JPH0625303B2 - Impact resistant polyarylene sulfide resin composition - Google Patents

Description

The present invention relates to a polyarylene sulfide resin, a polyamide, and a reaction product of a bismaleimide compound and a dicyanurate compound, and, if necessary, a filler in a specific ratio. And a polyarylene sulfide resin composition excellent in heat resistance, impact resistance and molding processability.

[Problems to be Solved by Conventional Techniques and Inventions] Polyarylene sulfide resins typified by polyphenylene sulfide resins (PPS resins) have excellent heat resistance, chemical resistance, rigidity, and fluidity during molding. Because of its goodness, in recent years, application development has been attempted particularly in fields requiring heat resistance and dimensional accuracy such as electric / electronic parts and automobile parts.

However, the resin has drawbacks of poor ductility and low impact resistance. Therefore, by adding a fibrous reinforcing material such as glass fiber or carbon fiber, the strength, elastic modulus, high-temperature mechanical properties are further improved and impact resistance is improved.

However, the level of improvement is not sufficient, and it can be applied to structural parts that require mechanical performance, encapsulants that require stress strain prevention during encapsulation, and other applications that require flexibility. The current situation is that it is severely limited.

Further, as another means for improving the impact resistance of the polyarylene sulfide resin, a method of adding a rubber component has been adopted, but while the impact resistance is somewhat improved, the heat resistance represented by the elastic modulus at high temperature is used. A decline in sex was unavoidable.

Further, as another method for improving the impact resistance of the polyarylene sulfide resin, polycarbonate (Japanese Patent Laid-Open No. Sho 5 (1999) -58138)
A method of blending with a thermoplastic resin having excellent impact resistance such as 5-45704, JP-A-51-59952) or polyamide-imide (refer to JP-A-55-21462) has been proposed. . However, for example, in the former case, when the blending ratio of polycarbonate is small, the improvement level of impact resistance is small, and when the blending ratio is large, there is a disadvantage that the heat resistance of polyarylene sulfide is significantly lowered. In the latter case, when the blending amount of polyamide-imide is small, the degree of impact resistance improvement is small, and when it is a large amount, the processability such as fluidity is lowered and the cost is increased.

Further, a resin composition (see Japanese Patent Laid-Open No. 62-62861) comprising a polyphenylene sulfide resin and a bismaleimide triazine resin for the purpose of improving heat resistance is disclosed, but this composition improves impact resistance. Has little effect.

On the other hand, the workability may be improved by blending a polyamide resin such as nylon 6, nylon 66 or the like, which is well-balanced in workability, mechanical properties and price, with a polyarylene sulfide resin (JP-A-55-135160). JP-A-61-126172), an example in which impact resistance and bending strength are improved (JP-A-53-69255).
(See Japanese Patent Publication). Nylon has a relatively good compatibility with polyarylene sulfide resins, and in these examples, the improvement in the properties in question was realized, but it did not reach the expected level, on the other hand, the heat resistance of polyarylene sulfide was decreased. It was inevitable.

In addition to this, there is an example (see Japanese Patent Application Laid-Open No. 61-53356) in which an amorphous polyamide is used as a polyamide to improve the appearance and thermal shape stability.

However, in the case of the blend of both, the bond strength between both component phases was not sufficient, and the expected improvement in properties was insufficient.

An object of the present invention is to provide a polyarylene sulfide resin composition which retains the high temperature mechanical properties of the polyarylene sulfide resin and is excellent in impact resistance and molding processability.

[Means for Solving the Problems] In view of the above situation, the present inventors have found that, in addition to the polyarylene sulfide resin and the polyamide resin, bis which has a chemical bonding ability between both components in order to strengthen the bond between both components. By blending the reaction product of the maleimide compound and the dicyanurate compound, the heat resistance of the polyarylene sulfide resin is maintained, the impact resistance is significantly improved, and a thermoplastic resin composition having improved moldability is obtained. It was found that the present invention has been completed.

That is, the present invention provides (A) 50 to 95 parts by weight of polyarylene sulfide and (B) 5 to 50 parts by weight of polyamide (A).
The reaction product of the (C) bismaleimide compound and the dicyanurate compound is added in an amount of 3 to 20 to 100 parts by weight of + (B) in total.
It is a polyarylene sulfide resin composition in which 20 parts by weight to 150 parts by weight of a fibrous filler as a filler (D) are blended, if necessary.

The polyarylene sulfide resin used in the present invention has 90 mol% or more of the repeating units of the structural formula from the viewpoint of heat resistance, molding processability and mechanical properties. Those represented by are preferred.

If the phenylene sulfide unit is less than 90 mol%, the heat resistance shown by the heat distortion temperature becomes low, which is not preferable. In addition, the remaining less than 10 mol%, the meta bond Ether bond Sulfone bond Biphenyl bond Naphthyl bond Substituted phenyl sulfide bond (Here, R is selected from the group consisting of an alkyl group or an alkoxy group having 12 or less carbon atoms, a phenyl group, and a nitro group.), And a trifunctional phenyl sulfide bond.

The polyamide used here means a resin having an amide group in the main chain, and the main constituent unit is any one selected from the group consisting of hexamethylene adipamide unit, tetramethylene adipamide unit, and caproamide unit. One or two or more are suitable from the viewpoint of melt moldability and miscibility with polyarylene resin, and an aromatic amide group or other aliphatic amide group may interfere with the present invention. It may be contained in a small amount to the extent that it does not exist.

Specific examples of polyamides include nylon 6 and nylon 6.
6, nylon 610, nylon 11, nylon 12, nylon MXD6 and the like.

