JP2877060B2 - Polyphenylene 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 molding polyphenylene sulfide (hereinafter referred to as P) in which corrosion of a mold during molding and corrosion of a metal part of an assembled part using the molded part are reduced.
(Abbreviated as PS)).

[0002]

2. Description of the Related Art PPS resins have extremely high heat resistance, chemical resistance, electrical properties, and combustion resistance, and have excellent mechanical strength, rigidity, and strength by being reinforced with a reinforcing filler. It is known to exhibit dimensional stability and is widely used for various molding applications such as electric / electronic parts, automobile parts, and mechanical parts.

[0003] However, PPS resin generates a metal corrosive gas at a high temperature and at the time of melting, so that a mold or a molding machine is corroded at the time of molding, or a molded product is heated to 100 ° C.
As described above, when the aging treatment is performed at a temperature lower than the melting point, problems such as corrosion of a metal part of an assembled part using the molded product or corrosion of an insert metal part occur.

For example, when a PPS resin is used for a relay base, troubles such as corrosion of a metal contact of the relay causing a contact failure and deterioration of solder adhesiveness at an insert metal portion due to corrosion occur. I have.

[0005] In order to solve such a problem, a method of adding an alkali metal hydroxide or carbonate (US Pat.
017450) or a method of adding a hydroxide, an oxide, or an aromatic carboxylate of a Group _A metal of the Periodic Table II (Japanese Patent Laid-Open No. Sho 62).
No. 109850) is known.

[0006] However, in each case, a sufficient effect cannot be obtained, and since the additive itself is water-soluble or has a hygroscopic property even if it is not water-soluble, the water resistance can be reduced by the addition of the above compound. At present, when used for insulating materials reinforced with glass fiber or the like, the insulating properties under humid conditions are greatly reduced.

[0007]

SUMMARY OF THE INVENTION The present invention makes use of the excellent properties of PPS resin without deteriorating the insulating properties particularly under high humidity when used for water resistance and insulating materials. It is still another object of the present invention to provide a PPS resin composition in which corrosion of a mold during molding and corrosion of a metal part of an assembled part using the molded product and corrosion of an insert metal part are reduced.

[0008]

The present invention SUMMARY OF] includes a PPS resin, a) zinc carbonate b) at least one metal corrosion reducing agent selected from manganese carbonate c) magnesium carbonate, black
Lead, molybdenum disulfide, polytetrafluoroethylene
A polyphenylene sulfide resin composition characterized by adding at least one lubricant selected from the group consisting of:

The most important feature of the composition of the present invention is that the corrosiveness of a molding die and a metal part of an assembled part using the molded part and an insert metal part is remarkably reduced, and furthermore, particularly good water resistance. Also, when used as an insulating material, it has excellent insulating properties under humid conditions.

As described above, the hydroxides and carbonates of Group _{A of} the periodic table IA are often readily soluble in water, and
_A group hydroxides, oxides others often hygroscopic.
On the other hand, the mold corrosion reducing agent added in the present invention is sparingly soluble in water, and has an extremely high ability to capture metal corrosive gas from the PPS resin.

Particularly, in addition to the effect of preventing corrosion of a mold or the like at the time of melting, an excellent effect of preventing corrosion of metal (particularly silver) during heat aging below the melting point is exhibited.

The composition of the present invention significantly reduces the metal corrosive gas generated from the PPS resin, has remarkably improved water resistance, and has a long-term high humidity when used for an insulating material. It is extremely excellent in insulation properties as represented by the volume specific resistance holding ability below.

The PPS resin used in the present invention has a general formula

[0014]

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Preferably, the composition contains at least 90 mol% of the structural unit represented by the formula (I), and if the amount is less than 90 mol%, it is difficult to obtain a composition having excellent properties. Examples of the polymerization method of this polymer include a method in which P-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, 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. And self-condensation of P-chlorothiophenol.
A suitable method is to react sodium sulfide with P-dichlorobenzene in an amide solvent such as methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. 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. As long as it is less than 10 mol% as a copolymer component, it may be in a range that does not significantly affect the crystallinity of the polymer even if it contains the following bonds, but preferably the copolymer component is 5 mol% or less. In particular, when a phenyl, biphenyl, naphnal sulfide bond or the like having three or more functionalities is selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

[0016]

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Such a PPS resin can be produced by a general production method, for example, (1) the reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2,513,188, JP-B-44).
-27671 and JP-B-45-3368)
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a complex salt (US Pat. No. 3,274,165;
(See British Patent No. 1160660) (3) Condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-27255, Belgian Patent No. 2943)
No. 7) and can be arbitrarily selected according to the purpose.

