JPH11315208A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylene sulfide resin compsn. having excellent antistatic property, mechanical characteristics, moldability and so on, by blending a polyarylene sulfide resin with a high molecular antistatic agent having a polyethylene glycol segment in the molecule and with a filler. SOLUTION: One hundred pts.wt. of a polyarylene sulfide (abbreviated PAS) is blended with 0.1-20 pts.wt. of a high polymer antistatic agent having a polyethylene glycol segment in the mol. and 0-200 pts.wt. of an organic or inorganic filler. The PAS has, as the arylene group, a phenylene group, a biphenylene group, a diphenylene ether group, or a naphthalene group, but the PAS pref. above all is such one having a repeating unit of a p-phenylene sulfide group using a p-phenylene group. The high polymer antistatic agent pref. is a polyethylene glycol, a copolymer thereof with a polypropylene glycol, and a borate thereof. The filler pref. is a glass fiber as the representative as well as a combination of potassium titanate whisker and a powdery and granular filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a permanent antistatic property,
The present invention relates to a polyarylene sulfide resin composition having excellent mechanical properties and moldability, and a molded product thereof. More specifically,
The present invention relates to a resin composition and a molded article which are less likely to be charged even by friction with a counterpart material, adsorb dirt, and have less adverse electrical effects.

[0002]

2. Description of the Related Art A polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by a polyphenylene sulfide (hereinafter abbreviated as PPS) resin has excellent mechanical properties and an antistatic agent. Therefore, it is widely used in the fields of automobiles, electricity, precision instruments and the like. As its use has expanded, the properties of its materials have also required more special properties.
A resin composition has been manufactured in which various additives are blended with an AS resin to improve its properties. One of them is the problem of adhesion of dust and dirt due to the generation of static electricity due to friction, etc.
Alternatively, in order to solve the problem of electrostatic noise, a PAS resin having antistatic properties has been desired. In response to such demands, attempts have been made to impart permanent antistatic properties by adding a conductive filler and a low-molecular-weight antistatic agent to PAS resins. However, conventional antistatic agents have poor affinity for PAS resins, and thus have a problem that the antistatic performance is not maintained. Longed for.

[0003]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by adding an antistatic agent having a specific composition to a PAS resin, the antistatic properties, mechanical properties, The inventors have found that a resin composition having excellent heat resistance, moldability and the like can be obtained, and have completed the present invention.
That is, the present invention relates to (A) polyarylene sulfide resin 1
(B) a polymer antistatic agent having at least a polyethylene glycol segment in its molecule, based on 100 parts by weight
0.1 to 20 parts by weight, (C) organic or inorganic filler 0 to 200
It is a polyarylene sulfide resin composition containing parts by weight.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION The constituents of the present invention will be described in detail below. PAS as the component (A) used in the present invention
The resin is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit. Examples of the arylene group include a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, a p, p′-biphenylene group, a p, p′-diphenylene ether group, and a p, p′-diene. A phenylenecarbonyl group, a naphthalene group and the like can be used. In this case, in the arylene sulfide group composed of the above-mentioned arylene group, in addition to a polymer using the same repeating unit, that is, a homopolymer, a copolymer containing a heterogeneous repeating unit from the viewpoint of processability of the composition may be used. It may be preferable. As the homopolymer, one having a p-phenylene sulfide group as a repeating unit using a p-phenylene group as an arylene group is particularly preferably used. Further, as the copolymer, among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used. Among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. Can be Among them, those containing a p-phenylene sulfide group in an amount of 70 mol% or more, preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. Further, a copolymer containing 5 to 30 mol%, particularly 10 to 20 mol% of m-phenylene sulfide group is preferable as a copolymer. In this case, those in which the repeating unit of the component is contained in a block form rather than in a random form (for example, JP-A-61-14228).
Which is excellent in processability and heat resistance,
It has excellent mechanical properties and can be preferably used. Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly containing a bifunctional halogen aromatic compound can be particularly preferably used. Such a linear P having substantially no branch
AS resin has excellent fluidity and mechanical properties, and is a suitable target resin for the purpose of the present invention. In addition, other than the PAS resin having a linear structure, when polycondensation is performed, a small amount of a monomer such as a polyhalo aromatic compound having three or more halogen substituents is used to partially form a branching or crosslinking agent. A polymer obtained by heating a low-molecular-weight linear-structured polymer at a high temperature in the presence of oxygen at a high temperature to increase the melt viscosity by oxidative crosslinking or thermal crosslinking and improving the moldability can also be used. The PAS resin as a base resin used in the present invention has a melt viscosity (310 ° C., shear rate 1200 sec ⁻¹ ) of 10 to 10 μm.
500 Pa · s is preferred, and those having a range of 20 to 300 Pa · s are particularly preferred because of their excellent balance between mechanical properties and fluidity. If the melt viscosity is too low, the mechanical strength is not sufficient because it is not preferable, and the melt viscosity is 500 Pa
If the value exceeds s, the flowability of the resin composition during injection molding is poor, and molding work is difficult, which is not preferable.

