JPS62295956A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which does not corrode metal, containing a specified polyphenylene sulfide resin and zeolite. CONSTITUTION:Not less than 0.0001pt.wt. porous material having pores having a pore size of 1-20Angstrom (e.g., zeolite) as an additive capable of absorbing dissolved oxygen is added to 100pts.wt. org. amide solvent. An arom. halide (e.g., p- dichlorobenzene) is reacted with Na2S in said solvent to obtain a polyphenylene sulfide resin (A) having an MI of not higher than 10,000(g/10min) or an intrinsic viscosity of not lower than 0.05, in which the half width of a main endothermic peak obtd. at a temperature rise rate of 10[deg/min] in the analysis of DSC (differential scanning calorimetric analysis) is not higher than 20[deg]. 100pts.wt. component A is blended with 0.01-5pts.wt. zeolite (B) having a pore size of not larger than 5Angstrom .

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Technical Field] This invention relates to polyphenylene sulfide resin (hereinafter referred to as
rpps resin) composition.

[Background technology]

PPS resin has excellent heat resistance, chemical resistance, mechanical properties, etc., so it is widely used in parts and housings of machines and equipment, laminates, films, fibers, etc. However, PPS resin
Extruder for PS resin composition.

When manufacturing or processing using kneading equipment, injection molding machines, molds, etc., there is a problem that these manufacturing equipment and processing equipment corrode, and when used for electrical and electronic parts, it corrodes the metal of the parts and causes failure. There was a problem in reaching . For this reason, the uses of PPS resin have been greatly limited.

Therefore, when PPS resin is used for films, fibers, various electrical and electronic parts, etc., it is desired to improve the drawbacks of PPS resin in order to bring out the inherent moldability and electrical insulation properties of PPS resin. ing. The cause of corrosion caused by PPS resin has been studied for some time [for example, (F.

Quel la, Kunststoffe 71, 3
86 et seq., 1981), etc.), it has even been found that the cause is the generation of corrosive gas when PPS resin is heated to high temperatures. Various studies have also been carried out to eliminate the above-mentioned causes. However, at present, a fully satisfactory PPS resin composition that does not corrode metals has not yet been developed.

[Purpose of the invention]

This invention was made in view of the above circumstances, and is intended to reduce the amount of electricity used in metal parts of manufacturing equipment, processing equipment, etc.
The object of the present invention is to provide a PPS resin composition that hardly corrodes the metal parts of electronic parts.

[Disclosure of the invention]

In order to achieve the above objective, the inventors conducted repeated research and found that the problem with PPS resin compositions is caused by the generation of SO□ gas, H, and S gases due to heating during the molding process, etc. I found out that there is one. This SOt gas, H,
S gas corrodes metals, leading to failures in manufacturing equipment, processing equipment, electrical parts, electronic parts, etc. Based on this, the inventors thought of reducing the amount of corrosive SO□ gas and H2S gas generated during the heating process and thereby reducing metal corrosion. Further research was conducted in an attempt to obtain a PPS resin that generates less amount. As a result, in thermal analysis called DSC (differential scanning calorimetry) analysis, the half-width of the endothermic main peak (melting point) obtained at a heating rate of 10 [deg/+in] is 10
[deg] or less, it is possible to obtain a PPS resin composition that generates less SO□ gas and H2S gas (and hardly corrodes metals), and has a half-width of 10 Cdeg. ) over 20
Cdeg) or less, the amount of SO□ gas and H2S gas generated will be reduced to a certain extent, and the PPS resin will be less corrosive to metals.
It has been found that a resin composition can be obtained.

The inventors believe that when the half-width is less than 10 [deg], the range is narrow, so when the half-width exceeds 10 [deg]
deg) Even when using PPS resin in the following range,
An attempt was made to obtain a PPS resin composition that hardly corrodes metals. As a result, if zeolite is used in combination, it is possible to obtain a PPS resin composition that hardly corrodes metals as long as the amount of HzS gas generated is even smaller (and the half-width is 20 degrees or less). We have now completed this invention.

Therefore, the present invention provides lO in DSC analysis.
PPS whose half-width of the endothermic main peak obtained at a heating rate of Cdeg/win) is 20 [deg] or less
Its gist is a PPS resin composition containing zeolite as well as resin.

The present invention will be explained in detail below.

A general method for producing PPS resin is, for example, a method in which an aromatic halide such as p-dichlorobenzene is reacted with sodium sulfide in an organic amide solvent (Japanese Patent Publication No. 45-3
No. 368). However, PP used in this invention
In the DSC analysis, the S resin was found to have a
The half-width of the endothermic main peak obtained at a heating rate of n) must be 20 Cdeg) or less. Such a PPS resin can be obtained, for example, by adjusting reaction conditions such as reaction temperature, reaction time, and cooling rate after completion of the reaction in the method described above. Further, in the above method, it can be easily obtained by adding an additive that absorbs dissolved oxygen to the organic amide solvent. A specific example of the additive is a porous body having 1 to 20 narrow pores. Preferred are zeolites. The amount of the additive added is usually 0.00 parts by weight (hereinafter referred to as "parts") per 100 parts by weight of the organic amide solvent.
It is preferable to add 0,001 parts or more. According to this method, it is also possible to obtain a PPS resin with a half width of 10 degrees or less.

