JPH0692537B2 - Resin and filler composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a polyphenylene oxide resin, a polyamide resin and a filler.

Molded articles made from the resin composition of the present invention have extremely small warpage, good mechanical strength, and excellent heat resistance and oil resistance.

[Prior Art] Conventionally, polyphenylene oxide-based resin molded products reinforced with fillers, especially glass fibers, are excellent in mechanical properties, electrical properties, and dimensional accuracy, but are known to be poor in oil resistance. .

Therefore, it was attempted to improve the oil resistance of the molded product by blending an appropriate amount of polyamide resin, which itself has excellent oil resistance.

However, since the polyphenylene oxide resin and the polyamide have poor compatibility with each other, a reinforced resin molded product containing a mixture of these does not exhibit the characteristics inherent to both resins and causes another drawback. . That is, there are problems that the warp of the molded product is very large and that good mechanical properties, especially strength, cannot be obtained.

[Problems to be Solved by the Invention] The present invention reduces warpage of a molded product made from a resin composition containing a polyphenylene oxide resin, a polyamide and a filler, and has a good mechanical strength. The purpose is to do. This object is solved by using a polyamide having a specific end group ratio in the above resin / filler composition.

[Structure of the Invention] That is, according to the present invention, (A) the polyphenylene oxide resin is 5 to 80 parts by weight, and (B) the molar ratio of terminal amino groups to terminal carboxyl groups is 1.
95 to 20 parts by weight of polyamide resin of 1 or more (C) 0.01 to 10 parts by weight of saturated aliphatic polycarboxylic acid and // to 100 parts by weight of the above components (A) and (B) in total
Or a derivative thereof (D) 5 to 150 parts by weight of a filler per 100 parts by weight of the above components (A) and (B) (E) a total of 100 parts by weight of the above components (A) and (B) 0 to 20 parts by weight of a rubber-like substance (F) 0 to 40 parts by weight of a halogen-based flame retardant per 100 parts by weight of the above components (A) and (B) (G) the above components (A) and ( There is provided a resin composition containing 0 to 20 parts by weight of an antimony compound based on 100 parts by weight of B) in total.

Here, the polyphenylene oxide resin is known per se, for example, the general formula [Wherein R ₁ , R ₂ , R _{3 and} R ₄ are hydrogen, halogen, an alkyl group, an alkoxy group, a haloalkyl group and a haloalkoxy group having at least two carbon atoms between the halogen atom and the phenyl ring] Represents a monovalent substituent selected from those containing no tertiary α-carbon, and n is an integer representing the degree of polymerization], and is a general term for polymers represented by the above general formula. The above may be a single type or a copolymer in which two or more types are combined. In a preferred embodiment R ₁
And R ₂ is an alkyl group having 1 to 4 carbon atoms, R ₃ ,
R ₄ is hydrogen or an alkyl group having 1 to 4 carbon atoms. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether , Poly (2-methyl-6-propyl-1,4
-Phenylene) ether, poly (2,6-dipropyl-1,4)
-Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether and the like.
A particularly preferred polyphenylene ether resin is poly (2,6
-Dimethyl-1,4-phenylene) ether. Examples of the polyphenylene ether copolymer include copolymers containing a part of alkyl tri-substituted phenol such as 2,3,6-trimethylphenol in the above polyphenylene ether repeating unit. Further, it may be a copolymer obtained by grafting a styrene compound on these polyphenylene ethers. As the styrene compound grafted polyphenylene ether, the above polyphenylene ether can be used, and as the styrene compound, for example, styrene,
It is a copolymer obtained by graft polymerization of α-methylstyrene, vinyltoluene, chlorostyrene and the like.

Polyamide resins themselves are known, for example nylon-
4, Nylon-6, Nylon-6,6, Nylon-12, Nylon-6,10, etc. are mentioned, but not limited thereto. What is essential in the present invention is that the molar ratio of the terminal amino group to the terminal carboxyl group is 1.1 or more. Such a polyamide can be obtained by adding an extra compound such as a diamine having a group that reacts with a carboxyl group during polymerization of the polyamide. Alternatively, it can also be obtained by reacting with a compound having a group which reacts with a carboxyl group after the polymerization of polyamide.

Generally used polyamide resins have an end group ratio of 1 or less. In addition, in polyamide for injection molding, an end-capping agent is added to the polymerization component in order to appropriately adjust the melt viscosity, but the end group ratio of such polyamide is smaller than 1. When a polyamide having an end group ratio of 1.1 or more is used in accordance with the present invention, the warp of the molded product is small and mechanical strength and appearance are dramatically improved as compared with the case where a polyamide having an end group ratio of 1 or less is used.
This was completely unexpected, and although there is no definitive theoretical reasoning so far, electron micrographs of molded articles show that the particles of the polyphenylene oxide resin dispersed in the polyamide matrix phase are The diameter is small and uniform. It is surprising that such a difference occurs due to the difference in the end group ratio of the polyamide. The terminal group ratio is
It is preferably 1.3 or more. In the present invention, component (C)
The above improvement cannot be achieved without adding.

