JP3113191B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improved polyarylene sulfide resin composition. More specifically, it is excellent in molding processability, in particular, it does not corrode and contaminate metal parts such as molds at the time of molding, and also has improved metal corrosion resistance in molded parts combining metal materials,
In addition, the present invention relates to a polyarylene sulfide resin composition having excellent mechanical properties of a molded article.

[0002]

2. Description of the Related Art In recent years, various mechanical parts such as electric / electronic equipment parts materials, automobile equipment parts materials, chemical equipment parts materials, etc. have high mechanical properties and are heat-resistant, chemical-resistant and flame-retardant. A need has arisen for thermoplastic resins. Polyarylene sulfide (PAS) resin typified by polyphenylene sulfide (PPS) is also one of the resins that meet this demand, and is blended with a filler such as glass fiber to improve its physical properties and increase its demand. However, this resin has a sulfur atom in its molecular structure, and its raw material contains an alkali metal such as sulfur, chlorine and sodium, and contains a large amount of sulfur, chlorine, alkali metal and the like during resin synthesis. It has the drawback that by-products are generated, has the disadvantage of corroding and contaminating metal materials such as molds during molding, and when used as a molded component material, a metal inserted into a component, There are problems such as corrosion and contamination of the plated or vapor-deposited metal, causing problems. As a technique for solving this problem, it is proposed that the polymerized PAS resin be deionized with an acid, hot water, an organic solvent, etc., washed and reduced to 500 ppm or less, and even 200 ppm or less. Although very effective, PAS resins and their compositions have extremely high molding processing temperatures of at least 280 ° C. Therefore, even if these impurities are removed and purified, corrosive gases are still generated during molding processing, and metal Corrosion resistance is insufficient. Further, by adding a scavenger for a corrosive substance to improve the corrosiveness of the conventional PAS resin,
Various methods have been proposed for the improvement.
JP-A-105857 discloses that as a corrosion inhibitor for metals of PAS resin, any one selected from zinc carbonate, zinc hydroxide, a double salt thereof and the like, or a mixture thereof is used.
It is disclosed that when mixed with a resin, it is extremely effective in preventing corrosion and contamination of a metal mold used in molding a PAS resin and a metal material incorporated in a molded product. However, as a result of further studies by the present inventors, the addition of such an anticorrosive is effective in preventing metal corrosion, but on the other hand, it tends to reduce mechanical properties, and is particularly noticeable in glass fiber and other inorganic reinforcing agents. It is recognized that the mechanical properties such as mechanical strength and toughness are reduced because the corrosion inhibitor impairs the adhesiveness between the PAS resin and the reinforcing agent or filler when compounding the filler or filler. The tendency is particularly remarkable when the amount of the anticorrosive agent is increased, and improvement in this respect has become an important problem.

[0003]

