JP3170306B2 - Polyamide / polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a polyamide-polyolefin resin compositions, and more particularly, combines the respective excellent characteristics of the polyamide resin and polypropylene resin, a polyamide-polyolefin having excellent shock <br/>撃性and paintability especially It relates to a resin composition.

[0002]

2. Description of the Related Art Generally, polyamide resins are widely used as synthetic fibers because of their excellent physical and chemical properties, but recently they are also used as molding materials. It has become. This is because polyamide resin is a thermoplastic resin and has high mechanical strength, excellent abrasion resistance, chemical resistance, heat resistance and relatively excellent electrical properties. It depends on having enough. However, on the other hand, the amide group (-CONH-) has undesired performances such as dimensional change due to water absorption and reduction in mechanical strength, and therefore, its marketability as a molding material. Is limited.

[0003] On the other hand, polypropylene resin is inexpensive and shows almost no water absorption, but it is soft and has disadvantages such as poor physical properties at high temperatures. Therefore, in order to improve the respective disadvantages of the polyamide resin and the polypropylene resin, it is conceivable to use these resins in combination.However, a resin mixture obtained by mixing a polyamide resin and a polypropylene resin by a usual method, or a mixture thereof A resin composition obtained simply by melt-kneading has poor compatibility and cannot be a composition having the desired excellent physical properties. Therefore, conventionally, a resin composition having both the excellent properties of a polyamide resin and a polypropylene resin, that is, the excellent wear resistance, electrical properties, heat resistance,
In order to obtain a resin composition that combines mechanical strength, oil resistance, and low water absorption, hot water resistance, metal halide resistance, and low-temperature impact resistance of polypropylene resin,
Melt and mix three components of polyamide resin, olefin polymer and modified polyolefin grafted with unsaturated carboxylic acid or its derivative to obtain strength, heat deformation resistance, appearance,
Japanese Patent Publication No. Sho 42-12546 and Japanese Patent Publication Sho No. 4 have already disclosed a method of obtaining a composition having an excellent balance of moldability.
No. 5,309,945 and Japanese Patent Publication No. 50-7636. Utilizing these excellent properties, commercialization is considered for applications requiring strength and heat-resistant deformation, such as automobile parts, electric appliances, machine parts, and industrial parts. It has been done.

[0004] However, even with the resin composition (polymer alloy composition) having such characteristics, there is a problem that the coatability and impact resistance are not yet sufficient. These polymer alloy compositions include polypropylene resins having poor paintability and impact resistance as compared with polyamide resins, so that at present, their uses are considerably limited. The present inventors have made intensive studies for the purpose of improving the impact resistance or the paintability and the impact resistance, while maintaining the excellent properties of the polyamide resin and the polypropylene resin. As a result, the combined use of a polyamide resin and polypropylene resin optionally, a phase as compatibilizing agent modified polypropylene resin, also blended with the modified polyolefin copolymer rubber as an impact modifier, a further ratio of melt viscosity at molding temperatures It has been found that by setting a certain relationship, both the paintability and the impact resistance can be improved.

The present invention has been completed based on such findings. That is, the present invention relates to (A) a polyamide resin (hereinafter referred to as a component (A)) 90 to 40 parts by weight, (B)
Modified polypropylene resin (hereinafter referred to as component (B)) 1
To 20 parts by weight, (C) 1 to 20 parts by weight of modified polyolefin copolymer rubber (hereinafter referred to as component (C)) and (D) polypropylene resin (hereinafter referred to as component (D))
10-60 parts by weight or Rana is, and the ratio of the molding temperature, the at a shear rate of 1,000 sec ^-1 and (A) the melt viscosity of the component η _PA (poise) (D) component of the melt viscosity η _PP (poise) is it is intended to provide Hisage polyamide-polyolefin resin composition characterized by satisfying the equation η _PP / η _PA> 5 ··· [I].

As the component (A) used in the present invention, various types can be used, and specifically, polylactams such as nylon 6, nylon 11, nylon 12, and the like; nylon 66, nylon 610, nylon 612, nylon 4
Polyamides obtained from dicarboxylic acids such as 6 and diamines; copolymer polyamides such as nylon 6/66, nylon 6/12, nylon 6/66/610; nylon 6 / 6T (T: terephthalic acid component); Semi-aromatic polyamides obtained from an aromatic dicarboxylic acid such as isophthalic acid and meta-xylene diamine or alicyclic diamine;
Mention may be made of polyesteramides, polyetheramides and polyesteretheramides. In addition,
As the component (A), the various polyamides described above may be used alone, or two or more polyamides may be used in combination. Furthermore, as long as the polyamide resin that can be used in the present invention is selected from the above-mentioned polyamides, various polyamide resins can be used without being limited by the type, concentration, molecular weight, and the like of the terminal groups of these polyamides. Although it is possible, a high amino-terminated polyamide is particularly preferred. Further, it is also possible to use a polyamide in which low molecular weight substances such as monomers and oligomers remaining or formed during polymerization of the polyamide are mixed.

