JPH09302167A - Production of resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition improved in the miscibility of a mixture comprising a polypropylene resin and a polyphenylene ether resin and remarkably improved in thermal creep resistance. SOLUTION: This method for producing a resin composition comprising (a) 55-10wt.% of a polyphenylene ether resin, (c) 45-90wt.% of a polypropylene resin, and (b) a hydrogenated block copolymer produced by hydrogenating a block copolymer comprising a copolymer block A consisting mainly of at least a vinyl aromatic compound and a copolymer B consisting mainly of a conjugated diene compound and having 1,2-vinyl bonds or 3,4-vinyl bonds in an amount of 56-80% based on the total amount of the double bonds in an amount of 5-30 pts.wt. per 100 pts.wt. of the total amount of the components (a) and (c) comprises adding the component (c) to the melt-kneaded mixture of the components (a) and (b) and further melt-kneading the mixture.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is excellent in oil resistance, chemical resistance, heat resistance, impact resistance and rigidity, and can be used in the fields of electric and electronic fields, automobile fields and various other industrial material fields. The present invention relates to a method for producing a resin composition having excellent durability (heat resistant creep).

[0002]

2. Description of the Related Art Polyphenylene ether has a mechanical property, an electrical property, a heat resistance, a low temperature property, a low water absorption property and excellent dimensional stability, but has a drawback that it is inferior in moldability and impact resistance. By blending with high-impact polystyrene, these problems are improved, and it is widely used as a resin composition for electric / electronic parts, office equipment housings, automobile parts, precision parts, various industrial parts, etc. However, the classical polyphenylene ether resin composition (US Pat. No. 3,383,435) consisting of this polyphenylene ether and high-impact polystyrene has the drawback of being poor in chemical resistance, although the impact resistance is improved. .

For this reason, for example, US Pat.
In the specification of Japanese Laid-Open Patent Publication No. 51, it has been proposed to blend polyphenylene ether with polyolefin to improve solvent resistance and impact resistance, and US Pat. No. 3,994,485.
No. 6 describes improvement in impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer, and US Pat. No. 4,145,377.
In the specification, a polyphenylene ether or a polyphenylene ether and a styrene resin are used as a polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 2
There is a description on improvement of impact resistance and solvent resistance by blending with 0 parts by weight of a premixture and a hydrogenated block copolymer.

Further, US Pat. No. 4,166,055 and US Pat. No. 4,239,673 describe improving impact resistance by blending polyphenylene ether with hydrogenated block copolymers and polyolefins. U.S. Pat. No. 4,383,082 and EP-A-115712 describe that polyphenylene ether is blended with a polyolefin and a hydrogenated block copolymer to improve impact resistance.

Further, Japanese Patent Laid-Open No. 63-113058,
JP-A-63-225642, US Pat. No. 4,863.
No. 997, JP-A-3-72512, JP-A-4-183748 and JP-A-5-320471 disclose specific hydrogenation for modifying a resin composition comprising a polyolefin resin and a polyphenylene ether resin. There has been proposed a resin composition containing a block copolymer and having excellent chemical resistance and processability.

[0006] The applicant of the present invention is also disclosed in JP-A-62-2055.
1, JP-A-62-25149, JP-A-62-62
-48757, JP-A-62-48758,
JP-A-62-199637 and US Pat. No. 47.
No. 72657 proposes a rubber composition comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer and having excellent rubber elasticity.
5563, Japanese Unexamined Patent Publication No. 3-185058, Japanese Unexamined Patent Publication No. 5-70679, Japanese Unexamined Patent Publication No. 5-295184, Japanese Unexamined Patent Publication No. 6-9828, Japanese Unexamined Patent Publication No. 6-16924.
JP-A-6-57130 and JP-A-6-57130.
JP-A-136202 proposes a resin composition comprising polyphenylene ether, a polyolefin and a specific hydrogenated block copolymer, which is excellent in compatibility, rigidity and heat resistance, and excellent in solvent resistance.

