JPH06116491A - Resin composition for blow molding - Google Patents

Abstract

PURPOSE:To provide a polyamide resin composition for blow molding having a high melt viscosity, a high melt tension and a small swell ratio. CONSTITUTION:The composition comprises 100 pts.wt. total of 50-98wt.% polyamide resin (A) having a ratio R of the terminal amino concentration to the terminal carboxyl concentration in the range: 0.6<=R<=5.0, 0.01-50wt.% block copolymer (B) prepared by carboxylating a hydrogenation product of a copolymer comprising a vinylaromatic compound (S) and a conjugated diene compound (J) (wherein the degree of unsaturation of J is not above 20%, and the amount of S is 10-50wt.% based on the total weight of S and J), and 0.01-20wt.% olefin polymer (C) having an acid anhydride group at only the terminals and having a number-average molecular weight of 500-50000, 0-200 pts.wt. carboxylated polyphenylene ether resin, 0-200 pts.wt. polyolefin resin other than component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has improved melt viscosity characteristics, and in particular, has a high melt viscosity and a high melt tension (melt tension), and is suitable for blow molding with a small swell ratio. It relates to a composition.

[0002]

2. Description of the Related Art When performing blow molding, it is necessary to maintain the shape of a polymer melt extruded from a die sufficiently to obtain a uniform molded product size and wall thickness. It is desirable to have a melt viscosity. This is especially important for obtaining blow-molded products of large capacity containers. Generally, a polyamide resin is considered to be suitable for a small molded product having a blow-up ratio of 2 or less because of its low melt viscosity, and is not suitable for blow molding of a large container. Hitherto, various attempts have been made to apply the polyamide resin to a large blow molding by increasing its viscosity. Generally, there is a method of increasing the polymerization degree of the polyamide resin in order to increase the melt viscosity of the polyamide resin, but this method is not suitable for large-scale blow molding which has poor thermal stability and long molding time. Therefore, a method of increasing the melt viscosity by compounding a material other than the polyamide resin has been performed. For example, a method of mixing a polyfunctional epoxy compound with a polyamide resin (Japanese Patent Publication No. 48-750).
9) or a method of obtaining an intimate mixture of a polyamide resin and an ethylene-based ionomer and / or a carboxy-modified nitrile rubber (Japanese Patent Publication No. 55-41659), and the materials obtained by these methods have a melt tension of Small, the large polymer-specific ballistic effect occurs,
A molding machine in which the ratio of the die diameter to the die diameter is close to 1 has a drawback that the polymer parison is not contained in the die and molding is difficult. Further, recently, a method of mixing a polyamide resin with a modified block copolymer obtained by grafting an α, β-unsaturated carboxylic acid on a copolymer of a vinyl aromatic compound and an olefin compound (JP-A-4-14696).
It has been found that 3) is also an effective means for increasing the melt viscosity of the polyamide resin. This method has a high melt tension and can obtain a melt viscosity necessary for blow molding, but has a large swell ratio and has a drawback that the die diameter and the die diameter at the time of molding are largely restricted, and thus it is not always satisfactory. It wasn't the material.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a polyamide resin composition for blow molding which has a high melt viscosity, a high melt tension, and a small swell ratio.

[0004]

The present invention achieves the above object, and its gist is as follows.

In the present invention, the ratio (A) of the terminal amino group concentration to the terminal carboxyl group concentration R = [NH ₂ ] / [COOH]
Is a polyamide resin 50 to 9 in which 0.6 ≦ R ≦ 5.0
Modification in which a molecular unit containing a carboxylic acid group or a derivative group thereof is graft-bonded to a part or all of the hydride of a copolymer composed of 8% by weight of (B) a vinyl aromatic compound and a conjugated diene compound. Block copolymer 0.01
˜50% by weight (however, in (B), the degree of unsaturation of the conjugated diene compound does not exceed 20%, and the amount of the vinyl aromatic compound is 10 to 50 relative to the total amount of the vinyl aromatic compound and the conjugated diene compound. %), And (C) 0.01 to 20% by weight of an olefin polymer having a number average molecular weight of 500 to 50,000 and having an acid anhydride group only at the terminal, (A) + (B) + (C) = 100 wt% of the resin composition (D) 100 parts by weight, the (E) polyphenylene ether resin is graft-bonded with a molecular unit containing a carboxylic acid group or a derivative group thereof. Modified polyphenylene ether resin 0-2
The present invention relates to a blow molding resin composition comprising 00 parts by weight and / or 0 to 200 parts by weight of a polyolefin resin other than (F) and (C).