Next, there are various types of component (B) used in the present invention. Usually, a carboxylic acid group (acetic acid group, acrylic acid group, methacrylic acid group, fumaric acid group, itaconic acid group, etc.) is used. ), Acid anhydride group (maleic anhydride group, etc.)
And at least one functional group selected from epoxy groups. Specific examples of such a modified polypropylene resin include a copolymer obtained by grafting the above-mentioned functional group onto polypropylene, such as a maleic anhydride-grafted modified polypropylene resin. These modified polypropylene resins may be used alone or in combination of two or more. The modified polypropylene resin also includes, in addition to a modified propylene homopolymer, a modified copolymer of ethylene and another comonomer.

[0008] The component (C) used in the present invention may be of various types, but is usually a carboxylic acid group (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, butyl ester group, vinyl ester group, etc.), acid anhydride A modified polyolefin copolymer rubber having at least one functional group selected from a group (maleic anhydride group and the like) and an epoxy group.
As the modified polyolefin copolymer rubber, there are various rubbers other than the modified polypropylene resin constituting the component (B). For example, polyethylene rubber, polybutene rubber, ethylene / propylene copolymer rubber, ethylene / butene copolymer rubber are available. Polymer rubbers, ethylene / hexene copolymer rubbers, and copolymer rubbers containing a small amount of a diene may be mentioned. Specific examples of such modified polyolefin copolymer rubber include ethylene / acrylic acid copolymer rubber, ethylene / methacrylic acid copolymer rubber, ethylene / fumaric acid copolymer rubber, ethylene / maleic anhydride / methacrylic acid. Copolymer rubber, ethylene /
Vinyl acetate / maleic anhydride copolymer rubber, ethylene /
Methacrylic acid / zinc methacrylate copolymer rubber, ethylene / acrylic acid / sodium methacrylate copolymer rubber, ethylene / isobutyl acrylate / methacrylic acid /
Zinc methacrylate copolymer rubber, ethylene / methyl methacrylate / methacrylic acid / magnesium methacrylate copolymer rubber, ethylene / ethyl acrylate copolymer rubber, ethylene / vinyl acetate copolymer rubber, ethylene / glycidyl methacrylate copolymer Polymer rubber, ethylene / vinyl acetate / glycidyl methacrylate copolymer rubber, maleic anhydride-grafted polyethylene rubber, acrylic acid-grafted polyethylene rubber, maleic anhydride-grafted ethylene /
Propylene copolymer rubber, acrylic acid-grafted ethylene / propylene copolymer rubber, fumaric acid-grafted ethylene / 1-butene copolymer rubber, ethylene / 1-hexene-
Itaconic acid copolymer rubber, ethylene / propylene-endobicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride copolymer rubber, ethylene / propylene-
Methacrylic acid grafted glycidyl copolymer rubber, maleic anhydride grafted ethylene / methacrylic acid copolymer rubber, maleic anhydride grafted ethylene / propylene /
1,4-hexadiene copolymer rubber, fumaric acid-grafted ethylene / propylene / dicyclopentadiene copolymer rubber, maleic acid-grafted ethylene / propylene / norbornadiene copolymer rubber, acrylic acid-grafted ethylene / vinyl acetate copolymer rubber, etc. These modified polyolefin copolymer rubbers may be used alone or in combination of two or more. The above modified polyolefin copolymer rubber can be produced by a known method, for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 46-275.
No. 27, Japanese Patent Publication No. 50-2630, Japanese Patent Publication No. 52
JP-B-43677, JP-B-53-5716, JP-B-53-19037, and JP-B-53-41173.
And JP-B-56-9925. The degree of polymerization of the modified polyolefin copolymer rubber used in the present invention is not particularly limited, but usually has a melt index of 0.01 to 10.
Those within the range of 0 g / 10 minutes can be arbitrarily selected.
The component (C) has an elastic modulus at room temperature of 5000 k.
g / cm ² or less. If a material having an elastic modulus at room temperature exceeding 5000 kg / cm ² is used, there is a disadvantage that the resulting composition has insufficient improvement in impact resistance.

