JP3151822B2 - Polyarylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyarylene sulfide (hereinafter abbreviated as PAS) resin composition having excellent moldability and mechanical properties. By blending PAS resin with a specific long-chain alcohol phthalate as a mold release agent, the mold releasability from the mold regardless of the mold temperature during the injection molding process ( The present invention relates to a PAS resin composition which has remarkably improved mold releasability, shortened molding processing time, and has good mechanical strength, so that it can be used in a wide range of fields.

[Related Art] In recent years, high heat-resistant thermoplastic resins have been required for electric / electronic device component materials, automotive device component materials, chemical device component materials, and the like. PAS resin is one of the resins that meet this requirement, but PAS resin must have good affinity with metal, low shrinkage when solidifying from a molten state, and precise molded products to be applied. Due to the fact that there are many molds with many complicated shapes, mold release from the mold is poor during molding, which may make continuous molding difficult, and the molding speed (molding cycle) is slow. In some cases.

As a measure for improving such a defect of the releasability, spraying of silicone oil into a mold cavity, zinc stearate (Japanese Patent Application Laid-Open No. 54-162752), N, N'-alkylenebisalkaneamide, etc. Measures have been taken to add amides of fatty acids (US Pat. No. 4,395,509) to PAS resins. However, as a measure against the above-mentioned releasability, spraying of silicone oil into the cavity or the like is extremely excellent in releasing effect, but it is necessary to perform spraying at least once every several shots. In addition, when the molded product has a weld portion, the silicone oil collects at the weld portion, which doubles the decrease in weld strength, which is a weak point of PAS. Furthermore, when the molded article is used for electric and electronic parts, various inconveniences have been pointed out, such as the possibility of electric contact failure due to the attached silicone oil.

Furthermore, any of the methods of adding an amide of a fatty acid such as zinc stearate and NN′-alkylenebisalkane amide is effective in decomposing the added compound although the thermal decomposition temperature of the added compound is low and the releasing effect is somewhat recognized. There are problems such as coloring of molded articles, reduction in mechanical strength, gas generation during kneading and molding, and the like. Further, the generated gas causes a problem that the strength of the resin is weak at the weld portion of the molded product.

[Problems to be Solved by the Invention] The present invention provides a PAS resin composition having improved releasability, excellent thermal decomposability, and reduced gas and the like during molding.

[Means for Solving the Problems] As a result of various studies, the present inventors have found that by adding and blending a specific long-chain alcohol phthalate to a PAS resin, the PAS resin is extremely stable even at the molding processing temperature of the PAS resin. Decomposition is not seen, gas generation is small, mold release properties without deteriorating mechanical properties, especially mold temperature finds good release effect in an extremely wide temperature range of 60 to 160 ° C, and to complete the present invention. Reached.

That is, the present invention relates to the general formula The long-chain alcohol phthalate represented by
It is a PAS resin composition formulated by weight.

PAS resin used in the present invention It is preferable that the composition contains 90 mol% or more of the structural unit represented by the formula. If the amount is less than 90 mol%, it is difficult to obtain a composition having excellent characteristics. In particular, polyphenylene sulfide (PPS) is preferably used. Examples of the polymerization method of this polymer include a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing sodium sulfide or sodium bisulfide in a polar solvent in the presence of sodium hydroxide, and a method of polymerizing p-chlorobenzene. Self-condensation of luthiophenol and the like can be mentioned, but a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable. At this time, it is preferable to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If less than 50 mol% as a copolymer component, a meta bond (Where R represents an alkyl group, a nitro group, a phenyl group, a carboxyl group, a metal base of a carboxylic acid, an alkoxy group or an amino group),
Preferably it is at most 40 mol%. Also, 5 mol% or less, more preferably 3 mol% or less.

Such a PAS resin can be produced by a general production method, for example, (1) the reaction of a halogen-substituted aromatic compound with an alkali sulfide (U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No.
No. 45-3368), (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat.
No. 3274165, British Patent No. 1160660), (3) Synthesis of aromatic compounds by condensation reaction with sulfur chloride in the presence of a Lewis acid catalyst (JP-B-46-27255, Belgian Patent No. 29439) Can be arbitrarily selected according to the purpose.

The additive compound to be added and blended as a component of the composition of the present invention is effective for any long-chain alcohol phthalate having the structure of the general formula, but the carbon number of R in the general formula is 25. That is all. That is, when the number of carbon atoms is less than 25, the mechanical strength of the PAS composition is significantly reduced, which is not preferable. Particularly preferred are those in which R in the general formula has 40 to 60 carbon atoms.

The amount of the long-chain alcohol phthalate used in the present invention is preferably 0.01 to 6 parts by weight per 100 parts by weight of the PPS resin. Is also optimal because it is also good.

