JPH0543797A - Reinforced 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, thus suitable for automotive parts, etc. CONSTITUTION:The objective composition can be obtained by incorporating a total of 100 pts.wt. of (A) 80-40 (pref. 80-45)wt.% of a polyamide resin, (B) 1-40 (pref. 3-30)wt.% of a modified polyolefin resin (e.g. ethylene/acrylic acid copolymer), and (C) 20-60 (pref. 20-50)wt.% of a polypropylene resin 1-50g/10min in MFR with (D) 1-200 (pref. 5-180) pts.wt. of a fibrous reinforcing material and/or inorganic filler (e.g. glass fiber, iron oxide). For the present composition, the ratio of the melt viscosity of the component C etapp (poise) to that of the component A etapA (poise): etapp/etapA is <=0.4 (pref. <=0.3).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforced polyamide / polyolefin resin composition, and more specifically, various reinforced polyamides having excellent properties of both polyamide resin and polypropylene resin, and further excellent in metal halide resistance. -It relates to a polyolefin resin composition.

[0002]

2. Description of the Related Art Generally, various reinforced polyamide resins have various properties such as mechanical strength, heat resistance (heat aging resistance, heat distortion resistance), chemical resistance, electrical characteristics and friction / wear characteristics. Due to its excellent properties, it is widely used as an engineering resin in various mechanical parts materials. On the other hand, it has some problems due to water absorption due to the amide group (-CONH-). In particular, the water-absorbed reinforced polyamide resin has many problems in practical use because it tends to contain bubbles and cause whitening or hydrolysis when it is molded. Further, not only the mechanical strength remarkably decreases due to water absorption, but also problems such as dimensional change and deformation occur. Since the reinforced polyamide resin has the above-mentioned drawbacks, its application as an engineering resin is limited, and it is often impossible to make use of the excellent characteristics inherent in the polyamide resin itself.

[0003] On the other hand, polypropylene resin has good characteristics that it is relatively inexpensive and exhibits almost no water absorption. However, it has the drawback of being soft and having poor physical properties at high temperatures. Therefore, in order to complement and improve the respective drawbacks of the polyamide resin and the polypropylene resin, it has been attempted to use them in combination. However, if the polyamide resin and the polypropylene resin are simply melt-kneaded, the compatibility is poor and peeling occurs between them, so even if they are reinforced with a fibrous reinforcing material or an inorganic filler, they have excellent properties. There is a problem that it cannot be a composition. Therefore, a resin composition having both excellent properties of a polyamide resin and a polypropylene resin in the past, that is, excellent mechanical strength, heat distortion resistance, abrasion resistance, oil resistance, etc. of a polyamide resin, and a polypropylene resin have Various studies have been accumulated for the purpose of obtaining a resin composition having excellent low water absorption, hot water resistance, metal halide resistance, and low temperature impact resistance (Japanese Patent Publication No. 42-12546, the same publication). 50-763
No. 6, etc.).

In the case of these various reinforced resin compositions, although some improvement in physical properties such as mechanical strength, heat distortion resistance, oil resistance, metal halide resistance, and low water absorption has been achieved, halogen resistance is improved. Metallicity is not always sufficient. The present inventors have completed the present invention as a result of earnestly researching for the purpose of improving the metal halide resistance while maintaining the excellent properties of the polyamide resin and the polypropylene resin.

That is, the present invention provides (A) a polyamide resin.
Fat 80 to 40% by weight, (B) Modified polyolefin 1 to 4
0% by weight and 20 to 60% by weight of (C) polypropylene resin
(D) fibrous with respect to 100 parts by weight of the mixture consisting of
1 to 200 parts by weight of a reinforcing material and / or an inorganic filler are mixed.
And molding temperature, shear rate 3500sec ^-1
Melt viscosity η of the (A) polyamide resin in_PA (po
ise) and (C) polypropylene resin melt viscosity η_PP (pois
The ratio of e) is_PP/ Η_PA≦ 0.4 ・ ・ ・ [I] is reinforced polyamide reinforced polyolefin
A resin composition is provided.

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; polyester amide, polyether amide, polyester ether amide and the like can be mentioned. 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. In particular, high amino terminated polyamides are preferred. It is also possible to use 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.

Next, the (B) modified polyolefin resin of the present invention includes carboxylic acid groups (acetic acid group, acrylic acid group,
Methacrylic acid group, fumaric acid group, itaconic acid group, etc., Carboxylic acid metal base (sodium salt, calcium salt, magnesium salt, zinc salt, etc.), Carboxylic acid ester group (methyl ester group, ethyl ester group, propyl ester group, A polyolefin having at least one functional group selected from a butyl ester group, a vinyl ester group), an acid anhydride group (maleic anhydride group, etc.) and an epoxy group. As the polyolefin, polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene /
Examples thereof include hexene copolymers and copolymers containing a small amount of diene.