As mentioned above, the half-width in DSC analysis was set to 20 [d
eg 'J or less, SO, gas, H of PPS resin
The amount of 2S gas generated is reduced, reducing corrosiveness.

Although the reason for this is not clear, it is probably because the molecular weight distribution of the PPS resin becomes sharper and there are more structures that are susceptible to thermal oxidative decomposition.

The PPS resin used in the present invention has an Ml (melt index) value measured according to the method of ASTM D1238-70, that is, a load of 5 kg and a temperature of 315.6°C (600°F). It is suitable that the molecular weight M is 10,000 (g/10 min) or less, or the molecular weight M calculated by conversion from the intrinsic viscosity as described below is 0.05 or more. However, the molecular weight M is not limited to such a value.
The natural logarithm of the value obtained by dividing the relative viscosity value obtained based on the viscosity when measured at 0.3°F (03°F) by the polymer concentration, that is, the following formula (A) [η) = In (relative viscosity value/polymer concentration) ... (A
) is graphed using the polymer concentration as a variable, it can be obtained by extrapolating the polymer concentration to infinitesimal (0).

PPS resin is copolymerized with other components as long as it contains 70 mol% or more, preferably 90 mol% or more of a structure having a repeating unit represented by the following formula (B). may be used in combination, and the copolymer alone may be used as long as the mol% of the repeating unit in the copolymer is 70 mol% or more, preferably 90 mol% or more. In this case, even if some of the other copolymer components have a branched or crosslinked structure, they can be used in combination or alone.

In this case, typical units for other copolymerization components include trifunctional units as shown below, ether units as shown below, sulfone units as shown below, and units as shown below. There are ketone units such as, meta units as shown below, substituted sulfide units as shown in the following general formula, etc.

However, R in the formula is an alkyl group or a phenyl group.

It is an alkoxy group, carboxyl group, amino group, sulfone group or nitro group.

In this invention, PPS resin and zeolite are used together. As a result, the amount of corrosive gas H2S generated is more effectively reduced than when the PPS resin as described above is used alone. That is, pps resin composition (PP
Most of the metal parts such as extruders, processing machines, molds, etc. for manufacturing and processing PPS resin composition (PPS resin) and various electrical and electronic parts in which PPS resin composition (PPS resin) are used are corroded. This results in a PPS resin composition that does not cause oxidation.

The proportion of zeolite used is not particularly limited, but it is preferably used in a proportion of 0.01 parts or more and 5 parts or less based on 100 parts of PPS resin. If it is less than 0.01 part, the inhibitory effect of reducing I4□S gas generated from the PPS resin tends to decrease, and if it exceeds 5 parts, the electrical properties of the PPS resin at high temperatures tend to deteriorate. It is in. Zeolite may be added at the time of synthesizing the PPS resin or at the time of melt-kneading to obtain the PPS resin composition.

Zeolite is M”ZO・Al2O3・n5iO□・mH2O or M”O・Alz03・nSiO2・ml(,0 or (M”z+M”)O・Al2O3・nSiO2・mH
It is a compound having a structure of 2O.

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

Among the above-mentioned zeolites, particularly preferred are those with pore diameters of 5 Å or less. This is because such materials have better adsorption performance.

In this invention, for example, when a PPS resin composition is used as a molding material, conventionally known inorganic fillers can be used. For example, glass fiber, fused silica, crystalline silica, alumina, zirconia, calcium silicate, talc 5 glass peas, glass powder, zinc white, calcium carbonate, clay, and
Metal powder or the like whose surface is coated with an insulating film can be used. The above inorganic fillers may be used alone, or two or more types may be used in combination.

Further, it is preferable that the inorganic filler is treated with a surface treatment agent such as a silane type or a titanate type.

Small amounts of additives, such as colorants, internal lubricants, etc., may be added to the pps resin composition according to the present invention.

The pps resin composition according to the present invention can be manufactured by a known method using the above-mentioned raw materials. For example, by mixing raw materials in a mixer such as a Henschel mixer or tumbler, and melt-kneading them in an extruder,
It can be easily made into a PPS resin molding material or the like.

In addition, in this invention, the half-width of the PPS resin contained in the PPS resin composition is regulated by DSC analysis, but it goes without saying that when the PPS resin composition is used for ordinary molding materials and paint applications, Even if the products are made into molding material compositions, molded articles, or paint coatings, by regulating the half-width of the pps resin contained in the products as determined by DSC analysis as described above, it is possible to prevent metal corrosion from occurring. It can be done.