Further, in JP-A-4-28739 and JP-A-4-28740, mechanical properties, particularly impact strength and rigidity, of polyphenylene ether, polyolefin and hydrogenated block copolymer or rubber-like polymer are disclosed. A method for producing a resin composition having excellent balance has been proposed. Further, JP-A No. 7-166026 proposes a method for producing a resin composition having a good compatibility between a polyphenylene ether resin and a polyolefin resin and having excellent mechanical properties, particularly impact resistance.

[0008]

SUMMARY OF THE INVENTION These prior arts are
Compared with the classical polyphenylene ether resin composition, it provides a resin composition having dramatically improved solvent resistance and an elastomer composition having excellent heat resistance. Also,
Such advancement of the conventional technology certainly brings about a remarkable improvement in terms of compatibility (presence or absence of delamination of the composition when both components are mixed) in mixing the polyolefin resin and the polyphenylene ether. However, it has been revealed that they do not always have sufficient miscibility when used in complicated molding processes accompanying recent advances in molding technology.

That is, in the resin composition obtained by the above-mentioned prior art, an effective admixture has not yet been selected as an admixture, and further, these components (polyolefin resin, polyphenylene) are used. At present, no method for producing a polymer alloy having a good dispersion form with an ether resin and an admixture) has been proposed.

[0010]

In view of the above situation, the present inventors have made a composition containing polypropylene and polyphenylene ether have a high level of miscibility, and have a heat resistance durability (heat creep). As a result of intensive studies on a hydrogenated block copolymer which can be an admixture and a polypropylene resin which can be a matrix material, a hydrogenated block copolymer having a specific structure is found to be a polypropylene resin and a polyphenylene ether resin. The present invention has been completed by finding that a resin composition having an improved miscibility of polypropylene-based resin and polyphenylene ether-based resin and heat-resistant creep, and having excellent durability as a heat-resistant material can be obtained by melt-kneading the above-mentioned resin by a specific method.

That is, according to the present invention, (a) polyphenylene ether resin 55 to 10% by weight, (c) polypropylene resin 45 to 90% by weight, and the above (a),
At least one conjugated diene compound in which the amount of 1,2-vinyl bonds or 3,4-vinyl bonds of the conjugated diene compound as the component (b) is 56 to 80% with respect to a total of 100 parts by weight of the component (c). Polymer block B mainly composed of
To produce a resin composition containing 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a polymer block A containing at least one vinyl aromatic compound as a main component. In the method, (a) component and (b)
The present invention provides a method for producing a resin composition, which comprises adding the component (c) to a composition in a melt-kneaded state and further melt-kneading the composition.

The polyphenylene ether (hereinafter abbreviated as PPE) used as the component (a) in the present invention is an essential component for imparting heat resistance and flame retardancy to the resin composition of the present invention. The PPE is a bonding unit represented by the following general formula

[0013]

Embedded image (Where R ₁ , R ₂ , R ₃ , and R ₄ are respectively
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 at least two carbon atoms are a halogen atom and an oxygen atom. Selected from the group consisting of halohydrocarbonoxy groups, which may be the same or different from each other, and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.), It is a homopolymer and / or copolymer in the range of 0.15 to 0.70, and more preferably in the range of 0.20 to 0.60.

Specific examples of this PPE 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-trimethyl). Also included are polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol). Especially poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-diphenylphenol)
6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing PPE is not particularly limited as long as it can be obtained by a known method. For example, the complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. It can be easily prepared by oxidative polymerization of 2,6-xylenol, for example.
No. 875, No. 3257357 and No. 32573.
No. 58, and Japanese Patent Publication No. 52-18880.
JP-A-50-51197 and JP-A-63-1526
It can be easily produced by the method described in each publication of No. 28, etc.

The PPE used in the present invention contains, in addition to the above-mentioned PPE, the PPE and a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof in the absence of a radical generator. A known modification (the styrene-based monomer and / or the α, β-unsaturated carboxylic acid or its derivative is obtained by reacting in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C.). (01 to 10 wt% graft or addition) PPE, or a mixture of the above PPE and the modified PPE in any proportion.

The PPE used in the present invention is the above-mentioned PPE.
In addition to PE, polystyrene (including syndiotactic polystyrene) or high-impact polystyrene added to 100 parts by weight of PPE in an amount not exceeding 400 parts by weight can also be suitably used.

