JPS62241961A - Polyphenylene sulfide composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having a high purity and excellent electrical characteristics and suitable for use as a sealing material or in coating electrical and electronic components, etc., containing a specified polyphenylene sulfide and an inorg. filler. CONSTITUTION:A highly purified polyphenylene sulfide (a), a compd. (b) selected from the group consisting of mercapto group-contg. compds. of formula I [wherein R is a hydrocarbon group or a residue of a heterocyclic compd.; M is H or an alkali metal; A is COOH, OH, (substd.) NH2 or NO2; x is a number of 1-6; and y is a number of 0-6] and disulfides of formula II (wherein R<1> is R; and x and y are each a number of 0-6) and optionally a base (c) are heat-treated in a solvent to obtain a polyphenylene sulfide (A) which is composed of not less than 90mol% of a structural unit of formula III (wherein n>=20) and other copolymerizable structural unit and has been purified to such a high purity that the content of bonded chlorine is not higher than 500ppm. 15-95wt% component A is blended with 15-85wt% powdered, granular or fibrous inorg. filler (B) (e.g., glass fiber, silica, TiO2).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to polymers with a bond/chlorine content of 500 pp
m or less polyphenylene sulfide (hereinafter referred to as PPl3
The present invention relates to a composition comprising an inorganic filler and an inorganic filler. The composition of the present invention has excellent electrical properties and is particularly useful as a coating or sealing material for electrical and electronic components.

[Conventional technology]

As a conventional molding PPE + composition, Japanese Patent Publication No. 45-35
A composition is known in which a filler is added to a raw material polymer obtained by oxidatively crosslinking PPS with a low degree of polymerization produced by the method disclosed in Publication No. 68 to increase the apparent melt viscosity. It is being

On the other hand, PPEI, which has a high molecular weight without oxidative crosslinking, is used as a raw material polymer by using an auxiliary agent during polymerization or by copolymerizing polyhalobenzene having three or more halogens in the molecule, and filler is added to it. Added compositions are also known.

However, when trying to apply these above-mentioned compositions to the fields of electrical and electronic parts, a large amount of salt, etc. in PPS, IJum, and chlorine cause deterioration of electrical properties, which poses a major obstacle. In other words, when PPS containing large amounts of sodium and chlorine is used to encapsulate electronic components such as ICs, the insulation of circuits may deteriorate due to moisture absorption, and electrodes and lead frames may corrode and break. This may cause deterioration of characteristics or failure of elements such as

Therefore, as a method to improve these drawbacks, JP-A-55-156342 discloses a method in which the amount of water-extractable sodium is reduced to 100 ppm or less by extracting pps powder several times with hot water. Disclosed.

However, according to the research of the present inventors, in this method, despite repeated extraction for an extremely long time,
The amount of sodium that is extracted is that which is attached to the surface of the polymer particles or is present in the very surface layer, and as more than 1000 ppm of sodium still exists in the polymer, the removal effect is poor. there were.

Further, when the chlorine content in PPS purified by this method was quantified, it was found to be about 2000 to 3000 ppm, and no effect of reducing chlorine in PPS was observed.

Furthermore, Japanese Patent Application Laid-Open No. 59-219551 discloses a method of reducing the sodium content by heat treating PPS in an aromatic solvent. According to this method, the sodium content can be reduced, but the chlorine content is 2000 to 50 q Oppm in the treated polymer.
No removal effect was observed.

As described above, even if attempts are made to purify PPl3 using conventional techniques, it is possible to reduce the IJium content, but it is impossible to reduce the chlorine content, and compositions using such PP8 as a raw material polymer are It still does not have sufficient purity to be used as a coating or sealing material for electrical and electronic parts.

[Problem that the invention seeks to solve]

The present invention was developed as a result of intensive research to meet these demands.
The present invention was completed based on the discovery that a composition prepared by using PP19, which has undergone the treatment described below, as a raw material polymer and to which an inorganic filler is added has excellent applicability in the fields of electrical and electronic components.

