JPH0782436A - Canister for automobile - Google Patents

Abstract

PURPOSE:To provide a canister excellent in metal chloride resistance and impact resistance and useful for automobiles by molding a composition comprising a specific mixture and a specific ethylenic copolymer in a specified ratio. CONSTITUTION:This canister for automobiles is molded from a composition containing 100 pts.wt. of a mixture (the total amount of the components A to C is 100wt.%) comprising (A) 39-80wt.% of a polyamide such as nylon 6, (B) 19-60wt.% of PP, and (C) 1-40wt.% of modified PP obtained e.g. by graft- reacting an unsaturated carboxylic acid anhydride such as maleic acid anhydride to PP, and 1-20 pts.wt. of an ethylenic copolymer containing carboxylic acid anhydride groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an automobile canister which is particularly excellent in metal halide resistance and impact resistance.

[0002]

2. Description of the Related Art Conventionally, a canister for an automobile is made of metal or resin such as polyamide and is installed at a place where it is not easily affected by the road surface.
However, in recent years, as the size of the canister has increased due to exhaust gas regulations, its installation location has come to be directly affected by the road surface. That is, water resistance against water splash from the road surface, impact resistance against stone splash, and metal halide resistance against antifreezing agents have been required. As a method for improving these, a resin composition composed of polyamide and polypropylene has been proposed (for example, Japanese Patent Publication No. 42-12546, Japanese Patent Publication No. 45-30945,
Japanese Patent Publication No. 50-7636).

[0003]

However, even the above method has a problem that the impact resistance is not sufficient for a canister. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a canister for an automobile, which is excellent in metal halide resistance and impact resistance.

[0004]

As a result of intensive studies, the present inventors have found that a composition containing a specific ethylene copolymer can achieve the above object, and based on this finding, As a result, the present invention has been completed. That is, the present invention is (A) polyamide 39 to 80% by weight,
(B) Polypropylene 19-60% by weight and (C)
Modified polypropylene 1 to 40% by weight mixture [where (A) + (B) + (C) = 100% by weight] 1
The present invention provides an automobile canister obtained by molding a composition containing 1 to 20 parts by weight of an ethylene-based copolymer (D) containing a carboxylic acid anhydride group with respect to 00 parts by weight.

The present invention will be specifically described below. The (A) polyamide used in the present invention has an acid amide bond (-CONH
It is a polymer compound having-) as a repeating unit and is commonly called nylon. Specifically, polylactams such as nylon 6, nylon 11, and 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
0, copolyamides such as nylon 6.66, 610; semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as nylon 6.6T and metaxylene diamine or alicyclic diamine; polyester amides, polyether amides and Examples include polyester ether amide. These polyamide resins may be used alone or in combination of two or more. Of these, nylon 6, nylon 66, nylon 6.66, and mixtures thereof are preferred.

The polypropylene (B) used in the present invention includes propylene homopolymers and copolymers of propylene and α-olefins. Examples of the α-olefin include ethylene and butene-1, which can be obtained by block or random polymerization of the α-olefin and propylene. The copolymerization ratio of α-olefin is at most 10% by weight, preferably 5% by weight or less. These polypropylene resins may be used alone or in combination of two or more kinds. MFR of polypropylene resin
(Measured according to JIS K6758) is usually 0.1
˜100 g / 10 min, particularly preferably 1 to 50 g / 10 min.

The modified polypropylene (C) used in the present invention is obtained by graft-reacting the above-mentioned polypropylene with an unsaturated carboxylic acid anhydride. The graft amount of the unsaturated carboxylic acid anhydride is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight, and more preferably 0.05 to 5% by weight. Specific examples of unsaturated carboxylic acid anhydrides include maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, and the like.

