JP3283590B2 - Glass fiber reinforced black polyamide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a glass fiber reinforced black polyamide resin composition. More specifically, the present invention relates to a glass fiber reinforced black polyamide resin composition having excellent durability against automobile antifreeze at high temperatures.

[0002]

2. Description of the Related Art Polyamide resin reinforced with glass fiber has excellent mechanical properties, chemical resistance, heat resistance, etc.
It is often used as a component of electricity and machinery. In particular, recently, from the viewpoints of improving fuel efficiency and streamlining the assembling process by reducing the weight, there has been a remarkable movement to change automobile parts using a conventional metal to glass fiber reinforced polyamide resin. Above all, radiator tanks, heater tanks, which are installed in the engine room and come into contact with automobile antifreeze
For components such as water valves and water pumps, glass fiber reinforced polyamide resins colored black with carbon black or black dye have attracted attention and have a considerable track record.
However, in combination with the rise in the temperature in the engine room due to the recent high performance of the engine, the above materials have a drawback that the mechanical strength is reduced due to the prolonged contact with the antifreeze in a high-temperature atmosphere, which is severe. It was not the optimal automotive component material that required reliability. In order to remedy this drawback, attempts have been made to increase the glass fiber concentration of the carbon black colored glass fiber reinforced polyamide resin to improve the initial mechanical properties, thereby extending the life of deterioration with respect to antifreeze. However, this technology increases the weight of parts due to the increase in glass fiber, which not only goes against the trend of lighter automobiles, but also significantly deteriorates the appearance of molded products, especially when applied to radiator tanks and heater tanks. There is a new defect that the antifreeze leaks from the resin or the sealing surface between the resin and the metal. In addition, for the purpose of obtaining a glass fiber polyamide resin having excellent antifreeze resistance, a glass fiber reinforced polyamide resin composition in which a modified polypropylene is blended with a polyamide resin has been proposed. Although the effect is recognized, the heat resistance, particularly the rigidity under heat, is large, and there is a problem in the use of parts mounted in an automobile engine room. Also, a technique for improving antifreeze resistance by adding a small amount of an alkyl acrylate copolymer containing a functional group capable of reacting with a terminal group of polyamide to a glass fiber reinforced polyamide resin (JP-A-60-13845) has been proposed. Proposed. When the glass fiber reinforced polyamide resin composition obtained by this technique is colored with carbon black, an azine-based dye, or the like, there is a problem that the weld strength when contacting with a high-temperature antifreeze solution is reduced as compared with a case where the glass fiber-reinforced polyamide resin composition is not colored, It was not always satisfactory.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a glass fiber which is colored black without impairing the excellent characteristics of the glass fiber reinforced polyamide resin and which has remarkably improved durability against an antifreeze solution at high temperatures. It is an object to provide a reinforced black polyamide resin composition.

[0004]

The present inventors have developed a glass fiber reinforced black polyamide resin composition which is colored black with a glass fiber reinforced polyamide resin and has remarkably improved durability against antifreeze at high temperatures. As a result of diligent research, a glass fiber reinforced black polyamide resin composition in which a specific glass fiber and a specific black colorant are blended with a polyamide resin, surprisingly, a new effect that shows a great effect on improving the durability against antifreeze. The present invention has been completed based on the findings.

That is, the present invention relates to a polyamide resin (A) 30
A glass having a mean diameter of 5 to 12 μm and an average diameter of 5 to 12 μm, and having been surface-treated with a sizing agent mainly comprising a copolymer of maleic anhydride and an unsaturated monomer and a silane coupling agent; The present invention relates to a glass fiber-reinforced black polyamide resin composition comprising 100 parts by weight of a glass fiber-reinforced polyamide resin comprising 70 to 5% by weight of a fiber (B) and 0.002 to 2 parts by weight of an azine dye (C).

Hereinafter, the present invention will be described in detail.

As the polyamide resin (A) used in the present invention, a general polyamide resin can be used.
For example, ring-opening polymerization of nylon 46, nylon 66, nylon 610, nylon 612, nylon 6T (polyhexamethylene terephthalamide), nylon 6I (polyhexamethylene isophthalamide), and lactam obtained by condensation polymerization of diamine and dicarboxylic acid. 6, nylon 12, nylon 11 obtained by self-polycondensation of ω-aminocarboxylic acid, and copolymers and blends of these polyamides. The molecular weight of these polyamides is not particularly limited, but may be within the molecular weight range usually used for the production of molded products used for injection molding and the like. Among the above polyamides, especially nylon 66
And nylon 66 and other polyamide resins (for example, nylon 610, nylon 612, nylon 11, nylon 1
2, nylon 6T / 66, nylon 6T / 6I, etc.) are particularly preferred.

