JPH06116493A - Polyarylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is very lowly corrosive to metals by mixing a polyarylene sulfide resin with an amorphous aluminosilicate, a fine metal carbonate and a fibrous or inorganic filler. CONSTITUTION:The composition is prepared by mixing 100 pts.wt. polyarylene sulfide resin with 0.1-10 pts.wt. amorphous aluminosilicate of formula I, II or III (wherein M, II and M are each an ion of a metal selected from among Mn, Fe, Co, Ni, Cu, Zn and Sn; and x >= 2), 0.1-10 pts.wt. fine metal carbonate (wherein the metal is selected from among Ca, Mg, Sr, Ba, Zn and Li) having a mean particle diameter of 0.5mum or below and a BET specific surface area of 15m<2>/g or above, and 0-300 pts.wt. fibrous filler and/or inorganic filler. This composition is very lowly corrosive to metals.

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 attracting attention in recent years as engineering plastics having excellent heat resistance, chemical resistance, and flame retardancy. Taking advantage of these various characteristics, the fields of automobile parts, electric / electronic parts, etc. 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, in order to exhibit the original molding processability and electrical insulating property of the polyarylene sulfide resin, reduce the corrosiveness of the polyarylene sulfide resin. It is necessary. For example, when a polyarylene sulfide resin is used as a coating / sealing material for electronic parts, the electrodes, wirings, lead frames, etc. of the 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 (JP-A-60-18).
6561), a method of adding zinc carbonate, manganese carbonate, magnesium carbonate (JP-A-2-191655) and the like are known. However, in any method, the effect of reducing the corrosiveness is insufficient.

Also known is a method of adding an alkali metal carbonate, silicate or hydroxide to a polyarylene sulfide resin (US Pat. No. 4,017,450). However, these effects are not sufficient, and there is a problem that the electrical properties are adversely affected. Further, lithium carbonate, which has relatively good performance, has an economical problem that it is expensive and a problem that mechanical strength is lowered due to its addition.

It is known to add a crystalline aluminosilicate (generic name: zeolite) to a polyarylene sulfide resin for the same purpose as in the present invention (JP-A-62-16).
7356, JP-A-62-295956, etc.). However, although adding crystalline aluminosilicate has a slight improvement effect, it does not corrode when it is used for coating or sealing applications of electrodes, lead frames, lead wires, etc. used in the field of electrical and electronic parts. Since the reduction of the property is insufficient, further improvement is desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a polyarylene sulfide resin which is improved in the above-mentioned problems, which significantly reduces the metal corrosiveness of the polyarylene sulfide resin, and has a lower corrosiveness than conventional products. is there.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned present situation, the present inventors have made earnest studies to reduce the metal corrosiveness of polyarylene sulfide resins. As a result, by adding both components of the amorphous aluminosilicate in which the cations in the aluminosilicate are exchanged with a specific metal ion and the specific metal carbonate, the corrosiveness of the polyarylene sulfide resin is significantly reduced. And completed the present invention.

That is, the present invention comprises (A) 100 parts by weight of a polyarylene sulfide resin, (B) 0.1 to 10 parts by weight of an amorphous aluminosilicate represented by the following general formula, M ^I ₂ O.Al ₂ O ₃ · xSiO ₂ M ^II O · Al ₂ O ₃ · xSiO ₂ M ^III ₂ O ₃ · Al ₂ O ₃ · xSiO ₂ (where M ^I , M ^II or M ^III are Mn, Fe, Co,
A metal ion selected from Ni, Cu, Zn and Sn,
x is a number of 2 or more) (C) Average particle size 0.5 μm or less, BET specific surface area 15
0.1 to 10 parts by weight of a fine metal carbonate of m ² / g or more and (where the metal is Ca, Mg, Sr, Ba, Zn, L
(D) A polyarylene sulfide resin composition having a remarkably improved corrosiveness against metals, characterized by comprising 0 to 300 parts by weight of (D) a fibrous filler and / or 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 composed of one or more units represented by -S-. Here, specific examples of -Ar-S- include those composed of the following structural units.