The polypropylene resin used as the component (c) in the present invention is a crystalline propylene homopolymer, a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene in the second and subsequent steps of polymerization. Crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer moiety obtained by copolymerizing ethylene and / or at least one other α-olefin (eg, butene-1, hexene-1 etc.) Further, it may be a mixture of these crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

The polypropylene resin is usually used in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound at a polymerization temperature of 0 to 100 ° C. It is obtained by polymerizing in the range of 3 to 100 atm. On this occasion,
It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer, and the polymerization method can be a batch method or a continuous method, butane, pentane, hexane, heptane, octane, etc. A method such as solution polymerization in a solvent, slurry polymerization or the like can also be selected, and further, a bulk polymerization in a monomer without a solvent, a gas phase polymerization method in a gaseous monomer or the like can be applied.

In addition to the above-mentioned polymerization catalyst, an electron donating compound can be used as an internal donor component or an external donor component as the third component in order to increase the isotacticity and the polymerization activity of the polypropylene obtained. As these electron donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl toluate; and triphenyl phosphite and tributyl phosphite. Phosphoric acid derivatives such as phosphoric acid esters and hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols And / or various phenols.

The polypropylene resin used in the present invention may have any crystallinity or melting point, and may be used alone or in combination as long as it is obtained by the above-mentioned method. Also, the melt flow rate (MFR) of this polypropylene resin (230 ° C, load 2.16 kg)
Is 0.01 to 300 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes, more preferably 0.3 to 5
It is in the range of 0 g / 10 minutes. Also, MF in these ranges
R can be used alone or in combination.

Next, the hydrogenated product of a block copolymer of a vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) used as the component (b) in the present invention is a conjugated diene compound. A polymer block B mainly composed of at least one conjugated diene compound having a 1,2-vinyl bond content or a 3,4-vinyl bond content of 56 to 80% and at least one polymer block B mainly composed of a vinyl aromatic compound. 50% of block copolymer consisting of united block A
It is a hydrogenated block copolymer obtained by hydrogenation as described above, for example, AB, ABA, BABAA, (AB
-) A hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as _4- Si and ABABABA.

The hydrogenated block copolymer as the component (b) contains 20 to 95% by weight, preferably 3% by weight, of the vinyl aromatic compound bonded with the block copolymer before hydrogenation.
0 to 80% by weight, more preferably 40 to 70% by weight. Further, referring to a block structure, a polymer block mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound containing a conjugated diene compound in an amount of more than 50% by weight, preferably 70% by weight or more. A polymer block A having a structure of a copolymer block with a vinyl aromatic compound and further containing a vinyl aromatic compound as a main component is a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound. It has a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound in an amount of more than 50% by weight, preferably 70% by weight or more.

The polymer block B mainly composed of these conjugated diene compounds and the polymer block A mainly composed of vinyl aromatic compounds are the vinyl aromatic compound or the conjugated diene in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped or any combination thereof, and the polymer having the conjugated diene compound as a main component Block B
When there are two or more polymer blocks A each containing the vinyl aromatic compound as a main component, the respective polymer blocks may have the same structure or different structures.

Examples of the conjugated diene compound constituting this block copolymer include butadiene, isoprene,
One or more kinds are selected from 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and butadiene, isoprene and a combination thereof are particularly preferable. In the polymer block mainly composed of the conjugated diene compound, the microstructure (bonding form of the conjugated diene compound) in the block can be arbitrarily selected. For example, in the polymer block mainly composed of butadiene, 1,2-vinyl is used. The bond is 56-80%. Further, in the polymer block mainly containing isoprene, 3,4
-Vinyl bonds of 56-80%. The bonding form of these conjugated diene compounds can usually be known by an infrared spectrophotometer, NMR, or the like.

Examples of vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene,
One or more of p-tert-butylstyrene and diphenylethylene can be selected, and styrene is preferable.