DISCLOSURE OF THE INVENTION In view of the above situation, the present invention improves the corrosion and contamination of a metal mold during the molding of a PAS resin composition and the metal used when the composition is used, and furthermore, uses a relatively large amount of a corrosion-resistant agent. It is an object of the present invention to provide a PAS resin composition which has no adverse effects on mechanical properties such as tensile strength and elongation, impact strength and toughness even when used, and has both excellent metal corrosion resistance and mechanical properties.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result,
Carbonates, hydroxides such as zinc, magnesium and barium,
By combining hypophosphorous acid or a salt thereof in combination with the anticorrosive agent composed of an oxide, the corrosion resistance of the anticorrosive agent is significantly improved, and the adverse effect on the mechanical properties of the anticorrosive agent is eliminated. The inventors have found that both physical properties are maintained and both properties are combined, and the present invention has been completed. That is, the present invention relates to (A) 100 parts by weight of a polyarylene sulfide resin, (B) a carbonate, hydroxide, oxide or a mixture or double salt of a metal selected from zinc, magnesium and barium.
0.1 to 10 parts by weight (C) 0.05 to 2 parts by weight of hypophosphorous acid or a salt thereof (D) Polyarylene sulfide resin composition obtained by blending and kneading 5 to 400 parts by weight of an inorganic filler as a basic component It is.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The components of the present invention will be described below in detail. First, PA as the component (A) used in the present invention
The S resin is mainly composed of a repeating unit (—Ar—S—) (where Ar is an arylene group). 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′-diphenylene sulfone group, a p, p′-biphenylene group, and p, p′-.
A diphenylene ether group, a p, p'-diphenylenecarbonyl group, a naphthalene group and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, a homopolymer composed of the same repeating unit can be used, and from the viewpoint of processability of the composition, a copolymer containing a heterogeneous repeating unit can be used. Good. As a homopolymer, poly-p-phenylene sulfide (PPS) using p-phenylene sulfide group as a repeating unit using p-phenylene group as an arylene group
Is the most typical, and among them, substantially linear polyphenylene sulfide is particularly preferably used. As the copolymer, the above-mentioned arylene group consisting of an arylene group is mainly used, and two or more different combinations can be used. Among them, a combination mainly containing a p-phenylene sulfide group and containing other repeating units is particularly preferable. It is preferably used. Among them, those containing a p-phenylene sulfide group in an amount of 60 mol% or more, more preferably 70 mol% or more, are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties. In this case, those in which the repeating unit of the component is contained in a block form rather than a random form are excellent in workability, heat resistance, and mechanical properties, and can be preferably used. A preferable copolymerization component includes, for example, an m-phenylene group, but is not limited thereto. The polyarylene sulfide resin used in the present invention is preferably a high molecular weight polymer having a substantially linear structure obtained by polycondensation from a bifunctional monomer, but a relatively low molecular weight linear polymer is melted by oxidative crosslinking or thermal crosslinking. It can also be applied to polymers having increased viscosity and improved moldability. Further, a PAS resin having an arbitrary branched or cross-linked structure, which is obtained by polymerizing a small amount of a monomer having three or more functional groups as a part of the monomer, can also be used. Further, the polyarylene sulfide resin used in the present invention may be a modified polyarylene sulfide resin into which various substituents are introduced.
Further, the PAS component (A) used in the present invention may be desirable to mix and use two or more of the various PAS resins in order to obtain desired properties according to the purpose,
For example, a combination of two kinds of PAS resins having different viscosities from the viewpoint of fluidity or the like, or a substantially linear PAS resin from the viewpoint of moldability (for example, prevention of burrs, molding cycle) and a small amount of moderately branched or Having a crosslinked structure, melt viscosity 200 ~
A combination with a PAS resin having a pressure of 2000 Pa · s (310 ° C., a shear rate of 1200 sec ⁻¹ ) is also an example of a particularly preferred combination. After polymerization, the PAS resin (A) used in the present invention is subjected to a deionization treatment by an appropriate method so that the content of alkali metals such as chlorine and sodium is less than a certain limit (each 500p).
pm or less, preferably 200 ppm or less), it is of course desirable to improve the metal corrosion properties aimed at by the present invention, but the present invention is not always required without such purification treatment. The effect of is exhibited.

[0006] The component (B) of the present invention is added for the purpose of improving corrosion resistance, and is a carbonate, hydroxide, oxide or a mixture thereof of a metal selected from zinc, magnesium and barium. Or a double salt, for example, zinc carbonate, zinc hydroxide, zinc oxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, barium carbonate, barium hydroxide, barium oxide, or a double salt or a mixture of two or more thereof. Illustratively, particularly preferred are zinc carbonate, zinc hydroxide, and their double salts (eg, basic zinc carbonate m
ZnCO ₃ .nZn (OH) ₂ ). The lower limit of the amount of the component (B) is at least 0.1 part by weight, preferably at least 0.2 part by weight, particularly preferably at least 0.3 part by weight, per 100 parts by weight of the PAS resin (A) from the viewpoint of corrosion resistance. The upper limit is 10 parts by weight or less, preferably 7 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of PAS (A) from the viewpoint of mechanical properties and dispersibility.

