JPH0543798A - Polyamide-polyolefin resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition capable of easily injection-molding, excellent in, in particular, metal halide resistance. CONSTITUTION:The objective composition can be obtained by incorporating a total of 100 pts.wt. of a blend of (A) 80-40wt.% of a polyamide resin, (B) 1-40wt.% of a modified polyolefin resin, and (C) 20-60wt.% of a polypropylene resin with (D) 0.01-10 pts.wt. of a metal chelating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide / polyolefin resin composition, and more specifically, it has excellent characteristics of both polyamide resin and polypropylene resin,
In particular, it relates to a polyamide / polyolefin resin composition having excellent metal halide resistance.

[0002]

2. Description of the Related Art Generally, polyamide resins are widely used as synthetic fibers because of their excellent physical and chemical properties.
In recent years, it has also come to be used as a molding material.
This is because the polyamide resin is in the thermoplastic resin,
It has high mechanical strength, excellent wear resistance, chemical resistance, heat resistance, and relatively excellent electrical properties, and has sufficient performance as an engineering plastic.
However, on the other hand, the amide group (-CONH-) has unfavorable performance such as dimensional change due to water absorption and a decrease in mechanical strength, which makes it a marketable material for molding. Limited.

On the other hand, polypropylene resin is inexpensive and exhibits almost no water absorption, but it has the drawbacks of being soft and having inferior physical properties at high temperatures. Therefore, in order to improve the respective drawbacks of the polyamide resin and the polypropylene resin, it is conceivable to use these resins together. However, a resin mixture obtained by mixing a polyamide resin and a polypropylene resin by a usual method, or a resin composition obtained by simply melt-kneading them has poor compatibility, and a composition having a desired excellent physical property. It cannot be. for that reason,
Conventionally, a resin composition having both excellent properties of polyamide resin and polypropylene resin, that is, excellent abrasion resistance, electrical properties, heat resistance, mechanical strength, oil resistance of polyamide resin, and low resistance of polypropylene resin For the purpose of obtaining a resin composition having water absorption, hot water resistance, metal halide resistance, and low temperature impact resistance, a polyamide resin, an olefin polymer, and a modified polyolefin grafted with an unsaturated carboxylic acid or a derivative thereof are used. Regarding melt-mixing of components to obtain a composition having an excellent balance of strength, heat distortion resistance, appearance, and moldability, Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 45-30945, and Japanese Patent Publication No. 30945 have been disclosed. No. 50-7636. Further, by utilizing such excellent properties, practical application is considered for some applications such as automobile parts, electric appliances, mechanical parts, and industrial parts that require strength and thermal deformation resistance, and some are not. Has been done.

However, even a resin composition (polymer alloy composition) having such characteristics has a problem that the water resistance or the resistance to metal ions such as zinc and calcium is still insufficient. This is due to the drawback of the polyamide resin, but it is presently the reason that its applications are considerably limited. The inventors of the present invention have conducted extensive studies particularly for the purpose of improving the resistance to metal halides while maintaining the excellent properties of polyamide resins and polypropylene resins. As a result, they have found that the object can be achieved by blending the metal chelating agent in a certain range. The present invention has been completed based on such findings.

That is, according to the present invention, (A) polyamide resin 80 to 40% by weight, (B) modified polyolefin resin 1
-40% by weight and (C) polypropylene resin 20-60
Provided is a polyamide / polyolefin resin composition comprising 0.01 to 10 parts by weight of a metal chelating agent (D) with respect to 100 parts by weight of a mixture composed by weight.

As the polyamide resin (A) used in the present invention, various types can be used. Specifically, polylactams such as nylon 6, nylon 11, nylon 12; nylon 66, nylon 610, nylon 612,
Polyamides obtained from dicarboxylic acids such as nylon 46 and diamines; nylon 6/66, nylon 6/1
2, copolymer polyamides such as nylon 6/66/610; half obtained from aromatic dicarboxylic acid such as nylon 6 / 6T (T: terephthalic acid component), isophthalic acid and metaxylene diamine or alicyclic diamine Aromatic polyamides; mention may be made of polyesteramides, polyetheramides and polyesteretheramides. As the polyamide resin as the component (A), the above various polyamides may be used alone, or two or more kinds of polyamides may be used in combination. Further, the polyamide resin that can be used in the present invention is not limited by the type, concentration and molecular weight of the end groups of these polyamides, as long as it is selected from the above-mentioned polyamides, various types can be used. However, high amino terminated polyamides are especially preferred. Also, a polyamide in which low molecular weight substances such as monomers and oligomers that remain or are formed during polymerization of the polyamide are mixed can be used.