[0011]

[Chemical 1]

(However, 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,
It is a nitrile group, a carboxyl group, a sulfone group or an amino group. X is a methylene, ethylene, isopropyl, ether, ketone or sulfone group. ) Particularly preferred is polyphenylene sulfide resin. Polyphenylene sulfide resin has the general formula

[0013]

[Chemical 2]

The structure having a repeating unit represented by is contained in an amount of 70 mol% or more, preferably 90 mol% or more, and other components may be copolymerized.

The polyarylene sulfide resin is generally used in Japanese Examined Patent Publication (Kokoku) No. 44-2761 and Japanese Examined Patent (Kokoku) No. 45-336.
No. 8, US Pat. No. 3,274,165, Japanese Patent Publication No. 46-27255, and other polymers having a relatively small molecular weight and Japanese Patent Publication No. 52-1.
There are essentially linear and relatively high molecular weight polymers typified by Japanese Patent No. 2240, and the former polymer is highly 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 polymerization degree.

The melt viscosity of the polyarylene sulfide resin suitable for use in the present invention (using a Koka flow tester (die: diameter = 0.5 mm, length = 2 mm) 300
In the case of a polymer having an essentially linear structure and a relatively high molecular weight, the measurement of 50 to 50,000 poises, preferably 100 to 30,000 poises can be used. If the polymer has a high degree of polymerization by heating in the presence of a cross-linking agent, the viscosity before heat treatment is 50 to
It has a viscosity of 20,000 poise and has a viscosity of 1 after heat treatment.
50 to 50000 poise, preferably 200 to 3000
0 poise can be used. Here, the melt viscosity is 50
If it is less than poise, the mechanical strength is reduced to 50,000
If it exceeds the poise, a problem may occur in moldability.

Next, the amorphous aluminosilicate of the component (B) used in the present invention is a compound in which the cations of the aluminosilicate are subjected to ion exchange treatment on the particle surface with a transition metal or the like. This aluminosilicate is a compound that is amorphous, does not show a diffraction pattern due to the crystal structure by an analysis method by X-ray diffraction, and has a chemical composition represented by the following general formula.

[0018] ^{_{M I 2 O · Al 2 O}} 3 · xSiO 2 M II O · Al 2 O 3 · xSiO 2 M III 2 O 3 · Al 2 O 3 · xSiO 2 ( where, M ^I, M ^II or M ^III is Mn, Fe, Co,
A metal ion selected from Ni, Cu, Zn and Sn,
x is a number of 2 or more) Among these, those having x in the range of 2 to 100 are preferably used.

The aluminosilicate used in the present invention is obtained by first and simultaneously reacting an alkali silicate aqueous solution and an aluminum-containing aqueous solution simultaneously to obtain an alkali metal salt of aluminosilicate, which is ion-exchanged with a desired metal ion. It can be produced by processing.

As the above-mentioned alkali silicate aqueous solution, each aqueous solution of sodium silicate, potassium silicate, lithium silicate, etc., and as the aluminum-containing aqueous solution, each aqueous solution of aluminum sulfate, aluminum chloride, sodium aluminate, etc. It is preferably used.

A preferred method for preparing the above-mentioned alkali metal salt of aluminosilicate is a method in which both aqueous solutions are simultaneously and continuously supplied to an overflow type reaction tank equipped with a stirrer under agitation for reaction. Is. As another implementation method for preparing an alkali metal salt of aluminosilicate, a batch-type preparation method in which both aqueous solutions are simultaneously supplied to a reaction tank under stirring conditions without discharging the reaction slurry can of course be applied. . Next, the obtained aluminosilicate can be easily ion-exchanged by bringing it into contact with a metal ion sulfate, nitrate, or chloride aqueous solution and washing. Here, the metal ions are Mn, Fe,
Co, Ni, Cu, Zn, Sn is used.

The aluminosilicate used in the present invention is added in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin. is there. Here, the addition amount is 0.
If it is less than 1 part by weight, the effect of reducing the corrosiveness is poor, and if it exceeds 10 parts by weight, the mechanical strength after molding is lowered, which is not preferable.

