JPH06256645A - Resin composition for blow molding - Google Patents

Abstract

PURPOSE:To obtain the subject composition having high high-temperature modulus of elasticity and good moldability and molding appearance by mixing a polyphenylene ether resin with a polyamide, a compatibilizer, an ethylenic ionomer resin and mica in a specified ratio. CONSTITUTION:This resin composition is prepared by mixing 10-90wt.% polyphenylene ether resin (A) obtained by oxidatively polymerizing at least one phenol compound of the formula (wherein R1 to R5 are each H, halogen or an (un)substituted hydrocarbon group, provided that at least one of them is H) with the aid of an oxidation coupling catalyst with 90-10wt.% polyamide (B) (e.g. nylon MXD6), 0.01-10 pts.wt., per 100 pts.wt. total of components A and B, compatibilizer (C) (e.g. maleic acid) which can improve the compatibility between components A and B, 3-50 pts.wt., ethylenic ionomer resin prepared by the addition reaction of an alpha-olefin/alpha,beta-unsaturated carboxylic acid copolymer with mono- to tri-valent metallic ions and 10-100 pts.wt. mica with a flake diameter of 300mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing a polyphenylene ether resin suitable for hollow blow molding. More specifically, it has a high high temperature elastic modulus,
The present invention relates to a blow molding resin composition having good moldability and good appearance.

[0002]

2. Description of the Related Art It is known that a resin composition comprising polyphenylene ether, polyamide and an ethylene ionomer resin is blow-molded by paying attention to its excellent chemical resistance, moldability and appearance. 4-39354
Issue). However, the composition has a disadvantage that the flexural modulus at high temperature use (high temperature modulus) is small. Glass fibers are added as a filler to improve the high temperature elastic modulus. However, when glass fibers are added, the blow-molded article becomes remarkably rough in appearance, and it is difficult to obtain a smooth surface appearance.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a blow molding resin composition which has a high elastic modulus at high temperature and a beautiful surface appearance of the blow molded product.

[0004]

Means for Solving the Problems As a result of intensive studies made by the present inventors in view of the above circumstances, as a result, a mica, which is a specific filler, is blended with a resin composition composed of PPE / PA / ethylene ionomer. It was found that a blow molded product having a high temperature elastic modulus and a beautiful surface appearance can be obtained by this, and the present invention has been accomplished.

That is, in the present invention, a) 10 to 90% by weight of polyphenylene ether resin, b) 90 to 10% by weight of polyamide, and c) [a) + b)] 100 parts by weight, a compatibilizing agent of 0.
01 to 10 parts by weight, 3) to 50 parts by weight of the ethylene-based ionomer resin per 100 parts by weight of d) [a) + b)], and 10 parts of mica to 100 parts by weight of e) [a) + b)].
The present invention relates to a blow molding resin composition comprising 100 parts by weight.

The a) polyphenylene ether resin used in the present invention is represented by the general formula 1 (in the formula, R ₁ , R ₂ and R
₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and one of them is always a hydrogen atom. ) Is a polymer obtained by oxidatively polymerizing one or more of the phenol compounds represented by the formula (1) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst.

[0007]

[Chemical 1]

In the above general formula 1, R ₁ , R ₂ ,
Specific examples of R ₃ , R ₄ and R ₅ include hydrogen, chlorine,
Bromine, fluorine, iodine, methyl, ethyl, n- or i
so-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl,
Methoxycarbonylethyl, cyanoethyl, phenyl,
Chlorophenyl, methylphenyl, dimethylphenyl,
Examples include ethylphenyl and allyl.

Specific examples of the above general formula 1 include phenol, o-, m-, or p-cresol, 2,6-,
2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2
-Methyl-6-ethylphenol, 2,3,5-, 2
3,6- or 2,4,6-trimethylphenol, 3
-Methyl-6-t-butylphenol, thymol, 2-
Methyl-6-allylphenol and the like can be mentioned. Furthermore, a phenol compound other than the above general formula 1, for example,
Bisphenol-A, tetrabromobisphenol-
Copolymerization of polyvalent hydroxyaromatic compounds such as A, resorcin, hydroquinone, and novolak resins with the above general formula 1 may also be used.

Preferred among these compounds are homopolymers of 2,6-dimethylphenol or 2,6-diphenylphenol and a large amount of 2,6-xylenol and a small amount of 3-methyl-6. A copolymer of -t-butylphenol or 2,3,6-trimethylphenol may be mentioned. The oxidative coupling catalyst used when oxidatively polymerizing the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.

