JPH1171466A - Method for producing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a resin composition excellent in heat creep resistance using an isoprene-based hydrogenated block copolymer as an admixture, a matrix of a polypropylene-based resin and a dispersed phase of a polyphenylene ether-based resin. Providing a way. A resin composition comprising at least two polystyrene blocks A and an isoprene-based hydrogenated block copolymer having isoprene-based blocks B having a total vinyl bond content of 40 to 80%, a polypropylene-based resin, and a polyphenylene ether-based resin. When the product is manufactured using a twin-screw extruder, for example, the barrel set temperature 310
℃, is supplied at the subsequent barrel set temperature 270 ℃,
The processing is performed with L1 / D1 = 5 and L2 / D1 = 4.5. Where L
1 and L2 are the effective lengths of the front and rear kneading sections, respectively, and D1 is the screw outer diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to the fields of electricity and electronics,
The present invention relates to a method for producing a resin composition having excellent oil resistance, chemical resistance, heat resistance, impact resistance, vibration damping properties, and rigidity that can be used in the automotive field and various other industrial materials fields, and furthermore, as a heat-resistant material. The present invention relates to a method for producing a resin composition having excellent heat resistance (heat creep).

[0002]

2. Description of the Related Art Polyphenylene ether has low mechanical properties, electrical properties, heat resistance, low temperature properties, low water absorption and excellent dimensional stability, but has the drawback of poor moldability and impact resistance. These problems are improved by blending with high impact polystyrene, and are widely used, for example, as resin compositions for electric / electronic parts, office equipment housings, automobile parts, precision parts, various industrial parts, and the like.

[0003] However, a classic polyphenylene ether resin composition comprising this polyphenylene ether and high-impact polystyrene (US Patent No. 33834).
No. 35) has the disadvantage that, although the impact resistance is improved, the chemical resistance is poor.
For this reason, for example, in U.S. Pat. No. 3,361,851, a proposal is made to improve solvent resistance and impact resistance by blending polyphenylene ether with a polyolefin. U.S. Pat. No. 3,994,856 describes,
There is a description of improving impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and a styrene resin with a hydrogenated block copolymer. US Pat. No. 4,145,377 discloses polyphenylene ether or polyphenylene ether. Impact resistance and solvent resistance by blending a styrene resin with a pre-mixture of polyolefin / hydrogenated block copolymer = 20-80 parts by weight / 80-20 parts by weight and hydrogenated block copolymer And U.S. Pat. Nos. 4,166,055 and 4,239,673 describe improvements in impact resistance by blending polyphenylene ethers with hydrogenated block copolymers and polyolefins. . U.S. Pat. No. 4,383,082 and EP-A-115,712 describe that polyphenylene ether is blended with a polyolefin and a hydrogenated block copolymer to improve impact resistance.

[0004] Also, Japanese Patent Application Laid-Open No. 63-113008,
JP-A-63-225642, U.S. Pat.
997, JP-A-3-72512, JP-A-4-183748, JP-A-5-320471
In Japanese Patent Application Laid-Open Publication No. H11-146, a resin composition comprising a specific hydrogenated block copolymer for modifying a resin composition comprising a polyolefin resin and a polyphenylene ether resin, and having excellent chemical resistance and processability is proposed.

[0005] The present applicant has disclosed in Japanese Patent Application Laid-Open No. H2-222556.
No. 3, JP-A-3-185058, JP-A-5-205
70679, JP-A-5-295184, JP-A-6-9828, JP-A-6-16924, JP-A-6-57130, JP-A-6-1362
In Japanese Patent Publication No. 02, a resin composition comprising polyphenylene ether, a polyolefin and a specific hydrogenated block copolymer, having excellent compatibility, rigidity and heat resistance, and having excellent solvent resistance was proposed.

Japanese Patent Application Laid-Open Nos. 4-28739 and 4-28740 disclose mechanical properties, particularly impact strength, comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer or rubbery polymer. A method for producing a resin composition having excellent rigidity balance has been proposed. Further, Japanese Patent Application Laid-Open No. Hei 7-16626 proposes a method for producing a resin composition having good compatibility between a polyphenylene ether-based resin and a polyolefin-based resin and having excellent mechanical properties, particularly impact resistance.

[0007] The hydrogenated block copolymer used in these prior arts functions as an admixture (emulsifier / dispersant) of a polyolefin resin and a polyphenylene ether resin which are originally immiscible. It is known that a resin composition in which these components are melt-kneaded at a high temperature of 250 ° C. or higher using a machine or the like, a polyolefin-based resin forms a matrix, and a polyphenylene ether-based resin forms a dispersed phase. I have.

