JPH0733480B2 - Colored polyamide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored polyamide resin composition which is excellent in discoloration or fading due to light or heat.

[Prior Art] Conventionally, an ABS resin molded product has been used for a baffle plate (register blade) of an outlet for hot and cold air inside a vehicle.
However, the demand for the color tone of the interior of the car became strict, and ABS
In consideration of light resistance, it has become difficult for resins to match the required color tone. Also, due to the design of the instrument panel, the number of horizontally long outlets has increased, and the length of one of the register blades has become longer, so that deformation (deflection) due to heat etc. tends to occur and resin with high heat resistance such as polyamide resin is used. It has been required to be used. However, currently commercially available polyamide resins have no problem with respect to deformation by heat, but are still insufficient in discoloration and fading due to light or heat and cannot satisfy the required performance under the present circumstances.

In order to solve these problems, there is a method of improving the weather resistance by adding a heat stabilizer or a weather resistance improver, but it is not sufficient in practical use.

[Problems to be Solved by the Invention] An object of the present invention is to provide a polyamide resin composition in which the above-mentioned conventional polyamide resin composition is improved in discoloration and fading due to heat and light.

[Means for Solving Problems] The present invention includes 100 parts by weight of a polyamide resin and 0.0% of an inorganic colorant.
1 to 1 parts by weight, zinc sulfide 0.005 to 0.5 parts by weight, copper halide (copper equivalent) 0.005 to 0.1 parts by weight, potassium halide 0.
A colored polyamide resin composition comprising 1 to 0.5 parts by weight and 0.01 to 0.1 parts by weight of a triazine derivative, which is excellent in fading resistance.

Polyamide resin is 6-nylon, 6.6-nylon, 12
-Nylon and their copolymers. The copolymer of 6-nylon is a copolymer of ω-amino-carboxylic acid and its lactam and ε-caprolactam or 6-aminocaproic acid, for example, ρ-enanthlactam, 7
-Aminohebutanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, α-pyrrolidone, α-piperidone and the like can be used as a copolymerization component. Also 6.6 −
As the copolymerization component of nylon, for example, diamines such as nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine and tetramethylenediamine, and dicarboxylic acids such as sebacic acid, terephthalic acid and isophthalic acid are appropriately added. And can be copolymerized. Also known as additives for this polyamide resin are lubricants, release agents, nucleating agents and reinforcing agent fillers (glass fiber,
Inorganic additives, etc.) can also be included.

The inorganic colorant is intended for coloring plastics and has a maximum particle size of about 10 millimicrons to several microns (μm) and is a substance which is not dissolved in water or an organic solvent. For example, iron black (Fe ₃ O ₄ ), cadmium red (C
d ・ S-CdSe), vermilion (HgS), red lead (Pb ₃ O ₄ ), red iron oxide (Fe ₂ O ₃ ), yellow lead (PbCrO ₄ ), chromium oxide (Cr ₂ O ₃ ), cobalt blue (CrO ・nAl ₂ O ₃ ), cobalt purple (Co (P
O ₄ ) ₃ ), titanium oxide (TiO ₂ ) and the like. The amount used is in the range of 0.001 to 0.5 part by weight and is appropriately determined depending on the shade of color. Zinc sulfide is added in an amount of 0.005 to 0.5 part by weight. It is preferably 0.01 to 0.2 parts by weight. When the content of zinc sulfide is less than 0.001 part by weight, the light resistance of the obtained polyamide composition is lowered, and even when the content of zinc sulfide is more than 0.5 part by weight, the light resistance is not improved. This inorganic colorant can be directly added to and mixed with the polyamide resin, but it is also possible to add a colored pellet (commonly known as a master batch) obtained by extrusion by mixing the inorganic colorant with a specific concentration in advance of the polyamide resin. Usually, colored pellets are prepared by adjusting the concentration of the resin so that it is mixed with the resin at a ratio of 1 of colored pellets.

