JPS6047060A - Fiber-reinforced polyamide resin composition - Google Patents

Abstract

PURPOSE:To provide a fiber-reinforced polyamide resin compsn. which gives moldings excellent weld strength (particularly thermal shock resistance at welded parts), by adding a bisphenol compd. and/or an azine compd. CONSTITUTION:A bisphenol compd. of the formula [wherein R1 is H, a 1-3C alkyl; R2, R3 are each H, a 1-4C alkyl, (alpha-methyl)cyclohexyl] such as 2,2'- methylene-bis(dimethyl-4,6-phenol) and/or an azine compd. (a reaction product obtd. by using aniline, nitrobenzene and hydrochloric acid as main starting materials in the presence of ferric oxide as a catalyst) are/is used as additives. 40- 95wt% polyamide (A) such as nylon 66, 60-5wt% reinforcing fiber (B) such as glass fiber having a length of 10mu or above and a diameter of 0.2 or above and 0.002-2pts.wt (per 100pts.wt of the combined quantity of components A and B) above additives are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fiber-reinforced polyamide compositions capable of providing molded articles with improved weld strength. More specifically, the present invention relates to a fiber-reinforced polyamide composition that can provide a molded article with significantly improved heat shock resistance in the weld area.

Reinforced polyamide 1 In particular, polyamide resin reinforced with fibrous reinforcement has excellent mechanical properties, chemical resistance, heat resistance, durability, etc., and is widely used as parts for automobiles, electricity, machinery, etc. Particularly recently, from the viewpoint of improving fuel efficiency through weight reduction and streamlining processes, there has been a remarkable movement to replace automobile parts that conventionally use metal with fiber-reinforced polyamide P.

However, in order to replace plastics in fields where metals have traditionally been used, reliability as a plastic material is required more than in previous applications. 1) Amide resin with fiber reinforced polyamide resin has good mechanical properties, heat resistance,
From the viewpoint of heat resistance, it is used as a component material in the engine compartment of automobiles, but the molded product is subject to sudden environmental changes, such as environmental temperatures from 120°C to -40°C.
A problem has arisen in which the weld portion selectively cracks due to rapid temperature changes and their repetition, that is, heat shock. In order to avoid the above drawbacks, conventional methods have been to design the mold so that welds do not occur in the molded product, or to move the weld to a location where it is not important for the strength of the molded product. Depending on the purpose and shape of the product,
In some cases, the above-mentioned treatment may not be able to cope with the problem, and its uses are severely restricted.Therefore, there has been a strong desire for a fiber-reinforced polyamide composition that has significantly improved heat shock resistance in the weld portion.

Therefore, the present inventors conducted intensive studies to obtain a fiber-reinforced polyamide composition that can provide a molded product with improved heat shrinkage resistance in the weld area, and as a result, they identified a system consisting of a polyamide resin and a fibrous reinforcing material. The present invention has been achieved by discovering that the above object can be effectively achieved by coexisting an organic compound.

That is, the present invention uses 100 parts by weight of a polyamide resin composition comprising 40 to 95% by weight of polyamide 1 resin and 60 to 5 parts by weight of fibrous reinforcing material, and 0.002 to 2 parts by weight of a bisphenol compound and/or an azine compound. The present invention relates to a fiber-reinforced polyamide composition comprising:

The bisphenol compound, which is one of the constituent components of the composition of the present invention, is known as a thermal deterioration inhibitor for various plastic materials. However, as illustrated in FIG. 1, when 4,4'-zothylidene bis-(3-methyl-6-tert-butylphenol), which is one of the bisphenol additives of the present invention, is added to fiber-reinforced polyamide P. However, there is no effect of improving the heat deterioration resistance of the first part of the well. However, surprisingly, when a small amount of this compound is added to the reinforced polyamide, the heat shock resistance of one part of the well is significantly improved. Another component, an azine compound, is known as a coloring agent for plastics, leather, etc., but it was unexpected that it would be effective in improving the heat shock resistance of fiber-reinforced polyamide. Furthermore, it was unexpected that a synergistic effect would be exhibited when these compounds were used in combination in fiber-reinforced polyamide.

