JPH05179142A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has a low corrosiveness. CONSTITUTION:The title compsn. comprises 20-99.9wt.%. polyarylene sulfide resin, 0.1-10wt.% composite material consisting of zinc oxide, titanium dioxide, and water, and 0-70wt.% fibrous filler and/or inorg. filler.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyarylene sulfide resin composition. More specifically, it relates to a polyarylene sulfide resin composition having a significantly reduced metal corrosion property.

[0002]

2. Description of the Related Art Polyarylene sulfide resins have been drawing attention in recent years as engineering plastics having excellent heat resistance, chemical resistance and flame retardancy. Taking advantage of these various characteristics, they are used in the fields of automobile parts and electric / electronic parts. And so on, there is a big demand growth. However,
When the polyarylene sulfide resin is used as a film, fiber, or molded body in electric / electronic parts, the corrosiveness of the polyarylene sulfide resin is reduced in order to exhibit the original moldability and electrical insulation of the polyarylene sulfide resin. It is necessary. For example, when the polyarylene sulfide resin is used as it is as a coating / sealing material for electronic parts, the electrodes, wirings, lead frames, etc. of parts are often corroded, causing troubles.

As a method for reducing the corrosiveness of the polyarylene sulfide resin, a method of adding a hydrotalcite compound to the polyarylene sulfide resin (for example, JP-A-60)
-186561), zinc carbonate, manganese carbonate,
A method of adding magnesium carbonate (for example, Japanese Patent Laid-Open No. 2-1
91655, etc.), a method of adding activated carbon (for example, Japanese Patent Application Laid-Open No. 1-294770, etc.), a method of adding fine calcium carbonate (for example, Japanese Patent Application No. 1-281809, etc.) and the like are known. However, in any of the methods, the effect of reducing corrosiveness is insufficient.

A method of adding a carbonate, silicate or hydroxide of an alkali metal to a polyarylene sulfide resin for the same purpose (US Pat. No. 4,017,450)
It has been known. However, these effects are not sufficient, and there is a problem that they adversely affect the electrical properties. Further, lithium carbonate, which has a relatively good performance, has an economical problem that it is expensive and a problem that the mechanical strength is lowered by its addition, and further improvement in corrosion resistance is desired.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a polyarylene sulfide resin which is improved in the above problems, reduces the metal corrosiveness of the polyarylene sulfide resin, and is less corrosive than conventional products. ..

[0006]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in order to reduce the metal corrosiveness of polyarylene sulfide resins in view of the above-mentioned current situation. As a result, they have found that the metal corrosion of the polyarylene sulfide resin is remarkably reduced by adding a complex composed of zinc oxide, titanium dioxide and water, and have completed the present invention.

That is, the present invention provides (A) a polyarylene sulfide resin in an amount of 20% by weight to 99.9% by weight, and (B) a composite of zinc oxide, titanium dioxide and water in an amount of 0.1% by weight to.
A resin composition comprising 10% by weight of (C) a fibrous filler and / or 0% by weight to 70% by weight of an inorganic filler.

The present invention will be described in detail below.

The polyarylene sulfide resin of the component (A) used in the present invention has a repeating unit of the general formula -Ar
It is a polymer selected from one kind or two or more kinds represented by -S-. Here, specifically, -Ar-S-
Examples include those composed of the following structural units.

[0010]

[Chemical 1] (However, in the formula, R ₁ and R ₂ are each a hydrogen atom, an alkyl group,
A phenyl group, an alkoxyl group, a nitro group, a halogen atom, an alkylene glycol group, a hydroxyl group, a nitrile group, a carboxyl group, a sulfone group or an amino group is shown. Further, in the formula, X represents a methylene, ethylene, isopropyl, ether, ketone or sulfone group. However, a polyphenylene sulfide resin is particularly preferable. Polyphenylene sulfide resin has the general formula

[0011]

[Chemical 2] 70 mol% or more of the structure having the repeating unit represented by
Other components may be copolymerized as long as the content is preferably 90 mol% or more.

Polyarylene sulfide resins are generally used in JP-B-44-2761, JP-B-45-3368, US Pat. No. 3,274,165, and JP-B-4.
A polymer having a relatively small molecular weight obtained by a production method represented by JP-A-6-27255, and JP-B-52-12.
There is an essentially linear and relatively high molecular weight polymer typified by JP-A-240 No. 240, and the former polymer is heated by heating in an oxygen atmosphere or in the presence of a crosslinking agent such as peroxide. It is also possible to use it after it is polymerized.

