JPS61120856A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has a low free electrolyte impurity content and excellent electrical characteristics and reliability on moisture resistance, by mixing a polyphenylene sulfide resin with hydrotalcite with heating. CONSTITUTION:0.1-5pts.wt. hydrotalcite of formula V (wherein M<2+> is a biva lent metal ion such as Mg, Mn, Fe, Co, Ni, Cu or Zn; M<3+> is a trivalent metal ion such as Al, Fe, Cr, Co or In; A<n-> is an n-valent anion such as OH, F, Cl, Br, NO3 or SO4; 0<x<=0.33) is mixed with 100pts.wt. polyphenylene sulfide resin having an MI of 10,000g/10min (under a load of 5kg at 315.6 deg.C) compound of at least 70mol% of a repeating unit of formula I and not more than 30mol% of repeating units of formulas II, III and IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This invention relates to a polyphenylene sulfide resin composition having a very low content of free electrolyte impurities.

[Background technology]

Polyphenylene sulfide resin composition (hereinafter referred to as rpps)
Polyphenylene sulfide resin (hereinafter referred to as "RPPS resin") has excellent heat resistance, chemical resistance, mechanical properties, etc. It is used in a variety of molded products such as equipment parts, housings, films, and fibers.

When using PPS resin compositions for films, fibers, and various electrical and electronic parts, it is necessary to use inorganic materials such as sodium chloride contained in the PPS resin in order to exhibit the inherent moldability and electrical insulation properties of pps48I resin. It is preferred to minimize electrolyte impurities. In addition, P is used as a coating and sealing material for electronic components such as ICs, transistors, and capacitors.
When using a PS resin composition, it is necessary to use an electrolyte as described above to prevent problems such as corrosion or disconnection of the electrodes and wiring of parts, which would result in large leakage current. It is necessary to reduce impurities as much as possible to improve moisture resistance and reliability.

By the way, as a general method for producing PPS resin, a method of reacting an aromatic halide such as p-dichlorohenzene with sodium sulfide in an organic amide solvent is disclosed in Japanese Patent Publication No. 45-3368, and also, High degree of polymerization P
In order to obtain a PS resin, an improved method using an alkali metal carboxylate as a polymerization aid is disclosed in Japanese Patent Publication No. 52-12240.

However, when PPS resin is produced by such a method, electrolyte impurities are inevitably produced as a by-product in an amount approximately equal to that of the produced PPS resin, and as a result, a considerably large amount of electrolyte impurities remains in normal processing. A composition (molded article) obtained using a PPS resin containing a large amount of such electrolyte impurities will have significantly poor electrical properties, moisture resistance reliability, and the like.

Therefore, as a method to remove electrolyte impurities, the PPS resin powder obtained through normal processing is repeatedly boiled in hot water for a long time using deionized water.
A method for reducing impurities by eluting water-extractable electrolyte components was developed, and published in JP-A-55-1563.
Lord No. 42? 134 have been disclosed.

However, this method has the drawback of requiring a long processing time, and no matter how many times the extraction operation is repeated, PPS with a satisfactory impurity content for use as a coating or sealing material for electronic components can be obtained. Another drawback is that it is difficult to obtain resin.

Solvent extraction treatment is used instead of hot water extraction, and P is removed during treatment.
Even if the PS resin is heated, the results are still not satisfactory.

Additionally, US Pat. No. 4,071,509 discloses a method for reducing the content of inorganic components in PPS resin by heating a mixture of PPS resin and alkali metal carboxylate or lithium halide in an organic amide solvent. Although disclosed, this method also
It is difficult to obtain a PPS resin with a satisfactory impurity content [Object of the Invention] This invention has been made in view of the above circumstances, and the content of free electrolyte impurities is extremely low. PP
The purpose of the present invention is to provide a S resin composition.

[Disclosure of the invention]

In order to achieve the above objects, the inventors conducted various studies. As a result, it was discovered that hydrotalcites should be mixed with PPS resin and heated, and the present invention was completed.

Therefore, the gist of the present invention is a PPS resin composition in which the PPS resin is a heated mixture with hydrotalcites. The present invention will be explained in detail below.

