JP2695490B2 - Reinforced polyamide / polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a reinforced polyamide / polyolefin resin composition, and more specifically, it has excellent characteristics of both polyamide and polypropylene, and further has various coating properties. The present invention relates to a reinforced polyamide / polyolefin resin composition.

[Problems to be solved by conventional technology and invention]

Generally, various reinforced polyamide resins have the following properties:
It has excellent heat resistance (heat aging resistance, heat deformation resistance), chemical resistance, electrical characteristics, and friction and wear characteristics, and is therefore widely used as an engineering resin for various machine parts materials. On the other hand, it has some problems due to water absorption due to the amide group (-CONH-). In particular, the reinforced polyamide resin that has absorbed water has many problems in practical use since it tends to contain bubbles and cause whitening or hydrolysis when it is molded. Further, water absorption not only causes a marked decrease in mechanical strength, but also causes problems such as dimensional change and deformation.

Since the reinforced polyamide resin has the above-mentioned drawbacks, its use as an engineering resin is limited, and it is often impossible to make use of the excellent characteristics inherent in the polyamide resin itself.

On the other hand, polypropylene resin is relatively inexpensive and has good characteristics that it exhibits almost no water absorption,
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, a composition having excellent properties is obtained. There is a problem that it cannot be a thing.

Therefore, conventionally, a resin composition having both excellent properties of polyamide resin and polypropylene resin,
That is, it has excellent mechanical strength, heat distortion resistance, wear resistance, oil resistance, etc. that polyamide resin has, and also has excellent low water absorption, hot water resistance, metal halide resistance, and low temperature impact resistance that polypropylene resin has. Various studies have been accumulated for the purpose of obtaining a resin composition. (Japanese Patent Publication No. 42-12546, No. 50-7636, etc.).

In the case of these various reinforced resin compositions, some improvement in physical properties such as mechanical strength, heat distortion resistance, oil resistance, metal halide resistance, and low water absorption has been achieved. The current situation is that research has not progressed so much. That is, since these resin compositions (polymer alloy compositions) include polypropylene resins having poor coatability as compared with polyamide resins, the coatability as a whole is insufficient, and as a result, their applications are considerably limited. Is the current situation.

The present inventors have completed the present invention as a result of earnest researches for the purpose of improving the paintability while maintaining the excellent properties of the polyamide resin and the polypropylene resin.

[Means for solving the problem]

That is, the present invention includes (A) polyamide resin 80 to 40% by weight, (B) modified polyolefin 1 to 40% by weight, and (C).
1 to 200 parts by weight of (D) a fibrous reinforcing material and / or an inorganic filler is added to 100 parts by weight of a mixture composed of 20 to 60% by weight of polypropylene resin, and the molding temperature is
The ratio of the melt viscosity η _PP (poise) of the (A) polyamide resin and the melt viscosity η _PA (poise) of the (C) polypropylene resin at a shear rate of 3500 sec ⁻¹ is expressed by the formula η _PP / η _PA > 0.75. I] to provide a reinforced polyamide / polyolefin resin composition.

As the (A) polyamide resin used in the present invention, various types can be used, but specifically, polylactams such as nylon 6, nylon 11, nylon 12; nylon 66, nylon 610, nylon 612, nylon 46, etc. Polyamides obtained from dicarboxylic acids and diamines; nylon 6/66,
Copolymer polyamides such as nylon 6/12, nylon 6/66/610; from aromatic dicarboxylic acids such as nylon 6 / 6T (T: terephthalic acid component), isophthalic acid and metaxylene diamine or alicyclic diamine The semi-aromatic polyamides obtained may include polyester amides, polyether amides and polyester ether amides. 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, and various types can be used. However, high amino terminated polyamides are especially 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, as the (B) modified polyolefin of the present invention,
Carboxylic acid groups (acetic acid group, acrylic acid group, methacrylic acid group, fumaric acid group, itaconic acid group, etc.), carboxylic acid metal bases (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 therein. .