The metal corrosion reducing agent to be added in the present invention is at least one selected from the following. at least one selected from a) zinc carbonate, b) manganese carbonate, and c) magnesium carbonate. As for zinc carbonate, commercially available basic zinc carbonate can be used as a reagent within a range not to impair the object of the present invention.

The amount of the compound to be added in the present invention is preferably 0.01 to 100 parts by weight of the PPS resin.
The addition amount is not preferred because the effect of reducing the metal corrosive gas is large, the melt fluidity of the composition is reduced, and the strength is further reduced.

In order to improve the mechanical properties, various reinforcing materials and fillers can be added to the composition of the present invention. Reinforcing agents and fillers that can be used in the present invention include calcium titanate, silicon carbide, bentonite, sericite, zeolite, PMF, ferrite, dolomite, antimony trioxide, and glass balloon.

[0021] The composition of the present invention comprises graphite, molybdenum disulfide.
At least selected from polytetrafluoroethylene
Also contains one kind of lubricant as a component of the soil.

Other essential reinforcing materials, fillers, and lubricants that can be used in combination as needed include glass fibers, carbon fibers, ceramic fibers, metal fibers, silicon nitride, barium sulfate, calcium sulfate, kaolin, Examples include clay, mica, mica, talc, wollastonite, calcium silicate, calcium carbonate, titanium oxide, iron oxide, milled glass, glass beads and the like.

The composition of the present invention contains an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent, a silane coupling agent, as long as the object of the present invention is not impaired.
There is no restriction by adding a release agent.

Further, the composition of the present invention may contain other thermosetting resins and thermoplastic resins, for example, epoxy resins, silicone resins, polyimides, polyphenylene ethers, polyamides, polycarbonates, polysulfones, as long as the object of the present invention is not impaired. , Polyether sulfone, polyarylate, polyacetal, polyether ketone, polyether ether ketone, polybutylene terephthalate, polyethylene terephthalate, polyamide imide, polyether imide and the like can be blended in a small amount.

The composition of the present invention can be prepared by various known methods. For example, a PPS resin and a compound to be added in the present invention are mixed in advance with a Henschel mixer or a tumbler, and then supplied to a single-screw or twin-screw extruder, melt-kneaded at 260 ° C. to 360 ° C., and granulated. Obtainable. Upon mixing, other reinforcing materials, fillers and various additives may be added as necessary.

The composition of the present invention is applied to various uses such as electric / electronic parts, mechanical parts, and automobile parts. Particularly, when used for insulating materials, it can be used as an industrial material such as switch parts. Useful.

[0027]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, preferred embodiments of the present invention will be described. 1. A polyphenylene sulfide resin, at least one metal corrosion reducing agent selected from a) zinc carbonate, b) manganese carbonate, and c) magnesium carbonate; and at least one lubricant selected from graphite, molybdenum disulfide, and polytetrafluoroethylene. And a polyphenylene sulfide resin composition.

2. Polyphenylene sulfide resin 10
0 to 1 part by weight of the metal corrosion inhibitor is 0.01 to 1
2. The polyphenylene sulfide resin composition according to the above 1, wherein 0 parts by weight are added.

[0029]

The present invention will be further described below with reference to examples. In addition, the test values of each characteristic shown in this example are based on the following methods and standards.

<Metal Corrosion> As shown in FIG. 1, 100 g of each of the granulated pellets 2 is placed in a metal hermetically sealed container 1 and placed on a 20-mesh wire mesh 3 fixed by a supporting metal plate 4 in the container. 1.5% by weight, Cr: 12.0% by weight, M
A steel material block 5 (surface roughness of 3 μm or less), which is a high alloy tool steel having a composition of o: 1.0% by weight and V: 0.4% by weight, is placed and heat-treated at 340 ° C. for 6 hours. . After the heat treatment, the SKD-11 steel material block 5 is taken out, placed in a constant temperature / humidity bath at 70 ° C./95% RH for 6 hours, and then the corrosion state of the steel material is observed.

