JPH02191665A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of diminishing mold corrosion in its molding processing and corrosion of the metallic parts of assembled components using the molded product thereof, thus suitable for e.g. electrical insulating materials by incorporating a polyphenylene sulfide resin with a specified amount of mold corrosion reducer(s) selected from zinc carbonate etc. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100 pts.wt. of a polyphenylene sulfide resin with (B) 0.01-10 pts.wt. of at least one mold corrosion reducer selected from zinc carbonate, manganese carbonate and magnesium carbonate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention reduces the corrosion of molds during molding and the corrosion of metal parts of assembled parts using the molded products. (abbreviated as)) relates to a resin composition.

[Prior art]

PPS resin has extremely high heat resistance and chemical resistance.

It has electrical properties and flame resistance, and when further strengthened with reinforcing fillers, it has excellent mechanical strength.

It is known to exhibit rigidity and stability in two dimensions, and is widely used in various molding applications such as electrical/electronic parts, automobile parts, and even mechanical parts.

However, pps resin generates metal corrosive gas at high temperatures and when melted, which can corrode the mold and molding machine during molding. In this process, corrosion occurs in the metal parts of the assembled parts using the molded product, or the insert metal parts corrode.

For example, if pps resin is used for the relay base,
Relay gold J! ! Problems have occurred such as poor contact due to corrosion of the contacts, and poor solder adhesion on the metal insert due to corrosion.

In order to solve this problem, a method of adding an alkali metal hydroxide or carbonate base (US Pat. No. 4,017,450) has been proposed.
(No.) and method of adding hydroxides, oxides, and aromatic cargenates of metals from group M of the periodic table (Japanese Patent Application Laid-open No. 62-10985
No. 0) are known.

However, in both cases, sufficient effects were not obtained;
Furthermore, since the additives themselves are water-soluble or have hygroscopic properties even if they are not water-soluble, the addition of the above-mentioned compounds lowers the water resistance.

Furthermore, when used as an insulating material reinforced with glass fiber or the like, the current situation is that the insulation properties under high humidity conditions are significantly reduced.

[Inventions to Solve Section J]

The present invention takes advantage of nine excellent properties of pps resin, and
Particularly for water resistance and insulating materials, without deteriorating the insulation properties under high humidity conditions when C is used.

Another object of the present invention is to provide a PPS resin composition in which corrosion of the mold during molding, corrosion of the metal parts of the assembled parts used for the molded product, and corrosion of the insert metal parts are reduced.

Means for Solving Problem C] The present invention provides a PPS resin composition comprising adding at least one mold corrosion reducing agent selected from a) zinc carbonate b) manganese carbonate C) magnesium carbonate to a pps resin. Provide item 1.

The most important feature of the composition of the present invention is that the corrosion resistance to the metal parts of the molding die and the assembled parts using the molded product, as well as the insert metal parts, is significantly reduced, and furthermore, it has particularly good water resistance. Also, when used as an insulating material, it has excellent insulating properties under high humidity.

As mentioned above, many of the hydroxides and carbonates in group 1A of the periodic table are easily soluble in water, and many of the oxides and oxides in group Q7 of the periodic table are highly hygroscopic. .

On the other hand, the mold corrosion reducing agent added in the present invention is a-soluble in water and has an extremely high ability to capture metal corrosive gases such as pps resin. Furthermore, the composition of the present invention significantly reduces the metal corrosive fs generated by pps resin, has significantly improved water resistance, and has a long-term durability when used as an insulating material. It is preferable that the composition contains t-90 moles or more of the structural unit, which exhibits excellent insulation properties such as the ability to maintain volume resistivity under high humidity. If the amount is less than 90 molar, compositions with excellent properties may not be obtained. The polymerization method for this polymer is as follows:
A method for polymerizing P-dichlorobenzene in the presence of sulfur and sodium carbonate, a method for polymerizing P-dichlorobenzene in the presence of sodium sulfide or sodium bisulfide and sodium hydroxide or sodium sulfide or sodium hydroxide in a polar solvent, Examples include self-condensation of ruthiophenol, but there is also a method in which sodium sulfide and P-dichlorobenzene are reacted in an abad solvent such as N-methyl vicritone or zomethylacetoid, or a sulfone solvent such as sulfolane. Appropriate. At this time, in order to adjust the degree of polymerization, it is preferable to add an alkali metal salt of calgenic acid or sulfonic acid, ttrS, or to add alkali gold hydroxide. Co-components include lOmolti unassociated +0~ri←S~ ), sulfone bond (-kuri) -so□- (large←S-), piphenyl bond (-@Σ-@-S-), substituted phenyl sulfide-linked enyl (representing an alkoxy group), trifunctional phenyl may be used as long as it does not significantly affect the crystallinity of Tellimer, but preferably the copolymerization component is 5 molar or less. Especially 3
When phenyl, biphenyl, naphnal sulfide bonds, etc. having higher functionality are selected for copolymerization, the mole ratio is preferably 3 molar or less, more preferably 1 molar or less.