In the hydrogenated block copolymer used as the admixture, it is known that the block copolymer before hydrogenation has a polystyrene-polybutadiene-polystyrene structure or a polystyrene-polyisoprene-polystyrene structure. Have been. However, a hydrogenated block copolymer obtained by hydrogenating a polyisoprene part of a block copolymer having a polystyrene-polyisoprene-polystyrene structure (isoprene-based hydrogenated block copolymer)
Is compared with a hydrogenated block copolymer (butadiene-based hydrogenated block copolymer) obtained by hydrogenating a polybutadiene portion of a block copolymer having a polystyrene-polybutadiene-polystyrene structure, and comparing the former with an isoprene-based hydrogenated block copolymer. The coalescence is inferior in heat resistance, and the fact is that when subjected to a heat history of 250 ° C. or more during processing, the molecular chains are severely cut.

And, due to this, polystyrene-
A resin composition comprising a polypropylene resin and a polyphenylene ether resin was produced using a twin-screw extruder using an isoprene-based hydrogenated block copolymer represented by hydrogenated polyisoprene-polystyrene as an admixture. In this case, the dispersed particles of the polyphenylene ether-based resin, which is the dispersed phase of the obtained resin composition, become extremely large, or a normally spherical (confirmed as a circle in an electron micrograph) collapses into an irregular shape, or In terms of physical properties, at present, impact strength is reduced and heat-resistant creep property is extremely reduced, making it unsuitable for practical use.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition having excellent heat creep resistance using a polypropylene resin as a matrix, a polyphenylene ether resin as a dispersed phase, and an isoprene-based hydrogenated block copolymer as an admixture. An object of the present invention is to provide a method for producing the same.

[0011]

Means for Solving the Problems In order to solve this problem, the present inventors have used an isoprene-based hydrogenated block copolymer as an admixture for a resin composition composed of a polypropylene-based resin and a polyphenylene ether-based resin. In the production method of heat-melt kneading using a twin-screw extruder, the microstructure (vinyl bonding amount) of the isoprene-based hydrogenated block copolymer to be provided, the screw part dimensions of the twin-screw extruder,
As a result of intensive studies on the extrusion temperature, the supply method of each component, and the dispersion state of the dispersed particles of the obtained resin composition and the heat creep resistance, an isoprene-based hydrogenated block copolymer having a specific vinyl bond amount was obtained. By melt-kneading a polypropylene resin and a polyphenylene ether resin by a specific method using a twin screw extruder, the polyphenylene ether resin is dispersed well in the polypropylene resin, and the resin composition has excellent heat creep. The present inventors have found that a product can be obtained, and have accomplished the present invention.

That is, the present invention is as follows. 1) 55 to 5% by weight of (a) polyphenylene ether-based resin, 45 to 95% by weight of (b) polypropylene-based resin, and (c) based on 100 parts by weight of the above components (a) and (b) in total. At least two polystyrene blocks A
And a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising at least one polymer block B mainly composed of isoprene having a total vinyl bond content of 40 to 80% by weight, 5 to 30 parts by weight , Using a twin-screw extruder, wherein the method satisfies the following conditions:

The component (a) or a part of the components (a) and (b) is supplied from the first supply port of the twin-screw extruder, and the barrel setting temperature in the former stage is 230 ° C. to 340 ° C. The component (b) and the component (c) or the remaining components (b) and (c) are supplied from the second supply port of the twin-screw extruder, and the barrel setting temperature in the subsequent stage is 230 ° C to 310 ° C. .

[0014] When the barrel setting temperature of the former stage exceeds 280 ° C, the barrel setting temperature of the former stage ≧ the barrel setting temperature of the latter stage. A preceding kneading section having an effective length L1 is provided in the front of a twin-screw extruder having a screw outer diameter of D1, and
D1 = 2 to 15. The rear kneading section of the effective length L2 is provided at the rear of the twin screw extruder having the screw outer diameter of D1, and
D1 = 2 to 15.

2) Component (a) or a part of component (a) and component (b) are supplied from the first supply port of the twin-screw extruder, melt-kneaded in the former kneading section, and then decompressed under reduced pressure. A volatilization unit (3) is provided and degassed under reduced pressure with a vacuum pump.
Further, the component (b) and the component (c), or the remaining component (b)
After a part of the components and the component (c) are supplied from the second supply port and melt-kneaded in the subsequent kneading section, a decompression devolatilizing section (4) is provided if necessary, and decompression is performed again by the vacuum pump. 2. The method for producing a resin composition according to the above item 1, wherein the method is performed.

3) When the component supplied to the first supply port of the twin-screw extruder is a part of the component (a) and the component (b),
The quantity ratio relationship between the component (a) and the component (b) is (b) /
(A) The method for producing a resin composition according to the above item 1 or 2, wherein <1 is satisfied. (4) The component (1), (2) or (3), wherein the component (a) is obtained by blending a styrene resin such as polystyrene or high impact polystyrene in an amount not exceeding 400 parts by weight with respect to 100 parts by weight of polyphenylene ether. A method for producing the resin composition described above.

