JPS62148567A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in both color tone and mechanical strength, suitable for electric and electronic parts especially connectors, etc., by blending specific polyphenylene sulfide resin, glass fiber, inorganic filler and pigment in each specified amount. CONSTITUTION:The objective composition can be obtained by blending (A) 80-30wt% of a polyphenylene sulfide resin (a copolymer from p-dichlorobenzene and trichlorobenzene) prepared by rinsing and extraction of an uncrosslinked polyphenylene sulfide resin having a melt viscosity (at 300 deg.C) 30-100Pa.s at a shear rate 500sec<-1> with an organic solvent (e.g. acetone) to such a point as to be <=1wt% in the oligomer content, (B) 10-50wt% of glass fiber (e.g. chopped strand with a diameter 20-5mu), (C) 0-40wt% of inorganic filler with an average particle size 30-1mum (e.g. calcium carbonate) and (D) 0.1-5wt% of pigment (e.g. titanium dioxide).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyphenylene sulfide resin composition with excellent coloring properties that is used for one purpose as electrical and electronic parts.

[Prior Art] Polyphenylene sulfide resin (hereinafter abbreviated as PPS) has excellent heat resistance, chemical resistance, and flame retardancy.
It is compounded with reinforcing materials such as glass fiber and is widely used in electrical/electronic parts and automobile parts.

In electronic parts, they are used as connectors, switches, etc. In these applications, each part is usually classified and sorted using stone Buddha statues, and there is a strong demand for coloring PPS as well. However, PPS is a powdery polymer obtained by polymerization in the presence of oxygen.
Since it is used after being oxidized and crosslinked at a high temperature of 0 to 260°C, it is inevitable that it will turn brown to blue. Therefore, the molded product has a chocolate color and can only be colored black. Other colors such as blue and green can be produced by using a large amount of galvanic material, Tio 2, etc. for whitening. Even when it was added, only a dull color could be obtained, and the strength was also forced to deteriorate significantly.

[Problems to be Solved by the Invention] The present invention aims to eliminate the above-mentioned drawbacks, and provides a composition that has excellent color tone and mechanical strength by combining a specific base resin, glass fiber, inorganic filler, and pigment. It is an attempt to obtain.

[Means for Solving the Problems] That is, the present invention provides: 1) Specific PPS resin 80-30% by weight2) Glass fiber 10-50% by weight3) Inorganic filler
0-40% by weight 4) Pigment 0.1-5% by weight
The present invention relates to a composition comprising:

The PPS resin used in the present invention has a melt viscosity of 3 at a shear rate of 500 sec-1 at 300°C.
It is an uncrosslinked resin of 0 to 100 Pa*s.

As a method for obtaining such PPS resin,
3368, p-dichlorobenzene and an alkali metal sulfide such as sodium sulfide are combined with N-methyl-2-
A method of polymerizing in pyrrolidone at a high temperature of 200 to 250°C can be adopted.

It is also possible to add a small amount of copolymerization component during polymerization. As a copolymerization component, m-dichlorobenzene, 0
-Dichlorobenzene, 4,4'-dichlorodiphenyl ether, dichlordiphenyl sulfone, 2,5-dichlorotoluene, trichlorobenzene, etc.
Any of the components exemplified in No. 368 can be used.

In particular, multihalogen derivatives such as trichlorobenzene are desirable from the viewpoint of increasing viscosity.

It is undesirable to add these copolymerization components to the extent that they greatly reduce the crystallinity of the PPS resin, and the amount of these copolymerization components is usually selected to be 5 mol % or less. Further, during the reaction, it is desirable to add an alkali metal carboxylate such as lithium acetate or sodium acetate from the viewpoint of increasing the viscosity.

The obtained PPS resin is washed and extracted with an organic solvent until the oligomer content becomes 1 wt % or less without further thermal crosslinking. The oligomer content referred to herein is the value extracted by performing extraction with THF using a Soxhlet extractor for 12 hours.

Although there are no particular restrictions on the method for washing and extracting PPS resin, it is preferable to use a method in which PPS powder and an organic solvent are present in a tank, heated and stirred, and then the PPS resin is separated and recovered by centrifugation or the like.

Organic solvents used in this cleaning operation include alcohols such as methanol, ethanol, and propatool, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and THF, and aliphatic hydrocarbons such as hexane and heptane. , aromatic hydrocarbons such as benzene, toluene, and xylene, esters such as ethyl acetate and butyl acetate, halogenated organic solvents such as chloroform, trichloroethylene, and carbon tetrachloride, DMF, DMSO, and N-methyl-2-pyrrolidone. Examples include various aprotic polar solvents. Especially acetone and THF.