A fibrous reinforcement, preferably glass and carbon fibers and / or other mineral fillers, can be added to the composition of the present invention. As glass fibers that can be used, the surface of a non-alkali glass fiber having a strand diameter of 5 to 20 μm is treated with an organic substance called a binder for silane coupling agent treatment and convergence, and cut into a length of 3 to 6 mm. Are preferred. Further, as the carbon fiber, any of polyacrylonitrile-based and pitch-based can be used. Usually, the wire diameter is 5 to 20 μm, and the epoxy resin,
It is preferable to use a resin surface-treated with a nylon resin or the like or a non-treated resin.

Further, as other inorganic fillers, calcium carbonate, talc, kaolin, clay, my wollastonite, calcium sulfate, silica, glass beads, milled glass fiber, milled carbon fiber, titanium oxide, graphite, processed mineral fiber, Etc. can be used.

The quantitative proportion of these fibrous reinforcing materials and other inorganic fillers is 20 to 70% by weight in the total resin composition. The fibrous reinforcing material and the other inorganic filler can be used alone or in combination.

Furthermore, the composition of the present invention may contain other thermoplastic resins within a range not impairing the object of the present invention, for example, polyphenylene ether, polyacetal, polyarylate, Teflon resin,
One or more of polyamide, polycarbonate, polysulfone, polyethersulfone, polyetheretherketone, polybutyleneterephthalate, polyethyleneterephthalate, polyamideimide, polyetherimide, polyethylene, polypropylene, epoxy resin, and the like can be added.

The addition of the specific long-chain alcohol phthalate in the present invention to the PAS resin can be performed by a known method. For example, PAS resin in powder or pellet form, powder,
Flake, granule, and pellet long-chain alcohol phthalates (if necessary, reinforcing agents such as glass fiber and / or
Or other inorganic fillers such as calcium carbonate)
It is mechanically homogeneously mixed in advance with a mixer such as a drum tumbler and the like.
It is performed by cooling, pelletizing through heating, melting and kneading steps.

In the composition of the present invention, a small amount of a colorant, a heat stabilizer, an ultraviolet stabilizer, a rust inhibitor, a nucleating agent, a modifier such as an organic silane compound, etc. are added within a range not departing from the object of the present invention. be able to.

The composition of the present invention is used for various molded article materials, that is, electric / electronic device parts, automobile device parts materials, chemical parts materials and the like.

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

Examples 1 to 6 and Comparative Examples 1 to 4 Powdery PPS resin commercially available from Philips Sekiyu U.S.A .; trade name RYTON "P-4" and various additive compounds in proportions shown in Table 1 (total 6Kg), mixed in a drum tumbler having a capacity of 30 liters, and uniformly mixed at a speed of 80 rpm for about 1 minute.

The above mixture (60% by weight; 15 kg / H. (Discharge rate)) and chopped glass fiber manufactured by Asahi Fiberglass Co., Ltd .; trade name: Glassron Chopped Strand “CS-03-
MA-497 "(40% by weight; 10Kg / H. (Discharge amount)) with a separate feed, screw diameter φ37mm, L / D = 32, vented high-speed co-axial twin-screw extruder (Toshiba Machine Co., Ltd.) TEM-35B) Cylinder temperature 320 ° C, screw rotation speed 250rpm, discharge rate 2
After kneading at 5 kg / h, the mixture was discharged from a nozzle having a hole diameter of 3.6 mm, and after air cooling, a pellet having a length of 3 mm was prepared using a strand cutter. Sumitomo Heavy Industries, Ltd. has a maximum clamping force of 75 tons. Sumitomo-Nestal injection molding machine SAYCAPS 165/75, φ30m
m, internal diameter φ28mm, length 10mm, draft angle 1 degree
℃, molding machine cylinder temperature 320 ° C, injection speed 30mm / sec, injection pressure (primary pressure: 35Kgf / cm ² , secondary pressure: 28Kgf / cm ² ), injection pressure time (primary pressure: 3 seconds, secondary Molding was performed under the conditions of a pressure of 3 seconds) and a cooling time of 15 seconds. After the cooling process is completed, the mold is opened, and in the protruding process, a release that acts on the protruding pin by a pressure sensor (9221 type pressure sensor manufactured by KISTLER, Switzerland) attached to one of three protruding pins having a diameter of 1 mm. The force was measured. The bending properties were measured as mechanical strength according to ASTM D790. The results are shown in Table 1.

[Effects of the Invention] The present invention is based on the fact that a specific long-chain alcohol phthalate is added to a PAS resin as a mold release agent, so that the mold release properties can be obtained regardless of the mold temperature during injection molding. Is dramatically improved, and the molding time can be shortened.

Claims (1)

(57) [Claims] 1. A general formula based on 100 parts by weight of a polyarylene sulfide resin. The long-chain alcohol phthalate represented by
A polyarylene sulfide resin composition formulated by weight.