The present invention will be explained in detail below.

Polyamylene according to the present invention refers to bouillon 66, nylon 6, which is obtained by condensation of diamine and dicalic acid.
10. Nylon 612, nylon 6 obtained by ring-opening polymerization of lactam, nylon 12, ω-amical d? These include nylon 11 obtained by self-condensation of phosphoric acid, copolymers and blends thereof, and the like. Among them, nylon 66 and blends of nylon 66 and other polyamide resins are preferred.

The fibrous reinforcing material used in the present invention is a fibrous material used as a reinforcing material for polyamide, and there is no particular restriction on the cross-sectional shape, the fiber length (g) is 10 μ' or more, and the fiber diameter .2μ or more, the ratio L of fiber length (L) to fiber diameter
/D is 1 or more. Examples of the fibrous reinforcing material include glass fiber, carbon fiber, aromatic polyamide fiber, metal fiber, and various whiskers. Among them, glass fiber is preferred. In addition, kaolin, calcined kaolin,
Great effects can also be obtained by applying the present invention to reinforced polyamide resins containing both so-called mineral powders such as talc, mica, and calcium carbonate, and fibrous reinforcing materials.

Polyamide resin and fiber in the composition of the present invention.

The blending ratio with the shape reinforcing material is 40 to 95% by weight, preferably 50 to 85% by weight of the former, and 6θ to 5% by weight of the latter.

Preferably it is 50 to 15% by weight. If the proportion of the fibrous reinforcing material is less than 5% by weight, the properties of the fiber-reinforced 4-soriamide resin composition will not be improved as much as expected, and if it exceeds 60% by weight, the composition will not be formed properly. The gender is markedly reduced and the head is not suitable for beheading.

The bisphenol compound used in the present invention has the following general formula (wherein R1 is a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and R and R3 are a hydrogen atom, a methyl group, an ethyl group, tert-butyl group, cyclohexyl group or α-methylcyclohexyl group), whose chemical name is 2,2'-methylene-bis-(dimethyl-4-6-phenol)%
2.2'-methylene-bis-(4-methyl-6-th-butylphenol), 2,2'-methylene-bis-(4-
methyl-6-cyclohexylfuenol), 2.27
-methylene-bis-(4-ethyl-6=tert-butyl-
phenol), 4,4'-methylene-bis=(2,6-
di-tert-butyl-phenol), 4,4'-butylidene-bis-(3-methyl-6-tert-butyl-phenol)
, 2,2'-dihydroxy; and -3,3'-di(α-methylcyclohexyl).

The azine compound used in the present invention is a reaction product obtained using aniline, nitrobenzene, and hydrochloric acid as main raw materials and using ferric oxide as a catalyst, such as NYB2762O.
B (manufactured by Sanyo Kako Co., Ltd.), Orient 5piritB
rack SB (manufactured by Orient), 5prit B
Lack A 850 (manufactured by Sumitomo Chemical Co., Ltd.), Nigros
A cloth coated with a trade name such as ine Ba5e LK (manufactured by BASF) can be used.

The above-mentioned bisphenol compounds and azine compounds can be used alone or in combination; however, when they are combined, the effect of improving the heat shock resistance of the weld part is significant. It's beautiful. The blending amount is 0.00 for the groin area of polyamide composition 1001 consisting of polyamide resin and fibrous reinforcing material.
It ranges from 2 to 21 parts, preferably from 0.01 to 11 parts. If the amount is less than 0.002 parts by weight, the effect of improving the heat shock resistance of the weld part will be small, and if it is more than 2 parts by weight, there will be no quantitative effect and other physical properties will be impaired, which is not preferable.

