JPH06234896A - Reinforced polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a reinforced polyamide resin composition which can be used as a radiator tank for motor cars because of its excellent water resistance, solvent resistance and high tensile strength by blending polyamide resin, modified polyolefin, polypropylene resin and inorganic fillers in specific ratios respectively. CONSTITUTION:The composition comprises (A) 100 pts.wt. polyamide resin such as nylon 66 or nylon 6, (B) 0.5 to 100 pts.wt. modified polyolefin, preferably grafted polyolefin, or modified polyolefin terpolymer, (C) 0 to 150 pts.wt., preferably 5 to 100 pts.wt. polypropylene resin and (D) 50 to 300 pts.wt., preferably 80 to 250 pts.wt. inorganic filler, preferably glass fiber treated with succinic acid (its anhydrided) of formula I or formula II (R1 through R3 are 1-10C alkyl; R4 to R5 are H, methyl; n is 1 to 15) or its anhydride.

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 is excellent in water resistance and solvent resistance and has a good tensile strength, which is particularly suitable for a radiator tank for automobiles.

[0002]

2. Description of the Related Art Polyamide resins are widely used in various fields as synthetic fibers, films and various molding materials because of their excellent physical and chemical properties.
However, on the other hand, it has a low impact resistance and water absorbency, so that it has a drawback that a dimensional change of a molded product and a decrease in mechanical strength occur over time.

As a method for improving this, a composition has been proposed in which a modified polyolefin obtained by grafting an olefin polymer and an unsaturated carboxylic acid or a derivative thereof on a polyamide resin is blended (for example, Japanese Patent Publication No. 42-1).
2546, Japanese Patent Publication No. 45-30945, Japanese Patent Publication No. 50-7636). Furthermore, as a composition reinforced with an inorganic filler, it has been extensively studied for practical use in the fields of automobile parts, electric / electronic parts, and mechanical parts, and some have been put into practical use.

[0004]

However, even the above-mentioned composition has a problem that the water resistance and the solvent resistance are still insufficient, and the application as a molding material is sometimes limited. From the above, the present invention provides a polyamide resin composition having excellent water resistance and solvent resistance, and also having good tensile strength, without impairing the excellent properties inherent in the polyamide resin. To aim.

[0005]

As a result of intensive studies, the inventors of the present invention have found that the above object can be achieved by using a specific succinic acid compound as a surface treatment agent for an inorganic filler. The present invention has been completed based on this finding. That is, the present invention is (A) 100 parts by weight of polyamide resin, (B) modified polyolefin 0.5 to
100 parts by weight, (C) polypropylene resin 0-150
A reinforced polyamide resin composition comprising 50 parts by weight and (D) 50 to 300 parts by weight of an inorganic filler surface-treated with a succinic acid-based or succinic anhydride-based compound represented by the following formula (I) or (II) To do.

[0006]

[Chemical 3]

[0007]

[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 and R ₅ each independently represent hydrogen or a methyl group, and n represents an integer of 1 to 15). .)

The present invention will be specifically described below. The polyamide resin used in the present invention has an amide bond (-CONH).
It is a linear polymer compound having-), and is roughly classified into a polyamide obtained by polycondensing a dibasic acid and a diamine and a polyamide obtained by self-polycondensing a cyclic lactam or an amino acid. Typical examples of the former are polycondensates of hexamethylenediamine and adipic acid (nylon 66), polycondensates of hexamethylenediamine and sebacic acid (nylon 610), and polycondensates of hexamethylenediamine and dodecanoic acid. (Nylon 612), polycondensate of hexamethylenediamine and terephthalic acid (nylon 6T), polycondensate of xylylenediamine and adipic acid (XD6 nylon), and polycondensate of xylylenediamine and sebacic acid (XD10 Nylon).

Typical examples of the latter include a self-polycondensate of caprolactam (nylon 6), a self-polycondensate of 10-aminoundecanoic acid (nylon 11) and a self-polycondensate of laurinlactam (nylon 12). Can be mentioned. These polyamide resins may be used alone or in combination of two or more. The degree of polymerization of these polyamide resins is not particularly limited, but generally has a relative viscosity of 2.0 to 5.0, and particularly 2.5 to 4.
5 is preferable.