Further, the ethylene-based copolymer (D) used in the present invention is a copolymer containing ethylene as a main component and a carboxylic acid anhydride group. The carboxylic acid anhydride group is obtained by copolymerizing ethylene with at least an unsaturated carboxylic acid anhydride monomer, and also by copolymerizing ethylene with a monomer other than the unsaturated carboxylic acid anhydride monomer. It is obtained by the above graft reaction of an unsaturated carboxylic acid anhydride monomer with a polymer, and any of them can be used in the present invention. The content of the carboxylic acid anhydride group is usually 0.05 to 2
It is 0% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.2 to 5% by weight.

Examples of the monomer other than the unsaturated carboxylic acid anhydride monomer include vinyl acetate, unsaturated carboxylic acid and its ester, (meth) acrylamide compound, unsaturated nitrile and aromatic vinyl. . Specific examples include (meth) acrylic acid, maleic acid, fumaric acid and their esters, (meth) acrylamide,
N, N-dimethylacrylamide, acrylonitrile,
Styrene etc. These monomers may be mixed with the unsaturated carboxylic acid anhydride monomer and copolymerized with ethylene.

The copolymerization ratio of these monomers is generally 0.01 to 20% by weight, preferably 0.5 to 10% by weight.
Is. Specific examples of the ethylene-based copolymer of the present invention include, for example, ethylene-methyl methacrylate-maleic anhydride copolymer, ethylene-methacrylamide-fumaric anhydride copolymer, maleic anhydride-modified ethylene-acrylic acid copolymer. Combined, maleic anhydride modified ethylene-methacrylic acid copolymer, maleic anhydride modified ethylene-N, N
-Dimethylacrylamide copolymer, fumaric anhydride-modified ethylene-vinyl acetate copolymer and the like can be mentioned. The ethylene copolymer may be used alone or in combination of two or more. Further, at the time of graft modification, other olefinic copolymers such as ethylene-propylene copolymer and ethylene-butene-1 copolymer may be added. The blending ratio is usually 0.5 to 90% by weight, preferably 50 to 70% by weight.

Of the above components, the proportion of the component (A) in the total amount of the components (A), (B) and (C) is 39.
-80% by weight, preferably 45-80% by weight.
If the proportion of the component (A) is less than 39% by weight, the heat resistance will decrease. On the other hand, when it exceeds 80% by weight, the metal halide resistance is lowered. The proportion of the component (B) is 19 to 60% by weight, preferably 20 to 50% by weight. If the proportion of the component (B) is less than 19% by weight, the resistance to metal halides decreases. On the other hand, if it exceeds 60% by weight, the heat resistance decreases. The ratio of the component (C) is 1 to 40% by weight, preferably 3
~ 30% by weight. When the proportion of the component (C) is less than 1% by weight, the compatibility is lowered and a uniform composition cannot be obtained. On the other hand, if it exceeds 40% by weight, the heat resistance decreases.

Further, the compounding amount of the component (D) is 1 to 100 parts by weight of the total amount of the components (A), (B) and (C).
20 parts by weight, preferably 5 to 10 parts by weight. (D)
If the amount of the component is less than 1 part by weight, the impact resistance is lowered. On the other hand, 2
Even if the amount exceeds 0 part by weight, the effect is slightly further improved, and on the contrary, the moldability may be deteriorated, which is not preferable. The above components are melt-kneaded by a known method to obtain a resin composition. For example, a Banbury mixer, a Henschel mixer, an extruder or the like may be used. The temperature at the time of melt kneading is usually 180 to 350 ° C., preferably 20.
It is in the range of 0 to 300 ° C.

In addition, various additives such as dyes, pigments, fillers, nucleating agents, plasticizers,
You may mix | blend an appropriate amount with a lubricant, a mold release agent, a coupling agent, a foaming agent, a heat resistance agent, a weather resistance agent, a flame retardant, an antistatic agent, a sliding agent, etc. The vehicle canister of the present invention can be formed by a known method such as injection molding, extrusion molding, compression molding transfer molding, or the like of the above resin composition.