Specific examples of such modified polyolefins include ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / fumaric acid copolymers, ethylene / methacrylic acid / zinc methacrylate copolymers, ethylene / acrylics. 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, maleic anhydride Acid-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 graft ethylene /
Propylene / dicyclopentadiene copolymer, maleic acid-grafted ethylene / propylene / norbornadiene copolymer, acrylic acid-grafted ethylene / vinyl acetate copolymer and the like, and these modified polyolefins may be used alone or in combination. It is also possible to use more than one species together.

The modified polyolefin can be produced by a known method, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 46-27527, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52-43677, and Japanese Patent Publication No. 53.
-5716, Japanese Patent Publication No. 53-19037, Japanese Patent Publication No. 53-411
It can be manufactured according to the method described in Japanese Patent Publication No. 73, Japanese Patent Publication No. 56-9925, etc. Regarding ethylene ionomers, "Surlyn", "Himilan",
Various grades marketed under the trade name of "COPOLEN" can be used. Further, the degree of polymerization of the modified polyolefin used in the present invention is not particularly limited, but one having a melt index in the range of 0.01 to 100 g / 10 minutes can be arbitrarily selected.

Then, as the polypropylene resin (C) of the present invention, 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 thereof 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, propylene homopolymer,
The molecular weight of the propylene copolymer is 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 are 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,
Examples thereof include metal carbide fibers and ultra high modulus polyethylene fibers.

Examples of the inorganic filler include iron oxide, alumina,
Oxides of magnesium oxide, calcium oxide, zinc oxide, etc., hydrated metal oxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate, etc. , Carbonate such as calcium carbonate, magnesium carbonate, silicate such as talc, clay, bentonite, attapulgite, borate such as barium borate, zinc borate, aluminum phosphate, sodium tripolyphosphate Examples thereof include phosphates such as, and sulfates or sulfites such as gypsum. 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 types of these fibrous reinforcements or inorganic fillers are
It can be appropriately selected according to the purpose, and when various fibrous reinforcements and inorganic fillers are mixed and used, when plural fibrous reinforcements are used, when plural inorganic fillers are used, etc. Is.

In the composition of the present invention, various components as described above can be used as the components (A) to (D). Among them, the molding processing temperature is different between the components (A) and (C). , Melt viscosity η _PA (poise) of component (A) and shear viscosity η _PP (pois of component (C) at a shear rate of 3500 sec ⁻¹
It is necessary that the ratio e) satisfies the formula η _PP / η _PA > 0.75 ・ ・ ・ [I], preferably the formula η _PP / η _PA > 1.00 ・ ・ ・ [I ′] is selected in combination. . Here, if the value of η _PP / η _PA is 0.75 or less, the polyamide resin forms a dispersed phase, which makes it impossible to impart desired coatability to the obtained resin composition, 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 mixing ratio of each component in the resin composition of the present invention is based on the total amount of the components (A), (B) and (C),
Component (A) 80 to 40% by weight, preferably 80 to 45% by weight,
The component (B) is selected in the range of 1 to 40% by weight, preferably 3 to 30% by weight, and the component (C) in the range of 20 to 60% by weight, preferably 20 to 50% by weight. The component (D) is in the range of 1 to 200 parts by weight, preferably 5 to 180 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C).

Here, if the amount of the component (A) is less than 40% by weight, it is not possible to impart sufficient coatability to the obtained composition. Also 80
When it exceeds the weight percentage, 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). Cannot be given the desired physical properties. Further, if the content of the component (B) exceeds 40% by weight, the effect corresponding to the blending amount is small, and rather various physical properties of the obtained composition may be deteriorated. Furthermore, (C) component
If it is less than 20% by weight, the original properties of polypropylene resin cannot be obtained. On the other hand, when it exceeds 60% by weight, it becomes difficult to impart sufficient paintability to the composition.

If 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 will have physical properties such as mechanical strength. On the contrary, even if the amount exceeds 200 parts by weight, the effect corresponding to the blending amount is small, and rather the physical properties of the resulting composition may be deteriorated.