Hereinafter, the present invention will be described in detail. In the present invention,
The component (a), a polyphenylene ether-based resin (hereinafter simply abbreviated as PPE), is an essential component for imparting heat resistance and flame retardancy to the resin composition of the present invention. Has a binding unit, reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is in the range of 0.15 to 0.70, more preferably 0.2
A homopolymer and / or a copolymer in the range of 0 to 0.60.

[0018]

Embedded image

(Where R1, R2, R3 and R4 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 hydrogenoxy 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.) Specific examples of 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-phenyl)
Phenylene ether), poly (2,6-dichloro-1,
4-phenylene ether), and 2,6
-Dimethylphenol and other phenols (for example,
2,3,6-trimethylphenol or 2-methyl-6
Polybutylene ether copolymer such as a copolymer with butylphenol). Poly (2,6)
-Dimethyl-1,4-phenylene ether), 2,6-
A copolymer of dimethylphenol and 2,3,6-trimethylphenol is preferred, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferred.

The PPE is not particularly limited as long as it can be obtained by a known production method.
U.S. Pat. No. 3,308,874 describes a complex of a cuprous salt and an amine according to Hay as a catalyst,
For example, it can be easily produced by oxidative polymerization of 2,6-xylenol, and in addition, US Pat.
No. 75, No. 3257357 and No. 325735
No. 8, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628.

The PPE used in the present invention may be prepared by combining the above-mentioned PPE with a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof in the presence or absence of a radical generator. A known modification obtained by reacting in the presence of the styrene monomer and / or the α, β-unsaturated carboxylic acid or a derivative thereof in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. (0.01 to 10% by weight of grafted or added) PPE, or a mixture of the above-mentioned PPE and the modified PPE in any ratio.

The PPE used in the present invention is, in addition to the above-mentioned PPE, 400 parts by weight of polystyrene or high-impact polystyrene per 100 parts by weight of the PPE.
Those added within a range not exceeding part by weight can also be suitably used. Next, in the present invention, the polypropylene resin used as the component (b) is a crystalline propylene homopolymer, and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene in the second and subsequent steps of polymerization. Ethylene and / or at least one other α-olefin (eg butene-1, hexene-1)
And the like. A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing the same, and a mixture of the crystalline propylene homopolymer and the crystalline propylene-ethylene block copolymer. It may be.

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

Further, in addition to the above-mentioned polymerization catalyst, an electron-donating compound may be used as an internal donor component or an external donor component as a third component in order to increase the isotacticity and polymerization activity of the obtained polypropylene. it can. Known electron-donating compounds can be used, for example, ε-caprolactone,
Ester compounds such as methyl methacrylate, ethyl benzoate and methyl toluate; phosphites such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoric triamide; and alkoxy ester compounds , Aromatic monocarboxylic acid esters and / or aromatic alkylalkoxysilanes, aliphatic hydrocarbonalkoxysilanes, various ether compounds,
Examples include various alcohols and / or various phenols.

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

In the present invention, the hydrogenated block copolymer used as the component (c) comprises at least two polystyrene blocks A and at least one polystyrene block having a total vinyl bond content of 40 to 80%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of a polymer block B and, for example, ABA, B
-ABA, (AB-) _4- Si, ABAB
A hydrogenated block copolymer obtained by subjecting an aliphatic double bond based on block B of a block copolymer having a structure such as -A to a hydrogenation reaction. The hydrogenation rate of such an aliphatic double bond exceeds at least 60%, preferably 80% or more, more preferably 85% from the viewpoint of heat stability.
% Or more. The hydrogenation rate can be usually determined by iodine titration before and after the hydrogenation reaction, infrared spectrophotometer, NMR, and the like.

Here, the number average molecular weight of the polystyrene block A is at least 15,000, preferably at least 18,000, more preferably at least 19,000 from the viewpoint of the heat creep resistance of the obtained resin composition. The polymer block B mainly composed of polyisoprene refers to a polyisoprene obtained by homopolymerizing isoprene alone or 50% by weight or more, more preferably 65% by weight of isoprene.
Other conjugated diene compounds (such as butadiene, 1,3-pentadiene, and 2,3-dimethylbutadiene) which can be copolymerized with isoprene (random copolymerization or block copolymerization), and vinyl aromatic compounds (styrene, α
-Methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, etc.).

Specific polymer blocks B include polyisoprene, poly (isoprene / butadiene) copolymer, poly (isoprene-butadiene) block copolymer, poly (isoprene / styrene) random copolymer,
A poly (isoprene / butadiene / styrene) random copolymer may be used. Also, the total vinyl bond amount (1,1) based on the isoprene of the block B mainly composed of polyisoprene or the polymerization bond form of isoprene and butadiene.
Total amount of 2-vinyl bond amount and 3,4-vinyl bond amount)
Is 40 to 80%, preferably 48 to 70%, more preferably 48 to 60%. When the total vinyl bond amount is 40
%, The miscibility of the polyphenylene-based resin and the polypropylene-based resin is reduced even if a production method in which the molecular chain of the isoprene-based hydrogenated block copolymer is less likely to be cut as in the present invention. The dispersed particle size of the polyphenylene ether-based resin forming the dispersed phase of the product tends to increase, and the heat creep resistance tends to decrease. Further, even when the total vinyl bond amount exceeds 80%, there is no significant change in the dispersed particle diameter of the polyphenylene resin in the dispersed phase, and the improvement in heat creep resistance and impact strength is not remarkable. Incidentally, the amount of these vinyl bonds is usually determined by an infrared spectrophotometer or an NMR spectrometer.
And so on.

