JPS6011062B2 - Glass fiber reinforced polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a glass fiber reinforced polyphenylene sulfide resin composition with excellent electrical and mechanical properties.

Although polyphenylene sulfide resin (hereinafter abbreviated as PPS) has excellent chemical resistance, heat resistance, and flame resistance, it is extremely brittle and has poor mechanical properties, so it usually contains fibrous reinforcing agents such as glass fiber. By increasing the temperature, the mechanical properties are improved, and the heat resistance is further improved, and it is put into practical use.

And the glass fiber reinforced P tower makes use of these characteristics,
Although it is being widely applied to electrical parts such as connectors for various home appliances and instruments, and substrates for printed wiring boards, it has a major drawback in these applications: the electrical properties deteriorate when moisture is absorbed.

In order to improve this drawback, methods have been adopted in which inorganic powders such as fused silica or barium titanate are used in place of glass fibers, or methods are used in which glass fibers and inorganic powders are used together. The problem is that not only the electrical properties are greatly deteriorated, but also the effect of suppressing the deterioration of the electrical properties upon moisture absorption is small. Therefore, the present inventors investigated with the aim of improving the deterioration in electrical properties during moisture absorption, which is essentially caused by adding glass fiber to P. As a result, the present inventors found that ,
Furthermore, the present inventors have discovered that by interposing a specific compound, not only can the deterioration of the glitter properties during moisture absorption be effectively suppressed, but also the mechanical properties of the composition can be further improved, and the present invention has been achieved.

That is, the present invention provides a glass fiber-reinforced polyphenylene sulfide resin composition characterized in that a halosilane compound represented by the following general formula (1) is interposed in a polyphenylene sulfide resin containing glass fibers.

(However, R in the formula is a straight mirror alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms, × is a halogen atom bonded to the terminal of R, and Y is an alkoxy group having 1 to 3 carbon atoms or a halogen The PR used in the present invention is a polymer containing 90 mol% or more, preferably 95 mol% or more of repeating units represented by the structural formula, at a temperature of 300°C and an apparent shear rate of 200/s.
The melt viscosity measured under EC conditions is 50% and 500%.
00 poise, preferably 100 poise, to 5000 poise is suitable.

Note that ordinary additives such as antioxidants, heat stabilizers, lubricants, crystal nucleating agents, ultraviolet absorbers, colorants, fillers, and mold release agents can be added to the P$ used, and the present invention It is also possible to blend a small proportion of Ikedate polymer within a range that does not impede the purpose of. The form of the glass fiber used in the present invention may be chopped fiber, chopped fiber mat, continuous long fiber mat, woven fabric, knitted fabric, or a combination of two or more of these, as long as the length in the molded product is 0.1 or more. It can be used in any condition.

The content of glass fiber is suitably 15 to 8% by weight,
If it is less than 15% by weight, sufficient mechanical properties cannot be obtained, which is not preferable. The halosilane compound used in the present invention is
As shown in the above general formula (1), it is a silane compound in which a halogen atom X is bonded to an organic functional moiety R. Specifically, the following compounds are mentioned, and two or more of these can be used in combination. can.

○1CH21CH2Si(OMe)3~y-chloropropyltrimethoxysilane, CI-CH2CH21Si
(OEt) 3-2-chloroethyltriethoxysilane,
CI-CH2-Si(OEt)3~chloromethyltriethoxysilane, PPS containing glass fiber in the present invention
On the other hand, as a means for intervening the above-mentioned halosilane compound, there is a method in which glass fibers are treated with a halosilane compound in advance and then blended and integrated with a P tower, and a method in which glass fibers, PPS
and a method of intimately mixing three halosilane compounds.

The appropriate amount of halosilane compound used in this case is 0.05 to 10% by weight based on the glass fiber used, and 0.0% to 10% by weight based on the glass fiber used.
If it is less than 5% by weight, the desired effect cannot be obtained, which is not preferable. Although the halosilane compound used in the present invention is generally known as a coupling agent for fibrous reinforcing agents, the effect of improving the electrical properties and mechanical properties of the present invention can be achieved regardless of the use of any silane coupling agent. However, even if unsaturated silanes and aminosilanes, which are other typical silane coupling agents, are used, the desired effects of the present invention cannot be obtained.

That is, in the present invention, the halosilane compound is used in combination with glass fiber and PP.
This unique novelty has the so-called coupling effect of increasing the adhesive strength at the S interface and improving the mechanical properties of molded products made of the composition, as well as suppressing the deterioration of electrical properties of molded products made of the composition when moisture is absorbed. The invention is based on the discovery that the invention is effective. There are no particular limitations on the means for preparing the composition of the present invention, such as melt-mixing glass fibers treated with a halosilane compound and PPS, or melt-mixing a halosilane compound, glass fibers, and PPS to form a pellet. Examples include chopped fibers treated with halosilane compounds, chopped fiber mats, continuous long fiber mats,
By spraying P-tower powder on glass fibers such as woven or knitted fabrics or laminating PPS sheets and integrating them under heat and pressure, sheet-like molded products or three-dimensional shaped products can be directly produced. However, the glass fiber-reinforced PPS sheet thus obtained is useful as a substrate for a printed wiring board to which metal foil such as copper foil is laminated. The molded product obtained from the glass fiber reinforced P-based composition of the present invention has excellent electrical, thermal, and mechanical properties and good heat resistance, so it is highly expected to be applied to the electrical industry. . The present invention will be explained in more detail with reference to Examples below.

