Glass-fiber-reinforced polyamide resin composition

Abstract

The present invention is a glass-fiber-reinforced polyamide resin composition which contains a crystalline aliphatic polyamide resin (A), an amorphous polyamide resin (B), an acrylic resin (C), mica (D), glass fiber (E) and carbon black (F) in a ratio by mass of (10 to 40):(2 to 20):(1 to 10):(2 to 25):(20 to 50):(0.1 to 5), respectively and further contains a copper compound (G) in a rate of 0.005 to 1.0 part by mass when a total amount of the ingredients (A) to (F) is taken as 100 parts by mass.

Claims

1. A glass-fiber-reinforced polyamide resin composition, comprising a crystalline aliphatic polyamide resin (A), an amorphous polyamide resin (B), poly(methyl methacrylate) (C), mica (D), glass fiber (E) and a carbon black master batch (F) in a ratio by mass of (20 to 30):(10 to 15):(2 to 6):(15 to 22):(25 to 45):(1 to 4.5), respectively, and further comprising a copper compound (G) in a ratio of 0.005 to 1.0 part by mass when a total amount of the ingredients (A) to (F) is taken as 100 parts by mass, wherein, when a flat plate is prepared by subjecting the glass-fiber-reinforced polyamide resin composition to an injection molding and the resulting plate is subjected to a weathering test in accordance with JIS K 7350-2, a color difference E before and after the weathering test is 3.5 or less.

2. The glass-fiber-reinforced polyamide resin composition according to claim 1, wherein the amorphous polyamide resin (B) is a semi-aromatic polyamide.

3. The glass-fiber-reinforced polyamide resin composition according to claim 1, comprising the crystalline aliphatic polyamide resin (A), the amorphous polyamide resin (B), the poly(methyl methacrylate) (C), the mica (D), the glass fiber (E) and the carbon black master batch (F) in a ratio by mass of (21.5 to 24):(11.5 to 14.5):(2 to 6):(16 to 20):(35 to 41):(1 to 4.5), respectively, and further comprising the copper compound (G) in a ratio of 0.02 to 0.3 part by mass when the total amount of the ingredients (A) to (F) is taken as 100 parts by mass, and wherein the color difference E before and after the weathering test is 3.3 or less.

4. A molded product for vehicle interior or vehicle exterior, wherein the molded product is molded from the glass-fiber-reinforced polyamide resin composition according to claim 1.

5. The molded product for vehicle interior or vehicle exterior according to claim 4, wherein the product is selected from the group consisting of an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, a spoiler and a slide door rail cover.

Description

EXAMPLES

(1) The present invention will now be illustrated in more detail as hereunder by Examples. However, the present invention is not limited to the following Examples so far as it does not exceed a gist thereof. Measurement of physical data in the Examples was carried out in accordance with the following methods.

(2) (1) Relative Viscosity of Polyamide Resin:

(3) A polyamide resin (0.25 g) was dissolved in 25 ml of 96 wt % sulfuric acid, and 10 ml of a resulting solution was placed in an Oswald viscometer. A measurement was conducted at 20 C. Relative viscosity was calculated according to the following formula.
RV=T/T0

(4) RV: Relative viscosity, T: Dropping time of a sample solution, T0: Dropping time of a solvent

(5) (2) Bending Strength and Bending Elastic Modulus:

(6) Bending strength and bending elastic modulus were measured in accordance with ISO 178.

(7) (3) Evaluation of Weather Resistance

(8) Color difference E: A wrinkled flat plate (100 mm100 mm2 mm) molded by an injection molding machine (IS 80 manufactured by Toshiba Machinery) adopting a cylinder temperature of 280 C. and a metal mold temperature of 90 C. was subjected to a weathering test in accordance with JIS K 7350-2 using a xenon weatherometer (XL 75 manufactured by Suga Shikenki KK) under the following conditions:

(9) black panel temperature: 632 C.

(10) relative humidity: 505%

(11) irradiation method: rainfall for 18 minutes during 120 minutes (being sprinkled with water)

(12) irradiation time: 1250 hours

(13) irradiation degree: 60 W/m.sup.2.S with 300 to 400 nm wavelength optical filters: quartz (inside) and borosilicate #275 (outside).

(14) For the wrinkled flat plate before and after the weathering test, value of L, a and b were measured using TC-1500 SX (spectrophotometer manufactured by Tokyo Denshoku) whereupon the color difference E was calculated.

(15) Surface Appearance of the Molded Product after the Exposure Test (to Check Whether a Reinforcement Material was Lifted):

(16) : No lifting of the reinforcement material was noted.

(17) x: Lifting of the reinforcement material was noted.

(18) State of Wrinkles on the Surface of the Molded Product after the Exposure Test:

(19) : Wrinkled pattern was clearly noted.

(20) x: Winkled pattern could not be confirmed.

