JPS62280258A - Polyphenylene sulfide resin composition and molded product obtained therefrom - Google Patents

Abstract

PURPOSE:To prevent molds or the metals of insert molded products from being corroded during molding, by blending specified amounts of dolomite and/or magnetic and silica with a polyphenylene sulfide resin. CONSTITUTION:100pts.wt. polyphenylene sulfide resin is blended with 0.05-100 pts.wt. dolomite and/or magnesite and 0-250pts.wt. silica. Dolomite or magnetic having an average particle size of not larger than 350mum is preferred. Silica may be in any form of fibrous, amorphous, spherical and hollow forms, has a size of 0.1-100mum and can be used in the form of a crystalline or non- crystalline product or a mixture thereof.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a polyphenylene sulfide (hereinafter abbreviated as PPS) resin composition that can reduce corrosion of molds during molding and metal corrosion of insert molded products. It relates to objects and their molded products.

<Conventional technology and its problems> PPS resin has excellent heat resistance and chemical resistance, and
Due to its good dimensional stability, mechanical strength, electrical properties, and moldability, it has recently been used in various fields as a high-performance engineering plastic.

However, pps resin generates a considerable amount of metal corrosive gas at high temperatures, so if the mold or molding machine is corroded during molding, or if the molded product is aged at temperatures above 100°C and below its melting point, corrosive properties may occur. Problems arise in that gas is generated and the insert metal parts are corroded.

For example, problems such as poor contact at the connector contact portion and poor solder adhesion of the metal insert may occur. In particular, when used as a sealing material for electronic components, which has been attracting attention recently, since a low molecular weight monomer is used as PPS resin, corrosive gases such as pyrochloride gas and brittle hydrogen are likely to be generated, and electronic This results in a decrease in the reliability of the parts.

Conventionally, alkali metal hydroxides or carbonates (US Pat. No. 4,01
7,450), an ammonia precursor having 0 to 8 carbon atoms (U.S. Pat. No. 4,115,344), and zinc oxide (Japanese Patent Application Laid-open No. 181.408/1989). However, because sufficient effects cannot be obtained, its use as a molding material is currently limited.

In view of the above situation, the inventors of the present invention conducted extensive studies to prevent the adverse effects of corrosive gas generation, and as a result, discovered that the addition of dolomite or magnesite to PP5I fat is effective, leading to the present invention. It is something.

That is, in the present invention, dolomite or/and magnesite Q, 0 is added to 100 parts by weight of P P S 9d fat.
A resin composition and a molded article using the same are provided to polyphenylene sulfide by adding 5 to 100 parts by weight and 0 to 250 parts by weight of silica.

The PPS resin of the present invention has 70 mol% or more of repeating units of the general formula ← = It is not possible to use . In addition, the melt flow rate of the ppsw fat can be selected at any level, but for injection molding and extrusion molding purposes, the melt flow rate measured according to ASTM D-1238-74 (315.6°C, 5 kg load) is recommended. Approximately to00~1
range is common. Also, when used as a sealing material for electronic components'! , 1111000-500 is suitable.

Dolomite in the present invention has a chemical composition of CaCOs.
It is a white or gray mineral with a specific gravity of 2.8 to 2.9 and a hardness of 3.5 to 4.0. The ore usually contains small amounts of At, 03, and Fe2O3 as impurities.
, 5i02, and the content of impurities varies somewhat depending on the ore deposit, but any of them can be used in the present invention.

Examples of dolomite ore production areas are shown in Table 1, but are not limited thereto.

Magnesite in the present invention has a chemical composition of MgCO.
It is a white or gray mineral with a glassy luster, a hardness of 3.5 to 4.5, and a specific gravity of about 6.1. The ore is usually Al
2O,, Fe2O3, 5io2, and CaO are briefly mentioned, but there is no problem in the present invention. Table 1 shows examples of magnesite ore production areas.

In the present invention, dolomite and magnesite ores are crushed into powder, or further calcined and crushed to be used as powder.

Table 1 (Location and chemical composition of dolomite and magnesite (phantom)) The average particle size of dolomite or magnesite is determined by A suitable thickness is 500 μm or less, preferably 300 μm or less.