The details of the invention will be described below.

The polyamide resin used as the component (A) in the present invention includes polycondensates of dicarboxylic acids and diamines, self-condensates of α-amino acids, ring-opening polymers of cyclic lactams, and the like. Is nylon 6, nylon 9, nylon 10, nylon 12, nylon 46,
They are aliphatic polyamides such as nylon 66, nylon 610 and nylon 612, aromatic polyamide resins such as nylon 6T and nylon 6I, and copolymers and blends of these nylons. The number average molecular weight of these polyamide resins is not particularly limited, but is about 5,000 to 1
It is 0,000, and more preferably 10,000 to 50,000.

The polyamide resin used in the present invention has a terminal group concentration ratio [NH ₂ ] / [COOH] = R of 0.
It is necessary that 6 ≦ R ≦ 5.0, and preferably,
0.6 ≦ R ≦ 4.0, more preferably 0.6 ≦ R ≦
It is 3.0. When the ratio R exceeds 5.0, the obtained resin composition is gelated, and it becomes difficult to extrude, and there is a problem that blow molding cannot be performed. Further, when R is 0.
If it is less than 6, the components (B) and (C) are poorly dispersed, and there is a drawback that delamination occurs in the molded product. Only when R is this ratio, the obtained polyamide resin composition does not cause gelation, has high melt viscosity and melt tension, and has a small swell ratio.

The compounding amount of the component (A) is 50 to 98% by weight.
Is. When it is less than 50% by weight, not only the extrudability is deteriorated, but also the excellent characteristics originally possessed by the polyamide resin are impaired. If it exceeds 98%, blow molding cannot be performed.

The modified block copolymer (B) used in the present invention is modified with a hydrogenated block copolymer as a raw material.

The hydrogenated block copolymer as referred to herein is composed of a vinyl aromatic compound block and a polymer block mainly composed of a conjugated diene compound block, and the degree of unsaturation of the conjugated diene portion of the block copolymer is It is selectively hydrogenated to an extent not exceeding 20%. In this hydrogenated block copolymer, the content of the vinyl aromatic compound block is 10 to 50% by weight, particularly preferably 13 to 4%.
It is in the range of 5% by weight. When the content of the vinyl aromatic compound in the hydrogenated block copolymer exceeds 50% by weight, the impact resistance at room temperature is maintained, but the impact resistance at low temperature is significantly reduced. On the other hand, when the content of the vinyl aromatic compound is less than 10% by weight, it becomes extremely difficult to pelletize the hydrogenated block copolymer, resulting in an industrially disadvantageous result. On the other hand, when the content of the vinyl aromatic compound is from 10 to 50% by weight, particularly preferably from 13 to 45% by weight, the obtained polyamide resin composition is less deteriorated in rigidity and excellent. Has low temperature impact resistance.

In the present invention, examples of the vinyl aromatic compound constituting the block copolymer before hydrogenation include styrene and α
-Methyl styrene, vinyl styrene, vinyl toluene,
Examples thereof include vinylnaphthalene, but styrene is particularly preferable. Further, as the conjugated diene compound, 1,3-
Examples thereof include butadiene, 1,3-pentadiene and isoprene, with 1,3-butadiene being particularly preferred.