Further, the reaction product of the bismaleimide compound and the dicyanurate compound, which is an important component of the present invention, includes a bismaleimide compound having an aromatic ring represented by the formula (I) and an aromatic dicyanurate compound represented by the formula (II). The reaction product is preferable from the viewpoint of bond formation between both resins and heat resistance.

As R ₁ of the formula (I), Is exemplified.

As R ₂ of the formula (II), And a bifunctional group having an aromatic ring such as

As the reaction product of the bismaleimide and the dicyanurate compound, for example, bismaleimide triazine resin BT resin manufactured by Mitsubishi Gas Chemical Co., Inc. can be preferably used.

Further, in the present invention, as the fibrous filler which is a filler used as necessary, glass fiber, carbon fiber, potassium titanate fiber, silicon nitride fiber, silicon carbide fiber, asbestos fiber, wollastonite fiber, alumina fiber and Discontinuous fibers such as aramid fibers can be used.

The blending ratio of each component in the present invention is (A) polyarylene sulfide 50 to 95 parts by weight and (B) polyamide resin 5 to 50 parts by weight (A) + (B) with respect to 100 parts by weight in total, (C) 3 to 20 parts by weight of a reaction product of a bismaleimide compound and a dicyanurate compound, and if necessary,
(D) Fibrous filler 20 to 150 parts by weight, preferably (A) polyarylene sulfide 65 to 90 parts by weight and (B) polyamide resin 10 to 35 parts by weight (A) + (B) in total 100 parts by weight. With respect to parts, 5 to 20 parts by weight of the reaction product of the (C) bismaleimide compound and the dicyanurate compound, and if necessary, 20 to 150 parts by weight of the (D) fibrous filler.

When the content of the polyamide resin as the component (B) exceeds 50 parts by weight, the heat resistance, which is a characteristic of the polyarylene sulfide resin, is impaired. Is small. Further, when the ratio of the reaction product of the (C) bismaleimide compound and the dicyanurate compound exceeds 20 parts by weight with respect to 100 parts by weight of (A) + (B) in total, the moldability is poor and It is difficult to obtain a stable composition having a large variation in mechanical properties. If it is less than 3 parts by weight, the impact resistance is improved,
The effect of the invention such as improvement of molding processability is small.

Further, the (D) fibrous filler causes a decrease in processability when blended in an amount of more than 150 parts by weight with respect to 100 parts by weight of the total of (A) + (B), and when less than 20 parts by weight, at room temperature and high temperature. The mechanical properties such as strength and elastic modulus are insufficient, which is not preferable.

Further, in order to improve sliding properties, a solid lubricant such as graphite, molybdenum disulfide, and silicon nitride for the composition of the present invention, and metal particles, metal fibers, and thermal conductivity for imparting conductivity. In order to improve the effect of the present invention, silica gel, magnesium oxide, silicon nitride, and particulate fillers such as silicon carbide, and calcium carbonate, talc, clay and mica to improve the arc resistance. You may add in the range which does not impair.

The composition of the present invention can be prepared by a usual melt-kneading machine such as an extruder or a twin-screw kneader, and can be molded into various molded articles by injection molding, compression molding, extrusion molding or the like. You can

EFFECTS OF THE INVENTION Since the present invention has the constitution as described above, the polyarylene sulfide resin composition in which the heat resistance of the polyarylene sulfide resin is maintained, the impact resistance is greatly improved, and the moldability is improved. You can get things.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

(Examples 1 to 3) Polyphenylene sulfide resin (trade name: Ryton R
-6, made by Philippe Petroleum) and nylon 66
(Product name: UBE Nylon 2022B, made by Ube Industries)
Melt-mix for 5 minutes with a twin-screw kneader set to 290 ° C.,
Bismaleimide triazine resin (Brand name: BT Resin 2
680, manufactured by Mitsubishi Gas Chemical Co., Inc.) and further kneaded for 5 minutes, and further, glass fibers having a length of 3 mm were blended at a blending ratio shown in Table 1 to obtain a predetermined composition. The obtained pellet-shaped resin composition was injection molded at a molding temperature of 310 ° C. and a mold temperature of 170 ° C. to obtain a test piece for measuring physical properties. Table 1 shows the impact strength of the obtained test piece and the bending test results at 23 ° C and 200 ° C.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that the bismaleimide triazine resin was not added at all. Table 1 shows the physical property evaluation results of the injection-molded test pieces.

(Comparative Example 2) A composition was obtained in the same manner as in Example 1 except that 2 parts by weight of the bismaleimide triazine resin was added to 100 parts by weight of the total of the polyphenylene sulfide resin and the polyamide resin. Table 1 shows the physical property evaluation results of the injection-molded test pieces.

(Comparative Example 3) A composition was obtained in the same manner as in Example except that the polyphenylene sulfide resin was 50% by weight and the nylon 66 was 50% by weight. Table 1 shows the physical property evaluation results of the injection-molded test pieces.
Shown in.

(Comparative Example 4) A composition comprising 100 parts by weight of polyphenylene sulfide resin and 67 parts by weight of glass fiber was melt-kneaded by a biaxial kneader set at 290 ° C to obtain a composition. Table 1 shows the physical property evaluation results of the injection-molded test pieces.

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Claims (1)

[Claims] 1. (A) Polyarylene sulfide 50-9
3 to 20 parts by weight of the reaction product of the (C) bismaleimide compound and the dicyanurate compound with respect to 5 parts by weight and a total of 100 parts by weight of (B) polyamide 5 to 50 parts by weight (A) + (B). An impact-resistant polyarylene sulfide resin composition, which is characterized by containing.