JPH059383A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide a polyarylene sulfide resin composition having improved mold-releasability in molding and causing suppressed corrosion of the mold and the metallic part of an assembled part produced by using the molded article. CONSTITUTION:The objective composition is produced by compounding 100 pts.wt. of a polyarylene sulfide resin with 0.01-10 pts.wt. (preferably 1-5 pts.wt.) of an isocyanuric acid metal salt and/or cyanuric acid metal salt selected from Na salt, Ca salt and Zn salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene having improved releasability at the time of molding process, and further reducing corrosion of a mold at the time of molding process and corrosion of a metal part of an assembly part using the molded product. The present invention relates to a sulfide (hereinafter abbreviated as PAS) resin composition.

[0002]

2. Description of the Related Art Conventionally, JP-A-63-289068 discloses a specific fatty acid for a PPS resin as a technique for improving mold releasability during molding of a polyphenylene sulfide (hereinafter abbreviated as PPS) resin. Techniques for adding esters are disclosed.

Further, the corrosion of a mold due to the generation of a metal corrosive gas at a high temperature and during melting of PPS resin, and PP
U.S. Pat. No. 4,017,450 discloses a technique for solving problems such as corrosion of a metal part of an assembly using the S resin molded product during aging treatment. JP-A-62-109850 discloses a technique of adding a salt, and a technique of adding a hydroxide, an oxide or an aromatic carboxylate of a metal of Group IIA of the periodic table.

[0004]

However, the above-mentioned Japanese Unexamined Patent Application Publication No.
In the technique described in JP-A-3-289068, the mold releasing effect is not yet sufficient, and since a decomposition temperature of the fatty acid ester to be added is low, a large amount of gas is generated during kneading and molding, Also, there is a problem that the mechanical properties are significantly reduced by adding these compounds.

Further, in the techniques described in US Pat. No. 4,017,450 and Japanese Patent Laid-Open No. 62-109850, a sufficient effect of preventing metal corrosion cannot be obtained. In the case of preventing silver corrosion, it is not effective at all, but rather tends to promote corrosion.

Further, in each of the above-mentioned prior arts, since the described additives have water solubility or hygroscopicity, the water resistance is lowered by the use of the additives, and the insulation is reinforced by glass fiber or the like. When it is used as a material, it also has a problem of significantly lowering the insulating properties under high humidity.

[0007] The problem to be solved and used by the present invention is that the mold releasability at the time of molding is remarkably improved while maintaining high mechanical properties, and in addition, it is used as a water resistant and insulating material. Without deteriorating the insulation characteristics under high humidity, especially metal corrosion at the time of molding process, metal part corrosion of the assembly parts using the molded product, and further insert metal when PAS resin is used for the relay base. It is an object of the present invention to provide a polyarylene sulfide resin composition in which corrosion of parts is significantly reduced.

[0008]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors added an isocyanuric acid metal salt and / or a cyanuric acid metal salt to a PPS resin. As a result, while maintaining high mechanical properties, releasability during molding is dramatically improved, and in addition, water resistance and insulation properties under high humidity when used as an insulating material are reduced. In particular, the inventors have found that the corrosion of the metal during the molding process, the corrosion of the metal part of the assembly using the molded product, and the corrosion of the insert metal part can be significantly reduced, and the present invention has been completed.

That is, the present invention relates to a polyarylene sulfide resin, a metal salt of isocyanic acid and / or a cyanuric acid.
The present invention relates to a polyarylene sulfide resin composition containing a metal acid salt.

The PAS resin used in the present invention is a random copolymer, a block copolymer, containing a repeating unit having a structure in which an aromatic ring which may have a substituent and a sulfur atom are bonded.
It may be a mixture thereof or a mixture with a homopolymer. Furthermore, the molecular weight of each PAS is not particularly limited, and non-crosslinked products or crosslinked products, and mixtures thereof are also included.