In the present invention, the block copolymer is usually a vinyl aromatic compound in an inert hydrocarbon solvent such as benzene, toluene, hexane or cyclohexane using an organolithium compound such as butyllithium or sodium naphthalene as a catalyst. Is synthesized by an anionic living polymerization method using a conjugated diene compound as a monomer, but in the present invention, any method may be used as long as it is within the above range. Not a thing.

The above block copolymer is prepared by a known method,
For example, by hydrogenating according to the method described in JP-A-42-8704, a portion which does not exceed 20% of the aromatic double bond of the vinyl aromatic compound and at least 80 of the aliphatic double bond of the conjugated diene compound can be obtained. Hydrogenated block copolymers are synthesized which are% hydrogenated.

The term "unsaturation degree of the conjugated diene compound" as used herein means a ratio of carbon-carbon double bonds contained in the conjugated diene compound, which is determined by a conventionally known technique such as an iodometric titration method. .

The modified block copolymer (B) used in the present invention is obtained by modifying the above-mentioned hydrogenated block copolymer by an addition reaction and / or a graft reaction with a molecular unit containing a carboxylic acid group or a derivative group thereof. To be done.

The molecular unit containing a carboxylic acid group or its derivative group used in the present invention includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, hymic acid, hymic acid anhydride, croton. Examples of the acid include maleic anhydride.

The addition amount of the molecular unit containing a carboxylic acid group or its derivative group to the hydrogenated block copolymer is 0.001 with respect to 100 parts by weight of the block copolymer.
To 20 parts by weight are preferred, and 0.1 to 5 parts by weight are particularly preferred. When the addition amount is less than 0.001 part by weight, when the composition is prepared, almost no modification is observed. If it exceeds 20 parts by weight, the blended polyamide resin will give unfavorable results such as coloring and reduction of molecular weight.

For the addition reaction and / or graft reaction of the molecular unit containing a carboxylic acid group or its derivative group to the hydrogenated block copolymer, a conventionally known method can be used in the presence of a solvent. , Or in the absence,
It is preferably carried out in the coexistence of a radical generator.

As the radical generator, benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 2,5 −
Dimethyl-di (t-butylperoxy) hexane and the like can be used.

The content of the component (B) is 0.01 to 50% by weight, preferably 1 to 50% by weight, more preferably 5%.
Is about 20% by weight. If it is less than 0.01% by weight, the thickening effect does not appear, and if it exceeds 50% by weight, the extrudability deteriorates, which is not preferable.

The number average molecular weight used in the present invention is from 500 to 5
The olefin-based polymer (C) having an acid anhydride group only at the terminal of 10,000 is a polymer described in WO89-08120, and has a main chain of polyethylene, polypropylene, polypentene, polyhexene, polyoctenylene, α-olefin. Ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-1,6-hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, diene-based copolymer Polybutadiene which is a homopolymer of monomers, butadiene-styrene copolymer which is a copolymer, hydrogenated product of butadiene-styrene copolymer, 1,
2-polybutadiene hydrogenated product, 1,4-polybutadiene hydrogenated product, and 1,2-polybutadiene and 1,
It is an olefin-based polymer such as a hydrogenated product of a mixture of 4-polybutadiene, and is a polymer in which a molecular unit containing an acid anhydride group is bonded to the terminal. The most preferable example of the olefin polymer (F) having an acid anhydride group at the terminals is a terminal trimellitic anhydride-modified water which is a reaction product of hydrogenated polybutadiene having hydroxyl groups at both terminals and trimetic anhydride chloride. Additional polybutadiene may be mentioned. It is important that the olefin-based polymer of the present invention has an acid anhydride group only at the terminal. At the end,
Either one end or both ends may be used, but it is preferable that they are bound to both ends.

In the present invention, the number average molecular weight of (C) is 5
If it is less than 00, it becomes thermally unstable and volatilizes during processing of the composition to cause unfavorable conditions such as foaming, and also functions as an admixture, which modifies the component (C) main chain portion and the component (B). Entanglement with the block copolymer is reduced, and further, toughness (tensile elongation and impact resistance) is not sufficient. It is preferably 1,000 or more.