Next, as the (B) modified polyolefin resin used in the present invention, there are various kinds, but usually, carboxylic acid groups (acetic acid group, acrylic acid group, methacrylic acid group, fumaric acid group, itaconic acid). Group), metal carboxylate base (sodium salt, calcium salt, magnesium salt,
Zinc salt, etc., carboxylic acid ester group (methyl ester group, ethyl ester group, propyl ester group, butyl ester group, vinyl ester group, etc.), acid anhydride group (maleic anhydride group, etc.), and epoxy group It is a polyolefin having at least one functional group. Examples of the polyolefin include polyethylene, polypropylene, polybutene, ethylene / propylene copolymers, ethylene / butene copolymers, ethylene / hexene copolymers, and copolymers containing a small amount of diene. it can. Specific examples of such modified polypropylene resin include ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / fumaric acid copolymer, ethylene / methacrylic acid / zinc methacrylate copolymer, ethylene / Acrylic acid / sodium methacrylate copolymer, ethylene / isobutyl acrylate /
Methacrylic acid / zinc methacrylate copolymer, ethylene /
Methyl methacrylate / methacrylic acid / magnesium methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer Combined, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene / propylene copolymer, acrylic acid grafted ethylene / propylene copolymer, fumaric acid grafted ethylene / 1-butene copolymerization Polymer, ethylene / 1-hexene-itaconic acid copolymer, ethylene / propylene-endobicyclo [2.2.1] -5-heptene-2,3-
Dicarboxylic anhydride copolymer, ethylene / propylene-methacrylic acid graft glycidyl copolymer, maleic anhydride graft ethylene / propylene / 1,4-hexadiene copolymer, fumaric acid graft ethylene / propylene /
Examples thereof include dicyclopentadiene copolymer, maleic acid-grafted ethylene / propylene / norbornadiene copolymer and acrylic acid-grafted ethylene / vinyl acetate copolymer. These modified polyolefin resins may be used alone or in combination of two kinds. It is also possible to use the above together.
The modified polyolefin resin can be produced by a known method, for example, Japanese Examined Patent Publication No. 39-6810 and Japanese Examined Patent Publication No. 46-2752.
No. 7, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-
It can be manufactured according to the methods shown in Japanese Patent Publication No. 43677, Japanese Patent Publication No. 53-5716, Japanese Patent Publication No. 53-19037, Japanese Patent Publication No. 53-41173, Japanese Patent Publication No. 56-9925. As the ethylene-based ionomer, various grades generally marketed under the trade names of "Surlyn", "Himilan" and "Corporen" can be used. The degree of polymerization of the modified polyolefin resin used in the present invention is not particularly limited, but usually the melt index is 0.01 to 100 g / 10.
Anything within the range of minutes can be arbitrarily selected.

Next, as the polypropylene resin (C), a propylene homopolymer and / or a propylene copolymer is used. Here, as the propylene copolymer, there are a propylene-ethylene copolymer, a propylene-butene-1 copolymer and the like, and a block copolymer or a random copolymer of these is used. As the polypropylene resin, one type of propylene homopolymer or propylene copolymer may be used, or two or more types may be used in combination. At this time, the molecular weights of the propylene homopolymer and the propylene copolymer are not particularly limited, but generally, the melt flow rate (MFR) is 1 to 50 g / 1.
Those of 0 minutes are preferably used.

The metal chelating agent (D) used in the present invention is not particularly limited as long as it has a strong binding ability to calcium or zinc, but the binding constant with calcium or zinc is preferably 10 ⁴ M. ^-More than ^-1 is used. Specific examples thereof include ethylenediamine-N, N, N ', N'-tetraacetic acid; nitrilotriacetic acid;
2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid; N-oxyethylethylenediamine-N, N', N '
-Triacetic acid; ethylene glycol bis (β-aminoethyl ether) -N, N, N ', N'-tetraacetic acid; ethylenediamine-N, N, N', N'-tetrapropionic acid and the like. These chelating agents may be used alone or in combination of two or more.