In the present invention, (A) a polyphenylene oxide resin and (B) a polyamide resin having a molar ratio of terminal amino groups to terminal carboxyl groups of 1.1 or more are blended in the ranges of 5 to 80 parts by weight and 95 to 20 parts by weight, respectively. To be done. If the amount of component (B) is larger than this, the desirable properties of component (A) itself will not be realized, while if it is smaller than this, the purpose of adding component (B), that is, improvement of oil resistance will not be achieved. A preferred blending ratio of the component (A) and the component (B) is 30 to 70 parts by weight of the component (A) and 70 to 30 parts by weight of the component (B).

(C) The saturated aliphatic polycarboxylic acid and its derivative are 0.01 to 1 with respect to 100 parts by weight of the total of the components (A) and (B).
0 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 2 parts by weight. If it is less than 0.01 part by weight, the intended effect is not exhibited, and if it exceeds 10 parts by weight, the appearance of the molded product may be deteriorated.

The saturated aliphatic polycarboxylic acid and its derivative in the present invention have the structures shown below.

(R ^I O) _m R (COOR ^II ) _n (CONR ^III R ^IV ) _s where R: straight chain or branched saturated aliphatic hydrocarbon [carbon number; 2 to 20, preferably 2 to 10] R ^I : Hydrogen, alkyl group, aryl group, acyl group or carbonyldioxy group [carbon number; 1 to 10, preferably 1 to 6, and more preferably 1
To 4, particularly preferably hydrogen] R ^II : hydrogen, an alkyl group, or an aryl group [carbon number; 1 to 20, preferably 1 to 10] R ^III and R ^IV : hydrogen, an alkyl group, or an aryl group [number of carbon atoms 1-10, preferably 1-6, more preferably 1
To 4] m = 1 n + S ≧ 2, preferably 2 or 3 n ≧ 0 S ≧ 0 (R ^I O) is located at the α-position or β-position of the carbonyl group, and between at least two carbonyl groups, There are 2 to 6 carbons.

The saturated aliphatic polycarboxylic acid derivative in the present invention is
Specifically, ester compounds, amide compounds, anhydrides, hydrates and salts of saturated aliphatic polycarboxylic acids are shown.
Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Examples of the acid ester compound include acetyl ester of citric acid, mono- or distearyl ester, and the like. As an acid amide compound,
Citric acid N, N'-diethylamide, N, N'-dipropylamide, N-phenylamide, N-dodecylamide, N, N '
-Didodecylamide, N-dodecylamide of malic acid and the like. Examples of the salt include calcium malate, calcium citrate, potassium malate, potassium citrate and the like.

Examples of the filler (D) used in the present invention include glass fiber, carbon fiber, metal fiber, glass beads, asbestos,
There are inorganic and organic fillers usually added to plastics such as wollastonite, calcium carbonate, talc and barium sulfate. These may be used alone or in combination. Of these fillers, glass fibers are particularly preferably used, and those having a shape having a fiber diameter of 6 μ to 30 μ and a fiber length of 30 μ or more are preferable.

The composition of the present invention preferably contains 5 to 150 parts by weight of the filler based on 100 parts by weight of the components (A) and (B) in total. If the amount of the filler is out of this range, a composition with favorable performance cannot be obtained. That is, if it is less than 5 parts by weight, the intended strengthening effect cannot be obtained, while if it exceeds 150 parts by weight, the surface appearance of the molded product deteriorates.

Rubber-like materials in the present invention include natural and synthetic polymeric materials that are elastic at room temperature. Specific examples thereof include natural rubber, butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer, graft copolymer, etc.), isoprene polymer, chlorobutadiene polymer, Butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester polymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer,
Examples thereof include thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber, (for example, polypropylene oxide), epichlorohydrin rubber and the like.

These rubber-like substances can be used in any production process (eg emulsion polymerization, solution polymerization), in any catalyst (eg peroxide, trialkylaluminum, lithium halide,
A nickel-based catalyst) may be used. Further, those having various degrees of crosslinking, those having various ratios of microstructures (for example, cis structure, trans structure, vinyl group, etc.), and those having various average rubber particle diameters are also used. As the copolymer, various copolymers such as random copolymers, block copolymers and graft copolymers can be used as the rubber-like substance of the present invention. Furthermore,
In making these rubber-like substances, copolymerization with other olefins, dienes, aromatic vinyl compounds, monomers such as acrylic acid, acrylic acid esters, and methacrylic acid esters is also possible. These copolymerization methods include random copolymerization, block copolymerization, graft copolymerization, etc.
Either method is possible. Specific examples of these monomers include ethylene, propylene, styrene,
Chlorostyrene, α-methylstyrene, butadiene, isoprene, chlorobutadiene, butene, isobutylene,
Examples thereof include methyl acrylate, acrylic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, acrylonitrile and the like. Further, although the rubber-like substance in the present invention is partially modified, it is within the scope of the present invention, and examples thereof include hydroxy- or carboxy-terminal modified polybutadiene, partially hydrogenated styrene-butadiene block copolymer and the like.