Next, as the component (D), a propylene homopolymer and / or a propylene copolymer are used. Here, as the propylene copolymer, propylene-
There are an ethylene copolymer, a propylene-butene-1 copolymer and the like, and a block copolymer and a random copolymer thereof are used. As the polypropylene resin, a propylene homopolymer or a propylene copolymer may be used alone, or two or more kinds 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 those having a melt flow rate (MFR) of 1 to 50 g / 10 minutes are suitably used.

In the composition of the present invention, the above (A) to (D)
Various components as described above can be used as components.
In the present invention, the mixing ratio of each component for producing a polyamide / polyolefin resin composition having excellent impact resistance and coating properties is 90 to 40 parts by weight, preferably 90 to 50 parts by weight of the component (A). , (B) component is 1 to 20 parts by weight, preferably 3 to 20 parts by weight. Component (C) is 1 to 20 parts by weight, preferably 3 to 20 parts by weight, and component (D) is 10 to 60 parts by weight, preferably 10 to 60 parts by weight.
40 parts by weight. Here, when the component (A) is less than 40 parts by weight, the mechanical strength and coatability of the obtained composition are not sufficiently improved. Conversely, if it exceeds 90 parts by weight, the inherent properties of the polypropylene resin will be lost. When the components (B) and (C) are less than 1 part by weight, the components (A) and (D)
It is difficult to improve the compatibility with the components, and as a result, it may not be possible to impart desired physical properties to the resulting composition. On the other hand, if the amount of the component (D) is less than 10 parts by weight, the inherent properties of polypropylene cannot be imparted to the composition. Conversely, if the amount exceeds 60 parts by weight, the desired effects of improving mechanical strength and coatability are not sufficiently exhibited.

In order to produce a polyamide / polyolefin resin composition having excellent impact resistance and coatability, the components (A) and (D) must have a molding temperature and a shear rate of 1000 sec. the ratio of the melt viscosity of the component (a) in the ^-1 η _PA (poise) and (D) melt viscosity of component η _PP (poise) has the formula η _PP / η _PA> 5 ··· [I] a good Mashiku is It is necessary to select a combination that satisfies the formula η _PP / η _PA > 5.5... [I ′] . Now is the eta value of _PP / eta _PA is 5 or less, have a Ki out to impart coatability to the resin composition obtained. Here, the molding temperature is the temperature at which the composition of the present invention is molded to produce various molded articles, and is generally 180 to 35.
It is in the range of 0 ° C.

The resin composition of the present invention comprises the above (A),
Although the four components of (B), (C) and (D) are the main components, other additives may be added as needed, as long as the characteristics of the above components are not impaired. Additives that can be blended here include dyes, pigments, fillers, nucleating agents, fibrous materials,
Examples include plasticizers, lubricants, release agents, coupling agents, foaming agents, heat-resistant agents, weathering agents, flame retardants, antistatic agents, and sliding agents. As described above, the resin composition of the present invention is a resin composition obtained by blending the above components and additives to be added as required in a predetermined amount. There is no particular limitation on the order of blending, and the components may be blended sequentially or simultaneously. For example, the components (B), (C) and (D) may be mixed with the powdery or pelletized component (A) after the completion of the polymerization reaction,
Alternatively, components (B), (C) and (D) may be blended with component (A) which is still in a molten state after the completion of the polymerization reaction and melt-kneaded.

The resin composition of the present invention is prepared by mixing or kneading the respective components in the above-mentioned mixing ratio, and a conventionally known melt kneading method is preferable. Mixing is performed using a Banbury mixer, a Henschel mixer, or the like, and a single-screw or twin-screw extruder is generally used as a kneader. The temperature at which the components are melted and kneaded may be appropriately selected depending on the components, the amount of the components, and the like, so that the components can be sufficiently melted and do not decompose. Usually 180-3
It is selected in the range of 50C, preferably 200-300C. The obtained resin composition may be formed 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 tube. Further, thereafter, processing such as plating and painting can be performed. In this way, the impact resistance and polyamide-polyolefin resin composition having excellent coating properties was obtained, automobile parts, etc., can be particularly effectively used as parts such as wheel covers.