The modified polyolefin used in the present invention includes various ones such as those obtained by grafting a reactive monomer onto polyolefin, and copolymers of α-olefin and a monomer having a functional group. The following two types are preferable. That is, (a) a graft-modified polyolefin obtained by grafting an α, β-unsaturated carboxylic acid or a derivative thereof onto a polyolefin in the presence of a radical generator, and (b) an olefin (particularly an α-olefin) with an α, β- Unsaturated carboxylic acid or its derivative,
And a ternary modified polyolefin obtained by copolymerizing methacrylic acid ester or acrylic acid ester.

Among the above graft-modified polyolefins (a), there are various polyolefins as the base, but low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, Polypropylene, polybutene-1,
Polymethylpentene-1, copolymers of ethylene and α-olefins (ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-butene-1 copolymer, etc.), ethylene and vinyl compounds Copolymer with ethylene (ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene- (Meth) acrylic acid (ester) -α, β-unsaturated carboxylic acid (derivative) terpolymer, ethylene-vinyl chloride copolymer, etc.) or a mixture thereof.

As the α, β-unsaturated carboxylic acid or its derivative used for the graft modification, acrylic acid,
Maleic acid, fumaric acid, itaconic acid, 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic acid or their anhydrides or esters, and alkylaminomethacrylates such as 2-dimethylaminoethylmethacrylate. And glycidyl methacrylate and the like. Among them, acrylic acid, maleic acid, maleic anhydride or anhydride of 3,6-endomethylene-1,2,3,6-tetrahydro-cis-phthalic acid is preferable. These may be used alone or in combination of two or more.

Further, as radical generators used for graft modification, dicumyl peroxide; benzoyl peroxide; di-t-butyl peroxide; 2,5
-Dimethyl-2,5- (t-butylperoxy) hexane; 2,5-dimethyl-2,5-di- (t-butylperoxy) hexene-3; lauroyl peroxide; t
Organic peroxides such as butyl peroxybenzoate are preferably used.

In producing the graft-modified polyolefin (a), the above-mentioned polyolefin is suspended or dissolved in a suitable solvent, and the above α, β-unsaturated carboxylic acid or its derivative, and a radical generator are added thereto. A method of adding and heating and stirring, or a mixture of a polyolefin and α, β-unsaturated carboxylic acid or a derivative thereof and a radical generator in advance, and a method of melt kneading using an extruder, a Banbury mixer, a kneader, etc., In particular, the latter method is preferably adopted. The amount of each mixture used in this case may be appropriately selected depending on the situation and is not particularly limited, but usually, α, β-unsaturated carboxylic acid or its derivative is 0.1 parts by weight per 100 parts by weight of the polyolefin. ~ 5.0 parts by weight and radical generator 0.1
5.0 parts by weight may be used as a guide.

Such a graft-modified polyolefin has a structure in which an α, β-unsaturated carboxylic acid or a derivative thereof is grafted onto the polyolefin, but the grafted functional group (that is, α, β-unsaturated carboxylic acid or its derivative). The number (concentration) of the derivative-derived carboxyl groups) may be constant, but a mixture of different functional groups or different kinds of polyolefin to be grafted is preferable. Particularly, it is preferable to select the graft addition amount in the range of 0.05 to 5% by weight. In this way, the particle size distribution of the propylene resin, which is the dispersed phase in the polyamide, is broadened by giving the functional group number and the type of polyolefin a width or distribution, and the resulting polyamide composition has impact resistance, heat resistance, and peel resistance. Moreover, the improvement of other physical properties becomes more remarkable.

On the other hand, in the ternary modified polyolefin (b), there are various olefin monomers, but ethylene, propylene, butene-1, methylpentene-1 and the like are preferable, and ethylene is particularly preferable.
The α, β-unsaturated carboxylic acid or its derivative is the same as described above. For the production of the ternary modified polyolefin, a usual polymerization method can be used. The amount of each compound used in this case may be appropriately selected depending on the situation and is not particularly limited, but normally, olifin 100 is used.
As a standard, 1 to 5 parts by weight of α, β-unsaturated carboxylic acid or its derivative and 8 to 25 parts by weight of methacrylic acid ester or acrylic acid ester may be used as a standard with respect to parts by weight.