When the number average molecular weight exceeds 50,000, the concentration of the acid anhydride group at the terminal becomes low, so that the function as an admixture becomes small and the compounding effect is not exhibited. Also,
When the molecular weight is high, the melt viscosity or solution viscosity becomes high, which makes it difficult to handle when introducing an acid anhydride group at the terminal. Therefore, the number average molecular weight is preferably 20,000.
Or less, more preferably 10,000 or less, and most preferably 6,000 or less.

The blending amount of the component (C) is 0.01 to 20% by weight. If it is less than 0.01% by weight, the thickening effect is not seen, and if it exceeds 20% by weight, the extrudability is deteriorated, which is not preferable.

The above (A) polyamide resin, (B) modified block copolymer, (C) olefin polymer resin composition, and (D) have a high melt viscosity required for blow molding and Resin composition (D) and modified polyphenylene ether resin (E), which are materials with excellent moldability
The resin composition (D ') composed of (1) and (2) has a high melt viscosity and a higher melt tension, and is therefore a material suitable for large-scale blow molding.

The modified polyphenylene ether resin (E) used in the present invention is obtained by using the polyphenylene ether resin represented by the following general formula.

[0028]

[Chemical 1]

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ represent hydrogen, a halogen atom, an alkyl group, and an aryl group, respectively, and n represents the degree of polymerization). And a poly (2,8-dimethyl-
1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-
Methyl-6-ethyl-1,4-phenylene ether),
Poly (2-ethyl-6-propyl-1,4-phenylene ether), poly (2,6-allyl-1,4-phenylene ether), poly (2-methyl-6-allyl-1,4)
-Phenylene ether), poly (2,6-dichloro-)
1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2-chloro-6-bromo-1,4-phenylene ether), poly (2,6-difluoro-) 1,4-phenylene ether), poly (2,8,6-trimethyl-1,4-phenylene ether), poly (2,3,5,6-tetraboromo-1,4-phenylene ether), or the like. A copolymer is mentioned.

Modified polyphenylene ether resin (E)
Can be obtained by using the above polyphenylene ether resin, a radical generator and an α, β-unsaturated carboxylic acid, or a derivative thereof.

Examples of the radical generator include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,5. −
Dimethyl-di (t-butylperoxy) hexane and the like can be used. Examples of the α, β-unsaturated carboxylic acid used herein or its derivative include maleic acid, maleic anhydride, succinic acid, succinic anhydride, hymic acid, itaconic acid, itaconic anhydride, citraconic anhydride, and aconitic anhydride. , Maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monoethyl ester metal salt, fumaric acid monoethyl ester,
Vinyl benzoic acid, vinyl fumaric acid, metal salts of fumaric acid monoethyl ester, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate, acrylic acid, methacrylic acid, maleimide, and the like.
A compound having an acid anhydride group is particularly preferable. The glast amount of the α, β-unsaturated carboxylic acid or its derivative of the component (E) used in the present invention is preferably in the range of 0.01 to 50 mol%, particularly preferably in the range of 0.05 to 10 mol%. If the amount of grafting exceeds 50 mol%, the resin blended will have unfavorable results such as coloring, molecular weight reduction, and gelation, and if it is 0.01 mol% or less, the effect of improving melt tension will not be recognized. In the present invention, the blending amount of the modified polyphenylene ether resin is 0 to 200 parts by weight with respect to 100 parts by weight of the polyamide resin composition (D) including (A), (B) and (C). It is particularly preferably 10 to 50 parts by weight. 200
When it exceeds the weight part, not only the blow moldability is deteriorated but also the effect of improving the melt tension is not observed, which is not desirable.

