JPH0688022A - Polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin composition having high mechanical strength and excellent heat, water and solvent resistances by mixing a polyamide resin with an inorganic filler surface-treated with a specified compound. CONSTITUTION:20-98 pts.wt. polyamide resin is mixed with 80-2 pts.wt. inorganic filler surface-treated with a succinic acid or anhydride compound of formula I or II (wherein R1, R2 and R3 are each 1-10C alkyl; R4 is H or CH3; and n is 1-15) to obtain a polyamide resin composition. This composition has excellent heat resistance, durability and solvent resistance as well as high mechanically strengths and therefore is useful in, e.g. the field of automobile parts.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition which, in a composite material comprising polyamide and an inorganic filler, has not only high mechanical strength but also excellent heat resistance, water resistance and solvent resistance.

[0002]

2. Description of the Related Art Conventionally, materials containing inorganic fillers such as glass fiber, talc and mica have been generally used in the field of application of polyamide resins. However, it is known that an organic material such as a resin and an inorganic filler generally have poor adhesiveness, and the desired performance may not be exhibited by simply mixing them. In order to solve this, the filler is treated with various surface treatment agents such as silicone type, titanate type or aluminate type,
Methods such as compounding a surface treatment agent with a resin have been adopted (for example, Editorial Committee of Material Technology Research Institute, “Composite Materials and Interfaces” pp. 137-156, published by SGS Sogo Gijutsu Publishing Co., Ltd. in 1986 and Kazumasa Nakao). Others, "Technology for Optimum Utilization of Coupling Agents", pp. 113-214, published by Institute of Science and Technology in 1988).

[0003]

However, in the polyamide resin, even if these techniques are adopted, the mechanical strength is not sufficient, and further, the mechanical strength decreases during use depending on the surrounding environment. The reality is that there are problems that limit their use.

The present invention has been made in view of the above circumstances, and not only overcomes the drawbacks of conventional polyamide / inorganic filler composite materials containing surface-treating agents and exhibits high mechanical strength, but also heat resistance, An object of the present invention is to provide a polyamide resin composition having excellent water resistance and solvent resistance.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by using a succinic acid compound having a specific mercaptosilane group as a surface treatment agent. The present invention has been completed based on this finding.

That is, in the present invention, (A) a polyamide resin of 20 to 98% by weight and (B) a succinic acid-based or succinic anhydride-based compound represented by the following formula (I) or (II) is surface-treated. Provided is a polyamide resin composition comprising 80 to 2% by weight of an inorganic filler.

[0007]

[Chemical 3]

[Chemical 4] (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms, R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 15.) Will be described in detail.

As the polyamide resin used in the present invention, various kinds can be used. Specifically, polylactams such as nylon 6, nylon 11, nylon 12; nylon 66, nylon 610, nylon 612,
Polyamides obtained from dicarboxylic acids such as nylon 46 and diamines; nylon 6-66, nylon 6-1
2. Copolymerized polyamides such as nylon 6-66-610; semi-aromatic polyamides obtained from aromatic dicarboxylic acid such as nylon 6-6T and isophthalic acid and metaxylylenediamine or aliphatic diamine; polyester amide, poly Examples thereof include ether amide and polyester ether amide. These polyamide resins may be used alone or in combination of two or more.

As the inorganic filler used in the present invention, various conventionally known fillers can be used. Examples thereof include, for example, oxides of iron oxide, alumina, magnesium oxide, zinc oxide, etc .; aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide,
Hydrated metal oxides such as tin oxide hydrate and zirconium oxide hydrate; carbonates such as calcium carbonate and magnesium carbonate; silicates such as talc, clay, bentonite and attapulgite; borate salts such as barium borate and zinc borate. Examples thereof include phosphates such as aluminum phosphate and sodium tripolyphosphate; sulfates such as gypsum. As the fibrous filler, for example, glass fiber,
Examples thereof include potassium titanate fiber, metal coated glass fiber, ceramic fiber, wollastonite, metal carbide fiber and the like. Other examples include glass beads, spherical materials such as glass balloons and shirasu balloons, glass powder, glass flakes, and mica. These inorganic fillers can be used alone or in combination of two or more.

The compounding ratio of the inorganic filler is 2 to 80% by weight,
It is more preferably 5 to 70% by weight. If the blending ratio is less than 2% by weight, the reinforcing effect of the filler is not sufficient. On the other hand, 8
If it exceeds 0% by weight, moldability is deteriorated, which is not preferable.

Further, the succinic acid-based or succinic anhydride-based compound used in the present invention is a compound represented by the following formula (I) or (II).

[Chemical 5]

[Chemical 6] (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms, R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 15.)

Specific examples of the compound include, for example, 1-
[1-Thio-4- (trimethoxysilyl) butyl] succinic acid, 1- [1-thio-5- (trimethoxysilyl) pentyl] succinic acid, 1- [1-thio-8- (trimethoxysilyl) Octyl] succinic acid, 1- [1-thio-6-
(Triethoxysilyl) hexyl] succinic acid, 1- [1
-Thio-7- (triethoxysilyl) heptyl] succinic acid, 1- [1-thio-2-methyl-4- (trimethoxysilyl) butyl] succinic acid and 1- [1-thio-3-
Examples include methyl-4- (triethoxysilyl) butyl] succinic acid and their anhydrides.

The above compounds may be used alone or in combination of two or more. Further, upon use, it can be used as an aqueous solution or an organic solvent solution of alcohol, ketone, halogenated hydrocarbon or the like, if necessary.