As the copper halide, copper (I) chloride, copper (II) chloride,
Examples thereof include copper (I) bromide, copper (II) bromide, and copper (I) iodide, with copper (I) iodide being preferred. The amount of copper halide is 0.005 to 100 parts by weight of polyamide in terms of copper atoms.
It is 0.1 part by weight, preferably 0.01 to 0.07 part by weight. The light resistance of the polyamide composition obtained when the content of the copper halide is less than 0.005 parts by weight is lowered, and the light resistance of the polyamide composition is improved even when the content of the copper halide is more than 0.1 part by weight. Instead, the molded product is rather colored, resulting in a problem.

Examples of the potassium halide include potassium chloride, potassium bromide and potassium iodide, and potassium iodide is particularly preferable. The amount of potassium halide compounded is preferably 0.1 to 0.5 part by weight, particularly 0.2 to 0.4 part by weight, per 100 parts by weight of polyamide. The light resistance of the polyamide resin composition is reduced when the content of potassium halide is less than 0.1 parts by weight, and the light resistance of the obtained polyamide resin composition is not improved even when the content is more than 0.5 parts by weight. Things get colored.

Triazine derivatives include melamine, cyanuric acid,
Examples thereof include compounds having a triazine ring such as melamine cyanurate, methylene dimelamine and ethylene dimelamine. These triazine derivatives are 20μm or less
It preferably has an average particle size of m or less.

The addition timing of the above-mentioned additives is not particularly limited, and the additives can be blended by a known method such as melt kneading before, during, or after the polymerization of polyamide.
Furthermore, this polyamide resin composition can be easily molded by a known molding method.

[Examples] The present invention will be described below with reference to Examples.

In Examples and Comparative Examples, the relative viscosity was measured according to JIS K6810. The light resistance test of the molded product is carried out with a standard fade meter made by Suga Test Instruments under the condition of no rain at 83 ° C, and the color tone change is made by the color computer SM-2 made by Suga Test Instruments.
Was measured.

(Example 1) 6-nylon containing 30% glass fiber having a relative viscosity of 2.30 (Ube nylon 1011GC6 manufactured by Ube Industries, Ltd.) 6 nylon containing a brown pigment component in 100 parts by weight (6N manufactured by Ube Industries)
4395SB), 10 parts by weight of zinc sulfide, 0.02 part by weight of zinc sulfide, 0.05 part by weight of copper iodide, 0.5 part by weight of potassium iodide, and 0.01 part by weight of melamine were melt-kneaded and pelletized by a single-screw extruder. Using this pellet, injection molding was performed at 260 ° C and a 30 × 100 × 3 mm test piece was used. I made a stop piece. After irradiating this test piece with a standard fade meter for 1000 hours, the degree of discoloration and fading was measured. Table 1 shows the amount of additive and the value of ΔE.

(Example 2) A test similar to that of Example 1 was performed except that 6-nylon containing the blue pigment component of Example 1 (2N8365SB manufactured by Ube Industries, Ltd.) and the amount of zinc sulfide compounded were changed to 0.03 part by weight.

(Comparative Example 1) The same test as in Example 1 was performed after zinc sulfide was not added.

(Comparative Example 2) The same test as in Example 2 was performed after zinc sulfide was not added.

The value of ΔE in the example is as small as 1.4 or less, and the light resistance is further improved as compared with 2.5 or more in the comparative example.

[Effect of the Invention] The present invention is a composition for preventing fading and discoloration of a polyamide resin, which contains an inorganic coloring pigment and contains zinc sulfide and a heat-resistant stabilizer of copper halide, potassium halide, and a triazine derivative in specific amounts. This shows that the fading after irradiation with the fade meter for 1000 hours has a smaller value of ΔE than that of the comparative example, and almost no fading occurs. Therefore, the polyamide resin composition of the present invention is excellent in light resistance and fading resistance, and exhibits discoloration resistance even in a delicate color tone product, so that it can be used in various applications.

Claims (1)

[Claims] 1. A polyamide resin 100 parts by weight, an inorganic colorant
0.01 to 1 part by weight, zinc sulfide 0.005 to 0.5 part by weight, copper halide (copper equivalent) 0.005 to 0.1 part by weight, potassium halide
A colored polyamide resin composition comprising 0.1 to 0.5 parts by weight and 0.01 to 0.1 parts by weight of a triazine derivative, which is excellent in fading resistance.