Next, Examples and Comparative Examples will be explained (Example 1) In a 51 autoclave equipped with a stirrer, 1385 g of N-methylpyrrolidone and crystalline sodium sulfide (water content 52%) were placed.
845 g was charged, and the temperature was gradually raised to 205° C. over 2 hours with stirring under a nitrogen atmosphere. And 30
5 g of water was distilled off. Next, after cooling the reaction system to 170°C, 750 g of P-dichlorohemeine and 500 g of N-methylpyrrolidone were added, and 1 kg was added with nitrogen.
/cn! I did the enclosing. And in about 30 minutes, 26
The temperature was raised to 5°C, and the reaction was carried out at 265°C for 3 hours.

After the reaction is complete, cool the autoclave (cooling rate approximately 1°C)
/m1n) The contents were filtered. The resulting solid was washed twice with deionized water at 80°C, then twice with acetone, and then twice with deionized water. After this, it is dried at 120°C to form a white powdery pps resin 51.
Obtained 0g. The yield was 94.5%.

The half width of the endothermic main peak of the obtained PPS resin was measured by DSC analysis. The measurement was carried out using a Rigaku Denki DSC8230 machine at a heating rate of 10 [d
eg/min), the amount of sample (PPS resin) is approximately 1
．． I went as 5■. The results are shown in Table 1.

To 100 parts of the PPS resin, 2 parts of zeolite (sodium aluminum silicate, NaX, pore size: 10) and 67 parts of glass fiber with a fiber length of 3 were added and mixed uniformly using a Henschel mixer. This mixture was melt-kneaded using a single screw extruder at an ambient temperature of 320°C. Thereafter, this kneaded material was pelletized using a pelletizer to obtain a PPS resin composition (molding material).

Using this PPS resin composition, injection molding experiments were conducted 1000 times under the following conditions.

(Injection time: 5 seconds After the injection molding experiment was completed, the corrosion state of the mold of this injection molding machine was visually determined. The results are shown in Table 1.

Table 1 (Example 2) PPS resin was added in the same manner as in Example 1, and the amount of zeolite (sodium aluminum silicate, NaX, pore size 10) was adjusted to 0 to 100 parts of PPS resin. A PPS resin composition was prepared in the same manner as in Example 1, except that the amount was changed to .01 part.

(Example 3) A PPS resin was made in the same manner as in Example 1, and zeolite (sodium aluminum silicate, NaX, pore size 1
A PPS resin composition was prepared in the same manner as in Example 1, except that the amount of PPS resin was 5 parts per 100 parts of PPS resin.

(Example 4) A PPS resin was made in the same manner as in Example 1, and zeolite (sodium aluminum silicate, NaX, pore size 1
Zeolite (aluminum silicate)
A PPS resin composition was prepared in the same manner as in Example 1, except that 1 part of magnesium, MgA, and pore size (pore size: 4) were added.

(Example 5) A PPS resin was made in the same manner as in Example 1, and instead of zeolite (sodium aluminum silicate, NaX, pore size 10), zeolite (calcium aluminum silicate, CaA, pore size 4) was used. A PPS resin composition was prepared in the same manner as in Example 1, except that 2 parts of zeolite (aluminum silicate) was added (Comparative Example 1). Same as Example 1 except that sodium, NaX, pore size 10) were not added,
A PPS resin composition was made (Comparative Example 2) When synthesizing PPS resin, the reaction temperature was set to 300°C and the reaction was allowed to proceed for 3 hours, and after the reaction was completed, the autoclave was rapidly cooled (cooling rate of 10°C/min or more). A PPS resin was produced in the same manner as in Example 1, except that zeolite was not added to the PPS resin, and a PPS resin composition was produced in the same manner as in Example 1. .

(Comparative Example 3) A PPS resin composition was prepared in the same manner as in Example 3 using the PPS resin prepared in the same manner as in Comparative Example 2.

In the same manner as Example 1, Examples 2 to 5 and Comparative Examples 1 to
For the PPS resin obtained in step 3, the half-width of the endothermic main peak was measured by DSC analysis method, and the PPS resin
Regarding the resin composition, the corrosion state of the mold was investigated. The results are shown in Table 1.

From Table 1, it can be seen that the PPS resin compositions of Examples 1 to 5 have extremely low corrosivity compared to those of Comparative Examples 1 to 3.

〔Effect of the invention〕

The PPS resin composition according to the present invention contains zeolite as well as a PPS resin whose half-value width of the endothermic main peak obtained at a temperature increase rate of 10 [deg/win] is 20 [deg/win] or less in DSC analysis.
It hardly corrodes the metal parts of manufacturing equipment, processing equipment, etc., and the metal parts of electrical and electronic parts used.

Agent: Patent Attorney Takehiko Matsumoto Procedural amendment (view) I layer phase July 1Z, 1961

Claims (1)

[Claims] (1) In DSC analysis, the half-width of the endothermic main peak obtained at a heating rate of 10 [deg/min] is 20 [deg/min].
deg] or less, a polyphenylene sulfide resin composition containing a polyphenylene sulfide resin and a zeolite.