts by weight of a styrene-butadiene copolymer (Sorprene T406; Young's modulus 2100 kg / cm ² , manufactured by Nippon Elastomer Co., Ltd.) were blended with a Henschel mixer, and the same extruder as in Example 1 was used. Melt kneading was performed under the same extrusion conditions. Ruthenic acid (Ru
When the section stained with O ₄ ) was photographed with a transmission electron microscope, the linear low-density polyethylene was substantially dispersed with a minor axis diameter of 0.5 μm or less, and the block copolymer of the compatibilizer was dispersed in the dispersed phase. The structure was such that it melted into the linear low-density polyethylene and was agglomerated in layers in the outer layer of the linear low-density polyethylene. Further, the block copolymer dispersed alone in polyphenylene ether is substantially 0.1 μm.
m or less.

Example 14 The pellets obtained in Example 1 were supplied to an injection molding set at 280 to 300 ° C, and a test piece compliant with ASTM D-648 was molded under the condition of a mold temperature of 90 ° C. The heat distortion temperature was measured to be 119 ° C. Further, under the same injection conditions, a test piece conforming to ASTM D-256 was molded, and the Izod impact strength at 23 ° C. measured according to the same method was 42 kg · cm / cm. Furthermore, using a 1/8 inch thick Izod impact test test piece, Bergen's 1/4 ellipse method (long axis 24 cm, short axis 8 cm 1 /
4Fix to an elliptical jig to give a constant strain. (SPE Journal, 667,1962)] Tempura oil was applied to a test piece and the critical strain at which cracks were generated was measured at 80 ° C., and the result was 0.5%.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing the particle structure (morphology) of the resin molded product obtained in Example 1, and FIG. 2 is the particle structure (morphology) of the resin molded product obtained in Example 5.
FIG.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08L 71:12 (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 71/12 C08L 53/02 C08J 5/00

Claims (1)

(57) [Claims] 1. A resin molded article comprising: (a) a polyphenylene ether as a continuous phase and (b) a polyaromatic outer layer in which a dispersed phase is substantially dispersed with a minor axis diameter of 0.5 μm or less. At least one copolymer selected from a hydrogenated product of a compound copolymer and a vinyl aromatic compound-conjugated diene compound copolymer is aggregated, and the copolymer alone has a substantially short axis diameter of 0.3. A resin molded product characterized by being dispersed at a particle size of not more than μm.