JP3077253B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylene sulfide resin composition. More specifically, the present invention relates to a polyarylene sulfide resin composition having significantly reduced metal corrosion.

[0002]

2. Description of the Related Art Polyarylene sulfide resins have recently been attracting attention as engineering plastics having excellent heat resistance, chemical resistance and flame retardancy. By taking advantage of these various properties, polyarylene sulfide resins are used in the fields of automobile parts and electric and electronic parts. The demand has been increasing significantly. However,
When polyarylene sulfide resin is used for electric / electronic parts as a film, fiber or molded article, the corrosiveness of the polyarylene sulfide resin is reduced in order to exhibit the inherent moldability and electrical insulation properties of the polyarylene sulfide resin. It is necessary. For example, when a polyarylene sulfide resin is used as a covering / sealing material for electronic components, electrodes, wiring, lead frames, etc. of components are often corroded and cause trouble.

As a method for reducing the corrosiveness of a polyarylene sulfide resin, a method of adding a hydrotalcite compound to a polyarylene sulfide resin (JP-A-60-18)
No. 6561), a method of adding zinc carbonate, manganese carbonate, and magnesium carbonate (Japanese Patent Application Laid-Open No. 2-191655) and the like. However, in any of the methods, the effect of reducing the corrosiveness is insufficient.

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

It is known that a crystalline aluminosilicate (general name: zeolite) is added to a polyarylene sulfide resin for the same purpose as in the present invention (JP-A-62-16).
7356, JP-A-62-29556, etc.). However, although the addition of the crystalline aluminosilicate has a slight improvement effect, when it is used for covering or sealing electrodes, lead frames, lead wires, etc. used in the field of electric and electronic components, it does not corrode. The reduction of the properties is insufficient, and further improvement is desired.

[0006]

An object of the present invention is to provide a polyarylene sulfide resin which solves the above-mentioned problems, reduces the metal corrosion of the polyarylene sulfide resin, and has a lower corrosion resistance than conventional products. .

[0007]

DISCLOSURE OF THE INVENTION In view of the above-mentioned situation, the present inventors have intensively studied to reduce the metal corrosivity of polyarylene sulfide resin. As a result, they found that the addition of an amorphous aluminosilicate (particularly, an aluminosilicate in which a cation was replaced with a specific metal ion) significantly reduced the corrosiveness of a polyarylene sulfide resin, and completed the present invention. I came to.

That is, the present invention relates to (A) 20% to 99.9% by weight of a polyarylene sulfide resin, (B) 0% to 70% by weight of a fibrous filler and / or an inorganic filler,
(C) one or more aluminosilicates selected from amorphous aluminosilicates represented by the following general formula:
It is a resin composition comprising 1% by weight to 10% by weight.

[0009] ^{_{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 various metal ions, x is a number of 2 or more) Hereinafter, the present invention will be described in detail.

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

[0011]

Embedded image (Wherein R ₁ and R ₂ each represent 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. In the formula, X represents a methylene, ethylene, isopropyl, ether, ketone or sulfone group.) However, particularly preferred is a polyphenylene sulfide resin. Polyphenylene sulfide resin has the general formula

[0012]

Embedded image As long as the structure having the repeating unit represented by the formula is contained in an amount of 70 mol% or more, preferably 90 mol% or more, other components may be copolymerized.

Polyarylene sulfide resins are generally disclosed in Japanese Patent Publication No. 44-2761, Japanese Patent Publication No. 45-3368, US Pat. No. 3,274,165, and Japanese Patent Publication No. Sho.
And a polymer having a relatively small molecular weight obtained by a production method typified by JP-A-6-27255.
There is an essentially linear polymer having a relatively high molecular weight represented by Japanese Patent Publication No. 40, and the former polymer can be obtained by heating under an oxygen atmosphere or in the presence of a crosslinking agent such as a peroxide. It is also possible to use it after polymerization.