(E) The rubber-like substance is 100 in total of the components (A) and (B).
0 to 20 parts by weight is added to parts by weight. This component (E) is added to improve the impact resistance of the molded product. A composition not containing this component (E) is also possible.

As for the flame retardant (F), even if a phosphorus-based flame retardant commonly used for polyphenylene oxide resins or a nitrogen-based flame retardant used for polyamide is used in the present invention, the effect is very small. However, excellent flame retardancy can be imparted by using a halogen-based flame retardant. If an antimony compound (G) is also used at this time, flame retardancy is further improved. In particular, halogenated flame retardants such as brominated polystyrene, brominated polyphenylenoxide, and brominated bisphenol-based epoxy compounds do not cause bleeding of molded products, so they can be said to be suitable flame retardants. Among them, brominated polystyrene is a good flame retardant that has the smallest thermal discoloration and excellent thermal stability when the resin composition is retained in the molding machine at 280 ° C for 10 minutes. Compositions free of components (F) and (G) are also possible, especially for applications where flame retardancy is not required.

In addition, conventionally used auxiliary materials such as pigments and stabilizers can be added to these compositions, if necessary.

The components (A) to (G) described above can be compounded in any order by a conventional method, heated and melted, and injection-molded.

Hereinafter, the present invention will be described with reference to examples.

Examples In the examples, poly (2,6-dimethyl-1,4-phenylene) ether was used as the component (A). Ingredient (B)
Two types of nylon-6 were prepared as polyamides. The first polyamide has terminal amino groups of 8.4 × 10 ^-5 mol / g and terminal carboxyl groups of 1.8 × 10 ^-5 mol / g.
The second polyamide has 4.6 × 10 ^-5 mol / g terminal amino groups and 7.0 × 10 ^-5 mol / g terminal carboxyl groups. Both have a molecular weight of 13,000. By properly mixing these two types of polyamide, a polyamide having the intended end group ratio was obtained. It should be noted that the same result was obtained in the molded article even if the product in which the end group ratio was adjusted during the polymerization was used without depending on the blending of the two types of polyamides. Citric acid was used as the component (C). Chopped glass was used as the component (D). SBS [styrene-butadiene-styrene block copolymer (Califlex TR1101 manufactured by Shell Co.)] was used as the component (E).

As the component (F) flame retardant, those shown in Table 2 were used.

In addition, antimony trioxide was used as the component (G).

First, pellets were prepared by extruding a mixture containing the above components at a temperature of 290 ° C. in a twin-screw extruder equipped with a vacuum vent. Cylinder temperature 280 ℃, injection pressure 1,200kg
Molded products were made with an injection molding machine set at a mold temperature of 80 ° C / cm ² .

As an evaluation of the molded product, an Izod impact test according to JIS K 7110 and a bending test according to ASTM-D790 were performed. The sled was evaluated using an injection molding machine in which the cylinder temperature was 280 ° C, the injection pressure was 800 kg / cm ² , and the mold temperature was 60 ° C to form a 150 × 150 × 3 mm square plate, and one corner was fixed with a tack. Then, after leaving it for one day, the diagonal deviation (mm) was measured.

The results are shown in Table 1 for examples in which the terminal group ratio of the polyamide was variously changed, examples in which the component (C) was not included, and examples in which the component (E) was and was not included.

In the above experiment, the relationship between the end group ratio and the sled of Comparative Examples 1 and 2 Examples 1, 2 and 3 which differ only in the end group ratio of the polyamide is shown in a graph as shown in the accompanying drawings. It is clear that the amount of warp is markedly reduced by increasing the amount of terminal amino groups over that of carboxyl groups.

Next, Table 2 shows the experimental results with and without the flame retardant components (F) and (G).

[Brief description of drawings]

The figure is a graph showing the relationship between the end group ratio of polyamide and warpage.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 77/00 KKV 9286-4J (56) Reference JP-A-59-18756 (JP, A) Special features Kai 63-10655 (JP, A) International publication 85/5372 (WO, A)

Claims (3)

[Claims] 1. A polyphenylene oxide resin 5 (A).
-80 parts by weight, (B) the molar ratio of terminal amino groups to terminal carboxyl groups is 1.
95 to 20 parts by weight of a polyamide resin of 1 or more, (C) 0.01 to 10 parts by weight of a saturated aliphatic polycarboxylic acid and / or a derivative thereof, based on 100 parts by weight of the components (A) and (B) in total. (D) 5 to 150 parts by weight of a filler based on 100 parts by weight of the components (A) and (B), (E) 0 based on 100 parts by weight of the components (A) and (B). To 20 parts by weight of a rubber-like substance, (F) 0 to 40 parts by weight of a halogen-based flame retardant per 100 parts by weight of the above components (A) and (B), and (G) the above components (A) and A resin composition containing 0 to 20 parts by weight of an antimony compound based on 100 parts by weight of (B) in total. 2. The resin composition according to claim 1, wherein the molar ratio of the terminal amino group to the terminal carboxyl group of the component (B) is 1.3 or more. 3. The resin composition according to any one of claims 1 and 2, wherein the component (C) is selected from the group consisting of citric acid, malic acid and derivatives thereof.