The hydrogenated block copolymer having the above-mentioned structure has a bound styrene content of 15 to 80% by weight, preferably 30 to 60% by weight. From the viewpoint of the rigidity and heat resistance of the obtained resin composition, Preferably it is 40 to 60% by weight. As the hydrogenated block copolymer of the component (c) used in the present invention, not only one kind but also two or more kinds can be used in combination as long as it has the above-mentioned structure.

The above-mentioned hydrogenated block copolymer of the component (c) may be obtained by any production method as long as it has the above-mentioned structure.
Examples of known production methods include, for example, JP-A-47-1
1486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255.
JP-A-56-10542, JP-A-56-10542
No. 62847, JP-A-56-100840,
JP-A-2-300218, British Patent No. 11307
No. 70, and U.S. Pat. Nos. 3,281,383 and 3,639,517; and British Patent No. 1,020,720 and U.S. Pat.
No. 33024 and No. 4,501,857.

The method for producing the resin composition of the present invention is carried out by the following method using the above-mentioned components (a), (b) and (c). That is, the component (a) or a part of the component (a) and the component (b) is supplied to a first supply port of a twin-screw extruder,
While melt-kneaded in a specific kneading section, the component (b) and the component (c) or the remaining components (b) and (c) are additionally supplied from the second supply port, and the specific knee is further added. This is a method of melting and kneading in the loading section. The twin screw extruder used here is specifically WE
Examples include ZSK series manufactured by RNER & PFLEIDERER, TEM series manufactured by Toshiba Machine Co., Ltd., and TEX series manufactured by Japan Steel Works, Ltd.

The twin-screw extruder used in the production method of the present invention comprises:
L / D (barrel effective length / barrel inner diameter) of twin screw extruder is 2
It is in the range of 0 to 60, preferably 30 to 50.
The range is as follows. FIG. 1 shows an example of a twin-screw extruder. In FIG. 1, the outer diameter of the screw is D1, and a first supply port (1) is located upstream with respect to the flow direction of the raw material, and a first vacuum vent port (3), which is a vacuum devolatilizing section, is located downstream of this. A second supply port (2) is provided downstream, and a second vacuum vent port (4), which is a decompression devolatilizing section, is provided further downstream thereof, and an upstream kneading section (4) is provided upstream of the first vacuum vent port (3). 6), and a kneading section (7) provided between the second supply port (2) and the second vacuum vent port (4).

Here, the preceding kneading section (6)
May exist continuously as one block between the first supply port (1) and the first vacuum vent port (3),
Alternatively, it may exist discontinuously as two or more blocks. However, the effective length (L1) of the preceding kneading section of the preceding kneading section (6) is L1 / L1.
D1 = 2 to 15, preferably 2 to 10. Similarly, in the rear kneading section (7), the effective length (L2) of the rear kneading section is L2 / D1 = 2 to 15, preferably 2 to 1.
0 must be satisfied.

The L1 / D1 and / or L2 /
When the ratio of D1 is less than 2, the dispersed particle system of the (a) component polyphenylene ether-based resin dispersed in the obtained resin composition becomes extremely large, or the (c) component isoprene-based hydrogenated block copolymer is dispersed. The union is dispersed alone in the matrix of the polypropylene resin of the component (b), and the heat creep resistance of the resulting resin composition is extremely deteriorated, which is not preferable. In addition, L1 / D1 and / or L2 /
When the ratio of D1 exceeds 15, the molecular chain scission of the isoprene-based hydrogenated block copolymer of the component (c) remarkably progresses, and the component (c) is contained in the obtained matrix of the polypropylene-based resin of the component (b). The ratio of the isoprene-based hydrogenated block copolymer alone dispersed extremely increases, and the dispersed particle system of the (a) component polyphenylene ether-based resin also becomes extremely large or deformed. The heat creep resistance is extremely deteriorated, which is not preferable.

The front kneading section and the rear kneading section each have a screw kneading disk as shown in FIG. 2, for example, and the blade width (L3) and the screw outer diameter (D
The relationship of 1), that is, L3 / D1 is 0.05 to 2.0, a kneading disk having a twist angle of 10 to 75 degrees, a kneading disk having a twist angle of 80 to 110 degrees, and a twisting angle of 120. One or more sets of kneading discs of up to 160 degrees are incorporated, and the screw flight portion is further combined with a mixing screw or a reverse flight screw cut at 5 to 15 places in one lead, and the twist angle of the kneading disc is set. Is 8
0 to 110 degrees, a twist angle of 120 to 160 degrees, or a combination of one or more sets of reverse flight screws and varistoring. As described above, the former kneading section and the latter kneading section may be divided into several places instead of only one place, but they must satisfy the above-mentioned ratio of L1 / D1 and L2 / D1.