Specific examples of such modified polyolefin 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, maleic anhydride grafted polyethylene, acrylic acid grafted polyethylene, maleic anhydride grafted polypropylene Ethylene, maleic anhydride grafted ethylene / propylene copolymer, acrylic acid grafted ethylene / propylene copolymer, fumaric acid grafted ethylene / 1-butene copolymer, 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-grafted ethylene / propylene / dicyclopentadiene copolymer, maleic acid-grafted ethylene /
Examples thereof include propylene / norbornadiene copolymer and acrylic acid graft ethylene / vinyl acetate copolymer. These modified polyolefin resins may be used alone or in combination of two or more kinds. The modified polyolefin resin can be produced by a known method, for example, Japanese Patent Publication No.
9-6810, Japanese Patent Publication No. 46-27527,
Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-43677
Publication, Japanese Examined Patent Publication No. 53-5716, Japanese Examined Patent Publication No. 53-1
It can be manufactured according to the methods shown in Japanese Patent Publication No. 9037, 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. Usually, those having a melt index in the range of 0.01 to 100 g / 10 minutes can be arbitrarily selected.

Subsequently, a propylene homopolymer and / or a propylene copolymer is used as the (C) polypropylene resin of the present invention. 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. Generally, those having an MFR of 1 to 50 g / 10 minutes are preferably used.

Further, in the present invention, (D) the fibrous reinforcing material and / or the inorganic filler is used. That is, one or both of the fibrous reinforcing material and the inorganic filler are used as the component (D). Here, as the fibrous reinforcing material, for example, glass fiber, potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber, aramid fiber, metal carbide fiber, ultra-high elastic polyethylene fiber, etc. may be mentioned. You can Examples of the inorganic filler include iron oxide, alumina, magnesium oxide,
Calcium oxide, oxides of zinc white, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate,
Hydrated metal oxides such as calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate, calcium carbonate,
Carbonates such as magnesium carbonate, silicates such as talc, clay, bentonite, attapulgite etc., borates such as barium borate, zinc borate etc., aluminum phosphate, sodium tripolyphosphate etc. Examples of sulfates such as phosphates and gypsum include sulfites. Other materials that can be used include spherical particles such as glass beads, glass balloons and shirasu balloons, glass powder, glass flakes, and mica. The type of these fibrous reinforcements or inorganic fillers can be appropriately selected according to the purpose, and when various fibrous reinforcements and inorganic fillers are mixed and used, a plurality of fibrous reinforcements are used. There are various cases such as the case of using a plurality of inorganic fillers.

In the composition of the present invention, various components as described above can be used as the components (A) to (D). Among these, between the components (A) and (C), Melt viscosity η _PA (poise) of component (A) and melt viscosity η of component (C) at a molding temperature and a shear rate of 3500 sec ⁻¹ .
The ratio of _PP (poise) satisfies the formula η _PP / η _PA ≦ 0.4 ・ ・ ・ [I], preferably the formula η _PP / η _PA ≦ 0.3 ・ ・ ・ [I ′] is selected in combination. It is necessary to. Here, if the value of η _PP / η _PA is 0.4 or more, the desired resin composition cannot be provided with desired metal halide resistance, which is not preferable. Here, the molding processing temperature is a temperature at which the composition of the present invention is molded to produce various molded products, and is generally in the range of 180 to 350 ° C.

The blending ratio of each component in the resin composition of the present invention is 80 to 40% by weight, preferably 80, based on the total amount of the above components (A), (B) and (C). ~
45% by weight, component (B) 1 to 40% by weight, preferably 3
-30% by weight, and the component (C) is 20-60% by weight, preferably 20-50% by weight. Also,
Component (D) is a total of 10 components (A), (B) and (C).
1 to 200 parts by weight, preferably 5 to 0 parts by weight
It is in the range of 180 parts by weight. Here, the component (A) is 40
If it is less than wt%, sufficient heat resistance cannot be imparted to the resulting composition. If it exceeds 80% by weight, the properties of the polypropylene resin are lost. on the other hand,
When the blending ratio of the component (B) is less than 1% by weight, it is difficult to improve the compatibility between the polyamide resin which is the component (A) and the polypropylene resin which is the component (C). It cannot give desired physical properties. Further, if the amount of the component (B) exceeds 40% by weight, the effect corresponding to the blending amount is small, and the various properties of the obtained composition may be deteriorated. Furthermore, the component (C) is 20% by weight.
If it is less than the above, the original characteristics of the polypropylene resin cannot be obtained. On the other hand, when it exceeds 60% by weight, it becomes difficult to impart sufficient heat resistance to the composition. Also,
When the amount of the component (D) is less than 1% by weight based on 100 parts by weight of the total of the components (A), (B) and (C), the composition may have physical properties such as mechanical strength. On the contrary, if the amount exceeds 200 parts by weight, the effect corresponding to the blending amount is small and the physical properties of the obtained composition may be deteriorated.

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, nucleating agents, plasticizers, lubricants, release agents,
Examples include coupling agents, foaming agents, heat resistant agents, weather resistant agents, flame retardants, antistatic agents, and sliding agents.