The number average molecular weight of the block copolymer having the above structure is in the range of 5,000 to 1,000,000, preferably 10,000 to 800,000, and more preferably 30,000 to 500,000. And the molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the above block copolymer. It can be used as the component (b) of the present invention as (a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer). The hydrogenation rate of such aliphatic double bonds is 50% or more, preferably 80% or more, more preferably 90% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR, or the like.

The hydrogenated block copolymer of the component (b) may be obtained by any production method as long as it has the above-mentioned structure. Examples of known manufacturing methods include, for example, JP-A-47-11486.
JP-A-49-66743, JP-A-50-
75651, JP-A-54-126255,
JP-A-56-10542, JP-A-56-6284
No. 7, JP-A-56-100840, British Patent No. 1130770, and US Pat. No. 3,281,383.
No. 3,369,517 and the methods described in the respective specifications, British Patent No. 1020720, and US Patent No. 3333.
No. 024 and No. 4501857, there are methods described in the respective specifications.

In the hydrogenated block copolymer used in the present invention, when the 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound is less than 56%, the polyphenylene ether resin is contained in the polypropylene resin. Is not preferable because it is difficult to emulsify and disperse. On the other hand, even if the 1,2-vinyl bond or the 3,4-vinyl bond of the conjugated diene compound exceeds 80%, a remarkable effect of improving the emulsified dispersion is not observed.

The manufacturing method of the present invention comprises the above-mentioned (a),
The components (b) and (c) are subjected to the following method. That is, it is a method in which the component (c) is additionally added to the melt-kneaded state of the component (a) and the component (b) and melt-kneaded together, which can be produced using various kneading extruders. Examples of the melt-kneader for performing these methods include a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender plastograph, and a hot-melt kneader such as a Banbury mixer. Among them, a melt kneading method using a twin screw extruder is most preferable. Specifically, WERNER &
ZSK series manufactured by PFLEIDERER, TEM series manufactured by Toshiba Machine Co., Ltd., TE manufactured by Japan Steel Works, Ltd.
Examples include the X series.

A preferred embodiment of the present invention using an extruder will be described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 or more and 60 or less, preferably 30 or less.
The range is not less than 50 and not more than 50. The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent downstream thereof, a second raw material supply port downstream thereof, and a second vacuum vent downstream thereof. Is preferred. Above all, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and a kneading section is provided between the second raw material supply port and the second vacuum vent. It is more preferable to provide a ding section.

The method of feeding the raw material to the second supply port is not particularly limited, but a forced side feeder is used from the extruder side opening port rather than the mere addition supply from the extruder second supply port opening port. Is more stable and preferable. In particular, when powders, fillers, etc. are contained, the forced side feeder supplied from the extruder side is more preferable, and the upper opening of the extruder second supply port should be opened to remove the air to be carried. You can also The melt-kneading temperature and the screw rotation speed at this time are not particularly limited, but can be arbitrarily selected from the melt-kneading temperature of 200 to 370 ° C. and the screw rotation speed of 100 to 1200 rpm.

In the present invention, 5 to 30 parts by weight of the component (b) is added to 100 parts by weight of the total of the components (a) and (c). The components (a) and (b) are supplied from the first raw material supply port for melt kneading, and the component (c) is supplied from the second raw material supply port to melt-knead the composition of components (a) and (b). In addition to the above, by further performing melt kneading, the component (a) forms a dispersed phase in the polypropylene resin matrix, and the average particle diameter of the dispersed phase is finely dispersed to 1.5 μm or less.

To know the dispersion form of the component (a),
The surface of the pellets obtained in the present invention in the direction parallel to the cut surface was dyed by a ruthenium acid dyeing method, and an ultra-thin section was made by an ultramicrotome (Ultracut E manufactured by Reichert), which was then subjected to a transmission electron microscope (made by JEOL). 1200E
X) makes it easy to observe. Specifically, based on the transmission electron micrograph obtained, an image analyzer (I Asahi Kasei Corp.
(P1000) to obtain the equivalent circle diameter from the perimeter of the dispersed phase and average the diameter to obtain the dispersed particle diameter.
This fine dispersion improves the miscibility of the resulting resin composition, improves the delamination of the resin composition, and significantly improves the heat resistance durability (heat resistant creep).