Toluene and the like are desirable because they are easy to use and have good extraction efficiency. The hue of the composition obtained by this washing and extraction operation is improved, and the mechanical strength is also greatly improved.
Improved to 11. The oligomer content at this time is 1wt
% or less. If the amount is more than this, the resulting composition will be inferior in both hue and mechanical strength.

The glass fiber used in the present invention has a diameter of 20 to 5μ.
Chopped strands, low pins, milled fibers, etc. are used. The amount added is selected within the range of 10 to 50% by weight.

If it is less than 10%, the mechanical strength of the molded product will be insufficient, and if it exceeds 50%, the fluidity will be extremely reduced, making molding difficult. Glass fibers are usually surface-treated with a silane coupling agent, and aminosilane, mercaptosilane, epoxysilane, etc. are selected as the silane. There are no particular restrictions on the inorganic filler, but it is desirable to use one with high white discoloration and high purity, and specific examples include calcium carbonate, talc, calcium silicate, silica, and calcium sulfate. The average particle size of these inorganic fillers is 30~
A range of 1 μm is desirable. Further, the amount added is selected within the range of 0 to 40% by weight. If it exceeds 40% by weight, problems such as a decrease in fluidity and a decrease in mechanical strength will occur.

The pigment used in the present invention does not particularly matter whether it is inorganic or organic, but it is desirable that it is sufficiently stable even at temperatures of 300°C or higher, which is the molding temperature of PPS, and from this point of view, inorganic pigments are suitable. ing. Specifically, titanium oxide, red iron oxide, ultramarine blue, cobalt blue, chrome green light,
Examples include cadmium red and yellow lead. Even organic pigments with excellent heat resistance such as quinacridone can be used. The amount added is selected within the range of 0.1 to 10% by weight. If it greatly exceeds 10% by weight, the color tone will be good, but the strength will drop significantly and there will be many practical problems.

It is also possible to further add heat stabilizers, antioxidants, ultraviolet stabilizers, antistatic agents, lubricants, mold corrosion inhibitors, etc. to the composition of the present invention, if necessary.

The composition of the present invention is mainly molded by injection molding, but it can also be molded by other methods such as compression molding and extrusion molding.

[Effects of the Invention] As is clear from the above explanation, the present invention provides (1) specific P
With a composition consisting of PS resin (2) glass fiber (3) inorganic filler (4) pigment, the following excellent effects can be obtained.

(2) A colored composition with a color tone that is almost impossible with conventional PPS resins can be obtained.

2) A coloring composition having high mechanical strength can be obtained.

Since this composition has excellent color tone in addition to the excellent properties of PPS resin, it is extremely effectively used for electrical and electronic parts, especially connectors, switches, etc.

[Example] An embodiment of the present invention will be illustrated below based on an example, but the present invention is not limited thereto.

(Manufacture of PPS resin-1) In a 15j2 capacity autoclave, add Na2S.2.
8H2014, 8 mol, N-methyl-2-pyrrolidone 4
．． 9A was added, stirred under a N2 stream, and heated to 210°C.
437 g of a predominantly water distillate were distilled off. system 17
After cooling to 0°C, 14.8 mol of p-dichlorobenzene was added, the system was sealed under a N2 stream, and the temperature was raised to 250°C.
Polymerization was carried out at ℃ for 3 hours. After cooling, the contents were poured into water, washed three times with warm water, filtered repeatedly, and then dried in a hot air dryer at 120° C. for 5 hours. The yield of the obtained PPS is 1
485 g, yield is 95%, melt viscosity at 300°C is 45 Pa at shear rate 500 sec-'
-3. The amount of oligomer nails contained was 4.2% as a result of 12-hour THF extraction using a Soxhlet extractor.

This unframed (, t, Hp ps) was designated as PP5 (A).

Return PP5(A) to +1i and 151 autoclave, add toluene from 81 and stir in reflux state for 3 hours.
Extraction was performed. After cooling, toluene and PPS were separated by filtration, and the resulting powder was thoroughly washed with toluene and thoroughly dried in a vacuum dryer. Obtained P
The melt viscosity of PS is 60 Pa·s, and the oligomer content is 0. It was 2%. PPS subjected to this washing extraction
was designated as PPS (B).