The resin composition of the present invention comprises the above (A), (B),
The main components are the four components (C) and (D), but if necessary, other additives may be added within a range that does not impair the characteristics of the above components. Examples of additives that can be added here include dyes, pigments, nucleating agents, plasticizers, lubricants, release agents, coupling agents, foaming agents, heat-resistant agents, weather-resistant agents, flame retardants, antistatic agents, and sliding agents. To be

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 to be added as necessary.
The order of compounding is not particularly limited, and the components may be compounded sequentially or simultaneously. Further, the powdery or pelletized component (A) after the completion of the polymerization reaction is added to the components (B) and (C).
You may mix | blend and (D) component. Alternatively, the component (A) still in a molten state after the completion of the polymerization reaction may be added to the component (B),
The components (C) and (D) may be blended and melt-kneaded.

As described above, the resin composition of the present invention is prepared by mixing or kneading the respective components in the above-mentioned mixing ratio, and as a method therefor, 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. Normally 180-350
C., preferably in the range of 200 to 300.degree.

The obtained resin composition is molded into an arbitrary shape by extrusion molding, compression molding, injection molding, etc.
A desired resin product such as a hollow molded product may be used. Furthermore, after that, processing such as plating and painting can be performed.

〔Example〕

Next, the present invention will be described in more detail based on Examples and Comparative Examples.

The reinforced polyamides obtained in each of the following examples
Various physical properties of the polyolefin resin composition are measured based on the following test methods.

Method for preparing flat plate for coating (100 × 100 × 3 mm thickness) The flat plate was formed by molding the composition with a screw in-line injection molding machine. The cylinder temperature at this time was 280 ° C. regardless of the type of the (A) polyamide resin. The mold temperature was 80 ° C.

Melt viscosity Using a Capillograph manufactured by Toyo Seiki Co., Ltd., set temperature
The melt viscosity was measured at 280 ° C and a shear rate of 3500 sec ^-1 .

Paintability A two-component polyurethane resin paint (Stron Ace # 680: manufactured by Cashew Co., Ltd.) was used as a paint, and was applied by spraying on a flat plate, and the drying condition was 100 ° C. for 40 minutes. After the sample was left at room temperature for one day, cross-cut peeling test and adhesion strength of the coating film were measured.

Examples 1 to 11 and Comparative Examples 1 to 4 (A) polyamide resin, (B) modified polyolefin, (C) polypropylene resin and (D) various reinforcing materials (fibrous reinforcing material, inorganic filler) shown in Table 1. A prescribed amount of
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) and 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 coating test was conducted. The results are shown in Table 1.

Table 1 also shows the melt viscosity ratio (η _PP / η _PA ) of the (A) polyamide resin and the (C) polypropylene resin at 280 ° C. and a shear rate of 3500 sec ⁻¹ .

[Effects of the Invention] As described above, according to the present invention, various reinforced polyamide / polypropylene resin compositions having excellent characteristics of polyamide resin and polypropylene resin respectively and having particularly excellent coatability are produced. It is possible to easily obtain a resin composition suitable for applications requiring paintability.

Therefore, the reinforced polyamide / polyolefin resin composition of the present invention is suitably used for automobile parts (outer plates, exteriors, etc.), machine parts, industrial parts, etc., which require paintability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 23:00)

Claims (1)

(57) [Claims] 1. A mixture of (A) 80 to 40% by weight of polyamide resin, 1 to 40% by weight of (B) modified polyolefin and 20 to 60% by weight of (C) polypropylene resin, and (D) 1 to 200 parts by weight of fibrous reinforcing material and / or inorganic filler is compounded, and molding temperature and shear rate 3500
Melt viscosity η of the (A) polyamide resin at sec ⁻¹
Melt viscosity of _PA (poise) and (C) polypropylene resin η
A reinforced polyamide-polyolefin resin composition characterized in that the ratio of _PA (poise) satisfies the formula η _PP / η _PA > 0.75 ... [I].