Typical examples of these resins include polyphenylene sulfide, polyphenylene sulfide ketone, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone sulfone. PAS
Among these, the bond of the repeating unit is preferably a structure in the para position with respect to the aromatic ring in terms of heat resistance and crystallinity.

In particular, a PPS resin containing 70 mol% or more of the structural unit represented by the following general formula 1 (which does not contain a substituent in the aromatic ring) is preferable in terms of physical properties and economy. If the amount is less than 70 mol%, it is difficult to obtain a composition having excellent properties.

[0013]

[Chemical 1]

As the method for polymerizing the PPS resin, for example, p-dichlorobenzene and, if necessary, other copolymerization components are polymerized in the presence of sulfur and sodium carbonate, p-dichlorobenzene. And further, if necessary, other copolymerization components in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or in the presence of hydrogen sulfide and sodium hydroxide, p-chlorothio. A method of self-condensing phenol with another copolymerization component if necessary, sodium sulfide and p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. Further, if necessary, there may be mentioned a method of reacting with another copolymerization component, and the method among them is suitable. At this time, it is preferable to add an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide to adjust the degree of polymerization.

Examples of the copolymerization component contained in the PPS resin include a meta bond represented by the following structural formula (2), an ether bond represented by the structural formula (3), and a structural formula (4). ), A sulfone bond represented by the structural formula (5), a biphenyl bond represented by the structural formula (6), a substituted phenyl sulfide bond represented by the general formula (7), and a structural formula (8). And a naphthyl bond represented by the structural formula (9), and the content thereof is preferably less than 30 mol%. However, the content in the case of containing a trifunctional or higher bond is usually 5 mol% or less, preferably 3 mol%
It is the following.

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

(In the formula, R represents an alkyl group, a nitro group, a phenyl group or an alkoxy group.)

[0023]

[Chemical 8]

[0024]

[Chemical 9]

The isocyanuric acid metal salt and / or cyanuric acid metal salt added in the present invention is an isocyanuric acid salt.
It is produced from acid and / or cyanuric acid. In general, isocyanuric acid and cyanuric acid are in a tautomeric relationship with each other, and the keto-type structure of isocyanuric acid is
The leu-shaped structure corresponds to cyanuric acid. It exists as a keto form in solids and crystals, that is, as isocyanuric acid, and in solution, it becomes an equilibrium solution of tautomers.

Therefore, the metal salt added in the present invention is
It can be selected from any form of isocyanuric acid metal salt, cyanuric acid metal salt, and a mixture of both metal salts depending on the production method and the like.

The metal salt added in the present invention is N
Examples thereof include alkali metal salts such as a salt, alkaline earth metal salts such as Ca salt, Zn salt, etc., but Ca salt, Na salt and Zn salt are preferable from the viewpoint of excellent mechanical properties, and Zn salt is particularly preferable.
Salt is preferred.

Examples of the metal salt added in the present invention include sodium isocyanurate, calcium isocyanurate, and zinc isocyanurate, and zinc isocyanurate is particularly preferable.

Further, the addition amount of the isocyanuric acid metal salt and / or the cyanuric acid metal salt in the present invention depends on the releasability effect during molding, the metal corrosive gas reducing effect, and the melt fluidity of the composition. And PPS from the viewpoint of improving mechanical strength
0.01 to 10 parts by weight is preferable with respect to 100 parts by weight of the resin, and above all, 0.5 to 3 parts by weight is preferable from the viewpoint of remarkable releasability improving effect and metal corrosive gas reducing effect during molding.

Various reinforcing materials and fillers can be added to the composition of the present invention in order to improve mechanical properties. As the reinforcing material and the filler which can be used in the present invention, glass fiber, carbon fiber, calcium titanate, potassium titanate, silicon carbide, aramid fiber, ceramic fiber, metal fiber, silicon nitride, barium sulfate, calcium sulfate, Kaolin, clay, bentonite, sericite, zeolite, mica, mica, talc, wollastonite,
Examples include PMF, ferrite, calcium silicate, calcium carbonate, dolomite, antimony trioxide, titanium oxide, iron oxide, milled glass, glass beads, glass balun and the like.

