JPH08253679A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, capable of reducing the evolution of a gas corroding a metal from a resin, excellent in water resistance and moisture-resistant insulating properties and useful as electronic parts, etc., by adding a metallic corrosion reducing agent and a specific reinforcing material, a specified flller or a specific lubricant to a polyphenylene sulfide resin. CONSTITUTION: This resin composition is obtained by adding (B) a metallic corrosion reducing agent which is zinc carbonate, manganese carbonate or magnesium carbonate and (C) a reinforcing material, a filler or a lubricant that is calcium titanate, silicon carbide, bentonite, sericite, zeolite, PMF, ferrite, dolomite, antimony trioxide, glass balloons, graphite, molybdenum disulfide or polytetrafluoroethylene to (A) a polyphenylene sulfide resin (e.g. a resin containing >=90mol% constituent 'unit of the formula). Furthermore, the amount of the component (B) is preferably 0.01-10 pts.wt. based on 100 pts.wt. of the component (A).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide for molding (hereinafter referred to as P) in which corrosion of a mold during molding and corrosion of a metal part of an assembly part using the molding part are reduced.
(Abbreviated as PS) resin composition.

[0002]

2. Description of the Related Art PPS resin has extremely high heat resistance, chemical resistance, electrical properties, and combustion resistance, and further has excellent mechanical strength and rigidity 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.

However, since the PPS resin generates a metal corrosive gas at a high temperature and at the time of melting, it corrodes a mold or a molding machine 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 equal to or lower than the melting point, there arises a problem that a metal part of an assembled part using the molded product is corroded or an insert metal part is corroded.

For example, when the PPS resin is used for the relay base, the metal contacts of the relay are corroded to cause contact failure, and the solder adhesion in the insert metal part is deteriorated due to the corrosion. There is.

A method of adding an alkali metal hydroxide or carbonate for the purpose of solving such problems (US Pat.
No. 017450) or a metal hydroxide, oxide or aromatic carboxylate of Group _A metal of Periodic Table II (JP-A-62-62).
No. 109850) is known.

However, in any case, a sufficient effect cannot be obtained, and since the additive itself is water-soluble or has hygroscopicity even if it is not water-soluble, the addition of the above-mentioned compound makes it water-resistant. Under the present circumstances, it is a cause of a significant decrease in the insulation characteristics under high humidity when it is used for an insulating material such as a glass fiber reinforced.

[0007]

DISCLOSURE OF THE INVENTION The present invention makes use of the excellent properties of PPS resin, and does not deteriorate the insulating properties under high humidity especially when used for water resistance and insulating materials, and Another object of the present invention is to provide a PPS resin composition in which corrosion of a mold during molding, 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 provides a PPS resin containing at least one metal corrosion inhibitor selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate, calcium titanate, silicon carbide and bentonite. , Sericite, zeolite, PMF, ferrite, dolomite, antimony trioxide, glass balloons, graphite, molybdenum disulfide, polytetrafluoroethylene and at least one reinforcing agent, filler or lubricant. Provided is a characteristic polyphenylene sulfide resin composition.

The greatest feature of the composition of the present invention is that the corrosion resistance to the metal part of the molding die and the assembly part using the molded product and further to the insert metal part is remarkably reduced, and particularly good water resistance is obtained. Also, when used as an insulating material, it has excellent insulating properties under high humidity.

As mentioned above, many of the hydroxides and carbonates of Group I _{A of} the Periodic Table are readily soluble in water, and II
_Many Group A hydroxides and oxides have high hygroscopicity.
On the other hand, the mold corrosion reducing agent added in the present invention is poorly soluble in water and has a very high ability to capture a metal corrosive gas from the PPS resin.

In particular, in addition to the effect of preventing corrosion of a mold or the like during melting, it exhibits an excellent effect of preventing metal (especially silver) corrosion during heat aging below the melting point.