Such PPS resins can be produced by common manufacturing methods, such as (1) reaction of an octyrin-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. 45-3368) (2) Condensation reaction of thiophenols in the coexistence of an alkali catalyst or complex salt, etc. (U.S. Pat. No. 3,274,165, British Patent No. 1)
! 60660) (3) Condensation reaction of aromatic compounds with sulfur chloride in the presence of a Lewis acid catalyst
No. 27255, Belsee Patent No. 29437), etc., and can be arbitrarily selected depending on the purpose.

The mold corrosion reducing agent added in the present invention is at least one
Species are selected from below.

At least one member selected from a) zinc carbonate, b) manganese carbonate, and C) magnesium carbonate. As for zinc carbonate, basic zinc carbonate, which is commercially available as a reagent, can be used as long as the purpose of the present invention is not impaired.

The amount of the compound added in the present invention is preferably 0.01 to 10 parts by weight per 100 parts by weight of the PPS resin. If this amount is added, the effect of reducing metals and corrosive gases is large, and the composition Dissolving things M? ! This is not preferable because it reduces the mobility and further reduces the strength.

The composition of the present invention has the following features in order to improve mechanical properties:
Various reinforcing materials and fillers can be added. Examples of reinforcing materials and fillers that can be used in the present invention include glass fiber, carbon fiber, calcium titanate, silicon carbide,
Ceramic fibers, metal fibers, silicon nitride, sulfuric acid/sodium, calcium sulfate, kaolin, clay, bentonite, sericite, zeolite, mica, mica, talc, wollastonite, PMF, ferrite, calcium silicate.

Calcium carbonate, dolomite, antimony dioxide.

Examples include titanium oxide, amorphous iron, silt lath, glass beads, and glass a4) Lt-ton.

The composition of the invention includes graphite and molybdenum disulfide.

Lubricants and stabilizers thereof, such as I-retetrafluoroethylene, may be included.

In addition, the composition of the present invention may contain an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a coloring agent, a silane coupling agent, and a mold release agent within a range that does not impair the purpose of the present invention. No restrictions are imposed by the addition.

Furthermore, the composition of the present invention may contain other thermosetting resins and thermoplastic resins, such as epoxy resins, silicone resins, and I-limide, within a range that does not impair the object of the present invention.

polyphenylene ether, /ria i-do, polycarmenate #irisal 7-on, polyether sal 7-on, 4-real arylate, polyacetal, polynee f ketone, yj
e riether ether ketone, f! Ligethylene terephthalate, I-liethylene terephthalate,! Reazu Toimido, /Reaterui can lend a small amount of t2 to one or more types of gold such as Do.

Compositions of the invention can be prepared in a variety of known ways. For example, the PPS resin and the compound to be added in the present invention are mixed in advance in a Henschel mixer or Tang 2, and then fed to a single or twin screw extrusion kneader or the like.
It can be obtained by melt-kneading and granulating at a temperature of 360°C to 360°C. During mixing, other reinforcing materials, fillers, and various additives may be added as necessary.

The composition of the present invention can be applied to electrical/electronic parts 1 mechanical parts.

It is applied to various applications such as automobile parts, but especially when used as an insulating material, it is used for switch parts,
It is useful as an industrial material for relay parts, connectors, etc.

〔Effect of the invention〕

The composition of the present invention significantly reduces the metal corrosive gas generated from PPS resin, thereby significantly reducing the corrosion of metal parts of molds and molded products used for subsequent assembly, as well as KFi insert metal parts, etc. 1) Furthermore, when used as an insulating material, it has good water resistance and excellent moisture-resistant insulation properties.

〔Example〕

The present invention will be further explained below with reference to Examples.

The test values for each characteristic shown in this example were obtained using the following method.
This is based on the standards.