In the manufacturing method of the present invention,
The component (b) is supplied from the second supply port together with the component (c), or a part of the component (b) is first supplied together with the component (a).
The resin composition obtained by a method of supplying the remaining component (b) together with the component (c) from the second raw material supply port from the raw material supply port is a polypropylene resin in which the component (a) is the component (c). It is not preferable because it is not finely dispersed in the composition, the miscibility is poor, the layer peeling is exhibited, and the heat resistance durability (heat resistant creep) is poor. Also, one of the methods different from the method of the present invention,
Similarly, a resin composition obtained by a method of collectively supplying the respective components (a), (b), and (c) from the first raw material supply port,
It is inferior in miscibility and heat resistance durability (heat creep), which is not preferable.

In the present invention, the resin composition of the present invention is produced by the above-mentioned method using the above-mentioned components, but if necessary, other additional components such as, for example, other components such as the features and effects of the present invention can be obtained. , Antioxidants, metal deactivators, flame retardants (organic phosphate ester compounds, ammonium polyphosphate compounds, aromatic halogen flame retardants, silicone flame retardants, etc.), fluoropolymers, plasticizers (low molecular weight) Polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather (light) resistance improver, nucleating agent for polyolefin,
Slip agents, inorganic or organic fillers and reinforcing materials (glass fiber, carbon fiber, polyacrylonitrile fiber, whiskers, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fibers , Conductive carbon black, etc.), various coloring agents, release agents, etc. may be added.

The resin composition of the present invention obtained by such a production method can be molded into various molded articles by various conventionally known methods such as injection molding, extrusion molding, extrusion profile molding, and blow molding. As these various parts,
For example, there are automobile parts, specifically, bumpers,
Fender, door panel, various malls, emblems,
It is suitable for exterior parts such as engine hoods, wheel caps, roofs, spoilers, and various aero parts, and interior parts such as instrument panels, console boxes, and trims. Further, it can be suitably used as an interior / exterior component of electric equipment, and is specifically suitable for various computer and its peripheral equipment, other office automation equipment, cabinets such as televisions, videos, various disc players, and parts such as refrigerators. There is.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Reference Example 1 Preparation of PPE as component (a) a-1: Polyphenylene ether having reduced viscosity of 0.43 obtained by oxidative polymerization of 2,6-xylenol Reference example 2 Preparation of polypropylene as component (c) c-1: Homo-polypropylene Melting point = 169 ° C., MFR = 0.3 g / 10 minutes Polypropylene MFR (melt flow rate) is AS
According to TM D1238, it was measured at 230 ° C. and a load of 2.16 Kg.

Reference Example 3 Preparation of hydrogenated block copolymer of component (b) b-1: polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 42%,
The number average molecular weight is 88,000, the molecular weight distribution is 1.05, and the 1,2-vinyl bond amount of the polybutadiene before hydrogenation is 74.
%, The hydrogenation rate of the polybutadiene part is 99.9%, and a selective hydrogenated block copolymer was synthesized.
1).

B-2: polystyrene-hydrogenated polybutadiene-polystyrene structure, 52% bound styrene, number average molecular weight 85.000, molecular weight distribution 1.04, polybutadiene 1,2 before hydrogenation -The vinyl bond content is 58%, and the hydrogenation rate of the polybutadiene part is 9
A selective hydrogenated block copolymer of 9.9% was synthesized, and this polymer was designated as (b-2).

B-3: Polystyrene-having a structure of hydrogenated polybutadiene-polystyrene, bound styrene content 60%, number average molecular weight 106,000, molecular weight distribution 1.15, polybutadiene 1,2 before hydrogenation -65% vinyl bond and 9 hydrogenated polybutadiene
A 9.9% selectively hydrogenated block copolymer was synthesized, and this polymer was designated as (b-3).

B-4: polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 47%, number average molecular weight 86,000, molecular weight distribution 1.05, polybutadiene 1,2 before hydrogenation -The vinyl bond content is 39% and the hydrogenation rate of the polybutadiene part is 9
A selective hydrogenated block copolymer of 9.9% was synthesized, and this polymer was designated as (b-4).