<Water resistance> From the granulated pellets, 1.6
A dumbbell specimen for a tensile test having a thickness of mm was molded, and the specimen was subjected to a pressure cooker treatment at 120 ° C. under a condition of ² kgf / cm ² for 30 hours (after PCT). Compared. (The tensile strength is AST
MD-638 compliant)

<Insulation characteristics> 1.6 from granulated pellets
After forming a disc for ASTM D-257 having a thickness of 2 mm and subjecting the specimen to a pressure cooker treatment at 120 ° C. under a condition of ² kgf / cm ² for 30 hours (after PCT), the volume resistivity was measured and the initial value was measured. And compared. (Volume resistivity measurement is based on ASTM D-257)

Reference Example 1 (Synthesis of PPS resin) N-methylpyrrolidone was added to a 50-liter autoclave at a molar ratio of 70, and sodium sulfide nonahydrate was added to a 50-liter autoclave.
99, sodium benzoate was added at a ratio of 0.60, and sodium hydroxide was added at a ratio of 0.15 mol (50 mol scale). The temperature was raised to 210 ° C. in a nitrogen stream, and dehydration was performed to a dehydration rate of 110%. The system was cooled to 160 ° C., charged with P-dichlorobenzene at a molar ratio of 1.0 and sealed, and then the internal pressure was reduced to 2 with nitrogen.
The pressure was increased to 5 kg / cm ² . The temperature was controlled while taking into account the heat generated by the polymerization, and the temperature was raised to 270 ° C.
The polymerization was carried out with stirring for a period of time. Internal pressure is 17kg / cm ²
Was rising. Next, the system was cooled and then depressurized, and the content was poured into a large amount of water to collect a flaky polymer. The polymer was repeatedly washed with hot water and acetone and finally washed 7 times.
It was white flake with a yield of 0%.

This PPS resin powder is charged into a ribbon blender, and stirred at 270 ° C. while blowing air.
In the powder state, PPS was partially crosslinked and heat-treated until the intrinsic viscosity finally became 0.3.

Example 1, Comparative Examples 1 to 5 Using the PPS resin synthesized in Reference Example 1, the raw materials shown in Table 1 were uniformly mixed at the mixing ratios shown in the table, and then mixed with 35 mmφ 2
The mixture was melt-kneaded at 320 ° C. in a screw extruder to obtain pellets. The metal corrosion was evaluated using the pellets.

Further, the pellets are in-line screened.
Using a three-ounce injection-molding machine with a cylinder temperature of 3
20 ° C, mold temperature 150 ° C, injection pressure 1000kgf /
cm ^Two, Water resistance and insulation properties evaluated at medium injection speed
A test piece was molded and both properties were evaluated. This result is
It is shown in the table.

[0037]

[Table 1]

Examples 2-3 and Comparative Examples 6-7 Using the PPS resin synthesized in Reference Example 1, the raw materials shown in Table 2 were uniformly mixed in the proportions shown in the table, and then mixed with a 35 mmφ twin screw extruder. At 320 ° C. to obtain pellets. The metal corrosion was evaluated using the pellets.

The pellets were further subjected to an in-line screw type 3 oz.
0 ° C, Mold temperature 150 ° C, Injection pressure 1000kgf / c
A 1.6 mm-thick dumbbell for tensile test was molded at m ² and medium injection speed, and the water resistance was evaluated. Table 2 shows the results.

[0040]

[Table 2]

[0041]

EFFECT OF THE INVENTION The composition of the present invention significantly reduces the amount of metal corrosive gas generated from PPS resin to form a molding die and a metal part of an assembled part using the molded product, as well as an insert metal part and the like. The corrosion resistance is greatly reduced, and furthermore, it has good water resistance and excellent moisture resistance insulation properties when used as an insulating material.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a state in which a metal corrosive property of each of the pellet-shaped compositions of Examples and Comparative Examples of the present invention is tested.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Metal closed container 2 Pellet-shaped resin composition 3 20-mesh wire net 4 Support metal plate 5 Steel block

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C08K 3:30) (C08L 81/02 27:18) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 81 / 02 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] To 1. A polyphenylene sulfide resin, and at least one metal corrosion reducing agent selected from a) zinc carbonate b) manganese c) magnesium carbonate, black
Lead, molybdenum disulfide, polytetrafluoroethylene
A polyphenylene sulfide resin composition comprising at least one lubricant selected from the group consisting of: 2. Polyphenylene sulfide resin 100
0.01 to 10 parts by weight of the metal corrosion reducing agent
The polyphenylene sulfide resin composition according to claim 1, which is added in parts by weight.