Further, a method for supplying raw materials to the second supply port is as follows.
Although not particularly limited, it is more stable and preferable to supply the second supply port of the twin-screw extruder from the side opening port of the extruder by using a forced side feeder than to simply add and drop the supply port through the opening port. In particular, when powders, fillers and the like are supplied together, a forced side feeder supplied from the side of the extruder is more preferable, and the upper opening of the second supply port of the twin-screw extruder is opened to remove the accompanying air. Vent (5) is preferred, and the upper opening of the second supply port is more preferably provided on the upstream side than immediately above the second supply port in order to prevent the resin from venting and scattering of the raw material from the side feeder. preferable.

In the structure of the twin-screw extruder described above, the extruder barrel set temperature for melting and kneading the resin composition in the present invention is set in the range of 230 to 340 in the former zone from the first supply port to the second supply port. ° C, preferably 260-330
° C, and the downstream zone from the second supply port to the extruder outlet is at 230 to 310 ° C, preferably 260 to 310 ° C. In the former zone, the temperature is set to 23 to sufficiently knead the component (a) or a part of the components (a) and (b).
The temperature is preferably in the range of 0 to 340 ° C, and can be arbitrarily selected depending on the ratio of the component (a) to the component (b). In the latter zone, the temperature is preferably in the range of 230 to 310 ° C. because the isoprene-based hydrogenated block copolymer of the component (c) is present. When the first-stage barrel setting temperature exceeds 280 ° C., it is necessary that the first-stage barrel setting temperature ≧ the second-stage barrel setting temperature.

Here, when the isoprene-based hydrogenated block copolymer of the component (c) is supplied from the first supply port of the twin-screw extruder together with the polyphenylene ether-based resin of the component (a), the heat history time due to high heat becomes longer. As a result, the dispersed particle system of the polyphenylene ether-based resin dispersed in the obtained resin composition becomes large or deformed, and the impact resistance and the heat creep resistance are reduced. In addition, when the isoprene-based hydrogenated block copolymer of the component (c) is supplied from the second supply port of the twin-screw extruder together with the polypropylene-based resin of the component (b), and the set temperature of the subsequent zone exceeds 310 ° C. The residence time of the component (c) isoprene-based hydrogenated block copolymer block in the twin-screw extruder is shortened, but because it is exposed to a high temperature, the dispersed particle system of the polyphenylene ether-based resin dispersed in the obtained resin composition is reduced. It becomes larger or deformed, and the impact resistance and heat creep resistance are reduced.

Next, the screw rotation speed of the twin-screw extruder is not particularly limited, but is 100 to 1200 rpm.
It can be arbitrarily selected from the range of m. A raw material supply device (hereinafter, abbreviated as a raw material feeder) for supplying a raw material to the twin-screw extruder is not particularly limited, but a single screw feeder, a twin screw feeder, a table feeder, a rotary feeder, or the like is used. it can. Above all, the loss-in-weight feeder is preferable because the fluctuation error of the raw material supply is small.

As described above, in the present invention, the component (a) or a part of the component (a) and the component (b) are melt-kneaded in the front part of the twin-screw extruder, and the components (b) and (c) Alternatively, it is preferable that the remaining components (b) and (c) are additionally added, and the mixture is further melt-kneaded in the latter part of the twin-screw extruder. That is, in the present invention, first, (a) from the first supply port of the twin-screw extruder.
55 to 5% by weight of the components are supplied and melting is performed in the former zone.
45 to 95% by weight of the component (b) from the second supply port;
For a total of 100 parts by weight of the components (a) and (b),
(C) 5 to 30 parts by weight of the component is supplied, and (a)
In addition to the components, a method in which melt kneading is continued in the subsequent zone, or 55 to 5% by weight of the component (a) and 1 to 30% by weight of the component (b) from the first supply port of the twin-screw extruder. ,
Preferably, 5 to 20% by weight, more preferably 5 to 15% by weight is supplied, and the composition in the melt-kneaded state in the former zone is supplied with the remaining 15 to 94% by weight, preferably the remaining component (b), from the second supply port. Is 25-90% by weight, more preferably 30%
By supplying 90 to 90% by weight and 5 to 30 parts by weight of the component (c) and continuously performing melt-kneading in the subsequent zone, the polyphenylene ether-based resin of the component (a) becomes a polypropylene-based resin matrix of the component (b). A dispersed phase is formed therein, and the dispersed phase is finely dispersed to an average particle size of 1.5 μm or less.