Example 1 Sodium sulfide 32.6k9 (25
0 mol, crystal water (contains 4 t%), sodium hydroxide 1
0M, sodium benzoate 36.1 kg (250 moles)
, and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 79.2k9 and gradually stirred to 20
The temperature was raised to 5° C., and 7.0 ml of crab extract containing 6.9 k9 of water was removed.

37.5 kg of 1,4-dichlorobenzene was added to the residual mixture.
(255 mol) and NMP20.0k9,
It was heated at 65 qo for 4 hours. The reaction product was washed 8 times with boiling water and dried at 80°C for 2 hours using a vacuum dryer.
Powder form with melt viscosity of 2900 poise and high degree of polymerization PR21.1
I got k9. Glass fibers (chopped strands with a length of 3 bars) treated with the above PPS and a 1% aqueous solution of the silane compounds shown in Table 1 were mixed with fused silica in the proportions shown in Table 1, and the injection molding temperature was 32,000 and the injection pressure was 1200～
Test pieces were prepared by injection molding in a 12 mm mold in a 1,500 k9/base system, and their physical properties were measured.

The results are shown in Table 1. It is clear from Table 1 that PPS using glass fibers treated with a halosilane compound has excellent mechanical and electrical properties.

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The qOL feeling is also good. The P powder of Example 1 was uniformly sprinkled on a mat, fed into a mold heated to 32 mm, compressed and shaped, and then cooled to 150° C. to produce a plate-shaped molded product.

Table 2 shows the results of measuring the insulation resistance of this test piece under normal conditions and after boiling it in water for 2 hours based on JISCM81.

As is clear from Table 2, by treating glass fiber with a halosilane compound, the electrical insulation properties during moisture absorption are significantly improved, but this effect is uniquely obtained in the case of halosilane among silane compounds. Even if other silane compounds such as vinyl silanes, aminosilanes, etc. are used, no improvement can be obtained.

Table 2 Note) a y-chloropropyltrimethoxysilane manufactured by Toray Silicone ■ b 2-chloroethyltrimethoxysilane C manufactured by Nippon ■ 1-(dimethylchlorosilyl)-2-(p, m-chloro Methylphenyl)ethane d Methyltrimethoxysilane e manufactured by Toray Silicone ■ Vinyltrichlorosilane f manufactured by NUC Corporation NUC
Pinyltriethoxysilane g Toray Silicone■
Manufactured Hexamethylene Silazane Part 3 Totane Publication of amendment pursuant to the provisions of Article 17-3 of the Patent Law Published on September 26, 1982 Patent Application No. 178363
No. (Special Publication No. 60-11062, Published in Patent Publication No. 3-22 [463] published on March 22, 8860) has been amended pursuant to the provisions of Article 17-3 of the Patent Law, so the following is as follows: Post.

Patent No. 1609056 lnt. C.I. 5 Identification symbol Internal office reference number C0
8L81/02 8721-4JC08K
7/14 CAH 7167-4J9/06
CAll 7167-4J Note 1 The "Claims" section was changed to "1. A polyphenylene sulfide resin containing glass fibers is characterized by intervening a halosilane compound represented by the following general formula (1). Glass fiber-reinforced PO1" phenylene sulfide resin composition.

(In the formula, R represents a linear alkyl group or aryl group having 1 to 10 carbon atoms, X represents a halogen atom bonded to the terminal of R, and Y represents an alkoxy group or halogen atom having 1 to 3 carbon atoms. .

)” is corrected. 2 Column 3, line 7, "aryl... group" is corrected to "or aryl group."

3 Column 3, lines 8-24 Delete.

4 Page 4, Table 1 (continued) Note: a) ASTM D638 b) 〃 D790 c) D256 d) 7-Chlorpropyltrimethoxysilane manufactured by Toray Silicone ■ e) Titsu, No ( Vertical chlorophenyltriethoxysilane f) Toray Silicone ■ Methyltrimethoxysilane”.

5 Refer to Table 2 on page 5 as "Table 2 Note) a) 7-chloropropyltrimethoxysilane manufactured by Toray Silicone ■ b) 2-chloroethyltrimethoxysilane manufactured by Chisso ■ c) Methyltrimethoxysilane manufactured by Toray Silicone ■ d ) Vinylt 1'' chlorosilane manufactured by NUC Corporation e) Vinyltriethoxysilane f) Hexamethylenesilazane manufactured by Toray Silicone■.

Claims (1)

[Scope of Claims] 1. A glass fiber-reinforced polyphenylene sulfide resin composition, characterized in that a halosilane compound represented by the following general formula (I) is interposed in a polyphenylene sulfide resin containing glass fibers. thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R in the formula is a linear alkyl group with 1 to 0 carbon atoms, an aryl group, or an aralkyl group, X is a halogen atom bonded to the terminal of R, and Y is a Indicates an alkoxy group having 1 to 3 carbon atoms or a halogen atom.)