Further, the a) polyphenylene ether-based resin in the present invention includes those obtained by mixing the above-mentioned polyphenylene ether with a styrene-based polymer, or those in which another polymer is grafted. The styrene-based resin is specifically a polymer composed of one or more kinds of polymerized units selected from styrene, α-methylstyrene, p-methylstyrene and the like, and specifically, polystyrene and rubber-reinforced polystyrene. , Poly α-methyl styrene, poly p-methyl styrene, styrene-acrylonitrile copolymer and the like.

The amount of styrene resin mixed or grafted is 100 parts by weight of polyphenylene ether.
It is preferably 500 parts by weight or less. If the styrene resin is mixed or the amount of grafting exceeds 500 parts by weight,
The heat resistance of the thermoplastic resin composition is significantly lowered, which is not preferable.

The b) polyamide used in the present invention is one or more polyamides selected from homopolyamides and copolyamides obtained by polymerization of lactam or aminocarboxylic acid and polycondensation of diamine and dicarboxylic acid, or That mixture. In particular,
Nylon 6, Nylon 66, Nylon 46, Nylon 1
0, nylon 11, nylon 12, nylon MXD6, which is a copolymer of metaxylylenediamine and adipic acid,
Nylon 66/6 copolymer, copolyamide of para-aminomethylbenzoic acid and ε-caprolactam (nylon AHBA / 6), 2,2,4- / 2,4,4-trimethylhexamethylenediamine terephthalate Polyamide as main component (nylon THDT, THDT / 6
I) and the like, but not limited thereto.

In the present invention, the compounding ratio of a) polyphenylene ether resin and b) polyamide is 10 to 90 parts by weight of polyphenylene ether and 90 to 1 of polyamide.
It is in the range of 0 parts by weight. Preferably, with respect to 20 to 80 parts by weight of polyphenylene ether, polyamide 80 to 20
Parts by weight, more preferably polyphenylene ether 2
It is in the range of 75 to 40 parts by weight of polyamide with respect to 5 to 60 parts by weight.

The c) compatibilizer used in the present invention originally has a poor affinity for the a) polyphenylene ether resin and the b) polyamide. Therefore, even if they are melt-kneaded at the same time, the PPE particles have a particle size of about 10 microns or more. It is compounded in order to improve the drawback that it disperses only in the particle size and exhibits extremely low mechanical properties, and one or more compounds selected from the group consisting of the following A) to F) are exemplified. It

A) In the molecule, a) a carbon-carbon double bond or a carbon-carbon triple bond, and a) a carboxyl group, an acid anhydride group, an amino group, an acid amide group, an imide group, an epoxy group, a carboxyl group. Acid ester group, isocyanate group,
A compound having a methylol group, a group having an oxazoline ring or a hydroxyl group at the same time. (Specific examples include maleic acid, maleic anhydride, fumaric acid, unsaturated amines, glycidyl methacrylate, etc., and the details of these compounds are described in JP-A-56-26913 and JP-A-56-4975.
No. 3, for example. )

B) Formula (R ₁ O) _m R (COOR ₂ ) _n (CONR ₃ R ₄ ) _s [wherein R is a linear or branched aliphatic hydrocarbon having 2 to 20 carbon atoms, preferably 2 to 20 carbon atoms] 10, R ₁ : hydrogen, an alkyl group, an aryl group, an acyl group, or a carbonyldioxy group, particularly preferably hydrogen, R ₂ : hydrogen, an alkyl group,
Or an aryl group having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms
0, R ₃ and R ₄ : hydrogen, an alkyl group, or an aryl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4, m = 1, n + s: an integer of 2 or more, preferably 2 Or 3, n: an integer of 0 or more, s: an integer of 0 or more,
(R ₁ O) is located at the α-position or β-position of the carbonyl group,
There are 2 to 6 carbons between at least two carbonyl groups. ] A saturated aliphatic polycarboxylic acid represented by the above and a derivative compound thereof. (Specifically, ester compounds, amide compounds, anhydrides, hydrates and salts of saturated aliphatic polycarboxylic acids are shown. Examples of saturated aliphatic polycarboxylic acids are citric acid, malic acid, agaricin acid, etc. The details of these compounds are shown in Table 61-50.
2195. )

C) Formula (I) -Z- (II) [wherein (I) is at least the formula: (X-CO)-(where X is F, Cl, B, I, OH, OR). , Or -O-
CO-R, R is H, an alkyl group or an aryl group), and (II) is at least a carboxylic acid, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an amino group or a hydroxyl group. And (I) and (II)
The groups are covalently bonded via a bond Z which is a divalent hydrocarbon. ] The compound represented by these. (Specifically, chloroformyl succinic acid anhydride, chloroethanoyl succinic acid anhydride, trimellitic acid anhydride acid chloride, trimellitic acid anhydride acetic acid anhydride, terephthalic acid chloride, etc.)