In the present invention, the amount of dolomite or/and magnesite added is preferably (105 to 100 parts by weight, more preferably Q, 2 to 10 parts by weight, based on 100 parts by weight of PPS resin).
Parts by weight. If the amount added is too small, the effect of reducing corrosive gas will be poor, and if the amount added is too large,
This tends to cause a decrease in electrical properties and poor bath melt flow during molding.

In addition, the silica that can be added is suitable for the composition for the electronic part 8 in terms of purity, and has various types of fibrous, amorphous, spherical, and hollow silica [11 to 100 μm], and is non-standard. Crystalline, crystalline or a mixture thereof may be used. The amount of silica used is 50 to 2 parts per 10oxi parts of pps resin.
50 parts by weight is preferred. The addition of silica prevents the deterioration of electrical properties caused by dolomite and magnesite.

Various other fillers can be added to the composition of the present invention in order to improve mechanical properties.

Other fillers that can be used in the present invention include glass fibers, asbestos fibers, silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, silicon carbide whiskers, Potassium titanate whisker, calcium silicate fiber,
Fibrous fillers such as wollastonite, gypsum fiber, polyamide fiber, phenolic fiber, Merck, clay, mica, glass, calcium silicate, montmorillonite,
Fillers such as silicic acid such as bentonite, calcium carbonate, calcium sulfate, barium sulfate, etc. can be used as commercially available natural products, refined products, crushed synthetic products, and spherical and hollow products.

The above-mentioned fibrous filler can be of any diameter and length, and its preferred amount is 1 to 250 parts by weight per 100 parts by weight of the PPS resin.

The composition of the present invention includes antioxidants, heat stabilizers, lubricants, crystal nucleating agents, colorants, ultraviolet absorbers, aluminum corrosion inhibitors, fluidity improvers, within the range that does not impede the purpose of the present invention.
Additives such as coupling agents can be added. For example, mercaptosilane, vinylsilane, aminosilane,
One or more types of silane coupling agents such as epoxysilane and halosilane may be added to improve various physical properties such as moisture resistance, frequency, and fluidity during melting.

Furthermore, the composition of the present invention includes various thermosetting resins, thermoplastic resins, such as epoxy resins, silicone resins, polyester resins, polybutadiene, diallyl phthalate resins, nylon resins, Small amounts of rubber, polycarbonate, polysulfone, polyphenylene oxide, hydrogenated styrene-butadiene rubber, etc. can be added.

As a method for preparing the ppsat fat composition of the present invention,
A mixture of PPS resin, dolomite or/and magnesite, and other fillers and additives as required can be mixed directly using a Henschel mixer, ■-blender, etc., or mixed and smoked using an extruder, etc. How to do grain,
Banbury mixer 1 single screw or multi screw extruder, kneader
A method of granulating or molding after melt-kneading in a bath can be adopted.

Further, the molded article of the present invention can be obtained using the above composition by a known molding method such as injection, extrusion, or transfer compression molding. The molded products of the present invention include, for example, brackets ('74 meters), coil bobbins, color corrector forms (TV parts), shafts (TV tuners), magnetic sensor heads (tape recorders), roller brackets (computer facsimiles), solid state Relays, frames, sockets, heat insulators (hair dryer grills), capacitor housings, heater drums (discs attached to both ends of the computer facsimile's heating roller), rotating gears and fan shafts (for secondary ovens),
Headphone case, insulation biller, knob ('?), screen (hair dryer cril), capacitor, microswitch, resistor, resistor network, motor drum, plush holder, fuse holder, contact breaker, chip carriers, transistors, diodes, triodes, thyristors, varistors, converters, crystal oscillators,
Rectifier, power supply, 1. C, parts, LSI, hybrid IC, TTL and other chairs and electronic parts, knobs (rice cooker valves), gears (copy machines, gear pumps), heater covers (copy machines), mechanical seals and glands, tower packing/gums, pumps Housing (oil pump), insulator (own tdjf-enso), heat insulator, housing (magnetic lock), pump impeller, pulp, flowmeter, level gauge pulley, hook, flange, spray nozzle, pipe bracket, meter, fan, etc. Machinery/equipment parts, tie rod end stabilizers, exhaust gas circulation modulators
, battery housing, orifice (gasoline pump), sheet lead pulp (carburetor), ignition system housing, motor brush holder, alternator terminal block, connector, carburetor, distributor part, radiator part, tie rod end stabilizer, reflector, brake Automotive parts such as parts, clutch parts, temperature sensors, transmission parts, oil pumps, igniter cases, alternator sockets, tachometer housings, insulators (level gauges), joints (casmeters), cameras, gears, clocks, measuring instruments, computers Examples include precision parts such as parts.