The melt viscosity of a polyarylene sulfide resin suitable for use in the present invention (300 by a Koka type flow tester (die: diameter = 0.5 mm, length = 2 mm))
C., 10 kg load) is 100 to 50,000 poises for an essentially linear and relatively high molecular weight polymer,
Preferably, those having a poise of 300 to 30,000 can be used. If the polymer has a high degree of polymerization by heating in the presence of a crosslinking agent, the melt viscosity before heat treatment is 1
The melt viscosity after heat treatment is 100 to 50,000 poise, preferably 200 to 10,000 poise.
30,000 poise can be used. Here, if the melt viscosity is less than 100 poise, the mechanical strength is lowered, which is not preferable. Also, if it exceeds 50,000 poise,
Moldability is disadvantageous, which is not preferable.

Next, the component (B) used in the present invention is a complex composed of zinc oxide, titanium dioxide and water, which contains a mixture of zinc oxide and titanium dioxide as a main component and contains some water. It is a complex that presents a fine white powder that may be obtained.

This complex was prepared by collecting, washing and drying a white precipitate consisting of zinc oxide, titanium dioxide and water produced by mixing a mixed aqueous solution of a water-soluble zinc compound and a water-soluble titanium compound with a basic aqueous solution. Is obtained.

As a raw material for the production of a composite of zinc oxide, titanium dioxide and water suitable for use in the present invention, a water soluble zinc compound, a water soluble titanium compound and a basic aqueous solution are used. Be done. As the zinc compound, for example, zinc sulfate, zinc chloride, zinc nitrate, zinc acetate or the like can be used, and as the titanium compound, for example, titanium sulfate, titanyl sulfate, titanium chloride, titanium nitrate or the like can be used. As the basic aqueous solution, for example, an aqueous solution of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonia or the like can be used. However, when the zinc compound or the titanium compound is a sulfate, it is not preferable to use calcium hydroxide or barium hydroxide as the basic aqueous solution because a salt insoluble in water is produced.

Next, as a method for preparing a complex composed of zinc oxide, titanium dioxide and water using the above raw materials, for example, a water-soluble zinc compound and a water-soluble zinc compound are mixed under stirring in an overflow type reaction tank equipped with a stirring device. A method of obtaining a precipitate by simultaneously and continuously supplying both aqueous solutions of titanium compounds and a basic aqueous solution to obtain a reaction, and a method in which a water-soluble zinc compound and a water-soluble zinc compound are mixed in a reaction tank under stirring conditions without discharging the reaction slurry out of the system. Examples of the method include a method in which both aqueous solutions of a water-soluble titanium compound and a basic aqueous solution are simultaneously supplied and reacted to obtain a precipitate. By either method, the pH of the mixed solution in the reaction tank is 6 to
It is important to mix so that the pH is 11, preferably 7-9. When the pH of the mixed solution during the reaction is lower than 6 or higher than 11, the solubility of zinc hydroxide in the aqueous solution is large and the yield of zinc in the precipitate is unfavorably low.

During the preparation of the complex consisting of zinc oxide, titanium dioxide and water, Z is changed by changing the mixing ratio of zinc oxide (ZnO) and titanium dioxide (TiO ₂ ).
It is possible to obtain a composite in which the molar ratio of nO / TiO ₂ is arbitrarily selected. Zinc oxide suitable for use in the present invention,
ZnO / TiO ₂ composite of titanium dioxide and water
The molar ratio of is not particularly limited, but is preferably in the range of 1/9 to 9/1, and particularly preferably in the range of 3/7 to 7/3.
However, when the molar ratio of ZnO / TiO ₂ is less than 1/9, Ti
In a composition region containing a large amount of O ₂ or a composition region containing a larger amount of ZnO than 9/1, it is difficult to sufficiently exhibit the performance of improving the corrosiveness due to the combined effect of ZnO and TiO _2.
It is desirable to use it within the range of 1.

The amount of water present in the composite is not particularly limited, but it is preferably in the range of 0 to 4 mol, and particularly preferably anhydrous, with respect to the total amount (1 mol) of zinc oxide and titanium dioxide. If the amount of water present in the composite exceeds 4 moles, the moldability will suffer, which is not preferable.

The added amount of the composite of zinc oxide, titanium dioxide and water used in the present invention is such that the composite of polyarylene sulfide resin and zinc oxide, titanium dioxide and water, the fibrous filler and / or the inorganic filler. It is in the range of 0.1% by weight to 10% by weight, preferably in the range of 0.5% by weight to 8% by weight, based on the total amount of the material. Here, if the addition amount is less than 0.1% by weight, the effect of reducing the corrosiveness is poor, and if it exceeds 10% by weight, the mechanical strength after molding decreases, which is not preferable.

The fibrous filler of the component (C) used in the present invention includes glass fiber, carbon fiber, graphitized fiber,
Whiskers, metal fibers, inorganic fibers, organic fibers, ore fibers, etc. can be used.

The following are examples of these fibrous fillers.

Examples of the glass fibers include glass fibers coated with metal such as nickel and copper, silane fibers, aluminosilicate glass fibers, hollow glass fibers and non-hollow glass fibers in addition to ordinary glass fibers.

