JPH0611864B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition used as a molding material, a paint or the like.

[Background technology]

Polyphenylene sulfide resin (hereinafter "PPS resin"
Is excellent in heat resistance, chemical resistance, mechanical properties, etc., and is therefore used in various types of molded products such as parts of machines and devices, housings, films, fibers and the like.

However, this PPS resin has a drawback that it corrodes metal parts such as an extruder, a processing machine, and a mold used for manufacturing and processing the PPS resin. The drawbacks of the PPS resin are also exhibited in practical applications, for example, when the PPS resin is used for electric and electronic parts, these parts are corroded and even lead to failure.
As a result, the use of PPS resins is greatly limited in the actual situation.

When the PPS resin is used for films, fibers, various electric and electronic parts, it is desired to improve the drawbacks of the PPS resin in order to exhibit the original molding processability and electric insulation of the PPS resin. The cause of corrosion, which is a drawback of this PPS resin, has been studied in the past, and various studies have been carried out to eliminate the cause, but satisfactory results have not been obtained.

[Object of the Invention]

The present invention has been made in view of such circumstances, and provides a PPS resin composition which is excellent in significantly reducing the corrosion of metal parts such as a processing machine, an extruder, a mold, and electric / electronic parts. It is intended to be provided.

[Disclosure of Invention]

The inventors have conducted extensive research in order to achieve the above-mentioned object. As a result, it has been found that the above-mentioned drawbacks of the PPS resin composition are caused by the fact that H ₂ S gas is generated by heating in the molding step and the like, and this gas causes corrosion. From such knowledge, it has been found that by reducing the amount of corrosive gas H ₂ S generated in the heating step, it is possible to significantly reduce the corrosion of metal parts such as the processing machine, the extruder and the mold. It was found that this can be achieved by adding zeolite to the PPS resin composition, and the present invention was completed here.

Therefore, the gist of the present invention is a PPS resin composition containing a PPS resin as a main component and zeolite added thereto.

The present invention will be described in detail below.

As a general method for producing a PPS resin, a method of reacting an aromatic halide such as p-dichlorobenzene with sodium sulfide in an organic amide solvent is disclosed in JP-B-45-33.
Since it is disclosed in Japanese Patent Publication No. 68, the PPS resin may be produced by this method or the like.

PPS used in the PPS resin composition according to the present invention
As the resin, MI (melt index) value measured according to the method of ASTM D1238-70, that is, a load of 5 k
g, value measured at 315.6 ° C (600 ° F) is 100
Or less than 00 (g / 10 minutes), or the molecular weight M obtained by conversion from the intrinsic viscosity as described below.
Is preferably 0.05 or more. But,
It is not limited to such a thing.

The molecular weight M of the polymer solution concentration of 0.4 g / 100 m was measured at 206 ° C. (403 ° C.) in α-chlornaphthalene.
The natural logarithm of the relative viscosity value obtained on the basis of the viscosity measured in F) divided by the polymer concentration, that is,
Formula (A) [η] = 1n (relative viscosity value / polymer concentration) ...
When η calculated in (A) is plotted as a graph with the polymer concentration as a variable, it is obtained by extrapolating the polymer concentration to infinity small (0).

The PPS resin has the following formula (B) A compound having a structure having a repeating unit represented by 70 mol% or more, preferably 90 mol% or more, may be used in combination with a copolymerized other component, As long as the mol% of the repeating unit in the copolymer is 70 mol% or more, preferably 90 mol% or more, only the copolymer may be used. In this case, even if a part of the other copolymerization component has a branched structure or a crosslinked structure, it can be used together or alone.

In this case, as a typical unit of the other copolymerization component, a trifunctional unit as shown below, An ether unit, as shown below, A sulfone unit, as shown below, A ketone unit, as shown below, A meta unit as shown below, Alternatively, there are substituted sulfide units and the like represented by the following general formula.

However, R in the formula is an alkyl group, a phenyl group, an alkoxy group, a carboxyl group, an amino group, a sulfone group or a nitro group.

In the present invention, the zeolite is added to the PPS resin composition. At that time, it is preferable to add 0.01 to 15 parts by weight of the zeolite to 100 parts by weight of the PPS resin, whereby the corrosive gas is added. The amount of H ₂ S generated is effectively reduced. That is, a PPS resin composition that hardly causes corrosion of metal parts of extruders, processors, molds, etc. for manufacturing and processing PPS resins and various electric and electronic parts using PPS resins is obtained. It comes.