The fine metal carbonate of the component (C) used in the present invention is a compound selected from calcium carbonate, magnesium carbonate, strontium carbonate, barium carbonate, zinc carbonate and lithium carbonate, and particularly Preferred are calcium carbonate, zinc carbonate and lithium carbonate.

The fine metal carbonate has an average particle diameter and BET specific surface area of 0.5 μm or less, preferably 0.1 μm or less, and BET specific surface area of 1 or less.
It is 5 m ² / g or more, preferably 25 m ² / g or more. Here, the average particle size is larger than 0.5 μm or BE
Those having a T specific surface area of less than 15 m ² / g are not preferable because the effect of reducing corrosiveness against metals is poor.

The amount of the fine metal carbonate added is 0.1 to 10 relative to 100 parts by weight of the polyarylene sulfide resin.
It is in the range of parts by weight, preferably in the range of 0.5 to 8 parts by weight. Here, if the addition amount is less than 0.1 parts by weight, the effect of reducing the corrosiveness is poor, and if it exceeds 10 parts by weight, the mechanical strength after molding decreases, which is not preferable.

The mixing ratio of the amorphous aluminosilicate of the component (B) and the fine metal carbonate of the component (C) is not particularly limited, but preferably (B) :( C) = 30 to 70: 7
It is in the range of 0 to 30. Here, when both the component (B) and the component (C) are not added to the polyarylene sulfide resin, the effect of reducing the corrosiveness of the metal is small, which is not preferable.

Further, the amorphous aluminosilicate of the component (B) and the fine metal carbonate of the component (C) used in the present invention are mixed with a resin acid, in order to improve dispersibility in the polyarylene sulfide resin. It is also possible to use it after surface-treating it with lignin or the like.

Next, the fibrous filler and / or the inorganic filler of the component (D) used in the present invention are not particularly limited,
The following fillers are used.

For example, as the fibrous filler, glass fiber, carbon fiber, graphitized fiber, whiskers, metal fiber, inorganic fiber, organic fiber, ore fiber, etc. can be used. To be done.

As the glass fibers, glass fibers coated with metal such as nickel and copper, silane fibers, aluminosilicate glass fibers, hollow glass fibers and non-hollow glass fibers can be used in addition to ordinary glass fibers.

As the carbon fibers, PAN-based fibers made of polyacrylonitrile and pitch-based fibers made of pitch are used.

As the inorganic fiber, various fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica and blast furnace slag are used.

As the ore fiber, asbestos, wollastenite, magnesium oxysulfate, etc. are used.

As the organic fibers, wholly aromatic polyamide fibers, phenol resin fibers, wholly aromatic polyester fibers and the like are used.

As the whiskers, silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers and the like are used.

Next, the inorganic filler is a plate-like or powdery inorganic substance such as calcium sulfate, barium sulfate, talc, mica, clay, silica, alumina, kaolin, zirconia, zeolite, gypsum, silicic acid. Calcium, magnesium silicate, aluminum silicate, calcium phosphate, magnesium phosphate, zinc phosphate, apatite, titanium oxide, zinc oxide, copper oxide, iron oxide, tin oxide, magnesium oxide, carbon black, graphite, glass powder, glass balloon , Quartz, quartz glass, hydrotalcite or lithium carbonate having a larger particle size or a smaller specific surface area than that used as component (C),
Calcium carbonate, magnesium carbonate, zinc carbonate, etc. can be used as the filler.

The amount of the fibrous filler and / or the inorganic filler added is in the range of 0 to 300 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the polyarylene sulfide resin.
It is in the range of 200 parts 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 300 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin, molding is difficult, which is not preferable.

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 by 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 adjusted.

Further, with respect to the composition of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold 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 ester,
Polymethacrylic acid ester, polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 1
2, polyamide such as nylon 11, nylon 46, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyester such as liquid crystal polymer,
Polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyether imide, polyamide imide, silicone resin, phenoxy resin, homopolymer such as fluororesin, random or One or more types of block and graft copolymers may be mixed with the resin composition of the present invention and used.