The resin composition of the present invention is a resin composition prepared by mixing the above-mentioned four components and a predetermined amount of an additive, if necessary. The order of blending is not particularly limited, and the components may be blended sequentially or simultaneously. In addition, the powdery or pelletized component (A) after the completion of the polymerization reaction,
You may mix | blend (B), (C), and (D) component. Alternatively, for the component (A) still in a molten state after the completion of the polymerization reaction,
The components (B), (C) and (D) may be blended and melt-kneaded. Thus, the resin composition of the present invention is prepared by mixing or kneading the respective components in the above-mentioned mixing ratio. As the method, a 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 18
It is selected in the range of 0 to 350 ° C, preferably 200 to 300 ° C. The obtained resin composition is extrusion molded, compression molded,
A desired resin product such as a pipe, a tube, a rod, or a hollow molded product may be formed by molding into an arbitrary shape by injection molding or the like.
Furthermore, after that, it is possible to perform processing such as plating and painting.

[0015]

EXAMPLES Next, the present invention will be described in more detail based on Examples and Comparative Examples. Various physical properties of the reinforced polyamide / polyolefin resin composition obtained in each of 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 into a thickness of 100 × 10 × 3 mm to obtain a test piece. Melt viscosity Capirograph manufactured by Toyo Seiki Co., Ltd., set temperature 2
The melt viscosity at 80 ° C. and a shear rate of 3500 sec ⁻¹ was measured. Metal Halide Resistance As a metal halide resistance, calcium chloride [Junsei Kagaku Co., Ltd., special grade reagent] was used as a 5% aqueous solution. With the center of the test piece as the fulcrum, a load of 250 gf was applied to each end. Brush the above aqueous solution onto it and apply 10
A heat cycle treatment was performed at 0 ° C for 2 hours and at 23 ° C for 2 hours. This operation was repeated until a crack was visually recognized on the test piece.

Examples 1 to 10 and Comparative Examples 1 to 4 (A) polyamide resin, (B) modified polyolefin resin, (C) polypropylene resin and (D) various reinforcing materials (fibrous reinforcing material, Inorganic filler) is blended in a specified amount,
Dry mix for 5 minutes with a Henschel mixer, and then mix the resulting mixture with a vented twin-screw extruder (inner diameter 30 mm,
L / D = 17) was melt-kneaded 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. In addition, in this Table 1, 280
The melt viscosity ratio (η _PP / η _PA ) of the (A) polyamide resin and the (C) polypropylene resin at a shear rate of 3500 sec ^{−1 at} ℃ is also shown.

Comparative Examples 5 to 6 Polyamide resins shown in Table 1 were blended with a reinforcing agent, pellets were prepared and molded in the same manner as in Example 1, and the same tests were conducted. The results are shown in Table 1.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

* 1 PA6 polyamide resin, relative viscosity 3.20 amino terminal group concentration 4.9 × 10 ⁻⁵ equivalent / g * 2 graft modified polypropylene, MFR at 230 ° C.
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 with MFR in JIS K6758 of 30 g / 10 min. * 4 Micron White 5000A Hayashi Kasei Co., Ltd. * 5 Chopped strand fiber with a length of 3 mm and a diameter of 10 μm, the surface of which has been treated with an aminosilane coupling agent. * 6 PA66 polyamide resin, relative viscosity 2.85 amino end group concentration. 5.2 × 10 ^-5 equivalent / g * 7 propylene block copolymer, JIS K675
Propylene block copolymer having an MFR of 70 g / 10 min * 8 PA66 polyamide resin, relative viscosity 2.30 Amino end group concentration 5.1 x 10 ^-5 equivalents / g * 9 PA6 polyamide resin, relative viscosity 2. 52 Amino end group concentration 4.9 × 10 ^-5 equivalent / g * 10 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. Next, 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). * 11 Propylene homopolymer, propylene homopolymer having an MFR of 0.8 g / 10 in JIS K6758 * a Percentage of the total amount of components (A), (B) and (C) * b (A), ( Parts by weight based on 100 parts by weight of the total of components B) and (C)

[0022]

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 reinforced polyamide / polyolefin resin composition of the present invention can be suitably used for automobile parts (outer panels, exteriors, etc.), mechanical parts, industrial parts, etc., which require metal halide resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 51/06 LLE 7142-4J (72) Inventor Satoshi Maruyama 3-Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa 2 Showa Denko Co., Ltd. Kawasaki Resin Research Laboratory

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). Melt viscosity η _PA (poise) and (C) of the (A) polyamide resin prepared by blending 1 to 200 parts by weight of a fibrous reinforcing material and / or an inorganic filler at a molding processing temperature and a shear rate of 3500 sec ^-1 .
A reinforced polyamide / polyolefin resin composition characterized in that the ratio of the melt viscosity η _PP (poise) of the polypropylene resin satisfies the formula η _PP / η _PA ≦ 0.4 ... [I].