[Means to solve the problem]

That is, the present invention uses PP8 as a raw material polymer, in which the bound chlorine content in the polymer is reduced to 500 ppm or less by processing PP19, and pps is prepared by adding an inorganic filler to this.
The present invention relates to a composition. The chlorine referred to in the present invention is covalent chlorine directly bonded to a carbon atom, and Nac
It does not mean ionic chlorine, such as that contained in polymers. Further, this covalent chlorine does not include the chlorine of dichlorobenzene as a residual monomer. The amount of covalent chlorine contained in such a polymer is determined by quantifying the sum of covalent chlorine and ionic chlorine using ion chromatography, etc., and then determining the Ic
e 0 A (B!)-ectron F3pect
roecopyfor chamtcaIAnalys
is), the ratio of covalent chlorine to ionic chlorine was determined and quantified.

'pps used in the present invention is highly purified, and the combined chlorine content in PPS is 500 ppm.
It is preferably 100 ppm or less.

The PPS used in the present invention is at least 90 mol or more, more preferably 95 mol or more %@-8
BoIJ (p-7 22lene sulfide) consisting of + structural units, and the remaining structural units may be copolymerizable units, such as ortho and metaphenylene sulfide,
Biphenylsulfide)', 2.6-su7thalene sulfide, diphenylsulfone sulfide, diphenylketone sulfide, and trivalent and 4-valent compounds introduced by copolymerizing monomers having three or more halogens in the molecule.
722lene sulfide and the like. Furthermore, the pps used in the present invention may be oxidatively crosslinked by heat treatment in the coexistence of oxygen.

In addition, the pps used in the present invention was determined to be 30
Melt viscosity measured at 0℃ and iokg load is 10-5oo
It is preferable to be in the range of oo voids.

The high-purity pps used in the composition of the present invention can be obtained from Japanese Patent Application No. 6O-2453f8 previously filed by the present inventor and Japanese Patent Application No. 60-245
PP by the method of No.-277913, that is, the known method as disclosed in Japanese Patent Publication No. 45-5368, etc.
After producing 8, the thus produced PP8 and an alkali metal salt of a mercapto group-containing compound or a mercapto group-containing compound or a disulfide and optionally a base are heated in a solvent capable of dissolving PPB. Manufactured. That is, polyphenylene sulfide and a mercapto group-containing compound represented by the general formula (1) (R is a hydrocarbon group or a heterocyclic compound residue, M is a hydrogen atom or an alkali metal, and A is a carboxyl group or a hydroxyl group or a substituted or unsubstituted amino group or a nitro group,
2 is an integer from 1 to 6, y & -z is an integer from o to 6)
and a disulfide represented by the general formula (2) (Ae-, R-8-s-R), (2) (R,
R' is a hydrocarbon group or a heterocyclic compound residue;
and R' may be the same, A is a carboxyl group, a hydroxyl group, a substituted or unsubstituted amine group, or a nitro group, and lti is an integer from 0 to 6) and optionally It is produced by heating a base and a solvent that can dissolve polyphenylene sulfide. For example, PPS produced by a known method, a mercapto group-containing compound such as 2-mercaptobenzimidazole, and a base such as sodium hydroxide are mixed in N-methylpyrrolidone at 220 to 2
This is a method such as reacting at 60°C for 5 to 10 hours. Through such treatment, both the IJ content and the chlorine content in PPB can be reduced to 500 ppm or less, and further to 100 ppm or less. Ru.

The pps composition of the present invention is obtained by blending the high purity PP8 obtained by the above method and an inorganic filler. The inorganic filler can be used in the form of, for example, powder, granules or fibers. Some examples of inorganic fillers that can be used in the present invention are glass fibers, asbestos fibers, ceramic fibers, carbon fibers, glass peas, glass powder, Merck, silica, clay, mica, alumina.