Such a ternary modified polyolefin is
The olefin unit and the units of α, β-unsaturated carboxylic acid or its derivative and the units of methacrylic acid ester or acrylic acid ester have a structure in which they are random or block-copolymerized, but the functional groups copolymerized (that is, α, The number (concentration) of the β-unsaturated carboxylic acid or the carboxyl group derived from the derivative thereof may be constant, but a mixture of different numbers of functional groups or different types of polyolefin units is preferable.
In this case, in particular, α, β-in the ternary modified polyolefin
When the content of unsaturated carboxylic acid or its derivative unit is 0.
It is preferably from 05 to 10% by weight.

The amount of the modified polyolefin compounded in the composition of the present invention is 0.
5 to 100 parts by weight. If the blending amount of the modified polyolefin is less than 0.5 part by weight, desired physical properties cannot be imparted.
On the other hand, if it exceeds 100 parts by weight, various physical properties may be deteriorated.

The polypropylene resin used in the present invention is a homopolymer of propylene and a copolymer of propylene and other α-olefin. Here, the copolymer includes a random or block copolymer. Examples of other α-olefins include ethylene and butene-1
And so on. Further, these polypropylene resins can be used in combination of two or more kinds. Furthermore, the resin contains a small amount of an olefinic copolymer rubber such as ethylene-propylene rubber, ethylene-butene rubber, propylene-butene rubber, ethylene-propylene-diene terpolymer rubber. Good. The molecular weight of the polypropylene resin is not particularly limited,
Usually, one having an MFR of 1 to 20 g / 10 minutes is suitable.

The compounding amount of the polypropylene resin in the composition of the present invention is 0 to 100 parts by weight of the polyamide resin.
It is 150 parts by weight, preferably 5 to 100 parts by weight. That is, in the composition of the present invention, the polypropylene resin may not be blended, but by blending it, more excellent water resistance and solvent resistance are exhibited. When the blending amount of the polypropylene resin exceeds 150 parts by weight, physical properties such as heat resistance and mechanical strength of the resulting composition deteriorate.

In addition, among the physical properties required for the composition of the present invention, when importance is attached to water absorption and calcium chloride resistance, the total amount of the modified polyolefin and the polypropylene resin to be blended should be larger than that of the polyamide resin. Is effective. If heat resistance is particularly desired,
It is preferable to increase the amount of the polyamide resin compounded.

The inorganic filler used in the present invention is surface-treated with a succinic acid-based or succinic anhydride-based compound represented by the following formula (I) or (II).

[Chemical 5]

[0023]

[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 and R ₅ each independently represent hydrogen or a methyl group, and n represents an integer of 1 to 15). .)

As the inorganic filler, various conventionally known fillers can be used. Examples thereof include oxides of iron oxide, alumina, magnesium oxide, zinc oxide, etc .; aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate. Hydrated metal oxides such as; carbonates such as calcium carbonate and magnesium carbonate; talc, clay,
Examples thereof include silicates such as bentonite and attapulgite; borates such as barium borate and zinc borate; phosphates such as aluminum phosphate and sodium tripolyphosphate; sulfates such as gypsum. Examples of the fibrous filler include glass fiber, 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. Among these, glass fiber is particularly preferable. The compounding amount of the surface-treated inorganic filler is 50 to 300 parts by weight, and more preferably 80 to 250 parts by weight, based on 100 parts by weight of the polyamide resin. If the amount is less than 50 parts by weight, the reinforcing effect of the filler is not sufficient. On the other hand, 300
If it exceeds the weight part, the moldability is deteriorated, which is not preferable.

Specific examples of the succinic acid-based or succinic anhydride-based compound include, for example, 1- [1-thio-3-
Carbonyloxy (3-trimethoxysilylpropyl)
Butyl] succinic acid, 1- [1-thio-3-carbonyloxy (3-triethoxysilylpropyl) butyl] succinic acid, 1- [1-thio-3-carbonyloxy (3-trimethoxysilylpropyl) propyl] Succinic acid, 1-
[1-thio-3-carbonyloxy (3-trimethoxysilylpentyl) butyl] succinic acid and 1- [1-thio-3-carbonyloxy (1-methyl-3-trimethoxysilylpropyl) butyl] succinic acid and These anhydrides are mentioned.

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. Further, 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 publication).

As a method for synthesizing the above compound, a radical addition of 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. To prepare the composition of the present invention, a mixer such as a Henschel mixer, a tumbler, a kneader, a Banbury mixer, and a screw extruder, which are commonly used in the art, may be used. In order to obtain a more uniform composition, two or more of these mixers may be used in combination. The temperature at the time of melt-kneading is generally 150 to 350 ° C, and particularly preferably 180 to 300 ° C.