The addition ratio of the zeolite to 100 parts by weight of the PPS resin is not limited, but if it is less than 0.01 part by weight, the inhibiting effect of reducing the corrosive gas H ₂ S generated from the PPS resin is small. If the addition ratio exceeds 15 parts by weight, the electrical characteristics of the PPS resin at high temperatures tend to deteriorate. The zeolite may be added either at the time of synthesizing the PPS resin or at the time of melt-kneading to obtain the composition.

Zeolites are M ^I ₂ O ・ Al ₂ O ₃・ nSiO ₂・ mH ₂ O or M ^II O ・ Al ₂ O ₃・ nSiO ₂・ mH ₂ O or (M ^I ₂ , M ^II ) O ・ Al ₂ It is a compound having a structure of O ₃ · nSiO ₂ · mH ₂ O.

M as a metal is Li, Na, K, Ca, Mg, B
a, Sr, etc.

Particularly preferred among the above zeolites are those having a pore size of 5 or less. This is because such a material is superior in adsorption performance.

When manufacturing a molding material using a PPS resin, a conventionally known inorganic filler can be used. This inorganic filler includes glass fiber, fused silica, crystalline silica,
Alumina, zirconia, calcium silicate, talc, glass beads, glass powder, zinc white, calcium carbonate, clay, and metal powder whose surface is covered with an insulating film. The above inorganic fillers may be used alone or in combination of two or more. The inorganic filler is preferably treated with a silane-based or titanate-based surface treatment agent.

A small amount of a colorant, an internal lubricant or the like may be added to the PPS resin composition.

In the present invention, the composition can be produced by a known method.
For example, they are mixed using a mixer such as a Henschel mixer or a tumbler, and melt-kneaded by using an extruder. By doing so, a PPS resin molding material or the like can be easily obtained.

Next, examples and comparative examples will be described.

(Example 1) In an autoclave equipped with a stirrer, 1385 g of N-methylpyrrolidone and crystalline sodium sulfide (water content 52%)
845g and, about 2 while stirring under a nitrogen atmosphere
The temperature was gradually raised to 205 ° C. over time, and 305 g of water was distilled off. Next, after cooling the reaction system to 170 ° C., 750 g of p-dichlorobenzene and 500 g of N-methylpyrrolidone were added, nitrogen was filled at 1 kg / cm ² , and the temperature was raised to 250 ° C. in about 25 minutes. The reaction was carried out at 250 ° C for 3 hours. Internal pressure at the end of the polymerization reaction is 9.8 kg / cm ²
Met.

After completion of the reaction, the autoclave was cooled and the contents were filtered off. The solid obtained is washed twice with deionized water at 80 ° C,
Next, it was washed twice with acetone, further washed twice with deionized water, and then dried at 120 ° C. to obtain 505 g of a white powdery PPS resin. The yield was 93.5%.

To 100 parts by weight of the PPS resin, 2 parts by weight of zeolite (sodium aluminum silicate, NaX, pore size 10) and 67 parts by weight of glass fiber having a fiber length of 3 mm were mixed and uniformly mixed using a Henschel mixer. This mixture was melt-kneaded using a uniaxial extruder at an ambient temperature of 320 ° C., and then this kneaded product was pelletized using a pelletizer.

Using the pelletized molding material, under the following conditions,
The injection molding experiment was performed 1000 times.

After completion of the injection molding experiment, the corrosion state of the mold of this injection molding machine was visually judged. The results are shown in Table 1. Also,
A molded product for measuring the volume resistivity (measured according to JIS K-6911) was molded using the pellets and the injection molding machine, and the measurement results are also shown in Table 1.

(Example 2) The same procedure was performed as in Example 1 except that the amount of zeolite (NaX) was 0.01 part by weight with respect to 100 parts by weight of the PPS resin.

(Example 3) The procedure of Example 1 was repeated, except that the amount of zeolite (NaX) was changed to 15 parts by weight based on 100 parts by weight of the PPS resin.

(Example 4) In place of zeolite (NaX), 1 zeolite (aluminum-magnesium silicate, MgA, pore size 4) was used.
The same procedure was performed as in Example 1 except that the addition of parts by weight was added.

(Example 5) Instead of zeolite (NaX), 2 zeolite (aluminum-calcium silicate, CaA, pore size 4) was used.
The same procedure was performed as in Example 1 except that the addition of parts by weight was added.

(Comparative Example 1) The same procedure as in Example 1 was performed except that zeolite (NaX) was not added.

Comparative Example 2 The procedure of Example 1 was repeated, except that the amount of zeolite (NaX) was 0.005 parts by weight with respect to 100 parts by weight of the PPS resin.