(21) Polyamide Resin (A):

(22) (A1) Polyamide 6 having a relative viscosity RV of 1.9; Nylon T-860 manufactured by Toyobo

(23) (A2) Polyamide 66 having a relative viscosity RV of 2.4; Stabamide 23E manufactured by Rhodia

(24) Amorphous Polyamide Resin (B)

(25) (B1) Polyamide 6T6I having a relative viscosity RV of 2.0; Glyboly G21 manufactured by Ems

(26) (B2) Polyamide 6T6I having a relative viscosity RV of 1.8; Glyboly G16 manufactured by Ems

(27) Acrylic Resin (C)

(28) Poly(methyl methacrylate) Parapet GF manufactured by Kuraray

(29) Mica (D)

(30) S-325 manufactured by Repco

(31) Glass Fiber (E)

(32) T-275H manufactured by Nippon Electric Glass Co., Ltd. (a chopped strand of glass fiber having a circular cross section: diameter 11 m)

(33) Carbon Black (F)

(34) Master batch: EPC-840 manufactured by SUMIKA COLOR CO., LTD., base resin LDPE resin, containing 43% by weight of carbon black

(35) Copper Compound (G)

(36) Cupric bromide: Manufactured by Wako Pure Chemicals; purity: 99.9%

(37) Other Ingredients Used:

(38) Wollastonite: NYGLOS 8 manufactured by Nyco Minerals (fiber diameter: 8 m; fiber length: 136 m)

(39) Light stabilizer: Nylostab S-eed (manufactured by Clariant)

Examples 1 to 9 and Comparative Examples 1 to 9

(40) Ingredients other than the mica (D), the glass fiber (E), and the wollastonite were subjected to a dry blending under compounding ratios as shown in Tables 1 and 2 and subjected to a melt mixing under an extruding condition wherein a cylinder temperature was 280 C. and a screw revolution was 250 rpm using a biaxial extruder STS 35 mm manufactured by Coperion which was a biaxial extruder of a bent type constituted from 12 blocks of barrel. After that, the mica (D), the glass fiber (E), and the wollastonite were fed by a side feeding method to conduct a melt kneading. Strand extruded from the extruder was quickly cooled and made into pellets using a strand cutter. The resulting pellets were dried at 100 C. for 12 hours, then molded into a wrinkled flat plate using an injection molding machine (IS 80 manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 280 C. and a metal mold temperature of 90 C. The resulting test pieces were subjected to evaluations. Results of the evaluations are also mentioned in Tables 1 and 2. In Tables 1 and 2, a compounding amount of carbon black master batch (F) is an amount as a master batch.

(41) TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 Compounding polyamide 6 (A1) 23.5 21.5 24 26.5 23.5 23.5 23.5 23.5 rate of polyamide 66 (A2) 23.5 composition amorphous polyamide (B1) 14.5 14.5 14.5 11.5 14.5 14.5 14.5 (part(s) amorphous polyamide (B2) 14.5 14.5 by mass) acrylic resin (C) 4 6 2 4 4 4 4 4 4 mica (D) 20 20 20 20 20 20 16 20 20 wollastonite glass fiber (E) 35 35 35 35 35 35 41 35 35 carbon black 3 3 4.5 3 3 3 1 3 3 master batch (F) copper bromide (G) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.1 0.3 light stabilizer Characteristics bending strength (MPa) 280 280 280 280 280 280 290 280 280 of bending elastic 18 18 18 18 18 18 19 18 18 composition modulus (GPa) weather color difference E 2.2 1.2 3.1 2.2 2.2 2.2 3.3 2.2 2.2 resistance lifting of reinforcement material state of wrinkles after the test

(42) TABLE-US-00002 TABLE 2 Comparative Examples 1 2 3 4 5 6 7 8 9 Compounding polyamide 6 (A1) 42 38 27.5 25.5 25.5 18 25.5 23.5 23.5 rate of polyamide 66 (A2) composition amorphous polyamide (B1) 14.5 14.5 30 4.5 16.5 14.5 14.5 (part(s) amorphous polyamide (B2) by mass) acrylic resin (C) 2 2 1 2 4 4 mica (D) 20 4 4 7 35 20 55 wollastonite 16 20 16 glass fiber (E) 35 35 35 35 35 35 35 55 carbon black master batch (F) 3 3 3 3 3 3 3 3 3 copper bromide (G) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 light stabilizer 0.4 Characteristics bending strength (MPa) 280 280 280 280 230 310 280 330 190 of bending elastic modulus (GPa) 18 18 18 18 9 21 18 19 9 composition weather color difference E 4.7 5.0 4.8 4.9 4.4 4.1 4.8 2.2 2.2 resistance lifting of x x x x x reinforcement material state of wrinkles x x x x x x x x after the test

(43) From Table 1, it is noted that, in the test pieces of Examples 1 to 9, the color difference E before and after the exposure test is small. This will mean that a fading of black color is suppressed. It is also noted that the lifting of the glass fiber is suppressed and the state of the wrinkles is good as well. On the contrary, from Table 2, it is noted that, in the test pieces of Comparative Examples 1 to 7, the color difference E before and after the exposure test is big. This will mean that a fading of black color is big. It is also noted that the wrinkled appearance is deteriorated. From Table 2, it is noted that, in the test piece of Comparative Example 8, although the color difference E is good in both, the test piece is inferior in terms of weather resistance. From Table 2, it is noted that, in the test piece of Comparative Example 9, although the color difference E is good in both, the test piece is inferior in terms of bending strength and bending elastic modulus.

INDUSTRIAL APPLICABILITY

(44) The glass-fiber-reinforced polyamide resin composition of the present invention is suitably used for vehicle interior or vehicle exterior such as an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, a spoiler and a slide door rail cover.