In the present invention, the blending ratio of each component for producing a polyamide / polyolefin resin composition excellent in metal halide resistance is based on the total amount of the components (A) to (C) (A ) Polyamide resin 80-40% by weight,
It is preferably 80 to 45% by weight, 1 to 40% by weight of (B) the modified polyolefin resin, and preferably 3 to 30% by weight. Further, the (C) polyolefin resin is 20 to 6
It is 0% by weight, preferably 20 to 50% by weight. Here, if the content of the (A) polyamide resin is less than 40% by weight, the heat resistance of the obtained composition is not sufficiently improved. Conversely, 80
When it exceeds the weight percentage, the original properties of the polypropylene resin are lost. Further, when the content of the modified polyolefin resin (B) is less than 1% by weight, the polyamide resin as the component (A) and (C)
It is difficult to improve the compatibility with the component polypropylene resin, and as a result, it may not be possible to impart desired physical properties to the resulting composition. On the other hand, even if the content of the modified polyolefin resin (B) exceeds 40% by weight, the effect corresponding to the blending amount is small, and rather various physical properties of the obtained resin composition may be deteriorated. Further, if the content of the polypropylene resin (C) is less than 20% by weight, the composition cannot be provided with the original properties of polypropylene. Conversely, 6
If it exceeds 0% by weight, heat resistance is not sufficiently exhibited. The compounding amount of the (D) chelating agent varies depending on the binding constant with the metal and the desired performance, and therefore cannot be specified unconditionally, but generally, the mixture 100 composed of (A), (B) and (C) is used. The amount is 0.01 to 10 parts by weight, preferably 0.05 to 3 parts by weight, based on parts by weight. If the blending amount is less than 0.01 parts by weight, the blending effect is not obtained, and if it exceeds 10 parts by weight, not only is it economical but also the moldability may be lowered.

The resin composition of the present invention comprises the above (A),
Although the four main components of (B), (C) and (D) are the main components, other additives may be added, if necessary, within a range that does not impair the characteristics of the above components. Additives that can be blended here include dyes, pigments, fillers, nucleating agents, fibrous materials, plasticizers, lubricants, release agents, coupling agents, foaming agents, heat resistant agents, weather resistant agents, flame retardants, antistatic agents. Agents and sliding agents. The resin composition of the present invention is a resin composition containing the above-mentioned four components and a predetermined amount of an additive to be added if necessary. The order of blending is not particularly limited, and the components may be blended sequentially or simultaneously. In addition, after the polymerization reaction, the powdery or pelletized component (A) may be added to (B),
You may mix | blend (C) and (D) component.

The resin composition of the present invention is prepared by mixing or kneading the respective components in the above-mentioned mixing ratio, and as the method, the conventionally known melt-kneading method is preferable. Mixing is performed using a Banbury mixer, a Henschel mixer, etc., and as a kneading machine, a single-screw or twin-screw extruder is generally used. The temperature at the time of melt-kneading may be appropriately selected depending on the components, the blending amount, etc., so that the melting of each component does not proceed sufficiently and does not decompose. Usually 180-3
It is selected in the range of 50 ° C, preferably 200 to 300 ° C. The obtained resin composition may be molded into an arbitrary shape by extrusion molding, compression molding, injection molding or the like to obtain a desired resin product such as a pipe or a tube. Furthermore, after that, it is possible to perform processing such as plating and painting.