B-5: polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 60%, number average molecular weight 103,000, molecular weight distribution 1.10, polybutadiene 1,2 before hydrogenation -The amount of vinyl bond is 53%, the hydrogenation rate of polybutadiene is 9
A 9.9% selectively hydrogenated block copolymer was synthesized, and this polymer was designated as (b-5).

[0045]

【Example】

Examples 1 to 4 and Comparative Examples 1 to 6 Polypropylene, polyphenylene ether, and admixture were blended in the composition shown in Table 1, and a first raw material feed port was provided upstream and a second raw material feed port was provided downstream with respect to the resin flow direction. A twin-screw extruder ZSK-40 which has a vacuum vent port upstream of the second feed port and between the second feed port and the die.
(Werner & Pfleiderer Co., Ltd.) was melt-kneaded under the conditions of an extrusion temperature of 290 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 60 kg / hour to obtain pellets.

The pellets were supplied to a screw in-line type injection molding machine set at 240 to 280 ° C.,
Under a condition of a mold temperature of 60 ° C., a test piece for flexural modulus measurement test, a test piece for Izod impact test and a test piece for heat distortion temperature measurement were injection-molded. Next, using these test pieces, the flexural modulus (ASTMD-
790 (measured at 23 ° C.), Izod (notched) impact strength (measured at 23 ° C. according to ASTM D-256), and heat distortion temperature (according to ASTM D-648) at 18.6 kg / cm ² load. Measurement) was performed.

Further, in order to confirm the effect of miscibility, the cross section of the pellet was examined with a transmission electron microscope (120 manufactured by JEOL Ltd.).
0EX) and an image analyzer were used to measure the average particle diameter of the component (a) dispersed in the resin composition. Further, in order to confirm the heat resistance durability (heat resistance creep) of the composition obtained by the production method of the present invention, a rod shape of 1 mm x 1 mm x 30 mm was used using Rheovibron (DDV-01 / 25FP type manufactured by Orientec Co., Ltd.). Sample, stress 1
Under conditions of a load equivalent to 30 kg / cm2f and a temperature of 65 ° C,
A heat-resistant creep test was performed, and the time to break was measured. The results are shown in Table 1.

As is clear from Table 1, the components (a) and (b) were supplied from the first supply port, and the component (c) was added to the composition in the melt-kneaded state from the second supply port. By further performing melt kneading, the polyphenylene ether resin forms a dispersed phase of 1.5 μm or less in the propylene resin matrix as compared with the comparative example.
The miscibility is improved and the heat resistance durability (heat creep) is remarkably improved. On the other hand, the component (b) other than the present invention is used, or the component (b) of the present invention is added by a method other than the present invention,
The resin composition obtained by melt-kneading is extremely inferior in heat resistance durability (heat resistance creep).

[0049]

[Table 1]

[0050]

Industrial Applicability The method for producing the resin composition of the present invention, that is, the component (a) polyphenylene ether resin, the component (b) 1,2-vinyl bond or 3,4-vinyl bond is 56 to 56%.
In producing a resin composition containing 80% hydrogenated block copolymer and component (c) polypropylene resin, the components (a) and (b) are fed from the first supply port of the extruder to melt them. At the pellet stage of the resin composition obtained by feeding the component (c) from the second supply port to the composition in a mixed state and further performing melt kneading,
Since the polyphenylene ether resin is dispersed at 1.5 μm or less, the heat-resistant creep performance of the obtained composition is remarkably improved.

Claims (1)

[Claims] 1. (a) Polyphenylene ether resin 5
5-10 wt% and (c) polypropylene resin 45-9
0% by weight and a total of 100 of the above components (a) and (c)
A polymer mainly composed of at least one conjugated diene compound having a 1,2-vinyl bond content or a 3,4-vinyl bond content of the conjugated diene compound of 56-80% as the component (b) with respect to parts by weight. A resin composition containing 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a block B and at least one polymer block A mainly composed of a vinyl aromatic compound. In the method for producing, a melt-kneaded product of the components (a) and (b) is added,
A method for producing a resin composition, which comprises adding the component (c) and further melt-kneading.