<Metal Corrosion> As shown in Figure 1, granulated pellets 2 10014 each
- Placed in a metal airtight container l and placed on a 20-mesh wire mesh 3 fixed therein by a supporting metal plate 4, C: 1.5% by weight, Cr: 12.0wt Ji4, Mo: 1.
SKD-11 steel block 5 (surface roughness of 3 μm or less), which is a high alloy tool steel having a composition of 0% by weight and V: 0.4% by weight, was placed and heat treated at 340° C. for 6 hours. After the heat treatment, the 5KD-11m steel block 5 was taken out and placed in a constant temperature and humidity chamber at 70° C./95% RH for 6 hours, after which the corrosion state of the steel material was observed.

Water resistance〉 A dumbbell test piece with a thickness of 1.6 mm was formed from the granulated pellet, and the # test piece was heated at 120°C at 2y f /a.
After being pressure-treated for 30 hours under conditions of m2 (after PCT), the tensile strength was measured and compared with the initial strength. (Tensile strength is based on ASTM D-638) <Insulating properties> ASTM D-257 with 1.6 glue thickness than granulated pellets
The specimen was heated to 2' pqt/cJ at 1120°C.
After pressure treatment for 30 hours under the conditions of (
After PCT) 1 Volume resistivity was measured and compared with the initial value. (Volume resistivity measurement is based on ASTM D-257) Reference example 1 (Synthesis of PPS resin) 501 scale autoclaved KN-methyl vicritone in a molar ratio of 70 and sodium sulfide nonahydrate as 0.99
, sodium benzoate 0.60, sodium hydroxide 'i0. The mixture was charged at a molar ratio of X5 (50 molar scale) and heated to 210"C in a nitrogen stream to achieve a dehydration rate of 110%. After cooling the system to 160°C, P-dicalbenzene was added at a molar ratio of 1.0 After filling and sealing, the mixture was pressurized with nitrogen to an internal pressure of f25 kg/e!n2.The temperature was controlled while taking into account the heat generated by polymerization, and the temperature was raised to 270°C, and polymerization was carried out with stirring for 5 hours. The internal pressure was 17
It had increased to q7cJ. Next, after the system was cooled, the pressure was released, and the internal solution was poured into a large amount of water to recover Flay 7-shaped I remer. After washing with hot water and acetone, the final product was white with a yield of 70%.

This PPS resin) I powder was added to Regen Prengie 9, and stirred at 270°C while blowing air.

PPS f was partially crosslinked in the Notau l-state and heat-treated until the final intrinsic viscosity reached 0.3K.

Examples 1 to 6 and 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 blending ratios shown in the table.

The mixture was melt-kneaded at 320° C. using a No. 35 twin-screw extruder to obtain a pellet. This pellet was used to evaluate metal corrosion.

Furthermore, this pellet was molded using an in-fin screw type 3 oz injection molding machine at a cylinder temperature of 320°C and gold moulding.
mvxso℃, injection pressure 11000I x /cytg
A test piece for evaluating water resistance and insulation properties was molded at a medium injection speed, and both properties were evaluated. The results are shown in Table 1.

Examples 7 to 10 and Comparative Examples 6 to 7 Using the PSS resin synthesized in Reference Example 1, the raw materials shown in Table 2 were mixed uniformly in the proportions shown in the table, and then mixed in a 35-diameter twin-screw extruder. A pellet was obtained by melt-kneading at 320°C. This pellet) 1 was used to evaluate metal corrosion.

Furthermore, an in-line screw type 3-ounce injection molding machine was used for this pellet', and the cylinder temperature was 320°C, the mold temperature was 150°C, and the injection pressure was 1000 kljl f/am.
2. Dumbbells for tensile testing with a thickness of 1.6 mm were molded at medium injection speed and water resistance was evaluated. This result is the second
Shown in the table.

/ 〆 ///

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of the pellet-shaped compositions of Examples of the present invention and Comparative Examples in which metal corrosivity was tested. DESCRIPTION OF SYMBOLS 1... Metal airtight container, 2... Pellet-shaped resin composition, 3... 20 messier wire mesh, 4... Support metal plate, 5... Steel block.

Claims (2)

[Claims] (1) A polyphenylene sulfide resin composition characterized in that at least one mold corrosion reducing agent selected from a) zinc carbonate b) manganese carbonate c) magnesium carbonate is added to the polyphenylene sulfide resin. (2) Add 0.01 to 0.01 to 100 parts by weight of the metal corrosion reducing agent according to claim 1 to 100 parts by weight of polyphenylene sulfide resin.
A polyphenylene sulfide resin composition characterized by adding 10 parts by weight.