To know the dispersion form of the component (a),
A surface parallel to the cut surface of the pellet obtained by the method of the present invention is stained by a ruthenic acid staining method, and an ultra-thin section is prepared with an ultramicrotome (manufactured by Reichert; Ultracut E). JEOL Ltd.
Manufactured by the company; 1200EX). Specifically, based on the obtained transmission electron micrograph, an image analyzer (IP1000 manufactured by Asahi Kasei Kogyo Co., Ltd .; IP1000) is used to obtain and average the equivalent circle diameter from the peripheral length of the dispersed phase. And the dispersed particle size can be determined. By the fine dispersion, the resulting resin composition has improved miscibility, improved delamination, and significantly improved heat creep resistance.

On the other hand, in the production method of the present invention, (a)
The component (c) is supplied from the first supply port together with the component (a) or from the first supply port together with the component (a) and the total amount of the component (b). The resulting resin composition is such that the component (a) is not always finely dispersed in the polypropylene resin of the component (b), is poor in miscibility, develops delamination, or has poor heat creep resistance. Become.

Similarly, a resin composition obtained by a method different from the method of the present invention, for example, a method in which the components (a), (b) and (c) are supplied collectively from the first supply port, is also used. ,
It is inferior in miscibility and heat creep resistance. In the present invention, a resin composition is produced by the above-mentioned production method using the above-mentioned components (a) to (c). However, other additional components may be added as necessary within a range not to impair the features and effects of the present invention. component,
For example, antioxidants, metal deactivators, flame retardants (organic phosphate compounds, inorganic phosphorus compounds, aromatic halogen flame retardants, nitrogen compound flame retardants, silicone flame retardants, etc.), fluorine-based polymers , Plasticizers (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather (light) improver, nucleating agent for polyolefin, slip agent , Inorganic or organic fillers and reinforcements (glass fiber, carbon fiber, polyacrylonitrile fiber,
Whisker, mica, talc, carbon black, magnesium sulfate, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fiber, conductive carbon black, etc.), various coloring agents, release agents, etc. It doesn't matter.

The resin composition obtained by the method of the present invention can be prepared by various methods known in the art, for example,
It can be molded as a molded body of various parts by injection molding, extrusion molding, extrusion molding, or hollow molding. These various parts include, for example, automobile parts.Specifically, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for interior parts such as instrument panel, console box, trim etc. Furthermore, it can be suitably used as an interior / exterior part of electric equipment, and specifically, various computer and its peripheral equipment, other OA equipment, televisions, videos, various disk players, etc., parts for chassis, cabinets, refrigerators and the like. Also, it is suitable for secondary battery case material.

[0045]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The raw materials used are as follows. The reduced viscosity obtained by oxidative polymerization of PPE 2,6-xylenol of component (a) is 0.1.
43 polyphenylene ether.

Component (b) high crystalline polypropylene homo-polypropylene (melting point = 166 ° C., MFR = 0.
3) The MFR (melt flow rate) of polypropylene is A
230 ° C, 2.16Kg according to STM D1238
The load was measured. (C) Hydrogenated block copolymer of component (c1): having a structure of polystyrene-hydrogenated polyisoprene-polystyrene and having a bound styrene content of 60
%, Number average molecular weight 85,000, molecular weight distribution 1.05,
Total amount of vinyl bonds of polyisoprene before hydrogenation (1,2
-The total amount of vinyl bonds and 3,4-vinyl bonds) is 5
A hydrogenated block copolymer having a hydrogenation rate of 35.9% and a hydrogenation rate of 85.9% was synthesized.

(C2): Polystyrene-hydrogenated polyisoprene-polystyrene structure, bonded styrene content 48%, number average molecular weight 86,000, molecular weight distribution 1.05, total polyisoprene before hydrogenation A hydrogenated block copolymer having a vinyl bond amount (total amount of 1,2-vinyl bond and 3,4-vinyl bond) of 55% and a hydrogenation ratio of 84.8% was synthesized.

(C3): polystyrene-hydrogenated poly (isoprene / butadiene = 67 wt% / 33 wt
% Of random copolymer) -polystyrene,
Bound styrene content 48%, number average molecular weight 82,000, molecular weight distribution 1.04, total vinyl bond content of random copolymer of polybutadiene and polyisoprene before hydrogenation (1,
A hydrogenated block copolymer having a total amount of 2-vinyl bonds and 3,4-vinyl bonds) of 50% and a hydrogenation ratio of 84.3% was synthesized.

(C4): Polystyrene-hydrogenated polyisoprene-polystyrene structure, bonded styrene content 48%, number average molecular weight 91,000, molecular weight distribution 1.06, total polyisoprene before hydrogenation A hydrogenated block copolymer having a vinyl bond amount (total amount of 1,2-vinyl bonds and 3,4-vinyl bonds) of 44% and a hydrogenation rate of 89.7% was synthesized.

(C5): Polystyrene-hydrogenated polyisoprene-polystyrene structure, bonded styrene content 48%, number average molecular weight 85,000, molecular weight distribution 1.07, total polyisoprene before hydrogenation A hydrogenated block copolymer having a vinyl bond amount (total amount of 1,2-vinyl bonds and 3,4-vinyl bonds) of 37% and a hydrogenation rate of 87.3% was synthesized.