Calcium sulfate, calcium carbonate, potassium titanate,
Examples include iron oxide, zinc oxide, titanium oxide, and the like. The amount of these inorganic fillers added is 5 to 85% by weight or 10 to 80% by weight. If the amount added is too small, a sufficient filling effect will not be obtained, resulting in a problem! S b
It is undesirable because it causes problems such as brittleness when it is crushed.

The PPS composition of the present invention obtained as described above can be molded into various molded products, films, sheets, pipes, etc. by injection molding, transfer molding, extrusion molding, etc., and is particularly suitable for electrical and electronic parts. It is extremely useful as a coating or sealing material.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, PPS used in the following examples and comparative examples
The sodium content in the sample was determined by wet decomposition of approximately 15 g of a sample in a quartz beaker with approximately 10 ml of sulfuric acid and approximately 1 ld of nitric acid, and then adding deionized water to a certain amount. was determined by atomic absorption spectrometry.The chlorine content in PPB was determined by incinerating a sample of about 30 ~ by the flask combustion method, absorbing it in N/100 NaOH&(l), and adjusting it to a constant amount by adding deionized water. After measuring the liquid with ion chromatography and quantifying the total amount of chlorine, ESC!
3CA-750) K, the ratio of covalent chlorine and ionic chlorine was determined, and the covalent chlorine was quantified from these values.aESC! A was measured using an Mg target as an X-ray source at an energy of 8 KV and 30 mA.

The melt viscosity of PPEI was measured at 300°C and
Measurement was performed with a load of 10kIi.

Example 1 Autoclave with a capacity of 15K Na1B-2,9H1
014.6 mol of N-methylpyrrolidone and 4.9 t of N-methylpyrrolidone were added thereto, and the temperature was raised to 210° C. with stirring under a nitrogen stream, and 340 mol of a distillate mainly consisting of water was distilled off. Then heat the yarn to 170℃
14.5 mol of P-dichlorobenzene was added, 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 polymerization was completed, N-methylpyrrolidone was distilled and recovered under reduced pressure, and the polymer was washed with water, dried, and isolated. The yield of the obtained polymer was 14909, the melt viscosity was 210 boids, and the sodium and chlorine contents in the polymer were 2200 ppm and 2900 ppm, respectively.
It was ppm.

Next, 81,400 g of this PP, 165 mol of 2-mercaptobenzimidazole, 65 mol of NaOHCL, and N-
Methylpyrrolidone5. After charging Ot into an autoclave with a capacity of 15% and purging the system with nitrogen, the temperature was raised to 260%.
The reaction was carried out at ℃ for 1 hour.

After the reaction was completed, N-methylpyrrolidone was distilled and recovered under reduced pressure, water was added, and the polymer was washed at 200° C. for 4 hours, dried, and isolated. The yield of the obtained polymer was j5s, 0
9. The melt viscosity is 204 voids and the sodium content in the polymer is 56 ppm.

The chlorine content was 100 ppm or less.

The high-purity PPS obtained by further heating was heat-treated at 260°C for 3 hours in the presence of oxygen to give a melt viscosity of 3070 mm.
After uniformly mixing 40 parts by weight of a 3μ length 3as chip with a V-blender, a screw diameter of 40
The mixture was made into a cross-wire pellet using an extruder with a cylinder temperature of 310°C.

Next, using an injection molding machine, the pellet was molded into a cylinder at a temperature of 310°C, an injection pressure of 800 ky/cit, and a metal temperature of 1.
It was injected at 55°C into a metal fitting into which an aluminum metal fitting had been inserted in advance.

Ten samples were arbitrarily taken out from the obtained molded product and heated at 80°C.
, 95% RH A, in an ambient atmosphere [j000 hours, and the corrosion status of the aluminum fittings was examined. As a result, corrosion of aluminum fittings was found in 0 out of 10 samples.