Further, the composition of the present invention may contain a lubricant such as graphite, molybdenum disulfide, polytetrafluoroethylene and the like, and a stabilizer thereof. Further, the composition of the present invention, within the range not impairing the object of the present invention, an antioxidant,
There is no restriction due to the addition of heat stabilizers, UV absorbers, lubricants, crystal nucleating agents, colorants, silane coupling agents and the like.

Further, the composition of the present invention contains a thermosetting resin and other thermoplastic resins such as epoxy resin, silicone resin, polyimide, polyphenylene ether, polyamide within a range not impairing the object of the present invention. , Polycarbonate, polysulfone, polyethersulfone, polyarylate, polyacetate, polyetherketone,
It is possible to blend one or more kinds of polyether ether ketone, polybutylene terephthalate, polyethylene terephthalate, liquid crystal polymer, polyamideimide, polyetherimide, and the like.

The composition of the present invention can be prepared by various known methods. For example, the PPS resin and the isocyanuric acid metal salt and / or the cyanuric acid metal salt to be added in the present invention are mixed in advance with a Henschel mixer, a tumbler or the like, and then added to a single-screw or twin-screw extrusion kneader. It can be obtained by supplying, melt-kneading at 260 to 360 ° C., and granulating.

If necessary, other reinforcing materials may be added during mixing.
Fillers and various additives may be added. The present invention will be further described below with reference to examples.

[0035]

EXAMPLES The test values of the respective characteristics shown in this example are based on the following methods and standards. <Mechanical properties: Flexural strength> 3 mm depending on pellets after granulation
A specimen for thick bending test was prepared, and the bending strength (based on ASTM D-790) was measured. <Releasing resistance> Cylindrical cavity with an outer diameter of 30 mm, an inner diameter of 28 mm, a length of 10 mm, and a draft of 1 degree using pellets after granulation.
A cylindrical molded product is molded with a mold of-, and the mold release resistance (load stress loaded on one ejector pin at the time of mold release) in the ejecting process at the time of molding is one of the three 1 mm diameter ejector pins. Pressure sensor attached to a book- (Swiss KI
It was measured by STLER 9221 type). <Metal corrosiveness> (Silver corrosiveness during heating and aging below melting point) As shown in FIG. ) put in,
Silver plate (3) in it (Plating thickness: 7 μm, Weight:
20 g) is completely buried, sealed with a metal fixing jig (4), and heated at 180 ° C. for 50 hours. After the heat treatment, the corrosion state of the silver plated plate (3) is observed.

[0036]

[Fig. 1] <Moisture resistant insulation properties> (Water resistance when used as an insulating material) A disc for ASTM D-257 having a thickness of 1.6 mm was formed from granulated pellets, and the test piece was made into 120 pieces. ℃ 2kgf / cm ² 3
After the pressure cooker treatment for 0 hours (after PCT), the volume resistivity value was measured and compared with the initial value. (Measurement of volume resistivity according to ASTM D-257) Reference Example 1 (Synthesis of PPS resin) N-methylpyrrolidone in molar ratio of 50-scale autoclave 70, sodium sulfide 9, hydrate To 0.99,
Sodium benzoate was charged at a molar ratio of 0.60 and sodium hydroxide at a molar ratio of 0.15 (50 mol scale), and the temperature was raised to 210 ° C. in a nitrogen stream to dehydrate to a dehydration rate of 110%. After cooling the system to 160 ° C, p-dichlorobenzene was charged at a molar ratio of 10 and sealed, and then the internal pressure was adjusted to 25 kg with nitrogen.
Pressurized to / cm ² . The temperature was controlled in consideration of the heat generated by the polymerization, the temperature was raised to 270 ° C., and the polymerization was carried out with stirring for 5 hours. The internal pressure had risen to 17 kg / cm ² . Next, after cooling the system, the pressure was released, the contents were poured into a large amount of water, and the flaky polymer was recovered.