Next, the present invention is characterized in that hypophosphorous acid or a salt thereof is blended as the component (C), for example, hypophosphorous acid or calcium hypophosphite, zinc hypophosphite, magnesium hypophosphite, hypophosphite. At least one or two or more selected from salts of zinc, alkali metal or alkaline earth metal, such as potassium phosphate and sodium hypophosphite, are preferred. Calcium hypophosphite, magnesium hypophosphite, and hypophosphorous acid are preferred. Zinc. The lower limit of the amount of the component (C) is at least 0.05 part by weight, preferably 0.1 part by weight, based on 100 parts by weight of the PAS resin (A) from the viewpoint of the effect of improving the physical properties. The upper limit is 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the PAS resin (A) from the viewpoint of mechanical properties and dispersibility. If the amount is too small, the effect of improving the intended mechanical properties cannot be obtained, and if the amount is too large, it is disadvantageous. By allowing the component (C) to coexist with the component (B), unexpectedly, the mechanical properties of the component (B) due to the interaction of the component (B) are not adversely affected by the component (B) without any hindrance. It was confirmed that the adverse effects were improved. In particular, the component (C) is effective even if added as it is.However, when the inorganic filler (D) described below is partially or entirely adhered in advance and blended with other components, the effect is further improved. Is obtained. There is no particular limitation on the method of attaching the component (C) .For example, a solution containing the above compound can be sprayed on a filler, or in the case of glass fiber or the like, the solution can be applied to the fiber using a roll coater. . Of course, it is of course possible to treat with a sizing agent for epoxy resin or urethane resin or a coupling agent such as aminosilane or epoxysilane, which is generally used as a surface treatment agent for glass fiber or the like.

[0008] As the inorganic filler of the component (D) used in the present invention, a fibrous, powdery or plate-like filler or a mixture thereof is used according to the purpose. As a fibrous filler,
Glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and metal such as stainless steel, aluminum, titanium, copper, brass Inorganic fibrous substances such as fibrous substances can be mentioned. Particularly typical fibrous fillers are glass fibers or carbon fibers. On the other hand, powdery fillers include carbon black, graphite, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Metal oxides such as salts, iron oxides, titanium oxides, and aluminas; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and other silicon carbide, silicon nitride, and boron nitride. Various metal powders and the like can be mentioned. In addition, mica,
Examples include glass flakes and various metal foils. These inorganic fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, particularly a glass fiber or a carbon fiber, and a particulate or plate-like filler is a preferable combination, particularly in terms of having both mechanical strength, dimensional accuracy, electrical properties and the like. When using these fillers, if necessary, it is preferable to use the component (C) by previously adhering it to the surface as described above, or to use a sizing agent or a surface treatment agent. Examples of the surface treatment agent include functional compounds such as an epoxy compound, an isocyanate compound, a silane compound including an alkoxysilane described later, and a titanate compound. (D) The lower limit of the amount of the inorganic filler as a component is at least 5 parts by weight, preferably 10 parts by weight or more, particularly preferably 10 parts by weight or more, based on 100 parts by weight of the PAS resin (A) in terms of rigidity and mechanical properties. Is not less than 15 parts by weight, and the upper limit thereof is not more than 400 parts by weight, preferably not more than 300 parts by weight, particularly preferably not more than 250 parts by weight, from the viewpoint of preparation of the composition and moldability.

Although the composition of the present invention is not an essential component, it is preferable to further incorporate an alkoxysilane compound (E). Examples of the alkoxysilane include aminoalkoxysilane, epoxyalkoxysilane, mercaptoalkoxysilane, vinylalkoxysilane and the like, and among them, aminoalkoxysilane is preferable. The amount of the alkoxysilane is 3 parts by weight or less, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the PAS resin. As described above, such a silane compound may be preliminarily attached to the inorganic filler (D) and blended, or may be added separately, or both may be used in combination.