[0013]

EXAMPLES Next, the present invention will be described in more detail based on Examples and Comparative Examples. The various physical properties of the polyamide / polyolefin resin compositions obtained in the following examples are measured based on the following test methods. Of metal halide resistance test pieces (100 × 10 × 3mm thickness)
Preparation Method A flat plate having a thickness of 100 × 100 × 3 mm was molded from the composition by a screw in-line injection molding machine. The cylinder temperature at this time is 28 regardless of the type of the (A) polyamide resin.
It was set to 0 ° C. The mold temperature was 80 ° C. The central portion of this flat plate was cut out into a thickness of 100 × 10 × 3 mm to obtain a test piece. Metal Halide Resistance As a metal halide resistance, calcium chloride [Junsei Kagaku Co., Ltd., special grade reagent] was used as a 5% aqueous solution. A load of 50 gf was applied to both ends of the test piece with the central portion as a fulcrum. Brush the solution with the above aqueous solution and apply 100
A heat cycle treatment of ℃ × 2 hours -23 ℃ × 2 hours was performed. This operation was repeated until a crack was visually recognized on the test piece.

Examples 1 to 8 and Comparative Examples 1 to 4 (A) polyamide resin, (B) modified polyolefin resin, (C) polypropylene resin and (D) chelating agent shown in Table 1 were blended in a predetermined amount, and Henschel was added. 5 by mixer
Dry mixing was carried out for a minute, and the obtained mixture was melt-kneaded by a twin-screw extruder with a vent (30 mm inner diameter, L / D = 17) to prepare pellets. The heating temperature at the time of pellet formation was also 280 ° C. After heating and drying the pellets under reduced pressure, a flat plate was formed by injection molding and a metal halide resistance test was conducted. The results are shown in Table 1.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

* 1 PA6 polyamide resin, relative viscosity 2.50 amino terminal group concentration 4.9 x 10 ^-5 equivalent / g * 2 graft modified polypropylene, MFR at 230 ° C
Is a graft-modified polypropylene obtained by adding 0.35% by weight of maleic anhydride to isotactic polypropylene having 1.0 g / 10 min. * 3 Propylene homopolymer, propylene homopolymer having a MFR of JIS K6758 of 30 g / 10 min. Combined * 4 Ethylenediamine-N, N, N ', N'-tetraacetic acid * 5 Ethylene glycol bis- (β-aminoethyl ether) -N, N, N', N'-tetraacetic acid * 6 PA66 Polyamide resin, relative Viscosity 2.30 Amino end group concentration 5.1 × 10 ⁻⁵ equivalent / g * 7 N-oxyethylethylenediamine-N, N ′,
N'-triacetic acid * 8 Glycidyl methacrylate grafted ethylene-
A vinyl acetate copolymer was produced by referring to the method described in JP-B-55-12449. That is, the ethylene-vinyl acetate copolymer pellets were mixed with glycidyl methacrylate in which dicumyl peroxide was dissolved in advance and allowed to permeate at room temperature. Then, the glycidyl methacrylate-impregnated pellets were extruded at a tip temperature of 170 ° C. using a vented same-direction twin-screw extruder having an inner diameter of 30 mm to obtain grafted epoxy group-containing copolymer pellets (glycidyl methacrylate content 2% by weight) .. * 9 Propylene block copolymer, JIS K675
Propylene block copolymer having an MFR of 10 g / 10 min * 10 * 10 Nitrilotriacetic acid * a Percentage of the total amount of components (A), (B) and (C) * b (A), (B) and ( C) Parts by weight based on 100 parts by weight

[0019]

As described above, according to the present invention,
It has both excellent properties of polyamide resin and polypropylene resin, and in particular, various reinforced polyamide / polypropylene resin compositions having excellent halogen resistance can be produced, and metal halide resistance is required. A resin composition suitable for the application can be easily obtained. Therefore, the polyamide / polyolefin resin composition of the present invention is suitably used for automobile parts (outer plates, exterior parts, etc.), machine parts, industrial parts, etc., which are required to have metal halide resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 77/00 LQY (72) Inventor Yushi Nagao 3-2 Chidori-cho, Kawasaki-ku, Kanagawa Prefecture Showa Denko (72) Inventor Satoshi Maruyama 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Showa Denko Co., Ltd.

Claims (1)

[Claims] 1. A mixture of (A) 80 to 40% by weight of polyamide resin, (B) 1 to 40% by weight of modified polyolefin resin and (C) 20 to 60% by weight of polypropylene resin (D) per 100 parts by weight of a mixture (D). Metal chelating agent 0.01
A polyamide / polyolefin resin composition containing 10 to 10 parts by weight.