(Manufacture of PPS resin-2) Na2S・2.8 in a 151 capacity autoclave
H2014, 8 mol, N-methyl-2-pyrrolidone 4.
91, stirred under N2 stream, heated to 210℃, and heated to 210℃.
41 g of a predominantly water distillate were distilled off. 170 system
After cooling to .degree. C., 14.8 mol of p-dichlorobenzene and 0.07 mol of trichlorobenzene were added, the system was sealed under a N2 stream, and the temperature was raised to 250.degree. C. for 3 hours to polymerize. After cooling, the contents were poured into water, washed three times with warm water, filtered repeatedly, and then dried in a hot air dryer at 120°C for 5 hours. The obtained PPS has a yield of 1469 g x 94% and a melt viscosity of 86 Pa at 300°C.
・It was s. Moreover, the oligomer content was 4.7%. This polymer was designated as PPS (C).

Return PPS (C) to the 151 autoclave 8
After cooling, the acetone was separated by filtration and thoroughly washed with acetone. The obtained powder was thoroughly dried in a vacuum dryer. The melt viscosity of the obtained PPS was 97Pass, and the oligomer content was 0.
．． It was 3%. This PPS was designated as PP5(D).

Example l PP5 (B) 1.4 kg (35 wt%), glass fiber (chopped strand with a diameter of 13 μm and a cut length of 3 mm) 1.4 kg (35 νt%), calcium carbonate 1, 1
2kg (28wt%), pigment (ulmarine blue) 80g (2wt%)
%) were premixed using a Henschel mixer, then fed to a 45 mm Nisuke extruder set at a cylinder temperature of 310° C., kneaded at a screw rotation speed of 100 rpm, and pelletized using a hot cutter. The obtained pellets were molded using a 2-ounce injection molding machine (horizontal type, mold clamping cuff 5Ton).
A strip for bending test (3X25X120mm) and a strip for measuring impact strength (3,2X12.
7X63. 5 mm) was molded at a mold temperature of 130°C.

The obtained test piece was free from dullness and had an excellent color tone. Also, as a result of measuring the mechanical strength, the bending strength was 180MP.
a. The Izot impact was 41 J/m on the notch side and 146 J/m on the ring notch side.

Comparative Example 1 The same operation as in Example 1 was performed except that PP5 (B) was replaced with PP5 (A). The resulting test piece had poor gloss and significant roughness on the side opposite the gate. As for the mechanical strength, the bending strength was 145 MPa, the isot impact strength was 32 J/[11 on the notch side, and 98 J/m on the ring notch side, which were significantly inferior to Example 1.

Comparative Example 2 PPS (B) was placed in a stainless steel vat and cured by heating for 1 hour in a hot air circulation oven heated to 250°C.

The melt viscosity of the obtained PPS resin was 80 Pa-8. Further, the oligomer content was 1.8 wt%. This PPS resin was designated as PP5(E).

The same operation as in Example 1 was performed using PPS (E).

The obtained test piece exhibited a dull blue color and was far inferior to Example 1. In addition, the mechanical strength is bending strength 176MPa, and the isot impact strength is 38MPa on the notch side.
J/m, and it was 135 J/m on the ring notch side.

Example 2 The same operation as in Example 1 was performed using PPS (D). The obtained test piece was free from dullness and had an excellent color tone. In addition, as a result of determining the mechanical strength by /l111, the bending strength was 17
6MPa, Izotsu impact strength is 40 J/ on the notch side
There was 129 J/m on the anti-notch side.

Comparative example 3 The same operation as in Example 2 was performed using PPS (C).

The resulting test piece had poor gloss and rough skin was observed on the opposite side of the gate area. Mechanical strength is bending strength 126MPa
The Izo impact strength was 27 J/m on the notch side and 89 J/m on the ring notch side, which was significantly inferior to Example 2.

PPS-35wt% O:
Good glass fiber - 35vt%
△: Slightly dull calcium carbonate - 28νt%
X: Defective pigment (ulmarine blue) -2wt%

Claims (1)

[Claims] 1. Melt viscosity at 300°C at shear rate of 500 se
An oligomer content of 1.0w is obtained by washing and extracting an uncrosslinked polyphenylene sulfide resin with an organic solvent of 30 Pa-s or more and 100 Pa-s or less at c^-^1.
t% or less resin 80-30% by weight, glass fiber 10-5%
0% by weight, inorganic filler 0~40% by weight, pigment 0.1~
A polyphenylene sulfide resin composition consisting of 5% by weight. 2. The composition according to claim 1, wherein the polyphenylene sulfide resin is a copolymer of p-dichlorobenzene and trichlorobenzene.