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. Melt kneading is generally 290
It can be performed at a temperature of ˜370 ° C. The pellets thus obtained can be molded into any desired shape by means of ordinary extrusion molding, injection molding or compression molding.

[0042]

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 corrosiveness test of the polyarylene sulfide resin composition used in the following examples was conducted by the following method.

Corrosion test (I) 10 g of pellets of the polyarylene sulfide resin composition was placed in a weighing bottle as shown in FIG. 1, and a lead frame plated with solder was placed therein, and the temperature was kept at 200 ° C.
Heat in the oven for 48 hours. Next, add a petri dish to 85
The sample was placed in a high temperature / humidity bath at 85 ° C. and 85 RH% and treated for 10 hours. After that, 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 gray discoloration Δ: Gray discoloration ×: Black discoloration (II) 10 g of the pellet of the polyarylene sulfide resin composition was placed in a weighing bottle as shown in FIG. A silver plate (0.2 mm (thickness) x 25 mm x 25 mm) was placed inside and heated in an oven at 150 ° C for 500 hours. Then, the petri dish was cooled to room temperature, and the corrosion degree of the silver plate was visually evaluated.

Judgment ⊚: No discoloration ○: Slightly gray discoloration Δ: Gray discoloration ×: Black discoloration Reference Example 1 Polyphenylene sulfide resin used in the present invention (hereinafter P
(Abbreviated as PS) was synthesized as follows. Sodium sulfide Na ₂ S.2.9H ₂ O was added to a 15 l autoclave.
1.8 mol and 4.5 kg of N-methyl-2pyrrolidone (hereinafter abbreviated as NMP) were added, and the mixture was stirred under a nitrogen stream at 200 ° C.
The temperature was raised to 636 g, and 636 g of a distillate consisting mainly of water was distilled off. After cooling the system to 170 ° C., 1.8 mol of p-dichlorobenzene was added together with 1.5 kg of NMP, the system was sealed under a nitrogen stream, the temperature was raised, and polymerization was carried out at 250 ° C. for 3 hours. After the completion of the polymerization, the system was cooled, the contents were poured into water to precipitate the polymer, and the precipitated polymer was collected with a glass funnel, washed with about 10 liters of warm water, repeatedly filtered, and dried under heating and vacuum overnight. The polymer was isolated. The obtained polymer had a yield of 1.85 kg and a yield of 95%, and the melt viscosity (value measured at 300 ° C. using a soybean having a diameter of 0.5 mm and a length of 2 mm under a load of 10 kg with a Koka flow tester) was It was 250 poise. Next, the obtained polymer was placed in an oven set to 250 ° C. in air and allowed to cure for 3 hours to obtain PPS having a melt viscosity of 1400 poise.
Got

Reference Example 2 <Preparation of aluminosilicate> Aqueous aluminum sulfate solution (Al ₂ O ₃ = 7.8% by weight, H ₂ SO ₄ = 22.5% by weight) and sodium silicate which had been kept at 40 ° C. in advance. An aqueous solution (SiO ₂ = 13.0% by weight, Na ₂ O = 5.4% by weight) was placed in an overflow-type reaction tank and 4 times each.
It was fed at a rate of ml / min and reacted under stirring. The pH of the reaction solution slurry at this time was 6.5.

The slurry-like product in which the reaction was completed was filtered and washed with water until sulfate ions were not detected in the washing liquid to obtain a washing cake. This washed cake was an amorphous aluminosilicate, and had a chemical composition determined by an atomic absorption spectrophotometry on a wet basis (Na ₂ O = 3.1% by weight, Al ₂ O).
₃ = 5.0% by weight and SiO ₂ = 29.9% by weight). The amorphous aluminosilicate was dried at 100 ° C. Hereinafter, it is abbreviated as Na-G.