The composition of the present invention may contain an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an ultraviolet absorber, a coloring agent, a release agent, a flame retardant, and other known additives according to the purpose. Can be added. The composition of the present invention may additionally contain other thermoplastic resins and organic fillers for the purpose of improving and supplementing its properties. Examples of the thermoplastic resin blended for this purpose include polyethylene,
Olefin-based polymers or copolymers based on polyolefins such as polypropylene or their modified polymers,
Nylon 6, nylon 66, other polyamide polymers or copolymers, polyester polymers or copolymers mainly composed of polyethylene terephthalate, polybutylene terephthalate, etc., liquid crystalline polyester polymers, polystyrene, polystyrene acrylonitrile, ABS, etc. Examples include styrene polymers, acrylic polymers such as polyalkyl acrylates, polycarbonates, polyphenylene oxides, polyacetals, polysulfones, polyethersulfones, polyetherimides, polyetherketones, and fluororesins. These thermoplastic resins can be used as a mixture of two or more kinds. or,
Examples of the organic filler include a high melting point fibrous or powdery polymer such as a fluororesin and an aromatic polyamide.

The resin composition of the present invention can be prepared by the equipment and method used for preparing general synthetic resin compositions. That is, the components (A), (B), (C), (D) and, if necessary, the component (E) are further mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded. A pellet for molding may be used.Also, as described above, the component (C) is preliminarily attached to the component (D) and blended, or a part of the resin component is preliminarily mixed with other components to form a master batch. It may be blended with the remaining components, melt-kneaded, or directly provided for molding.

The PAS resin composition of the present invention is suitable for injection molding, extrusion molding, blow molding, vacuum molding, compression molding and the like.

[0013]

The PAS composition of the present invention has excellent moldability, and is particularly suitable for various metals such as iron, copper, zinc, nickel, chromium, cobalt, aluminum, silver, and alloys mainly composed of these. Corrosion and contamination are remarkably improved, and there is no corrosive contamination of metal mold and other contacting members of molding equipment, and no corrosive contamination of metal members used in contact with molded products. In addition, it is possible to extend the life of processing equipment and molded parts, and to obtain molded products having accurate dimensions over a long period of time. Further, according to the present invention, it is possible to provide a PAS resin composition having significantly improved adverse effects on mechanical properties as seen in the conventional formulation of a corrosion inhibitor, and having both excellent metal corrosion resistance and mechanical properties. it can.

[0014]

EXAMPLES The present invention will be specifically illustrated by the following examples.
The present invention is not limited to this. The components (B), (C), (D) and (E) used in the examples and comparative examples are as follows. Component (B) (corrosion inhibitor) B-1: basic zinc carbonate _{(2ZnCO 3 · 3Zn (OH)} 2) B-2: zinc carbonate (ZnCO _{3) B-3:} zinc hydroxide (Zn (OH) ₂₎ B-4: Magnesium carbonate (MgCO ₃ ) B-5: Magnesium oxide (MgO) (C) component C-1: Calcium hypophosphite C-2: Zinc hypophosphite C-3: Hypophosphorous acid (D) component D-1: Glass fiber D-2: Calcium carbonate (E) alkoxysilane E-1: γ-aminopropyltriethoxysilane Examples 1 to 13, Comparative Examples 1 to 8 (A) As component, substantially linear Polyphenylene sulfide resin (viscosity 50 Pa · s (310 ° C, 1200 sec ^-1 )) 10
0 parts by weight, as shown in Table 1, the components (B), (C) and (D) were added, and if necessary, the component (E) was further added and mixed well. The mixture was melt-kneaded with an extruder to prepare pellets of the polyphenylene sulfide resin composition. The pellets were measured for metal corrosion, tensile strength and elongation, and Izod impact strength (Table 1). For comparison, component (B) and / or
In the case where no component (C) was contained, melt kneading and extrusion were carried out in the same manner to prepare composition pellets, which were similarly evaluated (Table 2). The evaluation results are shown in Table 1 (Example) and Table 2 (Comparative Example), respectively. The evaluation method is as follows. [Corrosion resistance] 22 g of the above pellets were placed in the bottom of a test tube with an inner diameter of 30 mm and a height of 150 mm, and a plate of stainless steel (SUS-304)
Cut into a size of mm x 12 mm and about 60 mm from the top of the pellet
Was hung so that the metal plate was located at the height of. After the test tube was capped at the top and kept at 310 ° C. for 5 hours, the metal plate was taken out and observed visually and microscopically to examine the corrosion state, and the relative grade was determined as follows depending on the degree of the corrosion state. . A B C D E ← ───────────────────── → Corrosion small Corrosion remarkable [Tensile strength and elongation] Cylinder temperature 320 ° C, gold with injection molding machine At a mold temperature of 150 ° C., tensile strength and tensile elongation were measured according to ASTM D-638. [Impact strength] Izod impact strength was measured according to ASTM D-256.