[0005] Next, the component (B) used in the present invention is necessary for shortening the charging half-life and making it difficult to be charged even by friction with a partner material. At least a polyethylene glycol segment is contained in the molecule. Polymer antistatic agent. As a segment other than the polyethylene glycol segment, a polyalkylene glycol segment such as a polypropylene glycol segment or a polytetramethylene glycol segment, or a polyamide segment is preferably used. The polyalkylene glycol segment containing these polyethylene glycols is connected to other polyalkylene glycol segments directly via an ether bond or via a bifunctional or higher functional hydroxyl group reactive unit (compound). Examples of the hydroxyl group-reactive compound include alcohols, epoxy compounds, isocyanate compounds, urethane compounds, and carboxyl compounds. Examples of alcohols include aliphatic polyhydric alcohols such as hexylene glycol, glycerol and pentaerythritol, aromatic polyhydric alcohols such as bisphenols and hydroquinones, and inorganic polyhydric alcohols such as boric acid.
Examples of epoxy compounds include epichlorohydrin, bisphenol A diglycidyl ether, and the like. Examples of the isocyanate compound include methane diisocyanate and isophorone diisocyanate. Examples of urethane compounds include various polyurethanes. Examples of the carboxyl compound include aliphatic polycarboxylic acids such as succinic acid and oxalic acid, and aromatic polycarboxylic acids such as terephthalic acid and pyromellitic acid. Further, a so-called polyetheramide or polyetheresteramide compound in which a polyamide segment is bonded to one end of a polyalkylene glycol segment is more preferably used from the viewpoint of improving dispersibility in a PAS resin. (B)
Specific examples of the polymer antistatic agent include polyethylene glycol, polyethylene glycol / polypropylene glycol copolymer, borate ester of polyethylene glycol, and polyether ester amide composed of bisphenol A / polyethylene glycol / polycaprolactone. Among them, polyethylene glycol / polypropylene glycol copolymers, borate esters of polyethylene glycol, and polyetheresteramides composed of bisphenol A / polyethylene glycol / polycaprolactone are preferably used.
(B) The amount of polymer antistatic agent used is (A) PAS resin 100
0.1 to 20 parts by weight per part by weight, preferably 0.5 to 20 parts by weight
20 parts by weight. If the amount is less than 0.1 part by weight, the effect of improvement is very small.
A problem also occurs in the mechanical properties of the molded product, which is not preferable.

Next, in the present invention, in order to obtain a molded article excellent in mechanical strength, rigidity, heat resistance, dimensional stability, and electrical properties, an organic or inorganic filler is blended as the component (C). Preferably, a fibrous, powdery, granular, plate-like, or hollow filler is used for this purpose. Examples of the fibrous filler include organic fibers typified by aramid fibers, glass fibers, asbestos fibers, carbon fibers, silica fibers, silica / alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, titanium fibers. Potassium whisker, stainless steel, aluminum, titanium,
Inorganic fibrous substances such as fibrous materials of metals such as copper and brass can be used. Particularly typical fibrous filler is glass fiber,
Carbon fiber. On the other hand, as the particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicate such as wollastonite, iron oxide Oxides of metals such as titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; sulfates of metals such as calcium sulfate and barium sulfate; and other silicon carbide, silicon nitride, boron nitride, various types Metal powder and the like. Examples of the plate-like filler include mica, glass flake, and various metal foils. Examples of the hollow filler include a shirasu balloon, a metal balloon, and a glass balloon. These inorganic fillers can be used alone or in combination of two or more. In particular, potassium titanate whiskers alone, and the combination use of potassium titanate whiskers and powdery and / or plate-like fillers,
This is a preferable combination in terms of reducing the absolute value of the charged voltage and having both mechanical strength and dimensional accuracy.

In the present invention, the amount of the filler is PA
It is not more than 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the S resin. If it is excessively large, the molding operation becomes difficult, and the mechanical properties of the molded product are undesirably problematic. The filler is preferably subjected to a surface treatment or a convergence treatment with a functional compound such as an epoxy compound, an isocyanate compound, a silane compound, a titanate compound, or a polymer. These compounds may be used after being subjected to a surface treatment or a convergence treatment, or may be added at the same time as the preparation of the material.

Although not essential in the present invention, it is preferable to blend polytetrafluoroethylene as the component (D). Polytetrafluoroethylene can improve sliding characteristics, reduce frictional resistance during friction with a mating component, and further reduce electrification due to friction. The amount of the polytetrafluoroethylene is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the PAS resin (A). If the amount is less than 1 part by weight, the effect of improvement is extremely small. If the amount is excessively large, the molding operation becomes difficult, and the mechanical properties of the molded article are disadvantageously unfavorable.