Examples of carbon fibers include PAN-based fibers made of polyacrylonitrile and pitch-based fibers made of pitch.

Examples of the inorganic fibers include various fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica and blast furnace slag.

Examples of the ore fiber include asbestos, wollastenite, magnesium oxysulfate and the like.

Examples of the organic fibers include wholly aromatic polyamide fibers, phenol resin fibers, wholly aromatic polyester fibers and the like.

Examples of the whiskers include silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers and the like.

Next, the inorganic filler of the component (C) used in the present invention is a plate-like or powdery inorganic substance. For example,
Calcium sulfate, barium sulfate, lithium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, talc, mica, clay, silica, alumina, kaolin, zirconia, gypsum, calcium silicate, magnesium silicate, aluminum silicate, calcium phosphate, phosphate Filling with magnesium, zinc phosphate, apatite, titanium oxide, zinc oxide, copper oxide, iron oxide, tin oxide, magnesium oxide, carbon black, graphite, glass powder, glass balloons, quartz, quartz glass, hydrotalcite, zeolite, etc. I can list materials.

The amount of the fibrous filler and / or the inorganic filler added is based on the total amount of the composite of the polyarylene sulfide resin, zinc oxide, titanium dioxide and water, the fibrous filler and / or the inorganic filler. It is in the range of 0% by weight to 70% by weight, preferably in the range of 20% by weight to 50% by weight. Here, the compounding ratio of the fibrous filler and / or the inorganic filler is not particularly limited. However, if the addition amount of the fibrous filler and / or the inorganic filler exceeds 70% by weight, it is not preferable because it causes a difficulty in moldability.

Further, the fibrous filler and / or the inorganic filler used in the present invention may be used in combination with a commonly used known surface treatment agent or sizing agent in order to enhance the adhesiveness with the polyarylene sulfide resin. Possible and preferred. Examples thereof include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after subjecting the filler to a surface treatment or a converging treatment in advance, or may be added at the same time when the material is prepared.

Further, with respect to the composition of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, coloring agents such as dyes and pigments, etc. One or more ordinary additives such as a flame retardant, a flame retardant aid and an antistatic agent may be added.

If necessary, polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, poly α-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylic acid ester,
Polymethacrylic acid ester, polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 1
2, polyamide such as nylon 11, nylon 46, polyphthalamide resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyester such as liquid crystal polymer, polyurethane, polyacetal,
Homopolymers such as polycarbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyimide, polyetherimide, polyamideimide, silicone resin, phenoxy resin and fluororesin, random or block, graft copolymer It is also possible to mix and use one or more polymers.

The resin composition of the present invention is obtained by melt-kneading the above-mentioned components. For example, after the above components are mixed in advance, they can be melt-kneaded and pelletized by using a Banbury mixer, a roll kneader, a uniaxial kneader, a biaxial kneader or the like.

The temperature of melt kneading is generally from 300 ° C to 42 ° C.
It can be carried out at a temperature of 0 ° C. The pellets obtained are
It can be molded into an arbitrary shape by using ordinary extrusion molding, injection molding, compression molding, or the like.

[0036]

EXAMPLES Next, the present invention will be described more specifically by showing Examples and Comparative Examples, but the present invention is not limited to these. The corrosion test of the polyarylene sulfide resin composition used in the following examples was conducted by the following method.

Corrosion test (I) 30 g of pellets of the polyarylene sulfide resin composition was put in a weighing bottle as shown in FIG. 1, and a lead frame plated with solder was put therein to 200 ° C.
Heated in oven for 48 hours. Next, the petri dish was placed in a thermostat / humidity bath at a temperature of 85 ° C. and a humidity of 85% for 10 hours. Then, the petri dish was cooled to room temperature, and the corrosion degree of the solder-plated lead frame was visually determined.

Judgment ⊚: No discoloration ○: Slightly discoloration Δ: Gray discoloration ×: Black discoloration (II) 30 g of the pellet of the polyarylene sulfide resin composition was placed in a weighing bottle as shown in FIG. A mold material (made by Daido Steel Co., Ltd., PD-613, 3.0 mm (thickness) × 25 mm × 25 mm) was put and heated in an oven at 330 ° C. for 4 hours. Next, put the dish on a temperature of 85 ° C.
The sample was placed in a constant temperature / humidity bath having a humidity of 85% and treated for 1 hour.
Then, the petri dish was cooled to room temperature, and the corrosion degree of the die material was visually evaluated.