There are no particular limitations on the method for preparing the fiber-reinforced polyamide composition of the present invention, such as adding a phenolic compound and/or an azine compound when melt-mixing the polyamide resin and the fibrous reinforcing material; A method is to tri-blend these additives to a pre-prepared fiber-reinforced polyamide resin and mold it, or a master patch of these additives is prepared using a polymer that is compatible with the polyamide 1-co resin, and then it is applied to the fibers. Examples include a method of diluting with reinforced polyamide 1 resin and molding.

The fiber-reinforced polyamide resin composition of the present invention may contain other components such as pigments, dyes, heat resistant agents, light stabilizers, lubricants, flame retardants, antistatic agents, mold release agents, etc., to the extent that their moldability and physical properties are not impaired. agents, plasticizers, other resin polymers, etc. can be added.

The molded product obtained by molding the fiber-reinforced polyamide resin composition of the present invention has significantly improved heat shock resistance in the weld part, and is suitable as a material for automobile parts that particularly requires strict reliability. It is the most suitable material.

The present invention will be explained in further detail below by giving examples.

The physical properties of the test pieces described in Examples and Comparative Examples were measured according to the following method.

(1) Tensile test: ASTM D638 (2) Bending test: ASTM D790 (3) Izot impact test: ASTM D256 (4) Heat shock resistance test Weld test mold (molten resin is fused at the center of the opposite side of the gate) A test piece as shown in FIG. 2 was obtained using a mold made as shown in FIG. This was cut to the dimensions shown in FIG. 2 to obtain a heat shock resistant test piece.

This test piece was placed on a fixed plate, and a 5m+n octopus-shaped spacer (material 5540) was inserted into the well r position as shown in FIG. 3, and both ends of the test piece were fixed with RG sill dots. The fixed test piece was placed in a rotary thermal shock tester (manufactured by Hejima Seisakusho, model TSE1t-2253-A), and
The cycle of 1 hour at 150° C. and 1 hour at 150° C. was repeated, and the number of cycles until the weld part broke was counted.

1300), 33 parts by weight of glass fiber (TP-24 manufactured by Nippon Glass Fibers), and 0.04 parts by weight of an azine compound (NYB27620B manufactured by Ryonari Kako) were premixed in a V-type blender, and then a 70IIIφ single-shaft blender was used. Using an extruder, the mixture was melt-mixed at 290°C and cooled to obtain a pellet.

The obtained pellet was molded into a test piece for measuring physical properties using an injection molding machine at a temperature of 290°C, and various physical properties were evaluated. The results are shown in Table 1.

Example 2 4-4'-butylidene bis(3-methyl-6-tert-zotylphenol) as a bisphenol compound in place of the azine compound; (manufactured by Sumitomo Chemical; Slyzer BBM)
A test piece for measuring physical properties was produced in exactly the same manner as in Example 1 except that 0.05 parts by weight was used, and various physical properties were evaluated. The results are shown in Table 1.

#.

Example 3 Azine-based compound (manufactured by Ryonari Kako: NYB27620B
) 0.04 parts by weight and bisphenol compound; 4-4
'-Butylidene bis(3-methyl-6-tert-zotylphenol) (Sumitomo Chemical: Sumilizer BBM) 0.0
A test piece for measuring physical properties was produced in exactly the same manner as in Example 1 except that 5 parts by weight of both were used in combination, and various physical properties were evaluated.

The results are shown in Table 1.

Comparative Example 1 A test piece for measuring physical properties was produced in exactly the same manner as in Example 1 except that no azine compound was used, and various physical properties were evaluated. The results are shown in Table 1.

Comparative Example 2 Azine compound (NYB27620B manufactured by Ryonari Kako) 0.
0005 parts by weight, bisphenol compound; 4-4'-
Butylidene bis(3-methyl-6 tertiary zoterphenol) (Sumitomo Chemical: Sumilizer BBM) A test piece for measuring physical properties was produced in the same manner as in Example 1 except that the amount was 0.0003 parts by weight, and various physical properties were measured. evaluated. The results are shown in Table 1.