The special glass fiber which is the component (B) used in the present invention has an average diameter of 5 to 12 μm, preferably 6 to 11 μm. Then, the final adhesion amount of the sizing agent (including a surface treatment agent for the purpose of adhesion and compatibility between the sizing component and the polyamide resin for the purpose of so-called sizing) to the surface after the drying finish is as follows: It is preferred that the content be in the range of 0.1 to 2% by weight of the glass fiber weight. If the amount of adhesion is less than 0.1% by weight, the adhesiveness between the polyamide resin and the glass fiber is deteriorated, and the strength is also reduced. On the other hand, if it exceeds 2% by weight, the glass fibers do not disperse, and a bundle of glass fibers is observed in the obtained molded product, which is not preferable in terms of physical properties.

The copolymer of maleic anhydride and unsaturated monomer constituting the sizing agent of the present invention includes styrene, α-
Of unsaturated monomers such as methylstyrene, butadiene, isoprene, chloroprene, 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene, methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate with maleic anhydride Copolymers are exemplified, and among them, copolymers with butadiene and styrene are preferred. These monomers may be used in combination of two or more. The maleic anhydride copolymer has an average molecular weight of 20.
It is preferably at least 00. Further, the ratio between maleic anhydride and unsaturated monomer is not particularly limited.

As the silane coupling agent which is another component constituting the sizing agent of the present invention, any silane coupling agent usually used for surface treatment of glass fibers can be used. Specific examples include aminosilanes such as γ-aminopropyltriethoxysilane, epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, and vinylsilanes such as vinyltrichlorosilane and vinyltriethoxysilane. One or more of these coupling agents can be used.

The proportions of the maleic anhydride copolymer and the silane coupling agent can be varied over a wide range, but a relatively good balance of physical properties is provided by the former, 0.01 to 10 parts by weight, per 100 parts by weight of the former. Percentage.

[0012] The maleic anhydride copolymer and the silane coupling are usually used as a sizing agent by mixing in an aqueous medium. If necessary, a surfactant, a lubricant, a softener, a charging agent, The sizing agent is composed of the components to which the inhibitor and the like are added, and the sizing agent is attached to the glass fiber and subjected to surface treatment in a process of producing the glass fiber or in a process after the production. When this is dried, a coating composed of the copolymer and the coupling agent is formed on the glass fiber surface. As described above, the adhesion amount is in the range of 0.02 to 2% by weight. As glass fiber, long fiber type (glass roving) to short fiber type (chopped strand)
Can be used.

Here, the average diameter of the glass fiber is a value observed by an electron microscope or the like, and the amount of sizing agent adhered is measured as a loss on burning of the glass fiber after burning for 60 minutes. Conventionally, when the glass fiber diameter is reduced from 13 μm to 11 μm or less, the antifreeze resistance is slightly improved,
Not noticeable. However, when a specific glass fiber having a diameter of 11 μm or less which is surface-treated with a sizing agent composed of a maleic anhydride copolymer and a silane coupling agent is mixed with a polyamide resin and reinforced, it is surprising that the antifreeze solution is surprising. The antifreeze resistance is remarkably improved when a specific amount of an azine dye is added to this system. 5μ
Even if the glass fiber diameter is made smaller than m, the effect of improving the antifreeze resistance reaches saturation, and rather, when mixed with polyamide resin, the glass fiber is broken even smaller and the fiber length becomes extremely short, so mechanical Not only does the strength drop,
The melt viscosity of the glass fiber reinforced polyamide resin composition is significantly increased, the molding fluidity is reduced, and the appearance of the obtained molded product is deteriorated.

The compounding ratio of the polyamide resin (A) and the specific glass fiber (B) in the composition of the present invention is as follows:
(A) is 30 to 95% by weight, preferably 40 to 85% by weight, and (B) is 70 to 5% by weight, preferably 60 to 15% by weight. If the glass fiber content is less than 5% by weight, the properties of the glass fiber reinforced polyamide resin composition are not improved as expected, and if it exceeds 70% by weight, the moldability of the composition is significantly reduced. But not preferred.

The azine dye used in the present invention is, for example, a reaction product obtained by using aniline, nitrobenzene and hydrochloric acid as main raw materials and using ferric oxide or the like as a catalyst, and is used as a black colorant for plastics, leather and the like. It is known that the glass fiber reinforced polyamide resin composition has improved antifreeze resistance,
It could not be expected that the antifreeze resistance would be synergistically improved only when a specific glass fiber was used. Examples of azine-based dyes include NYB27620B (manufactured by Sanyo Kako) and Orient Spirit BlackSB.
(Manufactured by Orient), Spirit Black N
o. 850 (manufactured by Sumitomo Chemical Co., Ltd.), Nigrosine B
A product marketed under a trade name such as "ase LK" (manufactured by BASF) can be used.

When the above-mentioned azine dye and a specific glass fiber are used in combination, a remarkable effect of improving the durability against antifreeze is exhibited. The compounding amount is 0.002 to 2 parts by weight based on 100 parts by weight of a glass fiber reinforced polyamide resin comprising a polyamide resin and a specific glass fiber,
Preferably it is in the range of 0.01 to 1 part by weight. When the amount is less than 0.002 parts by weight, not only the color is grayed out, but also the effect of improving the durability against the antifreeze is not recognized. When the amount is more than 2 parts by weight, there is no quantitative effect and the other physical properties are impaired. Not preferred.

