JP3214884B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition which is excellent in adhesiveness to metal, surface glossiness and surface smoothness and is suitably used as a molding material for exterior parts such as lamp reflectors. About.

[0002]

2. Description of the Related Art Polyarylene sulfide (PAS) is an engineering plastic excellent in heat resistance, chemical resistance, etc., but has high adhesion to metals, surface glossiness, and surface smoothness. In the field of exterior parts, applications have been limited. Therefore, in order to solve the above problems, it has been conventionally studied to mix various fillers in PAS, but it has been difficult to sufficiently improve the above-mentioned physical properties by any method.

Further, recently, for the purpose of improving adhesion to metal, a composition in which a special filler or glass fiber is blended with PAS has been proposed. However, this composition cannot directly deposit metal, and when depositing metal, first apply a primer (adhesive) to the resin substrate,
In addition, a complicated process of depositing a metal thereon must be taken. Therefore, when the above-mentioned composition was used, there was a problem that manufacturing cost of a product became high.

The present invention has been made in view of the above circumstances, and has excellent adhesion to metal, surface glossiness, and surface smoothness.
It is an object of the present invention to provide a polyarylene sulfide resin composition capable of forming a metal layer directly on a surface without going through a primer coating step.

[0005]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies on resins and fillers to be incorporated into PAS, and as a result, PAS and polyethersulfone (PES) were mixed at a specific ratio. When used in combination, furthermore, when a specific amount of titanium potassium whisker or zinc oxide whisker and glass fiber or glass sphere is blended as a filler, the adhesion with metal, surface glossiness, surface smoothness is greatly improved composition. Knowing that it can be obtained, the present invention has been accomplished.

Accordingly, the present invention relates to (A) polyarylene sulfide (PAS), (B) polyether sulfone (PES), (C) titanium potassium oxide whiskers and / or zinc oxide whiskers, and (D) glass. It consists of fibers and / or glass spheres, and the blending amount of each component is as follows: 5% by weight <B / (A + B) <50% by weight ... (I) 0% by weight <C <40 % By weight (II) 0% by weight ≦ D <20% by weight (III) [where B / (A + B) is the blending amount of the component (B) with respect to the total amount of the components (A) and (B). Represents the blending amount of the component (C) in the whole composition, and D represents the blending amount of the component (D) in the whole composition. And a polyarylene sulfide resin composition that satisfies the following.

As an example in which PAS and PES are used in combination, there is an example in which warpage of a molded article is suppressed by using a resin mixture of these as a molding material (Japanese Patent Laid-Open No. 24505/1990).
No. 9). However, simply blending PES with PAS cannot achieve the effects of the present invention of improving the adhesion to metal, the surface gloss, and the surface smoothness.

Hereinafter, the present invention will be described in more detail.
First, each component and the amount thereof will be described. (A) Component The kind of PAS used as the component (A) is not limited, and any of a linear type, a branched type, and a thermal cross-linking type can be used, and a mixture thereof can also be used. P
The proportion of the aromatic group in the AS is preferably at least 70 mol%, particularly preferably at least 80 mol%. When the proportion of the aromatic group is less than 70 mol%, the thermal melting temperature (Tm) of the PAS decreases, and the HDT may decrease. Further, the MI (melt index) of the PAS is 10 to 50.
It is preferably 00 g / 10 minutes, particularly preferably 5 to 2000 g / 10 minutes. If the MI is less than 1 g / 10 minutes, molding may be difficult. If the MI exceeds 5000 g / 10 minutes, molding may be difficult or burrs may be generated on the molded product.

The PAS that can be suitably used in the present invention includes, for example, the following chemical formula

Embedded image And polyphenylene sulfide having a repeating unit represented by the following formula:

The above polyphenylene sulfide includes:
The content of paraphenylene groups is 70 mol% or more, preferably 80 mol% or more, and the solvent α-chloronaphthalene 10
A solution viscosity η obtained at 205 ° C. by adding 0.4 g of solute to 0 ml is 0.05 dl / g or more, preferably 0.1 to
Those having 0.8 dl / g are particularly preferably used. In addition,
As the polyphenylene sulfide, a copolymer with, for example, 30 mol% or less of a metaphenylene group or an orthophenylene group can be used in addition to a paraphenylene group. In this case, the copolymer is preferably a block copolymer.

Further, the PAS used in the present invention includes:
The following chemical formula

Embedded image And those containing one or more kinds of repeating units represented by As the PAS, those manufactured by a known method (for example, JP-A-2-107666) can be used.