As described above, the resin composition (D) has a sufficiently high viscosity for blow molding, but the resin composition (D "comprising the resin composition (D) and the polyolefin resin (F). ) Is a material having a high melt viscosity and a low swell ratio, and is therefore suitable for blow molding when the die diameter and the die diameter are very close.

The polyolefin resin as the component (F) of the present invention is a polyolefin polymer other than the component (C), such as homopolymers of α-olefin monomers, copolymers of two or more types of α-olefin monomers, and the like. Can be mentioned.

As the α-olefin monomer, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-
Examples include decene and 1-dodecene. Examples of the α-olefin homopolymer include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctenylene, and the like, and examples of the α-olefin copolymer include an ethylene-propylene copolymer and an ethylene-propylene copolymer.
Butene copolymer, ethylene-propylene-1,6-hexadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-acrylic acid copolymer metal neutralization product, ethylene-methacrylic acid -Metal neutralized products of isobutyl methacrylate copolymer and the like.

The polyolefin resin as the component (F) in the present invention may be partially or wholly modified by introducing an acid anhydride group into the main chain or side chain.

The compounding amount of the component (F) is 0 to 200 parts by weight. It is preferably 0.1 to 100 parts by weight. 200
When it exceeds the weight part, the mechanical strength of the resin composition is remarkably lowered, which is not preferable.

It is also possible to mix the component (E) and the component (F) into the resin composition (D) simultaneously and separately. Within the ranges of the compounding amounts of (E) and component (F), the effects obtained when the component (E) and the component (F) are respectively compounded in the resin composition (D) are sufficiently exhibited. .

Antioxidants, heat stabilizers, UV absorbers, plasticizers, lubricants added to other rubbers, other thermoplastic resins and ordinary thermoplastic resins in the composition of the present invention, if necessary. The addition of various additives such as a tackifier, a dye, a pigment, a nucleating agent, and a reinforcing agent such as glass fiber is not particularly limited.

In order to produce the resin composition of the present invention,
Any conventionally known technique may be used, but a method of melt mixing using an extruder, a Banbury mixer, a kneader, or the like is preferably used.

In the present invention, a thermoplastic resin other than the polyamide resin may be mixed for the purpose of improving the physical properties.
Examples of the thermoplastic resin include polyether, polyester, polyarylene sulfite, polysulfone, polycarbonate, and polyamideimide.

[0041]

【Example】

(Evaluation method) The resin pellets shown in the following examples and comparative examples are evaluated as follows.

(1) Melt viscosity: Shimadzu Flow Tester CFT
-500A Measuring temperature 280 ° C Nozzle diameter 1x1mmφ Shearing speed 100sec ~ ¹ (2) Melt tension: Toyo Seiki Seisakusho Melt Tension Tester RE2 Measuring temperature 270 ° C Extrusion speed 20mm / min Take-off speed 1.57mm / min (3) Swell ratio: Capillary viscometer manufactured by Toyo Seiki Seisaku-sho, Ltd. Measurement temperature 280 ° C. Orifice diameter 2.095 mm Shear rate 130 sec ~ ¹ (orifice diameter and strand diameter were measured to determine the ratio). (4) Measurement of terminal group concentration Amino group: It was determined by potentiometric titration of a polyamide resin dissolved in a phenol aqueous solution with 1/10 N hydrochloric acid.

Carboxyl group: A polyamide resin was dissolved by heating in benzyl alcohol, phenolphthalein was added, and titration was performed with a 1 / 10N NaOH ethylene glycol solution.

(Material) Hydrogenated block copolymer: Asahi Kasei Kogyo Co., Ltd. Tuftec H1051 Olefin polymer: Terminal trimet acid anhydride modified hydrogenated polybutadiene Toho Chemical Industry Co., Ltd. TA-101 Polyolefin resin: Asahi Kasei Co., Ltd. ) PP homopolymer MFR = 0.5 (5) Blow moldability test: JSW-JB105CP
(Manufactured by Japan Steel Works Ltd.) 220 × 150 × 85 mm cubic container Production Example 1 After blending a predetermined amount of hexamethylenediamine or adipic acid with an equimolar salt of adipic acid and hexamethylenediamine, ordinary polymerization of nylon 66 is performed. Polymerization was performed according to the method to obtain polyamide resins A to D having different terminal group concentrations shown in Table 1.

