JPH0598156A - Composition for exterior part and exterior part - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in impact resistance, rigidity and appearance and suitable for exterior parts, etc., by melt-kneading polyamide 6, a modified olefinic polymer, etc., and an inorganic reinforcing material, and subsequently adding polyamide 66, etc., and an inorganic reinforcing material in a specified ratio. CONSTITUTION:(A) A polyamide 6, (B) a modified olefinic polymer to main chain of which maleic acid, etc., is introduced, (C) if necessary, an olefinic polymer such as PP, and (D) an inorganic reinforcing material such as glass fibers are melt-kneaded and subsequently compounded with (E) polyamide 66, and if necessary, the component C and the component D in an A:B:C:D:E of 1-90wt.%, 0.1-40wt.%, 0-40wt.%, 5-80wt.% and 1-90wt.%, respectively, to provide the subject composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composition for exterior parts using a polyamide resin. More specifically, it is a composition for exterior parts which has an improved surface appearance and can be suitably used as an exterior part, and an exterior part obtained by molding the composition.

[0002]

2. Description of the Related Art A composition obtained by melt-kneading a modified olefin polymer and an inorganic reinforcing agent with polyamide 66 is a resin having excellent mechanical properties, chemical resistance, moldability and the like, and is used in a wide variety of applications. However, there is a problem such as poor appearance, and the use thereof is limited in some applications under the present circumstances.

On the other hand, a composition obtained by melt-kneading a modified olefin polymer and an inorganic toughening agent in polyamide 6 has a relatively good appearance, but it is said that the mechanical properties and the dimensional change rate upon absorption of water become large. I have a problem.
Although various attempts have been made in the past to solve this problem, a composition that is still sufficiently satisfactory for applications having excellent mechanical properties and good appearance is still required. I couldn't get it.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the problem of providing a composition for exterior parts having excellent mechanical properties and having a good appearance.

[0005]

Means for Solving the Problems As a result of repeated studies for solving the above problems, the present inventors have found that only a composition obtained by a specific method can solve the above problems. completed. That is, in the present invention, polyamide 6 (A) is required to be melt-kneaded with modified olefin polymer (B) and, if necessary, olefin polymer (C) and inorganic reinforcing agent (D), and then polyamide 66 (E) is required. The composition for exterior parts is characterized by blending an olefin polymer (C) and an inorganic reinforcing agent (D) in accordance with the above, and an exterior part molded therefrom (however, polyamide 6 (A), modified Olefin polymer (B),
The blending amounts of the olefin polymer (C), the inorganic reinforcing agent (D) and the polyamide 66 (E) are a, b, c, d and e.
When it is defined as weight%, 1 ≦ a ≦ 90, 0.1 ≦ b ≦ 40,
0 ≦ c ≦ 40, 5 ≦ d ≦ 80, 1 ≦ e ≦ 90, and a + b
+ C + d + e = 100).

In the present invention, polyamide 6 (A) means a polymer obtained by polymerization of ε-caprolactam.
And 98% sulfuric acid relative viscosity (JIS K6810: η
rel) is preferably 1.8 to 3.0, and 2.0 to
Those of 2.8 are more preferable, and those of 2.3 to 2.6 are particularly preferable. When ηrel is 1.8 or less, it becomes brittle. Further, if ηrel is 3.0 or more, the appearance becomes poor.

In the present invention, the modified olefin polymer (B) means that a part or all of the olefin polymer (C) described later is modified by introducing a carboxylic acid or its derivative into the main chain or side chain. It is a polymer.
As the carboxylic acid or its derivative, maleic acid,
Maleic anhydride, maleic acid monomethyl ester, maleic acid monomethyl ester metal salt, fumaric acid, fumaric acid monomethyl ester, succinic acid, succinic anhydride, itaconic acid, acrylic acid, methacrylic acid, hymic acid, hymic acid anhydride, crotonic acid, Phthalic acid, phthalic anhydride,
Trimellitic acid, trimellitic anhydride, metal salts of methacrylic acid, metal salts of acrylic acid, maleimide, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate and the like can be exemplified, especially anhydrous. Maleic acid and trimellitic anhydride are preferred.