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

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

[0014]

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It is preferable that the content of the structural unit represented by the formula is 90 mol% or more. If the amount is less than 90 mol%, it is difficult to obtain a composition having excellent properties. The polymer can be polymerized by polymerizing P-dichlorobenzene in the presence of sulfur and sodium carbonate, or in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide in a polar solvent. Examples of the polymerization method include P-chlorothiophenol self-condensation, N-
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 a preferable method 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 the content of the copolymerization component is less than 10 mol%, it does not matter if the following bond is contained, as long as it does not significantly affect the crystallinity of the polymer. In particular, when a trifunctional or higher functional phenyl, biphenyl, naphthal sulfide bond or the like is selected for the copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

[0016]

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Such a PPS resin is produced by a general method, for example, (1) a reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 2,513,188, JP-B-44).
-27671 and Japanese Patent Publication No. 45-3368)
(2) Condensation reaction of thiophenols in the presence of an alkali catalyst or 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).
(See No. 7), etc., and can be arbitrarily selected according to the purpose.

At least one metal corrosion reducing agent to be added in the present invention is selected from the following. It is at least one selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate. Regarding zinc carbonate, commercially available basic zinc carbonate can be used as a reagent as long as the object of the present invention is not impaired.

The amount of the compound added in the present invention is preferably 0.01 based on 100 parts by weight of the PPS resin.
10 to 10 parts by weight, and such an addition amount is not preferable because the effect of reducing the metal corrosive gas is large, the melt fluidity of the composition is lowered, and the strength is further lowered.

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

The composition of the present invention may contain a lubricant such as graphite, molybdenum disulfide and polytetrafluoroethylene, and a stabilizer thereof.

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

Further, the composition of the present invention is an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent, a silane coupling agent, within a range not impairing the object of the present invention.
Not restricted by the addition of mold release agents.

Further, in the composition of the present invention, other thermosetting resins and thermoplastic resins such as epoxy resins, silicone resins, polyimides, polyphenylene ethers, polyamides, polycarbonates, polysulfones are included within the range not impairing the object of the present invention. , Polyether sulfone, polyarylate, polyacetal, polyether ketone, polyether ether ketone, polybutylene terephthalate, polyethylene terephthalate, polyamide imide, polyether imide, etc. can be blended in small amounts of one or more kinds.

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

The composition of the present invention is applied to various uses such as electric / electronic parts, mechanical parts and automobile parts. When it is used as an insulating material, it is used as an industrial material such as a switch part. It is useful.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Next, preferred embodiments of the present invention will be described. 1. Polyphenylene sulfide resin, at least one metal corrosion inhibitor selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate, and at least one lubricant selected from graphite, molybdenum disulfide, and polytetrafluoroethylene. A polyphenylene sulfide resin composition comprising the addition of:

2. Polyphenylene sulfide resin 10
The metal corrosion reducing agent is added in an amount of 0.01 to 1 with respect to 0 part by weight.
The polyphenylene sulfide resin composition according to 1 above, which is added in an amount of 0 part by weight.

[0029]

The present invention will be further described with reference to the following examples. The test values of the respective characteristics 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 was placed in a metal closed container 1, and C: was placed on a 20 mesh wire net 3 fixed by a supporting metal plate 4 therein. 1.5% by weight, Cr: 12.0% by weight, M
o: 1.0 wt%, V: 0.4 wt% SKD-11 steel material block 5 (surface roughness 3 μm or less), which is a high alloy tool steel, 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 and placed in a constant temperature and humidity bath at 70 ° C./95% RH for 6 hours, and then the corrosion state of the steel material is observed.

<Water resistance> From granulated pellets, 1.6
A mm-thick dumbbell test piece for a tensile test was formed, and the test piece was subjected to pressure cooker treatment at 120 ° C. under a condition of ² kgf / cm ² for 30 hours (after PCT), and then the tensile strength was measured to obtain an initial strength. Compared. (Tensile strength is AST
MD-638 compliant)

<Insulation characteristics> 1.6 from granulated pellets
After molding a disc for ASTM D-257 having a thickness of mm, the test piece was subjected to pressure cooker treatment at 120 ° C. under the condition of ² kgf / cm ² for 30 hours (after PCT), and then the volume resistivity value was measured to obtain an initial value. Compared with. (Volume resistivity measurement is based on ASTM D-257)