Melt viscosity of polyarylene sulfide resin suitable for use in the present invention (by a high-low flow tester (die: diameter = 0.5 mm, length = 2 mm) 300
(Measured at 10 ° C. under a load of 10 kg), it is possible to use a polymer having an essentially linear and relatively high molecular weight of 50 to 50,000 poise, preferably 100 to 30,000 poise. If the polymer has a high degree of polymerization by heating in the presence of a crosslinking agent, the melt viscosity before the heat treatment is 5%.
0 to 20,000 poise, and the melt viscosity after the heat treatment is 150 to 50,000 poise, preferably 200 to 50,000 poise.
30,000 poises can be used. Here, when the melt viscosity is less than 50 poise, the mechanical strength is undesirably reduced. On the other hand, if it exceeds 50,000 poise, it is not preferable because the moldability becomes difficult.

The aluminosilicate used in the present invention is an amorphous aluminosilicate, particularly a compound obtained by subjecting a cation to an ion exchange treatment with a transition metal or the like. This amorphous aluminosilicate is a compound that does not show a diffraction pattern due to a crystal structure by an X-ray diffraction analysis method, and has a chemical composition represented by the following general formula.

[0016] ^{_{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 various metal ions, x is a number of 2 or more), wherein x is preferably in the range of 2 to 100.

The aluminosilicate used in the present invention is obtained by simultaneously and continuously reacting an aqueous solution of an alkali silicate and an aqueous solution containing aluminum to obtain an alkali metal salt of aluminosilicate, which is ion-exchanged with a desired metal ion. It is efficient to process and manufacture.

The aqueous solutions of alkali silicate include aqueous solutions of sodium silicate, potassium silicate and lithium silicate, and the aqueous solutions containing aluminum include aqueous solutions of aluminum sulfate, aluminum chloride, sodium aluminate and the like. It is preferably used.

A preferred method for preparing the above alkali metal aluminosilicate is a method in which both aqueous solutions are simultaneously and continuously supplied to an overflow type reaction vessel equipped with a stirrer under stirring to cause a reaction. is there. In addition, as another 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 vessel under stirring conditions without discharging a reaction slurry may be applied. it can. Next, the obtained alkali metal salt of aluminosilicate is brought into contact with a sulfate, nitrate, or chloride aqueous solution of a metal ion and washed, whereby an amorphous aluminosilicate can be easily obtained.

Here, Mn, Fe, C are used as metal ions.
o, Ni, Cu, Zn, Sn, Cr, Ag, Cd, Mg
Is preferably used.

The amount of the aluminosilicate used in the present invention is from 0.1% by weight to 10% by weight based on the total amount of the polyarylene sulfide resin, the aluminosilicate and the fibrous filler and / or the inorganic filler. And preferably in the range of 0.5% to 8% by weight. Here, when the addition amount is less than 0.1% by weight, the effect of reducing the corrosiveness is poor, and when it exceeds 10% by weight, the mechanical strength after molding is unfavorably reduced.

The fibrous filler used in the present invention includes glass fiber, carbon fiber, graphitized fiber, whisker,
Metal fibers, inorganic fibers, organic fibers, ore fibers and the like can be used.

The following are examples of these fibrous fillers.

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

Examples of the carbon fiber include a PAN-based fiber using polyacrylonitrile as a raw material and a pitch-based fiber using pitch as a raw material.

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

Examples of ore-based fibers include asbestos, wollastenite, and magnesium oxysulfate.

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

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

Next, the inorganic filler used in the present invention is a plate-like or powder-like 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, magnesium phosphate, zinc phosphate, apatite, titanium oxide, zinc oxide, copper oxide,
Fillers such as iron oxide, tin oxide, magnesium oxide, carbon black, graphite, glass powder, glass balloon, quartz, quartz glass, hydrotalcite and the like can be mentioned.

The addition amount of the fibrous filler and / or the inorganic filler is 0 with respect to the total amount of the polyarylene sulfide resin, the aluminosilicate, the fibrous filler and / or the inorganic filler.
%, Preferably in the range of 20% to 50% by weight. Here, the compounding ratio of the fibrous filler and / or the inorganic filler is not particularly limited. However, the addition amount of the fibrous filler and / or the inorganic filler is 70%.
If the content is more than the weight%, it is not preferable because it causes difficulty in molding.