Reference Example 3 <Ion exchange of aluminosilicate> The amorphous aluminosilicate obtained in Reference Example 2 was subjected to ion exchange with aqueous solutions of copper sulfate, zinc sulfate and nickel sulfate, and after filtration, sulfate ion was removed. It was washed with water until it was not detected and dried at 100 ° C.
Hereinafter, the aluminosilicate after the ion exchange is Cu-
Abbreviated as G, Zn-G, and Ni-G. In addition, FIG. 2 shows an X-ray diffraction pattern of Cu-G measured here under the following apparatus and measurement conditions.

Equipment: Geiger Flex 2 manufactured by Rigaku Denki
013 type, tube 1.5 kW Measurement condition; light source: Cu-Kα ray, voltage: 40 kV, current: 25 mA PPS of Examples 1 to 3 Reference Example 1, glass fiber (Central Glass Fiber Co., Ltd., chopped strand) ), The ion-exchanged aluminosilicate prepared in Reference Example 3 and fine calcium carbonate having an average particle diameter of 0.03 μm and a BET specific surface area of 51 m ² / g (manufactured by Shiraishi Industry Co., Ltd.) were mixed in a composition shown in Table 1. , Twin-screw extruder (PCM-45, manufactured by Ikegai Tekko KK)
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 corrosiveness tests (I) and (II) were performed. The results are shown in Table 1.

Example 4 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), ion-exchanged aluminosilicate prepared in Reference Example 3 and average particle size 0.07 μm, BET ratio Fine calcium carbonate having a surface area of 17 m ² / g (manufactured by Shiraishi Industry Co., Ltd.) was mixed in the composition shown in Table 1, and a twin-screw extruder (manufactured by Ikegai Tekko KK, PCM-45) was mixed.
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 (■) and (II) were performed. The results are shown in Table 1.

Example 5 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), ion-exchanged aluminosilicate prepared in Reference Example 3 and average particle diameter 0.12 μm, BET ratio Fine zinc carbonate having a surface area of 34 m ² / g was mixed with the composition shown in Table 1, and the mixture was extruded and granulated at a temperature of 330 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) to form pellets Got

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 1 PPS of Reference Example 1 and glass fiber (Central Glass Fiber Co., Ltd., chopped strand) were mixed in a composition shown in Table 1 and a twin-screw extruder (Ikegai Tekko KK, PCM) was mixed. −
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 corrosiveness tests (I) and (II) were performed.
The results are shown in Table 1.

Comparative Example 2 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.) and the ion-exchanged aluminosilicate prepared in Reference Example 3 were mixed in the composition shown in Table 1, Twin-screw extruder (made by Ikegai Tekko KK, PCM
-45), extruding and granulating at a temperature of 330 ° C.
Pellets were obtained.

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 of Reference Example 1, glass fiber (Chopped strand manufactured by Central Glass Fiber Co., Ltd.) and fine calcium carbonate having an average particle diameter of 0.03 μm and a BET specific surface area of 51 m ² / g (Shiraishi Industry ( (Manufactured by Ikegai Iron Works Co., Ltd., PCM-45) by mixing with a composition shown in Table 1.
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 corrosiveness tests (I) and (II) were conducted. The results are shown in Table 1.

Comparative Example 4 Table 1 shows PPS of Reference Example 1, glass fibers (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.) and fine zinc carbonate having an average particle diameter of 0.12 μm and a BET specific surface area of 34 m ² / g. The mixture was mixed with the composition shown, and extruded and granulated at a temperature of 330 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Tekko KK) 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 5 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), ion-exchanged aluminosilicate prepared in Reference Example 3 and average particle diameter 4.0 μm, BET ratio. Calcium carbonate having a surface area of 1.2 m ² / g (manufactured by Shiraishi Industry Co., Ltd.) was mixed in the composition shown in Table 1, and a twin screw extruder (PCM-45 manufactured by Ikegai Iron Works Co., Ltd.) was used at 330 ° C. Extrusion and granulation were performed at a temperature 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 6 PPS of Reference Example 1, glass fiber (Central Glass Fiber Co., Ltd., chopped strand), ion-exchanged aluminosilicate prepared in Reference Example 3 and average particle size 2.0 μm, BET ratio. Zinc carbonate having a surface area of 7.1 m ² / g was mixed with the composition shown in Table 1, and extruded and granulated at a temperature of 330 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Tekko KK). Pellets were obtained.