PPS used in the PPS resin composition according to this invention
The resin has an Ml (melt index) value of 1.0000 (g /l 0 min) or less, or the molecular weight M determined by conversion from the intrinsic viscosity as shown below is 0.05 or more -1-. However, it is not limited to this. Molecular weight M is 0.4 g/100
m7! Polymer? The natural logarithm of the value obtained by dividing the relative viscosity by the polymer concentration based on the viscosity of a liquid sample in α-chlornaphthalene at 206°C (403°F), that is, the following equation ( A) [η)-1n (relative viscosity value/polymer concentration)... (
A) When η calculated by is plotted as a graph with polymer concentration as a variable, it is 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 structure or a crosslinked structure, they can be used in combination or alone.

In this case, typical units of other copolymerization components include trifunctional units as shown below, ether units as shown below, ÷0 or FS sulfone units as shown below. , -Q-soz -Q-s Ketone unit as shown below, meta unit as shown below, or substituted sulfuric acid F as shown in the following general formula
There are units 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.

Furthermore, the amount of inorganic electrolyte impurities contained in the resin is arbitrary, and there is no particular need to keep it small in advance. Note that, in general, the PPS resin in the present invention before heating and mixing contains at least 0.1% by weight of, for example, sodium ions.

Such PPS resin is known from the aforementioned Japanese Patent Publication No. 45-3368.
It can be manufactured by the manufacturing method disclosed in Japanese Patent Publication No. 52-1.22340.

Hydrotalcites have the following general formula (C)
Alternatively, it is a non-stoichiometric compound formed by (D).

[Mko+xM responsibility” (OH)Z) Needle
(Ar7,1 ・m H20) X-...
(C) Mz+ M,:+OI+X4...
(D) Here, M”: Mg”←, Mn”t, Fe”, C
o”, Ni2+lCu2+, Zn2÷, and other divalent metals.

M”: AI”, Fe”, Cr”,
Trivalent metals such as CO3'' and In3+.

A'-: OH-, Fm CI-, Br-, N O
3, CO3”-, SO4”-, Fe (CN)6”-
, CH3C00 - n-valent anions such as oxalate ion and salicylate ion.

X is in the range of Q<x≦0.33.

What is represented by formula (D) can be obtained by firing what is represented by formula (C).

Commercially available hydrotalcites include KW-1000, KW-1015, KW-1100, and K manufactured by Kyowa Kagaku ■.
t-2[)00. KW-2007゜KW-2015,K
There are t-2100 etc. KW-1000, KW-101
5, Kt-1100 is Mg4. s A I z (O
H) +3CO3・mH20 (m=3-3.5), K
W-2000, KW-2007, KW-2015 and KW-2100 are Mgo, qA I O, 30+, +s
Each has a chemical composition of

The PPS resin and hydrotalcites may be heated and mixed by any conventional method. For example, mixing rolls.

Both are placed in a kneading extruder or the like, and the PPS resin is melted and mixed by heating. Hydrotalzite is preferably used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the PPS resin.

Hydrotalcy H1' has anion exchange ability and neutralization ability in a high temperature and humid state B (preferably a humid state), so in that state it can ionize halogen ions such as CI- and other anions. In addition to replacing and adsorbing,
Adsorbs both metal ions such as Na+ by converting them into their hydroxides and adsorbing them.

Inactivate.

Therefore, when a heated mixture of PPS resin and hydrotalcites is used in a PPS resin composition, the content of free electrolyte impurities becomes very small.
The electrical properties, moisture resistance reliability, etc. are extremely excellent.

Note that, if necessary, additives such as reinforcing fibers and inorganic fillers may be included in the PPS resin composition. In this case, when mixing and kneading the PPS resin and the additives, hydrotalcium may be added and heated. In short, the PPS resin and the hydrotalcites need only be heated and mixed at any point in the process of forming the PPS resin composition.

Next, Examples and Comparative Examples will be described.