In addition to the above, extrusion molded products such as tubes, films, and fibers are exemplified.

Electronic components encapsulated with the composition of the present invention include, for example, capacitors, resistors, resistor networks, integrated circuits, transistors, diodes, triodes, thyristors, coils, varistors, connectors, converters, crystal oscillators, Includes fuses, rectifiers, power supplies, and microswitches, etc.

Each of the above definitions of electronic components is meant broadly and broadly.

For example, the term integrated circuit includes, but is not limited to, large scale integrated circuit, TTL [transistor-transistor logic], hybrid integrated circuit, linear amplifier, operational amplifier, instrumentation amplifier, buffer amplifier, multiplier, and divider. , log/anti-log amplifier, RMS-DC converter, voltage reference, converter, conditioner, instrumentation, digital-to-analog converter, analog-to-digital converter, voltage/frequency converter, synchro-to-digital converter, Sample/Track and Hold Amplifier, CMOS
Switches and multiplexers, data acquisition subsystems, power supplies, memory integrated circuits, microprocessors
Including.

<Effects of the Invention> The PPS resin composition of the present invention is effective in preventing the adverse effects caused by the generation of corrosive gases, so it can be used for injection molding, extrusion molding,
It is possible to reduce maintenance costs for molds and molding machines during compression molding. In addition, since the Tani glaze molded product molded with the P P S M resin composition of the present invention suppresses the generation of corrosive gas, it reduces the rate of defects such as corrosion of insert gold H4 parts and poor solder adhesion. It can be greatly improved.

<Example> Hereinafter, the invention will be explained with reference to Examples and Comparative Examples.

Examples 1 to 8, Comparative Examples 1 to 10 P P S g (fat, dolomite, magnesite, silica, etc. were mixed in a Henschel mixer in the proportions shown in Table 2,
The mixture was melt-kneaded using a twin-screw extruder with a cylinder temperature of 320° C. and pelletized. The pellet was crushed, and as shown in Figure 1, α5I was placed in a test tube, a 5 x 5n steel foil was suspended inside, and heated in a 660°C solder bath for 6 minutes to observe the degree of discoloration of the copper foil. did.

The results are shown in Table 2.

As shown in Table 2, it can be seen that the composition of the present invention greatly improves the generation of metal corrosive gas.

Examples 9 to 10, Comparative Examples 11 to 12 Injection of pellets obtained in Example 5 and pellets obtained by replacing the amount of silica in Example 5 with 25 overlapping parts at a cylinder temperature of 340 ° C. The transistor was sealed using a molding machine. Thereafter, a pressure test was carried out at 121° C. and 2 atm, and the failure rate after 50 hours was 0/100.9/100. On the other hand, when the pellets obtained in Comparative Example 6 and Comparative Example 6 were similarly tested, the defect rate was 60/100.80/100.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of a test to examine the degree of generation of metal corrosive gas in the Jugetsuji derivatives of Examples 1 to 8 and Comparative Examples 1 to 10. 1... Cork stopper, 2... Thin copper wire, 6... Glass test tube, 4... Steel foil, 5... Sample (resin composition)
powder.

Claims (1)

[Claims] 1. Dolomite or/and magnesite 0.05 to 100 parts by weight of polyphenylene sulfide resin
A polyphenylene sulfide resin composition characterized in that 100 parts by weight and 0 to 250 parts by weight of silica are added. 2. Dolomite or/and magnesite 0.05 to 100 parts by weight of polyphenylene sulfide resin
A molded article using a polyphenylene sulfide resin composition containing 100 parts by weight of silica and 0 to 250 parts by weight of silica. 3. The molded product according to claim 2, wherein a metal is inserted. 4. The molded product according to claim 2, which is a sealed electronic component.