In the present invention, the olefin polymer (C) means ethylene, propylene, polybutene-1,
Polypentene, polyhexene, ethylene-propylene copolymer, ethylene-propylene-1,6-hexadiene copolymer, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated polybutadiene, hydrogenated poly Isoprene, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-
Examples thereof include isoprene copolymer, and ethylene-propylene copolymer and hydrogenated styrene-butadiene copolymer are particularly preferable.

In the present invention, the inorganic toughening agent (D) is an inorganic toughening agent to be blended with a usual thermoplastic resin, such as glass fiber, carbon fiber, potassium titanate fiber, rock wool, silicon carbide fiber, ceramic. Fiber, metal fiber, silicon nitride fiber, barium sulfate, calcium, calcined kaolin, kaolin, clay, pyroflight, bentonite, sericite, zeolite, mica, mica, nepheline sinite, talc, atalpulgite, montmorillonite, wollastonite , Ferrite, calcium silicate, calcium carbonate, titanium oxide, molybdenum disulfide, carbon black, glass beads, and the like.

It is particularly preferable that these inorganic reinforcing agents are treated with a conventionally known coupling agent, sizing agent and the like. In the present invention, polyamide 66 (E) is a polymer obtained from hexamethylenediamine and adipic acid, and has a 98% sulfuric acid relative viscosity (JIS K681).
0: ηrel) is preferably 1.8 to 3.0,
It is more preferably from 2.0 to 2.8, and from 2.3 to 2.6.
Are especially preferred. When ηrel is 1.8 or less, it becomes brittle. Further, if ηrel is 3.0 or more, the appearance becomes poor.

In the present invention, polyamide 6
The (A) and the polyamide 66 (E) may contain a monomer component of another polyamide within a range of 20 mol% or less as a copolymerization component. The composition of the present invention is an additive that is added to a usual thermoplastic resin as necessary, for example, a dye, a pigment, a plasticizer, a nucleating agent, a lubricant, a flame retardant, a heat stabilizer, a weathering agent, and a light stabilizer. The inclusion of, etc. is not particularly limited.

The production of the composition of the present invention is accomplished by a conventionally known technique such as an extruder or a kneader. The molding of the composition of the present invention is achieved by a conventionally known technique such as an injection molding machine, a blow molding machine, an extrusion molding machine.

[0013]

〔material〕

(1) Ny6: Polyamide 6 Sulfuric acid relative viscosity (JIS K6810, 98% H ₂ S
O ₄ ) 2.45 (2) Ny66: Polyamide 66 Sulfuric acid relative viscosity (JIS K6810, 98% H ₂ S
O ₄ ) 2.55 (3) MHTR Hydrogenated styrene-butadiene copolymer: Asahi Kasei Kogyo Co., Ltd., Tuftec M1953, acid value 10 (mg
CH ₃ ONa / g, titration method) Styrene component about 40% by weight, tensile modulus 2300 kg / cm ² (4) HTR hydrogenated styrene-butadiene copolymer: Asahi Kasei Corporation's Tuftec H1052, styrene component about 2
0% by weight, tensile modulus 38 kg / cm ² (5) MEP ethylene-propylene copolymer maleic anhydride adduct: Exxon Chemical Co., Ltd., EXXELOR VA18
03, maleic anhydride 0.7% by weight (6) EP ethylene-propylene copolymer: Mitsui Petrochemical Co., Ltd.
Manufactured by Tufmer P0180 (7) THPB Terminal trimellitic anhydride modified hydrogenated polybutadiene obtained in Production Example (8) GF: glass fiber Asahi Fiber Glass Co., Ltd. 03JAFT-2A (9) HS-1 bis (2,6-di-t-butyl-4-methylphenyl)
Pentaerythr-Ziephosphite: ADEKA ARGUS CORPORATION MARK PEP-36 (10) HS-2 Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 -Butane tetracarboxylate: MARK LA-57 (11) HS-34,4'-butylidene-bis- (3-methyl-6-t-, manufactured by Adeka Argus Co., Ltd.
Butylphenol): Yoshitomi Pharmaceutical Co., Ltd., Yoshinox BB (12) HS-4 Manganese lactate: Wako Pharmaceutical Co., Ltd. [Test method] (1) Specular glossiness (60 degree specular glossiness: Gs (60
Degree)) The measurement was performed according to JIS K7105 (130 mm ×
A 130 mm flat plate was molded and used as a test sample). (2) Tensile Property (ASTM 1/8 inch) Measurement was performed according to ASTM D638. (3) Bending Property (ASTM 1/8 inch) Measurement was performed according to ASTM D790. (4) Izod impact characteristics (ASTM 1/8 inch, notched) Measurement was performed according to ASTM D256.