Example 4 Nylon 66 pellet (Asahi Kasei Leona 1300) 2
7 parts by weight and nylon 610 (ηr=2.50) 40
Parts by weight and 33 parts by weight of glass fiber were premixed in a V-type Zollender, and then heated at 290°C using a 70m+φ single screw extruder.
The mixture was melt-mixed and cooled to obtain a glass fiber-reinforced polyamide pellet. For 100 parts by weight of this reinforced pellet,
o, i parts by weight of powder of azine compound (NYB2762OB manufactured by Ryonari Kako Co., Ltd.) and bisphenol compound; 4-4'-
0.1 part by weight of powder of butylidene bis(3-methyl-6-tert-zotylphenol) (Sumilyzer BBM manufactured by Sumitomo Chemical) was added, mixed in a ■ type blender, and subjected to an injection molding machine, and the physical properties were determined at a temperature of 290°C. Manufacture test pieces for measurement,
Various physical properties were evaluated. The results are shown in Table 1.

Comparative Example 3 A test piece for measuring physical properties was produced in exactly the same manner as in Example 4, except that no azine compound and bisphenol compound were used, and various physical properties were evaluated. The results are shown in Table 1.

Example 5 Nylon 66 pellet (Leona 1300 manufactured by Fukasei) 5
7 parts by weight and glass fiber (TP-24 manufactured by Nippon Glass Fiber) 4
3 parts by weight and 2,2'-methylenebis-(4-ethyl-6
-Tertiary ditylphenol) (Kawaguchi Department of Chemistry: Antage W
-500) and 1.5 parts by weight were premixed in a ■-type Zollender, and then 2.90°C using a 70■φ single-screw extruder.
The mixture was melt-mixed and cooled to obtain a pellet.

Using the obtained pellet, a test piece for measuring physical properties was manufactured at a temperature of 290° C. using an injection molding machine, and various physical properties were evaluated. The results are shown in Table 1.

Example 6 A test piece for measuring physical properties was produced in exactly the same manner as in Example 4, except that 77 parts of nylon 66 and 23 parts by weight of glass fiber were used, and various physical properties were evaluated. The results are shown in Table 1.

Comparative Example 4 A test piece for measuring physical properties was produced in exactly the same manner as in Example 4, except that 97 parts by weight of nylon 66 and 3 parts by weight of glass fiber were used, and various physical properties were evaluated. The results are shown in Table 1.

Comparative Example 5 A test piece for measuring physical properties was produced in exactly the same manner as in Example 4, except that nylon 66 was used in 35 parts by weight and glass fiber was used in 65 parts by weight, and various physical properties were evaluated. The results are shown in Table 1.

Below margin

[Brief explanation of the drawing]

Figure 1 is a diagram showing the relationship between the amount added and the heat deterioration resistance and heat shock resistance of one part of the well when a bisphenol compound is added to reinforced polyamide. Test piece used for (
FIG. 4 is a plan view showing the dimensions and cutting position of a thickness of 4 rm. In the figure, 1 (shaded area) is a test piece for measurement, A is 23W, B
indicates 123 mm, O indicates 23 kaku, and D indicates 90 kaku. FIG. 3 is a diagram showing how the test piece is attached when measuring heat shock resistance. In the figure, l indicates the test piece', 2 indicates the fixing plate, 3 indicates the spacer, 4 indicates the fixing bolt/nut, and 5 indicates the well P position of the test sample. Patent applicant: Asahi Kasei Industries, Ltd. Figure 1

Claims (1)

[Scope of Claims] 1. A polyamide resin composite acid io comprising 40 to 95% by weight of a polyamide resin and 60 to 5% by weight of a fibrous reinforcing material.
0.002 to 2 parts by weight of a bisphenol compound and/or an azine compound. , an ethyl group, or a propyl group, and R1 and R3 are a hydrogen atom, a methyl group, an ethyl group, a tert-butyl group, a cyclohexyl group, or an α-methylcyclohexyl group. A patent characterized in that the azine-based compound is a reaction product obtained using aniline, nitrobenzene, and hydrochloric acid as main raw materials and using ferric oxide or the like as a catalyst. Fiber-reinforced polyamide resin composition according to claim 1