D) in the molecular structure: a) at least one silicon atom bonded to a carbon atom via an oxygen bridge.
And (a) having both an ethylenic carbon-carbon double bond or a carbon-carbon triple bond and / or a functional group selected from an amino group and a mercapto group, wherein the functional group is not bonded to a silicon atom, Silane compound

E) Oxidized polyolefin wax. F) A copolymer having a vinyl aromatic compound unit and an α, β-unsaturated dicarboxylic acid or dicarboxylic anhydride unit, or a vinyl aromatic compound unit and α, β-
The copolymer which has the unit of the imide compound of unsaturated dicarboxylic acid.

However, the compatibilizing agent in the present invention is not limited to the compounds exemplified here, and may be a compound used for the purpose of improving the compatibility between the polyphenylene ether resin and the polyamide, and may be used alone or Multiple compatibilizers may be used simultaneously. The compounding amount of the compatibilizer c) is
0.01 to 100 parts by weight of the total amount [a) + b)] of a) polyphenylene ether resin and b) polyamide.
When the amount is 10 parts by weight, it is not preferable that the amount is more than 10 parts by weight because the heat resistance is deteriorated and the strength is remarkably decreased due to decomposition. A preferred blending amount is 0.05 to 8 parts by weight,
More preferably, it is 0.1 to 5 parts by weight. Further, when this compatibilizer is blended, a radical initiator such as organic peroxide may be used together.

The d) ethylene ionomer resin used in the present invention is an α-olefin containing ethylene,
Copolymers with α, β-unsaturated carboxylic acids have a valence of 1
It is an ionic copolymer to which a metal ion of 3 is added. Here, typical examples of the α, β-unsaturated carboxylic acid include acrylic acid, methacrylic acid, and itaconic acid. Further, typical examples of the metal ion having a valence of 1 to 3 include Na ⁺ , K ⁺ , Ca ⁺⁺ , Zn ⁺⁺ , Al ^{+++ and the} like. These ethylene-based ionomer resins are
For example, it is marketed by DuPont under the registered trademark Surlyn. The blending amount of ethylene ionomer resin is [a)
+ B)] 3 to 50 parts by weight, preferably 5 to 50 parts by weight, relative to 100 parts by weight. If the blended amount of the ethylene-based ionomer resin exceeds 50 parts by weight, the elastic modulus is significantly lowered, which is not preferable.

The mica used in the present invention preferably has a flake diameter of 300 μ or less, and examples of the mica species include muscovite (muscovite) and phlogopite (phlogopite). The flake diameter is more preferably 150 μm or less. The amount of mica compounded is 10 to 100 parts by weight, preferably 10 to 100 parts by weight of [a) + b)].
80 parts by weight. In the present invention, additives such as pigments, antioxidants, weathering agents and flame retardants can be added as required.

The thermoplastic resin composition of the present invention has the above a)
The components (e) to (e) are blended by a known method and melt-kneaded by an extruder or the like. The order of blending and kneading at that time is arbitrary. For example, any combination of each component may be separately kneaded, and then each combination may be mixed and kneaded, or one extruder may be provided with a plurality of feed ports and one or more components may be sequentially mixed along a cylinder. You may feed.

That is, the components a) to e) are collectively added and melt-kneaded at the same time. The components a), c) and d) are melt-kneaded in the presence or absence of a radical initiator in advance and then the component b is added. ), E) are added and melt kneading is performed, and components a), c), d) and e) are melt kneaded in advance in the presence or absence of a radical initiator, and then component b).
Melt-kneading with additional addition, pre-kneading components a), c) and e) in advance, and then adding components b) and d) and melt-kneading with components a) and c) in advance. Any method such as kneading and then melt-kneading by additionally adding components b), d) and e) may be used, but at least b) before the kneading of polyamide, a) polyphenylene ether resin and c) phase. It is preferably kneaded with the compatibilizer.