The fibrous filler and / or inorganic filler used in the present invention may be used in combination with a known surface treating agent and sizing agent which are generally used in order to enhance the adhesion to the polyarylene sulfide resin. Possible and preferred. Examples are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds and the like. These compounds may be used after the filler is subjected to a surface treatment or a convergence treatment, or may be added at the same time as the preparation of the material.

Further, colorants such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, dyes and pigments may be added to the composition of the present invention as long as the object of the present invention is not impaired. One or more ordinary additives such as a flame retardant, a flame retardant aid, and an antistatic agent may be added.

Further, if necessary, polyethylene, polybutadiene, polyisoprene, polychloroprene, polystyrene, polybutene, polyα-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate,
Polymethacrylic acid ester, polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 1
2, polyamides such as nylon 11, nylon 46, and the like, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyarylate, and liquid crystal polymer;
Homopolymer, random or One or more of block and graft copolymers can be used as a mixture.

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

The melting and kneading temperature is generally from 330 ° C. to 42 ° C.
It can be performed at a temperature of 0 ° C. The resulting pellet is
It can be molded into an arbitrary shape by means of ordinary extrusion molding, injection molding, compression molding and the like.

[0037]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the corrosion test of the polyarylene sulfide resin composition used in the following Examples was performed by the following method.

(C) Corrosion test (I) 10 g of a pellet of the polyarylene sulfide resin composition was put into a weighing bottle as shown in FIG. 1, and a lead frame subjected to solder plating was put into the bottle and heated at 200 ° C. ,
Heat in oven for 48 hours. Next, the petri dish was placed in a high-temperature, constant-humidity bath at a temperature of 85 ° C. and a humidity of 85%, and was treated for 10 hours. Thereafter, the petri dish was cooled to room temperature, and the degree of corrosion of the solder-plated lead frame was visually determined.

Judgment ◎: No discoloration ○: Slightly discolored to gray △: Discolored to gray ×: Discolored to black (II) 10 g of PPS pellets were placed in a weighing bottle as shown in FIG. .2mm (thickness) x 25m
m × 25 mm) and heated in an oven at 150 ° C. for 500 hours. Thereafter, the petri dish was cooled to room temperature, and the degree of corrosion of the silver plate was visually determined.

Judgment ◎: No discoloration ○: Slightly discolored to gray △: Discolored to gray ×: Discolored to black Reference Example 1 The polyphenylene sulfide resin used in the present invention was synthesized as follows. 15l capacity O - Tokure - sodium sulfide to blanking _{Na 2} S · 2.9H 2 O 1.8 moles, N-
4.5 kg of methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
And stirred under a nitrogen stream to raise the temperature 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 were added to NM.
P1.5kg, and add the system under nitrogen flow.
The temperature was raised and polymerization was performed at 250 ° C. for 3 hours. After completion of the polymerization, the system was cooled, the content was poured into water, and the polymer was precipitated. Then, the precipitated polymer was collected by a glass funnel.
Washing with about 10 l of warm water and filtration were repeated, followed by heating under vacuum overnight to isolate the polymer. The obtained polymer was 1.
85 kg, yield 95%, melt viscosity (using a soybean having a diameter of 0.5 mm and a length of 2 mm at 300 ° C., a load of 10
(measured with a Koka type flow tester in kg) was 250 poise. Next, the obtained polymer is placed in air for 250 minutes.
C. in an oven set at .degree. C. and cured 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 <Preparation of aluminosilicate> An aqueous solution of aluminum sulfate (Al ₂ O ₃ = 7.8% by weight, H ₂ SO ₄ = 22.5% by weight) previously held at 40 ° C. and sodium silicate Aqueous solution (SiO ₂ = 13.0% by weight, Na ₂ O = 5.4)
% By weight) were supplied to an overflow type reaction tank at a rate of 4 cc / min, and reacted under stirring. At this time, the pH of the reaction solution slurry was 6.5.

The slurry product after the completion of the reaction was filtered and washed with water until no sulfate ion was detected in the washing solution to obtain a washing cake. This washed cake is an amorphous aluminosilicate, and its chemical composition determined by atomic absorption spectrometry is based on a wet basis (Na ₂ O = 3.1% by weight, Al ₂ O ₃
O ₃ = 5.0% by weight, 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 ion-exchanged with aqueous solutions of copper sulfate, zinc sulfate and nickel sulfate, and after filtration, sulfate ions were removed. It was washed with water until it was no longer detected and dried at 100 ° C.
Hereinafter, these are abbreviated as Cu-G, Zn-G, and Ni-G, respectively.
Here, the X-ray diffraction pattern of Cu-G is shown in FIG.