[0014]

[Production Example] (Synthesis of THPB) Hydrogenated polybutadiene having acid anhydride groups at both ends (NISSO-PB, DI-
3000 Nippon Soda Co., Ltd. 300 g, pyridine 1
5.8 g are dissolved in acetic acid ethyl ester. After water-cooling this mixed solution, 42.1 g of trimellitic anhydride chloride was added to 200 ml of ethyl acetate under a dry nitrogen atmosphere.
The solution dissolved in was added dropwise over 1 hour. After the dropping was completed, the temperature was naturally raised to the greenhouse, and the insoluble matter that had precipitated was further filtered by stirring for 8 hours, and the filtrate was concentrated with a rotary evaporator. The residue was dissolved in 500 ml of chloroform, the insoluble solution was filtered off, and the filtrate was passed through a silica gel column for purification. The solvent was distilled off with a rotary evaporator to obtain 295 g of a slightly yellow viscous liquid polymer.

It was confirmed by infrared absorption spectrum and ¹ H-NMR that a trimellitic anhydride group was bonded to the terminal. The number average molecular weight determined from quantitative determination of end groups is 486.
It was 0.

[0016]

[Examples 1 to 8 and Comparative Examples 1 to 6] PCM45 twin screw extruder (L / L) manufactured by Ikegai Tekko Ltd.
D = 33.5) was melt-kneaded at a cylinder setting temperature of 250 to 290 ° C., and further pelletized. 5 wt% of Leona LCO20 M33300M (black masterbatch) was added to the obtained pellets, and injection molding was performed at a cylinder temperature of 250 to 300 ° C and a mold temperature of 80 ° C to obtain a molded product.

The results are shown in Table 5.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

[Table 5]

[0023]

EFFECTS OF THE INVENTION The composition for exterior parts of the present invention is an excellent molded article having excellent impact resistance and rigidity and having a good appearance, and therefore a part which is required to have a good surface appearance. , Or parts that are exposed to the outside and require design, such as automobile parts (radiators, rear combination lamp housings, headlamp reflectors, ornament covers, rocker covers, motor housings, instrument panels etc.), and electrical / electronic parts. It is widely used as a structural material for housings, caps, covers, bicycle wheel rims, chairs, desk legs, etc.

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Claims (2)

[Claims] 1. A polyamide 6 (A) is melt-kneaded with a modified olefin polymer (B), and if necessary, an olefin polymer (C) and an inorganic reinforcing agent (D), and then the polyamide 66 (E) is necessary. A composition for exterior parts (provided that the polyamide 6 (A), the modified olefin polymer (B), the olefin polymer (C) and the inorganic reinforcing agent (D) are blended according to C), inorganic toughening agent (D) and polyamide 66 (E)
When the compounding amount of is a, b, c, d and e weight%, 1
≦ a ≦ 90, 0.1 ≦ b ≦ 40, 0 ≦ c ≦ 40, 5 ≦ d
≦ 80, 1 ≦ e ≦ 90, a + b + c + d + e = 10
0). 2. An exterior part molded from the composition according to claim 1.