(C6): Septon S4 manufactured by Kuraray Co., Ltd.
055: Polystyrene-hydrogenated (isoprene / butadiene = 55 wt% / 45 wt% isoprene tapered block copolymer) -polystyrene structure, bound styrene content 28%, number average molecular weight 170,00
0, molecular weight distribution 1.44, hydrogenated hydrogenated hydrogen butadiene-isoprene tapered block copolymer having a total vinyl bond content (total amount of 1,2-vinyl bonds and 3,4-vinyl bonds) of 12% Block copolymer.

[0052]

Examples 1 to 11 and Comparative Examples 1 to 11 Table 1 shows polyphenylene ether as the component (a), polypropylene as the component (b), and an isoprene-based hydrogenated block copolymer as an admixture as the component (c). 2 having a first supply port upstream and a second supply port downstream with respect to the resin flow direction, and a vacuum vent upstream of the second supply port and between the second supply port and the die. Twin screw extruder ZSK-4 with mouth
0 (manufactured by WERNER & PFLEIDERER), the front barrel setting temperature is 290 to 345 ° C, the rear barrel setting temperature is 230 to 320 ° C, and the former kneading section effective length (L1) is L1 / D1 = 1.4 to 15.7.
(Where the screw outer diameter D1 is 40.0 mm), and the effective length (L2) of the rear kneading section is L
2 / D1 = 1.5 to 15.5 (here, screw outer diameter D1 is 40.0 mm), screw rotation number 295
The mixture was melt-kneaded under the conditions of rpm and a discharge rate of 60 kg / hour to obtain pellets.

In order to confirm the effect of the miscibility of the resin composition obtained under the above production conditions, the cross section of the pellet obtained above was
Transmission electron microscope (manufactured by JEOL Ltd .; 1200EX)
Observation and photography were performed using an image analysis device (Asahi Kasei Kogyo Co., Ltd .; IP1000) based on the photograph.
The average particle size of the component (a) polyphenylene ether-based resin dispersed in the resin composition was measured.

Further, in order to confirm the heat creep resistance of the resin composition obtained by the production method of the present invention, the pellets obtained under the above production conditions were hot-pressed at 260 ° C. and 1 mm × 1
mm × 30 mm rod-shaped sample, and prepared using Leo Vibron (manufactured by Orientec Co., Ltd .; DDV-01 / 25FP).
A), a load equivalent to a stress of 130 kg / cm ² f,
Under a condition of a temperature of 65 ° C., a heat-resistant creep test was performed, and a time until rupture was measured. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, the component (a) or a part of the component (a) and the component (b) are supplied from the first supply port, and the melt-kneaded composition contains By adding the component (b) and the component (c) or the remaining component (b) and the component (c) from the second supply port and further performing melt-kneading, the polyphenylene ether-based resin becomes It was found that a fine dispersed phase was formed, the miscibility was improved, and the heat creep resistance was excellent.

On the other hand, a component other than the present invention is used as the component (c), the component (c) used in the present invention is added by a method other than the method of the present invention, or the component (b) is supplied to the first supply. Supply to the mouth, the resin composition obtained by melt-kneading at a temperature setting of a twin-screw extruder other than the production method of the present invention, the polyphenylene ether-based resin of the dispersed particles is present in irregularly dispersed particles, or large. It became clear that the heat creep resistance was remarkably inferior because of the presence of dispersed particles.

As can be seen from these examples, it has been clarified that the morphology and physical properties of compositions using the same material are significantly different depending on the production method.

[0058]

Examples 12 to 14 and Comparative Examples 12 and 13 (a)
Polyphenylene ether and polystyrene (GP685: manufactured by Asahi Kasei Corporation) as components, polypropylene as component (b), and an isoprene-based hydrogenated block copolymer as an admixture as component (c) with the composition shown in Table 3. A twin-screw with a first supply port upstream of the resin flow direction and a second supply port downstream of the resin flow direction, and a vacuum vent port upstream of the second supply port and between the second supply port and the die Extruder Z
Using SK-40 (manufactured by WERNER & PFLEIDERER), the pre-stage barrel setting temperature is 230 to 270 ° C, the post-stage barrel setting temperature is 260 ° C, and the pre-stage kneading section effective length (L1) is L1 / D1 = 5.0 (here, screw The outer diameter D1 is 40.0 mm), the effective length (L2) of the subsequent kneading section is L2 / D1 = 4.5 (where the screw outer diameter D1 is 40.0 mm), the screw rotation speed is 295 rpm, and the discharge rate is 60 kg / L. It was melt-kneaded under the conditions of time to obtain pellets.