Reference Example 1 (Synthesis of PPS Resin) A 50 liter scale autoclave was charged with N-methylpyrrolidone in a molar ratio of 70 and sodium sulfide nonahydrate in an amount of 0.1.
99, sodium benzoate (0.60) and sodium hydroxide (0.15 mol) were charged (50 mol scale), and the temperature was raised to 210 ° C. in a nitrogen stream to perform dehydration to a dehydration rate of 110%. The system was cooled to 160 ° C, charged with P-dichlorobenzene at a molar ratio of 1.0, sealed, and then the internal pressure was adjusted to 2 with nitrogen.
The pressure was increased to 5 kg / cm ² . The temperature is controlled to 270 ° C while controlling the heat generated by polymerization,
Polymerization was carried out with stirring for an hour. Internal pressure is 17 kg / cm ²
Was rising to. Next, the system was cooled and then depressurized, and the contents were poured into a large amount of water to recover a flake-like polymer. The polymer was repeatedly washed with hot water and acetone until the final 7
It was a white flake with a yield of 0%.

The PPS resin powder was put into a ribbon blender and stirred at 270 ° C. while blowing air,
PPS was partially crosslinked in the powder state and heat-treated until the intrinsic viscosity finally reached 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 compounding ratio shown in the table, and then 35 mmφ 2
The mixture was melt-kneaded at 320 ° C. with a shaft extruder to obtain pellets. The pellets were used to evaluate metal corrosion.

Further, the pellets are in-line screened.
Use a 3 ounce injection molding machine with a cylinder type and a cylinder temperature of 3
20 ℃, mold temperature 150 ℃, injection pressure 1000kgf /
cm ²Water resistance and insulation characteristics evaluation at medium injection speed
A test piece was molded and both properties were evaluated. This result is the first
Shown in the table.

[0037]

[Table 1]

Examples 2 to 3 and Comparative Examples 6 to 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 in a 35 mmφ twin-screw extruder. Melted and kneaded at 320 ° C. to obtain pellets. The pellets were used to evaluate metal corrosion.

Further, the pellets were heated at a cylinder temperature of 32 using an inline screw type 3 ounce injection molding machine.
0 ℃, mold temperature 150 ℃, injection pressure 1000kgf / c
A 1.6 mm thick dumbbell for a tensile test was molded at m ² at a medium injection speed to evaluate the water resistance. The results are shown in Table 2.

[0040]

[Table 2]

[0041]

EFFECTS OF THE INVENTION The composition of the present invention significantly reduces the metal corrosive gas generated from the PPS resin, thereby forming the metal mold, the metal part of the assembly part using the molded product, and the insert metal part, etc. It significantly reduces the corrosion of the steel, and also has good water resistance and excellent moisture-proof insulation properties when used as an insulating material.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a state in which metal corrosiveness of each pellet-shaped composition of an example of the present invention and a comparative example is tested.

[Explanation of symbols]

 1 Metal Closed Container 2 Pelletized Resin Composition 3 20 Mesh Wire Mesh 4 Support Metal Plate 5 Steel Block

Claims (3)

[Claims] 1. A polyphenylene sulfide resin containing at least one metal corrosion inhibitor selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate, calcium titanate, silicon carbide, bentonite, sericite, zeolite and PMF. Polyphenylene sulfide resin composition, characterized in that at least one reinforcing material, filler or lubricant selected from the group consisting of, ferrite, dolomite, antimony trioxide, glass balloon, graphite, molybdenum disulfide and polytetrafluoroethylene is added. Stuff. 2. A polyphenylene sulfide resin containing at least one metal corrosion inhibitor selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate, and at least one selected from graphite, molybdenum disulfide and polytetrafluoroethylene. A polyphenylene sulfide resin composition, characterized in that it is added with a lubricant. 3. A polyphenylene sulfide resin 100.
The amount of the metal corrosion reducing agent is 0.01 to 10 parts by weight.
The polyphenylene sulfide resin composition according to claim 1 or 2, which is added by weight.