Production Example 2 3.0 parts by weight of maleic anhydride and 0.2 parts by weight of 2,5-dimethyl-based on 100 parts by weight of hydrogenated styrene / butadiene block copolymer (Tuftec H1051).
Di (t-butylperoxy) hexane (Perhexa 25
B: manufactured by Nippon Oil & Fat Co., Ltd.) was uniformly dry blended, and then under a nitrogen atmosphere, the cylinder temperature was 220 ° C. to 25 ° C.
A modified block copolymer (B) was obtained by melt-kneading with a 45 mmφ twin-screw extruder (PCM-45 manufactured by Ikegai Tekko KK) installed at 0 °.

Production Example 3 Polyphenylene ether (manufactured by Asahi Kasei Corporation) 36.
4 g of maleic anhydride 29.4 g of p-xylene 200
It was dissolved in ml and heated and stirred at 120 ° C. under a stream of dry nitrogen. 50% of benzoyl peroxide in this solution,
Dioctyl terephthalate diluted product (Nyper B0 (manufactured by NOF CORPORATION)) 5.8 g dissolved in 50 ml of p-xylene was slowly added, and the mixture was dried under a dry nitrogen stream to give 120
The reaction was carried out at 0 ° C for 5 hours. After completion of the reaction, 200 ml of p-xylene was added to dilute the mixture, and the mixture was poured into acetone to precipitate a polymer. After washing thoroughly with acetone,
It was vacuum dried at ℃ and a modified polyphenylene ether resin was obtained. When the amount of maleic anhydride grafted was determined by titration with sodium methylate, 1.2 mol% of maleic anhydride was grafted onto polyphenylene ether.

Example 1 A dry blend of 90 parts by weight of the polyamide resin B of Production Example 1 and 10 parts by weight of the modified block copolymer of Production Example 2 was used as a 45 mmφ twin-screw extruder (Ikegai Iron Works Co., Ltd.).
In PCM-45), 1.2 parts by weight of the olefin polymer (TA101) was added through the vent port of the extruder and melt-mixed to prepare pellets, which were evaluated. The composition and the measurement results are shown in Table 2.

Example 2 A dry blend of 90 parts by weight of the polyamide resin C of Production Example 1 and 10 parts by weight of the same modified block copolymer as in Example 1 was used as a 45 mmφ twin-screw extruder (PCM of Ikegai Tekko KK). -45), from the extruder vent port,
The same olefin polymer as in Example 1 was added in an amount of 1.2 parts by weight and melt-mixed to prepare pellets, which were evaluated. The composition and the measurement results are shown in Table 2.

Example 3 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1 and 10 parts by weight of the modified polyphenylene ether resin of Production Example 3 were dry blended. Using a 45 mmφ twin-screw extruder (PCM-45, Ikegai Tekko Co., Ltd.), 1.2 parts by weight of the same olefin polymer as in Example 1 was added from the vent port of the extruder and melt-mixed to obtain pellets. Created and evaluated. The composition and the measurement results are shown in Table 2.

Example 4 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1 and 20 parts by weight of the same modified polyphenylene ether resin as in Example 3 were dry blended. The same olefin polymer as in Example 1 was obtained from the extruder vent port using a 45 mmφ twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.).
Pellets obtained by adding 2 parts by weight and melting and mixing were prepared and evaluated. The composition and the measurement results are shown in Table 2.

Example 5 A dry blend of 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1 and 10 parts by weight of a polyolefin resin was used.
5mmφ twin-screw extruder (Ikegai Tekko PCM-4
In 5), 1.2 parts by weight of the same olefin polymer as in Example 1 was added from the vent port of the extruder and melt-mixed to prepare pellets, which were evaluated. The composition and the measurement results are shown in Table 2.