[0015]

[Table 1]

[0016]

[Table 2]

Examples 14 to 15 and Comparative Example 9 In Examples 2 and 3 and Comparative Example 2, glass fibers (D
-1), whereas calcium hypophosphite dissolved in a solvent (C-1)
The composition was applied under the same conditions as in Examples 2 and 3 and Comparative Example 2 except that the composition was applied so that the proportions shown in Table 3 were obtained, dried sufficiently, and used beforehand. Prepared and evaluated. Table 3 shows the results.

[0018]

[Table 3]

Example 16 and Comparative Examples 10 to 12 Pellets were prepared and evaluated in the same manner except that the inorganic filler (D) was changed. Table 4 shows the results.

[0020]

[Table 4]

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08K 5/541 C08K 5/541 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08K 3/18-3/26 C08K 5/54-5/549 C08K 3/32

Claims (9)

(57) [Claims] (A) Polyarylene sulfide resin 100
(B) Carbonate, hydroxide, oxide or a mixture or double salt of a metal selected from zinc, magnesium and barium
0.1 to 10 parts by weight (C) 0.05 to 2 parts by weight of hypophosphorous acid or a salt thereof (D) 5 to 400 parts by weight of an inorganic filler is blended and melt-kneaded to obtain a polyarylene sulfide resin composition. 2. The polyarylene sulfide resin composition according to claim 1, wherein part or all of the component (C) is preliminarily attached to the component (D), blended with other components, and melt-kneaded. 3. The composition of claim 1, further comprising (E) an alkoxysilane compound in an amount of 0.1 to 3 parts by weight per 100 parts by weight of the component (A).
Or the polyarylene sulfide resin composition according to 2. (4) The polyarylene sulfide resin comprises:
The polyarylene sulfide resin composition according to any one of claims 1 to 3, wherein the composition is mainly composed of a substantially linear polyphenylene sulfide resin having at least 70 mol% of a p-phenylene sulfide group. (5) The polyarylene sulfide resin is (A)
The polyarylene sulfide resin composition according to any one of claims 1 to 4, which is a polyarylene sulfide having a chlorine content and an alkali metal content of 500 ppm or less, respectively, which are deionized after polymerization. 6. The composition according to claim 1, wherein the component (B) is one selected from zinc carbonate, zinc hydroxide and a double salt of both (basic zinc carbonate), or a mixture thereof. Polyarylene sulfide resin composition. 7. The polyarylene sulfide resin composition according to claim 1, wherein the hypophosphite as the component (C) is a salt of zinc, an alkali metal or an alkaline earth metal. 8. The polypolymer according to claim 1, wherein the inorganic filler as the component (D) is at least one kind or a mixture of two or more kinds of fibrous, powdery and plate-like fillers. Arylene sulfide resin composition. 9. The polyarylene sulfide resin composition according to claim 1, wherein the inorganic filler as the component (D) is a glass filler.