Examples 1 to 4 The 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 with the composition shown in Table 1. Twin screw extruder (Ikegai Iron Works Co., Ltd., PCM
Using -45), extrusion granulation was performed at a temperature of 330 ° C.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then subjected to corrosion tests (I) and (II). Table 1 shows the results.

Examples 5 to 6 The PPS of Reference Example 1, glass fiber (Chopped Strand, manufactured by Central Glass Fiber Co., Ltd.) and the aluminosilicate prepared in Reference Example 2 were mixed in the composition shown in Table 1,
Extrusion granulation was performed at a temperature of 330 ° C. using a twin-screw extruder (PCM-45, manufactured by Ikegai Iron Works Co., Ltd.).

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then subjected to corrosion tests (I) and (II). Table 1 shows the results.

Comparative Example 1 The PPS of Reference Example 1 and glass fiber (Chopped Strand, manufactured by Central Glass Fiber Co., Ltd.) were mixed with the composition shown in Table 1, and a twin-screw extruder (PCM, manufactured by Ikega Iron Works, Ltd.) −
Using 45), extrusion granulation was performed at a temperature of 330 ° C.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then subjected to corrosion tests (I) and (II). Table 1 shows the results.

Comparative Example 2 PPS of Reference Example 1, glass fiber (Choped Strand, manufactured by Central Glass Fiber Co., Ltd.), mordenite type zeolite (manufactured by Kunimine Industries, SiO ₂ / Al ₂ O)
₃ = 10 (molar ratio) with the composition shown in Table 1 and mixed using a twin-screw extruder (PCM-45, manufactured by Ikegai Iron Works Co., Ltd.).
Extrusion granulation was performed at a temperature of 30 ° C.

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then subjected to corrosion tests (I) and (II). Table 1 shows the results.

Comparative Example 3 PPS of Reference Example 1, glass fiber (manufactured by Central Glass Fiber Co., Ltd., chopped strand), and lithium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in the composition shown in Table 1.
Extrusion granulation was performed at a temperature of 330 ° C. using a twin-screw extruder (PCM-45, manufactured by Ikegai Iron Works Co., Ltd.).

Next, the pellets were dehumidified and dried at 120 ° C. for 2 hours, and then subjected to corrosion tests (I) and (II). Table 1 shows the results.

[0054]

[Table 1]

[0055]

According to the present invention, a polyarylene sulfide resin composition having significantly reduced corrosiveness can be obtained by blending an amorphous aluminosilicate with the polyarylene sulfide resin.

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

[Brief description of the drawings]

FIG. 1 is a schematic view of a test for examining the corrosiveness of a metal when the resins of Examples 1 to 6 and Comparative Examples 1 to 3 were subjected to heat treatment.

FIG. 2 is an X-ray diffraction pattern of the amorphous copper aluminosilicate prepared in Reference Example 3. Apparatus: Rigaku Denki, Geiger Flex 2013 type, 1.5 kW tube Measurement conditions; Light source: Cu-Kα ray Voltage: 40 kV Current: 25 mA

[Description of Signs] 1; oven 2; weighing bottle 3; dish 4; solder-plated lead frame or silver plate 5; sample (resin pellet)

Claims (2)

(57) [Claims] 1. A polyarylene sulfide resin (A)
(B) 0 to 70% by weight of a fibrous filler and / or an inorganic filler; (C) 1 selected from amorphous aluminosilicates represented by the following general formula:
One or several kinds of aluminosilicates 0.1% by weight to 10%
A resin composition consisting of% by weight. ^{_{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 various Metal ion, x is a number of 2 or more) 2. An amorphous aluminosilicate M ^I , M ^II
Or M ^III is Mn, Fe, Co, Ni, Cu, Z
The resin composition according to claim 1, which is a metal ion selected from n, Sn, Cr, Ag, Cd, and Mg.