The present invention is described in detail below with reference to examples, but these are merely examples and the present invention is not limited thereto. The evaluation methods used in Examples and Comparative Examples are as follows. (1) High temperature elastic modulus Using a Toyo Seiki (manufactured by) Strograph-T, the bending elastic modulus at 80 ° C was measured. (2) Surface appearance of blow molded product Using an extrusion blow molding machine with a cylinder diameter of 65 mmφ and a die with a true diameter of 100 mmφ at a molding temperature of 260 ° C., long side 1
A box having a length of 20 mm, a short side of 30 mm, and a length of 900 mm was blow-molded. The surface appearance was visually observed.

Example 1 Poly (2,6-dimethyl-) having an intrinsic viscosity of 0.57 measured at 30 ° C. in a chloroform solution having a concentration of 0.5 g / dl.
25 parts by weight of 1,4-phenylene ether) and 0.2 parts by weight of maleic anhydride as a compatibilizer were introduced from the first hopper of the continuous twin-screw kneader, and further provided between the first hopper and the vent hole. From the second hopper, 50 parts by weight of polyamide (Unitika Nylon registered trademark A1030BRL), 5 parts by weight of ethylene ionomer resin (Surlyn A1706 manufactured by DuPont) and mica (Kuraray Co., Ltd.)
20 parts by weight of Clarite Mica (400 W) manufactured by the present invention was charged using a weight feeder, the cylinder temperature was set to 260 ° C., and melt kneading was performed at a screw rotation speed of 330 rpm to granulate to obtain a thermoplastic resin composition. A test piece was prepared by injection molding the obtained composition, and the high temperature elastic modulus was measured. A blow molding machine was used to make a molded product and the surface appearance was observed. The evaluation results are shown in Table 1.

Example 2 Poly (2,6-dimethyl-) having an intrinsic viscosity of 0.57 measured at 30 ° C. in a chloroform solution having a concentration of 0.5 g / dl.
10 parts by weight of 1,4-phenylene ether) and 0.1 part by weight of maleic anhydride as a compatibilizer were introduced from the first hopper of the continuous twin-screw kneader, and further provided between the first hopper and the vent hole. From the second hopper, 50 parts by weight of polyamide (Unitika Nylon registered trademark A1030BRL), 20 parts by weight of ethylene ionomer resin (Surlyn A1706 manufactured by DuPont) and 20 parts by weight of mica (Clarite mica 400W manufactured by Kuraray Co., Ltd.) are used. A thermoplastic resin composition was obtained by charging using a weight feeder, setting the cylinder temperature to 260 ° C., melt-kneading at a screw rotation speed of 330 rpm, and granulating. A test piece was prepared by injection molding the obtained composition, and the high temperature elastic modulus was measured. A blow molding machine was used to make a molded product and the surface appearance was observed. The evaluation results are shown in Table 1.

Comparative Example 1 Kneading and molding were carried out in the same manner as in Example 2 except that the mica was replaced by glass fiber (RES-03-TP64 manufactured by Nippon Glass Fiber Co., Ltd.) in Example 2, and the physical properties were evaluated. The evaluation results are shown in Table 1.

Comparative Example 2 The physical properties were evaluated by kneading and molding in the same manner as in Example 2 except that mica was not added. The evaluation results are shown in Table 1.

[0031]

[Table 1]

[0032]

Industrial Applicability According to the present invention, a blow molding resin composition having a high elastic modulus at high temperature, good moldability and good appearance can be provided.

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Claims (2)

[Claims] 1. A) Polyphenylene ether resin 10
To 90% by weight, b) 90 to 10% by weight of polyamide, and 100% by weight of c) [a) + b)], a compatibilizer of 0.
01 to 10 parts by weight, 3) to 50 parts by weight of the ethylene-based ionomer resin per 100 parts by weight of d) [a) + b)], and 10 parts of mica to 100 parts by weight of e) [a) + b)].
100 parts by weight of a blow molding resin composition. 2. The c) compatibilizing agent comprises a) a carbon-carbon double bond or a carbon-carbon triple bond and a) a carboxyl group, an acid anhydride group, an amino group, an acid amide group in the molecule. The resin composition according to claim 1, which is a compound having at the same time an imide group, an epoxy group, a carboxylic acid ester group, an isocyanate group, a methylol group, a group having an oxazoline ring or a hydroxyl group.