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 7 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), aluminosilicate prepared in Reference Example 2 and average particle size 0.03 μm,
Fine calcium carbonate having a BET specific surface area of 51 m ² / g (manufactured by Shiraishi Industry Co., Ltd.) was mixed in a composition shown in Table 1, and a twin screw extruder (PCM-45 manufactured by Ikegai Tekko KK) was used to obtain 330
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 8 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), aluminosilicate prepared in Reference Example 2 and an average particle diameter of 0.12 μm,
Zinc carbonate having a BET specific surface area of 34 m ² / g was mixed with the composition shown in Table 1 and a twin-screw extruder (PCM- manufactured by Ikegai Tekko KK) was mixed.
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.

Comparative Example 9 PPS of Reference Example 1, glass fiber (Chopped Strand manufactured by Central Glass Fiber Co., Ltd.), calcium carbonate having an average particle diameter of 4.0 μm and a BET specific surface area of 1.2 m ² / g (Shiroishi Industry) (Manufactured by Co., Ltd.) having the composition shown in Table 1 was mixed and extruded at a temperature of 330 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Tekko KK) 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 10 PPS of Reference Example 1, glass fiber (Chopped strand manufactured by Central Glass Fiber Co., Ltd.), zinc carbonate having an average particle diameter of 2.0 μm and a BET specific surface area of 7.1 m ² / g are shown in Table 1. The mixture was mixed with the composition shown in (1) and extruded and granulated at a temperature of 330 ° C. using a twin-screw extruder (PCM-45 manufactured by Ikegai Tekko KK) to obtain pellets.

Comparative Example 11 PPS of Reference Example 1, glass fiber (Central Glass Fiber Co., Ltd., chopped strand), mordenite type zeolite (Kunimine Industries, SiO ₂ / Al ₂ O _3).
Calcium carbonate having a molar ratio of 10), an average particle size of 0.03 μm, and a BET specific surface area of 51 m ² / g (Shiraishi Industry Co., Ltd.)
(Made by IKEGAI TEKKO Co., Ltd., PCM-45) was mixed with the composition shown in Table 1 to carry out extrusion granulation 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.

[0073]

[Table 1]

[0074]

According to the present invention, by mixing an ion-exchanged aluminosilicate and a fine metal carbonate with a polyarylene sulfide resin, it is possible to obtain a polyarylene sulfide resin with significantly reduced corrosiveness. .

As a result, it is widely used in fields where metal corrosion is a problem, such as electric and electronic parts, and has a high industrial value.

[Brief description of drawings]

FIG. 1 is a schematic view of a test for examining the corrosiveness of the heat-treated resins of Examples 1 to 5 and Comparative Examples 1 to 11 to metal.

FIG. 2 is a view showing an X-ray diffraction pattern of an amorphous copper aluminosilicate salt prepared in Reference Example 3.

[Explanation of symbols]

 1; Oven 2; Weighing bottle 3; Petri dish 4; Solder plated lead frame or Ginzaka 5; Sample (PPS pellet)

Claims (1)

[Claims] 1. A polyarylene sulfide resin (A) 10
0 parts by weight, (B) aluminosilicate 0.1-10 parts by weight of amorphous represented by the following general ^{_{formula, M I 2 O · Al 2}} O 3 · xSiO 2 M II O · Al 2 O 3 · xSiO 2 M ^III ₂ O ₃ .Al ₂ O ₃ .xSiO ₂ (where M ^I , M ^II or M ^III are Mn, Fe, Co,
A metal ion selected from Ni, Cu, Zn and Sn,
x is a number of 2 or more) (C) Average particle size 0.5 μm or less, BET specific surface area 15
0.1 to 10 parts by weight of a fine metal carbonate of m ² / g or more and (where the metal is Ca, Mg, Sr, Ba, Zn, L
i)) (D) A resin composition comprising 0 to 300 parts by weight of a fibrous filler and / or an inorganic filler.