The method for preparing the glass fiber reinforced black polyamide resin composition of the present invention is not particularly limited. For example, a method in which an azine dye is added when a polyamide resin and glass fiber are melt-mixed, which is prepared in advance. A method of blending and molding an azine-based dye with glass fiber reinforced polyamide resin, or preparing a master batch of an azine-based dye using a polymer compatible with the polyamide resin,
A method of diluting it with a glass fiber reinforced polyamide resin and molding the same may be used.

The glass fiber reinforced black polyamide resin composition of the present invention contains other components such as a heat stabilizer, an antioxidant, an antioxidant, a light stabilizer, a lubricant, a flame retardant as long as the moldability and physical properties are not impaired. Antistatic agent, release agent, plasticizer,
Inorganic fillers, other resin polymers and the like can be added. Further, black coloring can be performed by using carbon black in combination with the azine dye.

[0019]

Next, the present invention will be described in more detail by way of examples.

Example 1 A copolymer consisting of maleic anhydride and butadiene in a molar ratio of 1: 1 was added to an ammoniacal aqueous solution (concentration: 0.5%) and stirred well. Triethoxysilane was added and mixed to prepare a sizing agent solution.
In this case, the silane compound was used in a ratio of 0.6 part by weight based on 2 parts by weight of the copolymer.

The sizing agent solution is applied to glass fibers having an average diameter of 9 μm which are melt-spun into filaments by an applicator provided on the way to be wound on a rotating drum. After drying, a glass fiber bundle surface-treated with a sizing agent comprising the above copolymer and a coupling agent was obtained. At this time, the sizing agent adhesion amount is 0.4% by weight. This was cut into a length of 3 mm to obtain a glass fiber chopped strand. 33 parts by weight of the above glass fiber chopped strands, 67 parts by weight of nylon 66 pellets (R Leona 1300 manufactured by Asahi Kasei) and azine-based dye (NYB27620B manufactured by Sanyo Kako)
0.04 parts by weight of a twin screw extruder (PCM4
The mixture was melt-mixed at 290 ° C. using 5) and cooled to obtain pellets. The obtained pellets were subjected to injection molding using an injection molding machine.
A test piece for measuring physical properties was formed at a temperature of 90 ° C., and various physical properties were evaluated by the following methods. Table 1 shows the results.

(1) Tensile test: ASTM D638 (2) Bending test: ASTM D790 (3) Izod impact test: ASTM D256 (4) Antifreeze test: Antifreeze containing ethylene glycol as a main component (Toyota Genuine Long Life Coola)
nt) was heated to 140 ° C., the test piece was immersed for a predetermined time, and then a tensile test was performed.

Comparative Example 1 A test piece for measuring physical properties was obtained in the same manner as in Example 1 except that no azine dye was used, and various physical properties were evaluated. Table 1 shows the results.

Comparative Example 2 A test piece for measuring physical properties was obtained in the same manner as in Example 1 except that carbon black was used instead of the azine dye, and various physical properties were evaluated. Table 1 shows the results.

Examples 2-3 and Comparative Examples 3-4 Except that the amounts of the azine-based dyes were as shown in Table 1, a test piece for measuring physical properties was obtained in exactly the same manner as in Example 1, and various physical properties were measured. evaluated. Table 1 shows the results.

Examples 4 to 5 and Comparative Examples 5 to 6 Except that the average diameter of glass fibers and the amount of sizing agent adhered were as shown in Table 1, a test piece for measuring physical properties was prepared in the same manner as in Example 1. Obtained and evaluated various physical properties. Table 1 shows the results.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

The molded article obtained by molding the glass fiber reinforced black polyamide resin composition of the present invention is excellent in durability against automobile antifreeze at high temperatures, so that a radiator which requires particularly strict reliability is required. It is the most suitable material for automobile parts that come into contact with high-temperature antifreeze such as tanks, car heater tanks, water valves, and water pumps.

Continuation of front page (56) References JP-A-60-46951 (JP, A) JP-A-60-47060 (JP, A) JP-A-62-246958 (JP, A) JP-A-3-80135 (JP) , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 77/00-77/12

Claims (3)

(57) [Claims] 1. A polyamide resin (A) having a content of 30 to 95% by weight.
And glass fibers (B) having an average diameter of 5 to 12 μm and surface-treated with a sizing agent containing a copolymer of maleic anhydride and an unsaturated monomer and a silane coupling agent as main components. ) 70 to 5% by weight of a glass fiber reinforced polyamide resin (100 parts by weight) and an azine dye (C)
A glass fiber reinforced black polyamide resin composition comprising 0.002 to 2 parts by weight. 2. The amount of a sizing agent comprising a copolymer of maleic anhydride and an unsaturated monomer and a silane coupling agent as main components is 0.1 to 2% by weight based on glass fiber. The glass fiber reinforced black polyamide resin composition according to claim 1, wherein 3. A glass fiber reinforced black polyamide resin composition wherein the azine dye (C) is a reaction product obtained by using aniline, nitrobenzene and hydrochloric acid as main raw materials and using ferric oxide or the like as a catalyst. .