Example 2 PPS polymerized and highly purified by the same method as Example 1
(melt viscosity 200 boise, sodium content 40 ppm
, chlorine content of 100 ppm or less) was heated at 230°C for 2 hours in the presence of oxygen to give a melt viscosity of 550 voids, and then 855 parts by weight of PP and glass fiber (15 μm in diameter)
In the same manner as in Example 1, 35 parts by weight of 35 parts by weight of a 1 ml chip strand) and 50 parts by weight of calcium carbonate were cross-wired and made into pellets in the same manner as in Example 1. Using this pellet, insert molding was performed by injection molding in the same manner as in Example 1, and the resulting molded product was subjected to a moisture resistance test under the same conditions as in Example 1.

As a result, corrosion of the aluminum fittings was found in 0 out of 10 samples.

Example 3 Polymerization was carried out in the same manner as in Example 1, and the melt viscosity was 25.
PP81520 was obtained with 0 voids, a sodium content of 2400 ppm, and a chlorine content of SOOOppm. Next, this PP81400g and phenyl disulfide α65 mo/l/
, NaOH (L 65 mol, N-methylpyrrolidone)
L was charged into an autoclave having a capacity of 15, and after purging the system with nitrogen, the temperature was raised to 200'CK and a reaction was carried out for 2 hours. After the reaction was completed, drained water from which N-methylpyrrolidone was distilled and recovered under reduced pressure was added, and the polymer was washed at 200° C. for 4 hours, dried, and isolated. The yield of the obtained polymer was 13
00, the melt viscosity is 105 voids, the IJ content in the polymer is 25 ppm, and the chlorine content is 1.
00 ppm or less.

The high-purity pps thus obtained was heat-treated at 260°C for 4 hours in the presence of oxygen to give a melt viscosity of 3140 voids, and then 860 parts by weight of this PP and glass fibers (diameter 15 μm
, chopped strands having a length of 3 mm) were cross-wired and pelletized in the same manner as in Example 1. Using this pellet, insert molding was performed by injection molding in the same manner as in Example 1, and the resulting molded product was subjected to a moisture resistance test under the same conditions as in Example 1. As a result, corrosion of aluminum fittings was found in sample 1.
There were 0 medium-sized pieces.

Comparative Example 1 Polymerization was carried out by the same known method as in Example 1, and the melt viscosity was 2.
PP515002 with an IJ cum content of 2000 ppm*chlorine content of 2800 ppm was obtained.

This PP560
40 parts by weight of glass fibers (chopped strands with a diameter of 13 μm and a length of 5 m) were mixed in the same manner as in Example 1,
Pelleted. Using this pellet, insert molding was performed by injection molding in the same manner as in Example 1, and the resulting molded product was subjected to a moisture resistance test under the same conditions as in Example 1.

As a result, corrosion of the aluminum fittings was observed in all 10 medium-sized samples.

〔Effect of the invention〕

As is clear from the above explanation, the PPS composition of the present invention has excellent applicability in the fields of electrical and electronic parts, and
It is extremely useful for use as a coating or sealing material for electronic components.

Patent applicant: Toyo Soda Kogyo Co., Ltd. Heavy procedural amendments April 25, 1986

Claims (1)

[Claims] (1) Polyphenylene sulfide and a mercapto group-containing compound represented by the general formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (1) (R is a hydrocarbon group or a residue of a heterocyclic compound, M
is a hydrogen atom or an alkali metal, A is a carboxyl group, a hydroxyl group, a substituted or unsubstituted amino group, or a nitro group, x is an integer of 1 to 6, and y is an integer of 0 to 6) and the general formula ( 2) Disulfide (A)-xR-S-S-R'-(A)_y (2)(R
, R' is a hydrocarbon group or a heterocyclic compound residue,
R and R' may be the same, A is a carboxyl group, a hydroxyl group, a substituted or unsubstituted amino group, or a nitro group, and x and y are integers of 0 to 6); The melt viscosity is 10 to 5000 by heating the base and the base in a solvent that can dissolve polyphenylene sulfide to reduce the bound base content to 500 ppm or less.
0 poise polyphenylene sulfide 15-95% by weight
and 5 to 85% by weight of an inorganic filler.