(B) Component The PES used as the component (B) is not particularly limited, but may be a copolymer of a biphenyl group, a phenyl ether group, or the like, in addition to a paraphenylene group. More specifically, a compound represented by the following chemical formula can be suitably used. In the following formula, n shows the integer of 10 or more. Further, the phenyl group in the following compounds may be substituted with hydrogen or an alkyl group. Among these, compound (1) is particularly preferred.

[0013]

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[0014]

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The PES used as the component (B) has a melt viscosity of 2,000 to 20,000 poise, particularly 3,000 to 10,
It is preferably 2,000 poise. 200 melt viscosity
If it is less than 0 poise, it may be in a non-uniform dispersion state with the PAS, and if it exceeds 20,000 poise, it may not be possible to extrude and pellets may not be obtained.

In the resin composition of the present invention, the adhesion to metal is improved by the addition of PES. For example, PAS and PES are immiscible, but if B / (A + B) is about 40% by weight, PES becomes a continuous phase, so that the S = O bond part emerges on the molded product surface, As a result, the adhesion to the metal increases.

(C) Component In the present invention, one or both of titanium potassium oxide whisker and zinc oxide whisker are blended as the component (C). As a result, the dispersibility of PES is improved, and as a result, the adhesion to metal is dramatically increased. The shape, structure and dimensions of the titanium potassium oxide whisker and the zinc oxide whisker are not limited, but the zinc oxide whisker is particularly preferably a zinc oxide whisker having a three-dimensional structure. The zinc oxide whisker having the three-dimensional structure is composed of a core portion and a needle-like crystal portion extending from the core portion in a plurality of different axial directions. In this case, the diameter of the base of the needle-shaped crystal part is 0.3 to
It is preferable that the length from the base to the tip of the needle-shaped crystal part is 3 to 200 μm.

Component (D) In the present invention, one or both of a glass fiber and a glass sphere are used as the component (D). Thereby, the mechanical strength can be improved. The shape, structure and dimensions of the glass fibers and glass spheres are not limited, but the glass spheres are preferably hollow bead-like ones, whereby the specific gravity can be reduced.

[0019] In the amount present invention resin composition, the respective components, the following formula (I)
To (III). 5% by weight <B / (A + B) <50% by weight ... (I) 0% by weight <C <40% by weight ... (II) 0% by weight <D <20% by weight ... (III) B / (A + B) :( A: The amount of the component (B) relative to the total amount of the components and the (B) component C: The amount of the component (C) in the entire composition D: The amount of the component (D) in the entire composition

That is, the blending amount of the component (B) with respect to the total amount of the components (A) and (B) exceeds 5% by weight,
Less than 50% by weight. If B / (A + B) is 5% by weight or less, the adhesiveness to a metal is reduced. If B / (A + B) is 50% by weight or more, the flexural modulus is remarkably reduced and sufficient product strength cannot be obtained. A more preferable value of B / (A + B) is 15 to 40.
% By weight, and within this range, it is possible to ensure good adhesion to metal, surface gloss, and mechanical strength. The total amount of the components (A) and (B) in the total composition is 50 to 95% by weight, particularly 60% by weight.
It is preferable to set it to 90% by weight. If it is less than 50% by weight, the mechanical strength may be remarkably reduced, and if it exceeds 95% by weight, the adhesiveness to metal may be extremely reduced.

The amount of component (C) in the total composition is more than 0% by weight and less than 40% by weight. When the amount of the component (C) is at least 40% by weight, kneadability and moldability will be reduced. The compounding amount of the component (C) is more preferably 5
３５35% by weight, especially 20-30% by weight.

The amount of the component (D) in the entire composition is at least 0% by weight and less than 20% by weight. When the amount of the component (D) is 20% by weight or more, the surface gloss is reduced. When glass fibers and glass spheres, particularly medium sphere bead-shaped glass spheres, are used in combination, a weight ratio of 1: 1 to 10 is preferable in terms of balance of surface gloss, specific gravity, and mechanical strength. . The amount of the component (D) is more preferably 0.
-15% by weight, especially 5-10% by weight.

The resin composition of the present invention contains (A)
In addition to the components (D) to (D), a general inorganic filler can be blended as an optional component as long as the surface gloss and the adhesion to metal are not impaired. As such an inorganic filler, for example, mica, glass fiber flake, milled fiber, or the like can be blended for improving surface smoothness, preventing warpage, and improving surface hardness. Further, various additives such as a pigment, a heat stabilizer, an antioxidant, an ultraviolet absorber, a surfactant, and an adhesive can be added to the resin composition of the present invention as needed.