Example 6 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1, 10 parts by weight of the same modified polyphenylene ether resin as in Example 3 and 10 parts by weight of polyolefin resin. 45mmφ twin-screw extruder (IKEMIGAI TEKKO CO., LTD. PCM)
In -45), 1.2 parts by weight of the same olefin polymer as in Example 1 was added from the vent port of the extruder and melt-mixed to obtain pellets, which were evaluated. The composition and the measurement results are shown in Table 2.

Comparative Example 1 A dry blend of 90 parts by weight of the same polyamide resin B as in Example 1 and 10 parts by weight of the same modified block copolymer as in Example 1 was used as a 45 mmφ twin-screw extruder (Ikegai Tekko Co., Ltd.). In PCM-45), pellets obtained by melt mixing were prepared and evaluated. Table 2 shows the composition and measurement results
Shown in.

Comparative Example 2 90 parts by weight of the polyamide resin A of Production Example 1 and 10 parts by weight of the same modified block copolymer as in Example 1 were dry blended, and a 45 mmφ twin-screw extruder (PCM of Ikegai Tekko KK) was used. In -45), pellets obtained by melt mixing were prepared and evaluated. The composition and the measurement results are shown in Table 2.

Comparative Example 3 90 parts by weight of the polyamide resin D of Production Example 1 and 10 parts by weight of the same modified block copolymer as in Example 1 were dry blended, and a 45 mmφ twin-screw extruder (PCM of Ikegai Tekko KK) was used. In -45), pellets obtained by melt mixing were prepared and evaluated. The composition and the measurement results are shown in Table 2.

Comparative Example 4 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1 and 10 parts by weight of the same modified polyphenylene ether resin as in Example 3 were dry blended. Pellets obtained by melt-mixing the obtained materials with a 45 mmφ biaxial extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) were prepared and evaluated. The composition and the measurement results are shown in Table 2.

Comparative Example 5 A dry blend of 90 parts by weight of the same polyamide resin B as in Example 1, 10 parts by weight of the same modified block copolymer as in Example 1 and 10 parts by weight of a polyolefin resin was used.
5mmφ twin-screw extruder (Ikegai Tekko PCM-4
In 5), pellets obtained by melt mixing were prepared and evaluated. The composition and the measurement results are shown in Table 2.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

According to the present invention, it is possible to provide a resin composition having a high melt viscosity, a large melt tension, and a small swell ratio. Since this resin composition has a high mechanical strength, it is blow molded. It can be used in a wide range of applications such as automobile parts and other parts that require processing.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 53/02 LLZ 7142-4J 71/12 LQP 9167-4J

Claims (1)

[Claims] 1. A ratio (A) of terminal amino group concentration to terminal carboxyl group concentration R = [NH ₂ ] / [COOH] is 0.
50 to 98% by weight of polyamide resin with 6 ≦ R ≦ 5.0
And (B) a modified block copolymer in which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded to a part or all of a hydride of a copolymer composed of a vinyl aromatic compound and a conjugated diene compound. 0.01 to 50% by weight (however, for (B), the degree of unsaturation of the conjugated diene compound does not exceed 20%, and the amount of the vinyl aromatic compound is relative to the total amount of the vinyl aromatic compound and the conjugated diene compound. 10
˜50% by weight) and (C) 0.01 to 20% by weight of an olefin polymer having a number average molecular weight of 500 to 50,000 and having an acid anhydride group only at the terminal.
(E) Polyphenylene ether resin contains a carboxylic acid group or its derivative group with respect to 100 parts by weight of the resin composition (D) satisfying (A) + (B) + (C) = 100% by weight. Modified polyphenylene ether resin in which molecular units are bonded 0 to 200 parts by weight, (F) (C)
A blow molding resin composition comprising 0 to 200 parts by weight of a polyolefin resin other than the above.