[0014]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. The various physical properties of the polyamide / polyolefin resin compositions obtained in the following examples were measured based on the following test methods. Melt viscosity Using Toyo Seiki Co., Ltd. Capillograph, set temperature 26
The melt viscosity at 0 ° C. and a shear rate of 1000 sec ⁻¹ was measured. A two-pack type acrylic urethane resin paint (Lecrac, manufactured by Asakura Kasei Co., Ltd.) was used as a paint, and was applied to a wheel cover-like molded product by a spray method. The drying condition was 80 ° C. for 30 minutes. After the sample was left at room temperature for one day, a cross-cut peeling test and a measurement of the adhesion strength of the coating film were performed. Falling ball impact test A molded test piece having a size of 15 × 15 cm and a thickness of 3 mm was cooled in a -40 ° C. atmosphere, and a steel ball of 500 g was dropped to measure a height at which breakage occurred.

Examples 1 to 6 and Comparative Examples 1 to 5 A predetermined amount of the components (A), (B), (C) and (D) shown in Table 1 was blended, and dried by a Henschel mixer for 5 minutes. Mixing was performed, and the resulting mixture was melt-kneaded with a vented co-directional twin-screw extruder (inner diameter 30 mm, L / D = 17) to produce pellets. The heating temperature at the time of making the pellets was also 260 ° C. After heating and drying the pellet under reduced pressure, a wheel cover-like molded product was molded by injection molding, and the above test was performed. The results are shown in Table 1. Table 1 shows 260 ° C. and a shear rate of 1000.
η _PP / η _PA at sec ⁻¹ is also shown.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

* 1 PA6 with an amino terminal group concentration of 4.9 × 10 ⁻⁵ equivalents * 2 Several types of polypropylene resins having a MFR of 0.03 to 3 according to JIS K6785, which are propylene homopolymers and propylene block copolymers. 3. Melt viscosity ratio at 260 ° C., 1000 sec ⁻¹ * 4 Modified polypropylene resin: graft-modified polypropylene resin, isotactic polypropylene having an MFR of 1.0 g / 10 min at 230 ° C., and maleic anhydride added to 0 Graft-modified polypropylene resin added with .35% by weight * 5 Modified polyolefin copolymer rubber: 75 parts by weight of ethylene-methyl methacrylate-maleic anhydride terpolymer rubber, ethylene-propylene copolymer rubber 2
5 parts by weight, 0.011 parts by weight of 2,5-di (t-butylperoxy) hexane and 0.375 parts by weight of maleic anhydride were dry-mixed using a Henschel mixer, and were subjected to a non-vented extruder (40 mm inner diameter). Melt kneading was performed at 220 to 240 ° C. * 6 ○ ・ ・ No peeling * 7 △ ・ ・ Partial peeling * 8 ○ ・ ・ 25kg ・ cm or more (-40 ℃) * 9 × ・ ・ 25kg ・ cm or less (-40 ℃) * 10 Possible

[0021]

As described above, according to the present invention, various reinforced polyamide / polypropylene resin compositions having both the excellent properties of a polyamide resin and a polypropylene resin, and particularly having excellent impact resistance and coating properties , can be obtained. can be prepared, impact resistance and paintability Ru can be easily obtained a resin composition which is suitable for applications requiring. What slave, polyamide polyolefin resin composition of the present invention include automotive parts and impact resistance and paintability are required (wheel cover, skins, etc. exterior), it is suitably used for machine parts, industrial parts, etc. You.

────────────────────────────────────────────────── (5) Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 23:02) (56) References JP-A-62-158739 (JP, A) JP-A-2-24357 (JP, A) JP-A-2-24356 (JP, A) JP-A-64-87656 (JP, A) JP-A-1-3111147 (JP, A) JP-A-3-124748 (JP, A) (58) (Int.Cl. ⁷ , DB name) C08L 77 / 02,23 / 10 B60B 7/00

Claims (2)

(57) [Claims] (A) 90 to 40 parts by weight of a polyamide resin, (B) 1 to 20 parts by weight of a modified polypropylene resin,
(C) a modified polyolefin copolymer rubber 1 to 20 parts by weight of (D) Ri Na <br/> a polypropylene resin 10 to 60 parts by weight, and molding temperature, the shear rate of 1,000 sec ^-1
(A) melt viscosity of polyamide resin η _PA (pois
e) and (D) melt viscosity of polypropylene resin η _PP (poise)
Wherein the ratio satisfies the formula η _PP / η _PA > 5 (I) . 2. Polyamide / polyolefin according to claim 1.
Wheel cover made of thin resin composition with excellent impact resistance
-