(Example 1) In a 200cc autoclave equipped with a stirrer, 55.4 g of N-methylpyrrolidone and 4 Bg of sulfuric acid chloride/lium nonahydrate were added.
(0.2 mol) and gradually raised the temperature to 200°C over about 2 hours while stirring under a nitrogen atmosphere.
g of water was distilled off. Next, after cooling the reaction system to 160°C, 30g of p-dichlorobenzene (0,204
mol) and 10 g of N-methylpyrrolidone were added, the temperature was raised to 245°C over 20 minutes, and the mixture was reacted at 245°C for 3 hours. The internal pressure at the end of the polymerization reaction was 7.6 kg/cffl. After the reaction was completed, the autoclave was cooled and the contents were filtered. The obtained solid content was diluted with deionized water at 80°C.
After washing 0 times, and washing twice with acetone, 1
Dry at 20°C and add 1 part of pale gray fine powder PPS resin.
7.8 g was obtained. The yield was 95%.

100 parts by weight of the obtained PPS resin and 3 parts by weight of bitrotalcite (KW-1000 manufactured by Kyowa Chemical Industry Department)
mixer (vertical mixer)
) for 2 minutes, and then put into a 320"c kneading extruder and heated and mixed to obtain a homogeneous composition. This composition was pulverized to form a PPS resin composition (powder) of 100 mesh under. I got it.

(Example 2) 100 mesh under was prepared in the same manner as in Example 1, except that 1 part by weight of hydrotalcites (KW-2000 manufactured by Kyowa Chemical Industry ■) was used for 100 parts by weight of PPS resin. A PPS resin composition was obtained.

(Comparative Example) Only the PPS resin was pulverized to make 100 mesh under.

For the PPS resin composition of Example 1.2 and the comparative example,
The impurity ion concentrations of Na+ and C were measured. The results are shown in Table 1. However, the impurity ion concentrations were measured as follows.

After putting 2.5 g of sample into a 100 cc glass container, add 4 cc of methanol special reagent and 46 cc of deionized water.
was added and treated under boiling conditions for 20 hours. Treating solution with Na3
A test solution was prepared by filtration with filter paper. Measure impurity ions in the test solution using ion chromatography (product number HLC-803D) manufactured by Toyo Soda Kogyo ■, and compare the measured values with a calibration curve prepared in advance using a sodium chloride standard solution.
The amount of impure ions was obtained.

It can be seen that Na+ and CI- are significantly lower than those of the comparative example.

As a result of measuring the concentration of impurity ions generated from electrolytes other than sodium chloride, the concentration of impurity ions in Example 1.2 was significantly lower than in the comparative example.

〔Effect of the invention〕

In the PPS resin composition according to the present invention, since the PPS resin is heated and mixed with hydrotalcites, the content of free electrolyte impurities is extremely small.

Agent Patent Attorney Matsuki Takehiko Xueding-Li Qian1iyFA4F (self-motivated) 17m160 January] 5 B 1981 Special Application No. 242009 2, Title of Invention Polyphenylene Sulfide LII Fat M11 Product 3, Amended Relationship with the patent case Wv< Address 1048 Oaza Kadoma, Kadoma City, Osaka Name (583) Matsushita Electric Works Co., Ltd. Representative Representative Director Iku Kobayashi 4, Agent 6, Specification subject to amendment 7, Amendment Contents (1) In the 17th line of page 2 of the specification, the word "totsu" is replaced with "
“-” is corrected.

(2) r52-122340-1 on page 9, line 4 of the specification
(3) From page 10, line 6 of the specification to line 7 of the same page, [Kyowa Kagaku fjl
)Correct J to "Kyowa Chemical Industry ■".

(4) The statement “95%” on page 12, line 19 of the specification,
I corrected it to ``83%.''

Claims (2)

[Claims] (1) A polyphenylene sulfide resin composition, which is a heated mixture of polyphenylene sulfide resin and hydrotalcites. (2) Claim 1, wherein the mixing ratio of polyphenylene sulfide resin and hydrotalcites in the heated mixture is 0.1 to 5 parts by weight of hydrotalcites per 100 parts by weight of polyphenylene sulfide resin. The polyphenylene sulfide resin composition described.