The polymer was repeatedly washed with hot water and acetone, and finally it was in the form of white flakes with a yield of 70%. This PPS resin powder was put into a ribbon blender and stirred at 270 ° C. while blowing air, and the PPS was partially crosslinked in the powder state and finally heat-treated until the intrinsic viscosity became 0.3.

Examples 1 to 6 and Comparative Examples 1 to 7 Using the PPS resin synthesized in Reference Example 1, Tables 1 and 2
After uniformly mixing the raw materials shown in the table at the ratio shown in the table, 35 mm
Pellets were obtained by melt-kneading at 320 ° C. with a φ twin-screw extruder. The pellets were used to evaluate metal corrosion.

A cylinder temperature of 320 is obtained by using an in-line screw type injection molding machine using the pellets.
° C., mold temperature 0.99 ° C., injection pressure 1000 kgf / cm ^2, injection spin - C. in de speed, molded flexural strength, moisture resistance insulation characteristic evaluation each test piece was evaluated both characteristics.

Further, after the granulation, the pellets are used and the injection molding machine:
A SYCAP S165 / 75 was used to mold a cylindrical molded product under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and the release resistance was measured. The results are shown in Tables 1 and 2.

[0041]

[Table 1]

[0042]

[Table 2]

* Additional compound metal salt A: Zinc isocyanurate metal salt B: Sodium isocyanurate metal salt C: Calcium isocyanurate PETS: Pentaerythritol tetrastearate ** PTFE: Polytetrafluoroethylene *** Metal corrosion Judgment of properties ◎: No corrosion at all ○: Slight corrosion △: Significant corrosion ×: Significant corrosion

[0044]

EFFECTS OF THE INVENTION According to the present invention, while maintaining a high degree of mechanical properties, the releasability at the time of molding is dramatically improved, and in addition, water resistance and high humidity when used as an insulating material are obtained. In particular, metal corrosion at the time of molding, corrosion of the metal parts of the assembled parts using the molded products, and even the insertion metal parts when PAS resin is used for the relay base, It is possible to provide a polyarylene sulfide resin composition in which corrosion is greatly reduced.

Further, the composition of the present invention is applied to various uses such as electric / electronic parts, mechanical parts, automobile parts, etc., but when it is used as an insulating material, it can be used as a switch part or a relay part. -Useful as an industrial material for parts, connectors, etc.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a state in which silver corrosiveness of heat aging below melting point is tested for each pelletized composition of Examples of the present invention and Comparative Examples. (1)… Pelletized resin composition (2)… Glass pressure resistant bottle (3)… Silver plated plate (4)… Fixing jig

Claims (6)

[Claims] 1. A polyarylene sulfide resin composition comprising a polyarylene sulfide resin and an isocyanuric acid metal salt and / or a cyanuric acid metal salt. 2. The isocyanuric acid metal salt and / or the cyanuric acid metal salt is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyarylene sulfide resin. Composition. 3. The content of the isocyanuric acid metal salt and / or the cyanuric acid metal salt is 1.0 to 5.0 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin. The composition as described. 4. The composition according to claim 1, 2 or 3, wherein the isocyanuric acid metal salt and / or the cyanuric acid metal salt is selected from the group consisting of Na salt, Ca salt and Zn salt. 5. The composition according to claim 1, 2, 3 or 4, wherein the isocyanuric acid metal salt and / or the cyanuric acid metal salt is a Zn salt. 6. The polyarylene sulfide resin is a polyphenylene sulfide resin, and the polyarylene sulfide resin is a polyphenylene sulfide resin.
The composition according to 4 or 5.