In order to confirm the effect of miscibility of the resin composition obtained under the above production conditions, the cross section of the pellet obtained above was
Transmission electron microscope (manufactured by JEOL Ltd .; 1200EX)
Observation and photography were performed using an image analysis device (Asahi Kasei Kogyo Co., Ltd .; IP1000) based on the photograph.
The average particle size of the polyphenylene ether-based resin (comprising polyphenylene ether and polystyrene) as the component (a) dispersed in the resin composition was measured.

Further, in order to confirm the heat creep resistance of the resin composition obtained by the production method of the present invention, the pellets obtained under the above production conditions were hot-pressed at 260 ° C. and 1 mm × 1 mm.
mm × 30 mm rod-shaped sample, and prepared using Leo Vibron (DDV-01 / 25FP manufactured by Orientec Co., Ltd.).
A), a load equivalent to a stress of 130 kg / cm ² f,
Under a condition of a temperature of 65 ° C., a heat-resistant creep test was performed, and a time until rupture was measured. The results are shown in Table 3.

As is clear from Table 3, the component (a) or (a) was supplied from the first supply port by the production method of the present invention.
The component and a part of the component (b) are supplied, and the component (b) and the component (c) or the remaining component (b) and the component (c) are supplied to the melt-kneaded composition at a second supply port. In addition, by further performing melt-kneading, in the polypropylene-based resin matrix, the polyphenylene ether-based resin forms a fine dispersed phase, the miscibility is improved, and a resin composition having excellent heat creep resistance is obtained. It became clear.

When the ratio of the components (a) and (b) supplied from the first supply port deviates from (b) / (a) <1, the dispersed particle diameter is apparently small but the heat-resistant creep is obtained. Performance was found to decrease.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

According to the production method of the present invention, the polyphenylene ether resin (a), the polypropylene resin (b), and the isoprene-based hydrogenated block copolymer (c) have a specific structure. By supplying from the specified supply port of the twin-screw extruder, setting the temperature of the twin-screw extruder to a specific temperature range, and further setting the screw configuration of the twin-screw extruder to specific conditions, the polypropylene-based resin is The polyphenylene ether-based resin is finely dispersed, and the heat-resistant creep performance of the obtained composition is remarkably improved.

[Brief description of the drawings]

FIG. 1 is a schematic view of a twin-screw extruder as an example of a production apparatus used in the present invention.

FIG. 2 is an example of a screw kneading disc of a twin-screw extruder used in a production apparatus according to the present invention;
(I) is a front view, and (II) is a side view.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1st supply port 2 2nd supply port 3 1st vacuum vent port (decompression devolatilization part) 4 2nd vacuum vent port (decompression devolatilization part) 5 open vent port 6 front kneading section 7 rear kneading section

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 71/12 23:10 53:02)

Claims (4)

[Claims] 1. (a) Polyphenylene ether resin 5
5 to 5% by weight, (b) polypropylene resin 45 to 95
(C) at least two polystyrene blocks A and isoprene having a total vinyl bond amount of 40 to 80% based on 100% by weight of the total of the components (a) and (b). At least one polymer block B
A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of 5 to 30 parts by weight, using a twin-screw extruder to produce a resin composition, comprising:
A method for producing a resin composition, characterized by satisfying the following. The component (a) or a part of the component (a) and the component (b) is supplied from the first supply port of the twin-screw extruder, and the barrel setting temperature in the former stage is 230 ° C to 340 ° C. The component (b) and the component (c) or the remaining components (b) and (c) are supplied from the second supply port of the twin-screw extruder, and the barrel setting temperature in the subsequent stage is 230 ° C to 310 ° C. . If the pre-stage barrel set temperature exceeds 280 ° C, the pre-stage barrel set temperature ≥ the post-stage barrel set temperature. A preceding kneading section having an effective length L1 is provided in the front of a twin-screw extruder having a screw outer diameter of D1, and
D1 = 2 to 15. The rear kneading section of the effective length L2 is provided at the rear of the twin screw extruder having the screw outer diameter of D1, and
D1 = 2 to 15. 2. A component (a) or a part of the components (a) and (b) is supplied from a first supply port of a twin-screw extruder, melt-kneaded in a former kneading section, and then decompressed. A volatilization unit (3) is provided and degassed under reduced pressure with a vacuum pump.
Further, the component (b) and the component (c), or the remaining component (b)
After a part of the components and the component (c) are supplied from the second supply port and melt-kneaded in the subsequent kneading section, a decompression devolatilizing section (4) is provided if necessary, and decompression is performed again by the vacuum pump. The method for producing a resin composition according to claim 1, wherein volatilization is performed. 3. When the component supplied to the first supply port of the twin-screw extruder is part of the component (a) and the component (b), (a)
The relationship between the quantity ratio of the component and part of the component (b) is (b) / (a)
3. The method for producing a resin composition according to claim 1, wherein <1. 4. The composition according to claim 1, wherein the component (a) comprises a styrene-based resin such as polystyrene or high-impact polystyrene in an amount not exceeding 400 parts by weight per 100 parts by weight of polyphenylene ether. 4. The method for producing a resin composition according to 2 or 3.