Judgment ⊚: No discoloration ○: Slightly discoloration Δ: Gray discoloration ×: Black discoloration Reference Example 1 The polyarylene sulfide resin used in the present invention was synthesized as follows. Sodium sulfide Na ₂ S.2.9H ₂ O 1.8 mol, N-
Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 4.5k
g was added, and the mixture was stirred under a nitrogen stream and heated to 200 ° C., and 636 g of a distillate mainly composed of water was distilled off. After cooling the system to 170 ° C., 1.8 mol of p-dichlorobenzene was added to NM
P1.5kg and add the system under a nitrogen stream,
The temperature was raised and polymerization was carried out at 250 ° C. for 3 hours. After completion of the polymerization, the system was cooled, the contents were put into water to precipitate the polymer, and the precipitated polymer was collected with a glass funnel,
The polymer was isolated by repeatedly washing with 10 l of warm water and repeating filtration and heating and vacuum drying overnight. The polymer obtained is 1.
85 kg, yield 95%, melt viscosity (value measured at 300 ° C. with a die of diameter = 0.5 mm, length = 2 mm, load 10 kg, using a Koka flow tester) 25
It was 0 poise. Next, the obtained polymer is added to the air in 2
It was placed in an oven set at 50 ° C. and cured as it was for 3 hours to obtain a polyphenylene sulfide resin having a melt viscosity of 1400 poise. Hereinafter, it is abbreviated as PPS.

Reference Example 2 The complex composed of zinc oxide, titanium dioxide and water used in the present invention is as follows.

In this composite, a mixed aqueous solution of zinc sulfate as a ZnO raw material and titanium sulfate as a TiO ₂ raw material, and an aqueous ammonia solution were treated at about 60 ° C., taking care to maintain the pH of the total mixed solution at 7.5. It is a white fine powder obtained by gradually dropping it into pure water to form a precipitate, and separating, washing and drying the precipitate. A desired ZnO / TiO ₂ (molar ratio) composite is obtained by converting and mixing ZnO and TiO ₂ in the mixing ratio of zinc sulfate and titanium sulfate, respectively.

The ZnO / T of the various composites obtained are described below.
iO ₂ (molar ratio) and BET surface area are shown.

Examples 1 to 6 PPS obtained in Reference Example 1, glass fiber (chopped strand) and the composite prepared in Reference Example 2 were mixed in a composition shown in Table 1 and a twin-screw extruder (Ikegai Tekko Co., Ltd. ), PCM-4
Using 5), extrusion granulation was performed at a temperature of 330 ° C. to obtain pellets.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then the corrosiveness tests (I) and (II) were conducted. The results are shown in Table 1.

Comparative Example 1 PPS and glass fibers (chopped strands) obtained in Reference Example 1 were mixed in a composition shown in Table 1, and a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) was used. Extrusion and granulation were performed at a temperature of ° C to obtain pellets.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then the corrosion tests (I) and (II) were conducted. The results are shown in Table 1.

Comparative Example 2 PPS obtained in Reference Example 1, glass fibers (chopped strands) and zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in a composition shown in Table 1 and a twin-screw extruder (Ikegai Tekko Co., Ltd.) was used. Manufactured by P
CM-45) was used to extrude and granulate at a temperature of 330 ° C. to obtain pellets.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then the corrosiveness tests (I) and (II) were conducted. The results are shown in Table 1.

Comparative Example 3 PPS obtained in Reference Example 1, glass fiber (chopped strand) and titanium dioxide (manufactured by Ishihara Sangyo Co., Ltd.) were mixed in a composition shown in Table 1 and a twin-screw extruder (Ikegai Tekko Co., Ltd. ), P
CM-45) was used to extrude and granulate at a temperature of 330 ° C. to obtain pellets.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then the corrosiveness tests (I) and (II) were conducted. The results are shown in Table 1.

Comparative Example 4 PPS obtained in Reference Example 1, glass fiber (chopped strand) and lithium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in a composition shown in Table 1 and a twin-screw extruder (Ikegai Tekko Co., Ltd.) was used. (stock)
Manufactured by PCM-45) was extruded and granulated at a temperature of 330 ° C. to obtain pellets.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then the corrosion tests (I) and (II) were conducted. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

According to the present invention, a polyarylene sulfide resin composition having reduced corrosiveness can be obtained by blending a complex of zinc oxide, titanium dioxide and water with the polyarylene sulfide resin. this is,
It can be widely used in fields where metal corrosion is a problem, such as electric / electronic parts, automobile parts, and OA precision equipment, and has a high industrial value.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a test for investigating the corrosiveness of metals with respect to heat treatment of the resins of Examples 1 to 6 and Comparative Examples 1 to 4.

[Explanation of symbols]

 1; oven 2; weighing bottle 3; petri dish 4; solder-plated lead frame or mold material 5; sample (PPS pellet)

Claims (1)

[Claims] 1. A polyarylene sulfide resin (A) 20.
% To 99.9% by weight, (B) a composite of zinc oxide, titanium dioxide and water 0.1% to 10% by weight,
(C) Fibrous filler and / or inorganic filler 0% by weight to 7
A resin composition comprising 0% by weight.