The amount of the above compound is usually 0.5 to 20 parts by weight, more preferably 1.0 to 15 parts by weight, based on 100 parts by weight of the inorganic filler. The surface treatment can be carried out by a known means (for example, Japanese Patent Publication No. 41-17049, Japanese Patent Publication No. 60-6739, etc.).

As a method for synthesizing the above compound, a method of radically adding mercaptosilane and maleic acid or maleic anhydride in the presence of a radical initiator such as heat or an azo type or peroxide, or a base such as diethylamine or triethylamine. A method of anion addition in the presence of a neutral catalyst and a method of cation addition in the presence of an acidic catalyst such as paratoluenesulfonic acid.

In the resin composition of the present invention, if desired, various additives usually used, for example, lubricants, plasticizers, stabilizers, antistatic agents, foaming agents, mold release agents, dyes, pigments, flame retardants. Etc. can be added.

[0017]

EXAMPLES The present invention will now be described in more detail with reference to examples. The tensile strength was based on ASTM D638. Further, in the solvent resistance test, ASTM No. 1 dumbbell was used, and the tensile strength was measured after dipping for 1000 hours in a 50% by weight ethylene glycol aqueous solution at 120 ° C.

Production Example The succinic acid-based or succinic anhydride-based compound used in the present invention was prepared by the following method. Maleic anhydride 19.8
g to γ-mercaptopropyltrimethoxysilane 39.
Dissolve in 2 g, add 20 g of anhydrous magnesium sulfate, stir-dry, and filter off anhydrous magnesium sulfate, then 500 ml
The flask was charged. Furthermore, triethylamine 0.1
g was added, and the mixture was reacted at 40 ° C. for 2 hours and then at 60 ° C. for 1 hour. The obtained crude product was purified using cellulose column chromatography (distillation solvent: hexane / ethyl acetate = 5/5 (volume ratio)), and colorless and transparent 1- [1-thio-4
-(Trimethoxysilyl) butyl] succinic anhydride (hereinafter referred to as KM) was obtained.

Further, 23.2 g of maleic acid and 50 ml of ethylene glycol monoethyl ether were put into a flask and dissolved. Furthermore, 39.2 g of γ-mercaptopropyltrimethoxysilane and 0.374 g of 2,2′-azobisisovaleronitrile were added, and bubbling was performed at room temperature for 1 hour with 0.3 l / hr of dry nitrogen while stirring. After that, the reaction was carried out at 55 ° C for 3 hours, then at 65 ° C for 1 hour, and further at 80 ° C for 1 hour. The obtained crude product was purified using the above-mentioned chromatography to give a colorless transparent 1-
[1-Thio-4- (trimethoxysilyl) butyl] succinic acid (hereinafter referred to as KA-1) was obtained. Similarly, γ
-With mercaptohexyltrimethoxysilane 1-
[1-Thio-7- (trimethoxysilyl) heptyl] succinic acid (hereinafter referred to as KA-2) was obtained.

As the polyamide resin, nylon 66 resin (Technyl A216 manufactured by Showa Denko KK) (hereinafter referred to as PA6
6), nylon 6 resin (Technyl C216 manufactured by Showa Denko KK) (hereinafter referred to as PA6) and nylon 66.
-6 resin (Technyl B216 manufactured by Showa Denko KK) (hereinafter referred to as PA66-6) was used. As an inorganic filler, E glass fiber having a diameter of 13 μ and a length of 3 mm (hereinafter, G glass)
F), mica (Tokyo Miken A-31S) and talc (Hayashi Kasei 5000S) were used.

Further, as a surface treatment agent for comparison, 3-
Aminopropyltrimethoxysilane (hereinafter referred to as S-1), γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as S-2), γ-mercaptopropyltrimethoxysilane (hereinafter referred to as S-3), vinyltriethoxy Silane (hereinafter referred to as S-4), γ-glycidoxypropyltrimethoxysilane (hereinafter referred to as S-5), N-β (aminoethyl) γ-aminopropyltrimethoxysilane (hereinafter referred to as S-6) and 3-Isocyanatopropyltrimethoxysilane (hereinafter referred to as S-7) was used.

Examples 1 to 7 and Comparative Examples 1 to 13 Kneading at 280 ° C. in a co-directional twin-screw extruder using polyamide resins, inorganic fillers and surface treatments whose types and amounts are shown in Table 1. did. Next, knead mixture
Injection molded into a No. dumbbell. The tensile strength of the obtained molded product was measured. Further, a solvent resistance test was conducted, and then the tensile strength was measured. The results are shown in Table 1. The surface treatment of the filler was carried out by preparing a 1% methanol solution of the surface treating agent to be used, immersing the filler in this at room temperature for 1 hour, and then vacuum drying at 30 ° C.

[0023]

[Table 1]

[0024]

INDUSTRIAL APPLICABILITY The composition of the present invention not only has high mechanical strength but also excellent heat resistance, water resistance and solvent resistance, and is therefore particularly useful in the field of automobile parts.

Claims (1)

[Claims] 1. An inorganic filler surface-treated with 20 to 98% by weight of (A) a polyamide resin and (B) a succinic acid-based or succinic anhydride-based compound represented by the following formula (I) or (II): A polyamide resin composition comprising 2% by weight. [Chemical 1] [Chemical 2] (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms, R ₄ represents hydrogen or a methyl group, and n represents an integer of 1 to 15.)