[0014]

EXAMPLES The present invention will now be described in more detail with reference to examples. The Izod impact strength is ASTM D25
According to No. 6, it was measured at 23 ° C. with a notch. Also, the metal halide resistance is flat (10 x 10 mm, thickness 3 mm)
A load of 50 g was applied to both ends with the central part of the as a fulcrum. A 5 wt% calcium chloride aqueous solution was brush-applied to this, and this was subjected to heat cycle treatment at a temperature of 100 ° C. for 2 hours and subsequently at a temperature of 23 ° C. for 2 hours. One cycle from brush coating to heat cycle treatment was repeated, and the number of times until cracks could be visually confirmed was measured. The falling ball impact test is 20c on the cylindrical surface of the fixed molded product.
An iron ball (weight: 1 kg) dropped from a height of m and no cracks in the cylindrical portion was represented by O, and a crack was represented by X.

As the polyamide, the relative viscosity is 2.5.
0, polyamide 6 (hereinafter referred to as PA6) having an amino terminal group concentration of 4.9 × 10 ⁻⁵ equivalent / g and a relative viscosity of 2.
Polyamide 66 (hereinafter, referred to as PA66) having a concentration of amino end groups of 5.1 × 10 ⁻⁵ equivalent / g was used. As polypropylene, a propylene homopolymer having an MFR of 30 g / 10 min (hereinafter referred to as homo PP) and M
A propylene block copolymer having an FR of 10 g / 10 minutes (hereinafter referred to as block PP) was used. As the modified polypropylene, polypropylene having an MFR of 1.0 g / 10 minutes and grafted with maleic anhydride in an amount of 0.35% by weight was used. Also, as an ethylene-based copolymer,
Butyl acrylate 8.1% by weight, maleic anhydride 2.
An ethylene-butyl acrylate-maleic anhydride terpolymer of 8% by weight (hereinafter referred to as a copolymer) was used.

An ethylene-propylene copolymer 70 having a copolymer content of 30 parts by weight and a propylene content of 25% by weight.
Parts by weight, 0.4 parts by weight of maleic anhydride and 0.012 parts by weight of 2,5-di (t-butylperoxy) hexane in a Henschel mixer, then melt-kneaded using an extruder with a vent, and grafted. (Hereinafter referred to as modified product 1)
Was used). Similarly, 50 parts by weight of the copolymer,
Ethylene-butene-with a butene-1 content of 18% by weight
Graft product consisting of 50 parts by weight of 1 copolymer (hereinafter referred to as modified product 2), 30 parts by weight of ethylene-methacrylic acid copolymer having a methacrylic acid content of 7.1% by weight, 70 parts by weight of ethylene-propylene copolymer A graft body (hereinafter referred to as modified body 3) composed of parts was used.

Examples 1 to 8 and Comparative Examples 1 and 2 Components (A) to (D) having the types and blending amounts shown in Table 1 were mixed with a Henschel mixer for 5 minutes, and then a twin-screw extruder with a vent was used. Was melt-kneaded into pellets. After drying each obtained pellet under reduced pressure, a flat plate and a test piece were prepared by injection molding. Izod impact strength and metal halide resistance were measured using these flat plates and test pieces. In addition, molded products for impact tests (inner diameter 12 cm,
A bottomed cylinder having a height of 18 cm and a thickness of 3 mm was prepared and a falling ball impact test was performed. The above results are shown in Table 1.

[0018]

[Table 1]

[0019]

INDUSTRIAL APPLICABILITY The canister for automobiles of the present invention is very useful because it is excellent in metal halide resistance and impact resistance.

Front page continued (72) Inventor Satoshi Maruyama 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Akira Kawasaki Plastics Research Laboratory

Claims (1)

[Claims] 1. (A) Polyamide 39 to 80% by weight,
(B) Polypropylene 19-60% by weight and (C)
Modified polypropylene 1 to 40% by weight mixture [where (A) + (B) + (C) = 100% by weight] 1
An automotive canister obtained by molding a composition containing 1 to 20 parts by weight of (D) a carboxylic acid anhydride group-containing ethylene copolymer with respect to 00 parts by weight.