Further, the polyarylene sulfide resin composition of the present invention contains a known substance generally added to a synthetic resin, that is, a stabilizer such as an antioxidant or an ultraviolet absorber,
Antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants,
A release agent, a crystallization accelerator, a crystal nucleating agent, and the like can be appropriately added according to required performance.

[0010] The resin composition of the present invention can be prepared by equipment and a method generally used for preparing a synthetic resin composition. Generally, necessary components are mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form molding pellets. It is also a preferable method to melt-extrude a resin component and add and mix an inorganic component such as glass fiber during the extrusion.

In the present invention, it is one of the important items to control the friction band voltage to zero or positive side. In other words, the friction band voltage represented by friction with the cotton cloth is on the minus side, that is, the state in which electrons are excessively present is due to a so-called discharge phenomenon due to the movement of electrons to other parts in the saturation process. In many cases, electrostatic noise is generated, which is likely to cause malfunction. However, even if the charge is positive, not to mention the case of zero, such electrostatic noise is hardly observed, and in order to prevent the electrostatic noise, control of the friction band voltage is important. You can see that.

[0012]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, each (A), (B), (C),
Specific substances of (D) are as follows. (A) Polyphenylene sulfide (PPS) resin, manufactured by Kureha Chemical Industry Co., Ltd., FORTRON KPS (B) Polymer antistatic agent B-1 Polyethylene glycol / polypropylene glycol copolymer B-2 Polyethylene glycol borate B- 3 Bisphenol A / polyethylene glycol / polycaprolactone copolymer (C) Filler C-1 Potassium titanate whisker, 0.5 μm in diameter, 20 μm in length, C-2 talc, particle size 5 μm (D) Polytetrafluoroethylene (PTFE) Examples 1 to 5 The components (A) and (B) shown in Table 1 were mixed, melt-kneaded at 310 ° C. using a 30 mm twin-screw extruder, pelletized, and evaluated as follows. Table 1 shows the results. [Bending test] Using the above pellets, a bending test piece was prepared by injection molding at a resin temperature of 320 ° C. A bending test according to ASTM D-790 was performed, and the flexural modulus was measured. [Antistatic property] Using the above pellets, resin temperature 320 ° C
A 70 mm long, 50 mm wide, 3 mm thick flat plate is formed by injection molding, treated according to the following conditions, and then the half-life of the charged voltage at an applied voltage of 2000 V is applied using a static neostometer manufactured by Shishido Shokai. Was measured.・ Initial antistatic property After molding, leave for 1 week in 23 ℃ × 0% RH atmosphere ・ Permanent antistatic property After molding, leave for 1 week in 23 ℃ × 0% RH atmosphere, then in 120 ℃ atmosphere After standing for 10 days [Friction charge voltage] Place the flat plate on a taper wear tester,
It was slid with a cotton cloth attached to a friction wheel, and the surface potential one minute after the start was measured.

Examples 6 to 13 As shown in Table 2, the components (C) and / or (D) were further added, and evaluations were made in the same manner as in the above Examples. Table 2 shows the results. Comparative Examples 1 to 4 As shown in Table 3, the evaluation was performed in the same manner as in the above Examples without adding the component (B). Table 3 shows the results.

[0014]

[Table 1]

[0015]

[Table 2]

[0016]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 81/02 71:02 77:12)

Claims (6)

[Claims] (A) Polyarylene sulfide resin 100
Polyarylene comprising (B) 0.1 to 20 parts by weight of a polymer antistatic agent having at least a polyethylene glycol segment in the molecule thereof, and (C) 0 to 200 parts by weight of an organic or inorganic filler. A sulfide resin composition. 2. The polymer antistatic agent as the component (B) is formed by combining a) a polyalkylene glycol segment containing at least a polyethylene glycol unit as a part, and b) a difunctional or higher functional hydroxyl-reactive compound. The polyarylene sulfide resin composition according to claim 1, which is a polymer antistatic agent obtained. 3. The polyarylene according to claim 1, wherein the polymer antistatic agent as the component (B) is a polyetheresteramide comprising a) a polyethylene glycol segment, b) a polyamide segment, and c) a bisphenol. A sulfide resin composition. 4. The polyarylene sulfide resin composition according to claim 1, wherein the filler as the component (C) is a potassium titanate whisker. 5. The polyarylene sulfide according to claim 1, further comprising 1 to 100 parts by weight of polytetrafluoroethylene as component (D) per 100 parts by weight of component (A). Resin composition. 6. A resin molded article produced by using the polyarylene sulfide resin composition according to any one of claims 1 to 5 and having a charged voltage of 0 kv or more when slid with a cotton cloth.