In the composition of the present invention, if desired, various additives usually used, for example, lubricants, antioxidants, ultraviolet absorbers, antistatic agents, release agents, plasticizers, dyes, pigments, various additives Fillers and the like can be added. Further, the composition of the present invention can be molded into a desired shape using a generally used extrusion molding machine, injection molding machine, compression molding machine or the like.

[0029]

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. Mercaptosuccinic acid 15
g to γ-methacryloxypropyltrimethoxysilane 2
It was dissolved in 4.8 g, 20 g of anhydrous magnesium sulfate was added, and the mixture was stirred and dried. After removing the anhydrous magnesium sulfate by filtration, 500
Add to a ml flask. Furthermore, diethylamine 0.
24g was added and the mixture was heated at 40 ° C for 8 hours and then in a nitrogen atmosphere 1
The reaction was carried out at 20 ° C for 4 hours. The obtained crude product was subjected to cellulose column chromatography (distillation solvent: hexane / ethyl acetate =
5/5 (volume ratio)) to obtain a colorless transparent 1-
[1-Thio-3-carbonyloxy (3-trimethoxysilylpropyl) butyl] succinic anhydride (hereinafter KM
I got).

Further, 15 g of mercaptosuccinic acid was dissolved in 24.8 g of γ-methacryloxypropyltrimethoxysilane, 20 g of anhydrous magnesium sulfate was added, the mixture was stirred and dried, and anhydrous magnesium sulfate was filtered off and put into a 500 ml flask. Further, 0.24 g of 2,2′-azobisisovaleronitrile was added, and after bubbling with dry nitrogen of 0.3 l / hr for 30 minutes while stirring at room temperature, the mixture was heated at 50 ° C. for 1 hour and then at 60 ° C. The reaction was carried out at 1 ° C for 1 hour, 70 ° C for 30 minutes, and 80 ° C for 1 hour. The obtained crude product was purified by using the above-mentioned chromatography to obtain colorless and transparent 1- [1-thio-3-carbonyloxy (3-trimethoxysilylpropyl) butyl] succinic acid (hereinafter referred to as KA-1). Obtained. Similarly, using γ-methacrylooxypropyltriethoxysilane, 1
-[1-Thio-3-carbonyloxy (3-triethoxysilylpropyl) butyl] succinic acid (hereinafter referred to as KA-2
I got).

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.

The modified polyolefin has an MFR of 1.
A graft modified product in which 0.35% by weight of maleic anhydride was grafted to 0 g / 10 min of isotactic polypropylene was used.

The polypropylene resin has an MFR of 18
A polypropylene (Showaroma MA610H manufactured by Showa Denko KK) having a rate of g / 10 minutes was used. As the inorganic filler, E glass fiber having a diameter of 13 μ and a length of 3 mm was used. For comparison, as a surface treatment agent, 3-aminopropyltrimethoxysilane (hereinafter referred to as S-1), γ
-Methacryloxypropyltrimethoxysilane (hereinafter,
S-2), γ-mercaptopropyltrimethoxysilane (hereinafter referred to as S-3), vinyltriethoxysilane (hereinafter referred to as S-4), γ-glycidoxypropyltrimethoxysilane (hereinafter referred to as S-5). , N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane (hereinafter, S-6) and 3-isocyanatopropyltrimethoxysilane (hereinafter, S-7) were used.

Examples 1 to 7 and Comparative Examples 1 to 7 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.

[0036]

[Table 1]

[0037]

The resin composition of the present invention is excellent in water resistance and solvent resistance, and has good tensile strength, and is therefore promising in the field of automobile parts, electric / electronic device parts and other industrial parts. is there.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Maruyama 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Akira Kawasaki Plastics Research Laboratory

Claims (1)

[Claims] 1. (A) Polyamide resin 100 parts by weight,
(B) Modified polyolefin 0.5 to 100 parts by weight,
(C) Polypropylene resin 0 to 150 parts by weight and (D) Inorganic filler surface-treated with succinic acid-based or succinic anhydride-based compound represented by the following formula (I) or (II) From 50 to 300 parts by weight Reinforced polyamide resin composition. [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 and R ₅ each independently represent hydrogen or a methyl group, and n represents an integer of 1 to 15). .)