The method for producing the resin composition of the present invention is not limited.
It can be manufactured by a conventional method. For example, it can be manufactured by blending each component with a Henschel mixer, Banbury mixer or the like, kneading with a twin-screw extruder or a short-screw extruder, and pelletizing. In this case, (A) P
It is preferable to knead AS (neat product or compound product) and (C) whisker with an extruder to produce a master batch and then re-knead (B) PES from the viewpoint of improving the dispersibility of PES. When (D) glass fiber and glass spheres are added, it is preferable to supply from a side feeder and knead with the master batch and PES.

[0025]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. Using the components shown in Tables 1 and 2 below, resin compositions of the following Examples and Comparative Examples were produced, and physical properties were measured.

The following components are used in the table: PAS MI: 200 g / 10 min Linear PPS (polyphenylene sulfide) PES-1 ICI: D3601GM20 PES-2 ICI: PDX-87152

Potassium titanate whisker Otsuka Chemical Co., Ltd .: Teismo D, D101, D102 Zinc oxide whisker Zinc oxide whisker having a three-dimensional structure (Matsushita Amtech Co., Ltd .: Panatetra) glass fiber Asahi Fiberglass Co., Ltd .: FT104 glass Spherical hollow bead-shaped glass sphere (Asahi Glass Co., Ltd .: Cell Star) polyethylene (PE) Idemitsu Petrochemical Co., Ltd .: HF210 Calcium carbonate Shiraishi Industry Co., Ltd .: Whiten P-30 Talc Asada Milling Co., Ltd .: JET-S MMR

Examples 1 to 6 The components shown in Table 1 were blended and kneaded at 320 ° C. using a twin screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.).
Thereafter, a flat plate having a length of 80 mm, a width of 80 mm and a thickness of 3 mm was molded at a mold temperature of 120 ° C. using a 50-t injection molding machine (manufactured by Nippon Steel Works) using the obtained composition. Comparative Examples 1 to 6 The components shown in Table 2 were used in the same manner as in Examples.

Next, the physical properties of the obtained flat plate were measured as follows. The results are shown in Tables 1 and 2. Tensile strength Measured according to ASTM D638. Flexural strength and flexural modulus were measured in accordance with ASTM D796. Izod (with notch, without notch) Measured according to ASTM D256. The density was measured according to ASTM D257. Surface glossiness Measured according to JIS K7105 (1981).

Further, aluminum was deposited on the flat plate without performing primer coating, and the metal film adhesion and the metal film appearance were evaluated by the following methods. Aluminum is deposited using a high-speed high-vacuum deposition device (UPC-41 manufactured by Vacuum Kiko Co., Ltd.).
0A), a pressure of 1.5 × 10 ⁻⁵ Torr, a deposition time of 10 seconds, and a film thickness of 50 μm. Table 1 shows the results.
It is shown in FIG.

Metal film adhesion ( cross-cut peeling test) On a flat plate on which aluminum was deposited, a 10 mm-square aluminum deposited film was cut into 1 mm by using a cutter knife.
Scratches were made at intervals, and the aluminum deposited film was divided into a total of 100 grid-like sections. A cellophane tape was stuck on this flat plate, and the number of sections of the aluminum vapor-deposited film remaining in a flat plate shape when peeled was counted.

Metal Film Appearance The glossiness of an aluminum deposited film was measured according to JIS K7105 (198
It was measured according to 1) and evaluated in four steps based on the following criteria. ：: glossiness of 120 or more ○: glossiness of 111 or more and less than 120 Δ: glossiness of 100 or more and less than 110 ×: glossiness of less than 100

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

As described above, the polyarylene sulfide resin composition of the present invention is excellent in adhesiveness to metal, surface glossiness, and surface smoothness, and has a metal film formed on its surface. It can be used particularly effectively as a component, for example, a molding material for a lamp reflector.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 81/06 C08K 7/00-7/08 C08K 7/14-7/20

Claims (1)

(57) [Claims] (A) a polyarylene sulfide;
(B) polyether sulfone, (C) titanium potassium oxide whiskers and / or zinc oxide whiskers, and (D)
It consists of glass fibers and / or glass spheres, and the blending amount of each component is as follows: 5% by weight <B / (A + B) <50% by weight ... (I) 0% by weight <C < 40% by weight (II) 0% by weight ≦ D <20% by weight (III) [where B / (A + B) is the blending amount of the component (B) with respect to the total amount of the components (A) and (B). C indicates the amount of the component (C) in the entire composition, and D indicates the amount of the component (D) in the entire composition. And a polyarylene sulfide resin composition.