(Comparative Example 3) The procedure of Example 1 was repeated, except that the amount of zeolite (NaX) was 20 parts by weight with respect to 100 parts by weight of the PPS resin.

Next, examples and comparative examples using the pyrolysis gas generator will be described. This device, as shown in FIG.
A stirring blade 6 made of a four-fucca ethylene resin is inserted into the three-neck flask 2 from the upper port 3 of the three-neck flask 2, a leak valve is fitted into one side port 4, and the other side port 5 Is connected to a vacuum pump (not shown) via a pipe 8.

(Example 6) 100 parts by weight of the PPS resin obtained in Example 1 and zeolite (hydrous aluminum silicate calcium [Product No. C
S-100, manufactured by Koshosha Co., Ltd.)) and 1 part by weight of the mixture are mixed in an agate mortar, and the mixture is placed in the three-necked flask 2. After that, the inside of the three-necked flask 2 is depressurized to 300 mmHg by a vacuum pump and sealed to maintain the decompressed state of the pyrolysis gas generator 1. Next, the pyrolysis gas generator 1 held in this reduced pressure state is set in a heating furnace (not shown) at 350 ° C., and heat treatment is performed for 10 minutes while stirring the mixture with the stirring blades 6. After that, the pyrolysis gas generator 1 is cooled to the same temperature as room temperature. In this way, the decomposition gas H generated in the thermal decomposition gas generator 1 is generated.
₂ S was collected through the leak valve 7 and quantified with a gas chromatograph (G3800 manufactured by Yanagimoto Seisakusho).

(Example 7) Zeolite (hydrous aluminum silicate calcium, C
Same as Example 6 except that the amount of S-100) was 0.01 part by weight.

(Example 8) Zeolite (hydrous aluminum silicate calcium, C
Same as Example 6 except that the amount of (S-100) was 0.005 parts by weight.

(Example 9) Zeolite (hydrous aluminum silicate calcium, C
Example 6 was performed in the same manner as in Example 6 except that zeolite (hydrous aluminum / magnesium silicate) was used instead of S-100).

(Comparative Example 4) Zeolite (hydrous aluminum silicate calcium, C
Same as Example 6 except that S-100) was not added.

Table 2 shows H ₂ S gas generation amounts obtained from the above Examples 6 to 9 and Comparative Example 4.

Next, molding materials were applied to Examples 6 to 9 and Comparative Example 4. Fiber length of 3 mm in 60 parts by weight of each composition
40 parts by weight of the glass fiber of Example 1 were uniformly mixed by a Henschel mixer, and melt-kneaded at an ambient temperature of 300 ° C. using a uniaxial extruder to obtain a molding material.

Using this molding material, as shown below,
An injection molding experiment was conducted under the same conditions as in No. 5.

The injection molding experiment was performed 1000 times under the same conditions, and the corrosion state of the mold was visually determined.

The "amount of H ₂ S gas generated" seen in Table ₂ and the first
"Mold surface condition" after injection molding as seen in Tables and 3
Judging from the above, it was found that if the amount of zeolite was added in an amount of 0.01 parts by weight or more based on 100 parts by weight of the PPS resin, the metal material such as the mold would not be corroded.

Further, as can be seen from the measurement results of Examples 4 and 5 shown in Table 1, addition of the alkaline earth metal zeolite to the PPS resin reduces metal corrosion, and
It has been found that there is an effect of suppressing deterioration of electrical characteristics.

Judging from the "volume resistivity" shown in Table 1 and the "surface condition of the mold" seen from Tables 1 to 3,
The most preferable addition ratio of the zeolite is 0.01 to 15 parts by weight with respect to 100 parts by weight of the PPS resin, but it is not limited to this range.

Further, when the pore size of the zeolite is 5 or less, H
_The ability to adsorb ₂ S gas is increased, and it is effective in preventing corrosion of metal materials, but is not limited thereto.

〔The invention's effect〕

As described above, since the PPS resin composition according to the present invention is added with zeolite, it has an effect of remarkably reducing corrosion of metal parts such as a processing machine, an extruder, a mold, and electric / electronic parts. Play.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a pyrolysis gas generator for generating a corrosive gas from a PPS resin composition. 1 ... Pyrolysis gas generator, 2 ... Three-necked flask, 6
...... Stirring blade

Claims (3)

[Claims] 1. A polyphenylene sulfide resin composition comprising a polyphenylene sulfide resin as a main component and zeolite added thereto. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the addition ratio of the polyphenylene sulfide resin and the zeolite is 0.01 to 15 parts by weight of the zeolite with respect to 100 parts by weight of the polyphenylene sulfide resin. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the pore size of the zeolite is 5 or less.