JPH0627261B2 - Polyphenylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a specific silane compound-containing polyphenylene sulfide resin composition having excellent mechanical properties and electrical properties.

(Prior art and its problems) Polyphenylene sulfide resin is known as a high-performance engineering plastic with excellent chemical resistance, electrical characteristics, heat resistance, and flame retardancy, but the resin alone is extremely brittle. Generally, an inorganic filler such as glass fiber is contained to improve mechanical properties and heat resistance.

And glass fiber reinforced polyphenylene sulfide,
Utilizing these performances, it is applied to various electric parts applications,
Further, in recent years, it has been attracting attention as a sealing material for electronic parts, but it has a drawback that electrical characteristics are deteriorated when absorbing moisture. In order to improve this, US Pat. No. 433
7182 and 4176098, JP-A-51-12
861, JP-A-55-29526, JP-A-59-3
No. 1503 suggests that a polyphenylene sulfide resin composition contains a silane compound having an alkyl group, an epoxy group, an amino group, a vinyl group, and a mercapto group at the end, but it has an alkyl group, a vinyl group, and a mercapto group. However, the moisture resistance is improved, but the strength is not improved. In addition, those having an epoxy group or an amino group have not yet obtained sufficient performance such that the strength is improved but the moisture resistance is not improved. Further, a coupling agent having both a vinyl group and an amino group, which is in the form of a hydrochloride salt, is also presented, but this is a corrosion of the mold or discoloration of the lead frame when used as a sealing material. Had the drawback of causing

(Means for Solving the Problems) As a result of intensive studies in view of the above situation, the present inventors have further investigated the polyphenylene sulfide resin and the fibrous filler and / or other siliceous filler. The inventors have found that the strength characteristics and the electric characteristics upon moisture absorption are remarkably improved by interposing a specific compound, and the present invention has been completed.

That is, the present invention relates to a polyphenylene sulfide resin, a fibrous filler and / or another siliceous filler, a silane compound having at least two unsaturated double bonds in one molecule, and / or at least one silane compound in one molecule. A polyphenylene sulfide resin composition comprising a non-hydrochloric silane compound having an unsaturated double bond and at least one amino group.

The polyphenylene sulfide resin used in the present invention has a general formula Those containing 70 mol% or more of the structural unit represented by are preferable, and uncrosslinked products, partially crosslinked products or mixtures thereof are used. The resin has a logarithmic viscosity of 0.05 to 0.4,
Particularly preferred is 0.08 to 0.35. However, the logarithmic viscosity [η] was measured at 200 ° C. in α-chloronaphthalene so that the polymer concentration was 0.4 g / 100 ml, and the following formula It is calculated by.

As the fibrous filler used in the present invention, glass fiber,
Asbestos fiber, silica fiber, silica-alumina fiber,
Alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, silicon carbide whiskers, potassium titanate whiskers, calcium silicate fibers, polyamide fibers and the like can be mentioned.

The fibrous filler is not particularly specified in terms of fiber length and fiber diameter, but in general, the number average fiber length is 20 mm or less,
Preferably 5 mm or less, more preferably 500 μm or less, particularly preferably 100 μm or less, fiber diameter 20 μm
Or less, preferably 13 μm or less, more preferably 10 μm or less.
A particle size of less than or equal to μm, particularly preferably less than or equal to 6 μm is used, and it may be treated with a sizing agent or another coupling agent and may be used at all.

Next, other siliceous fillers include silica, talc, clay, mica, glass, calcium silicate, montmorillonite, bentonite, and the like, commercially available natural products, purified products, pulverized products of synthetic products, spherical and Hollow ones are available. For example, silica is preferable as a sealing material in which electrical characteristics are particularly important and a small coefficient of thermal expansion is required.

The particle size of the filler is not particularly limited, but generally 500 μm or less is used, and it may be treated with other coupling agents.

The silane compound having at least two vinyl groups in the molecule used in the present invention does not usually contain an amino group, and not only a usual silane coupling agent but also an oligomerized one, a resin A modified product can be used.

For example, 2-trichlorosilyl-
1,3 butadiene, 2-trimethoxysilyl-1,3 butadiene, 2-dimethoxyethoxysilyl-1,3 butadiene, 2-dimethylchlorosilyl-1,3 butadiene, 2-methyldiethoxysilyl-1,3 butadiene and These polymers include vinylsilanes, and cohydrolysates such as vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltrimethoxyethoxysilane.

The non-hydrochloric acid silane compound used in the present invention has two reactive functional groups, that is, at least one unsaturated double bond and at least one amino group, preferably three or less amino groups,
More preferably, it is a silane compound having two or less, and particularly preferably one, which is not a hydrochloride. Hydrochloric acid is not preferable because hydrochloric acid remains in the composition and gas is generated during molding. The two functional groups may be at the terminal of the molecule or in the molecular chain, and not only usual silane coupling agents but also oligomerized ones and resin-modified ones can be used. For example, N-β- (N-vinylbenzylamino) ethyl-δ-aminopropyltrimethoxysilane, N-vinylbenzyl-δ-aminopropyltriethoxysilane and N-vinylmethyl-δ- Examples include aminopropyltriethoxysilane, a cohydrolyzate of vinylethoxysilane and γ-aminopropyltriethoxysilane, and the like.

As the silane compound in the present invention, the above-mentioned non-hydrochloric acid silane compound is preferable since it has a large effect of improving strength.

The proportion of (a) polyphenylene sulfide resin, (a) fibrous filler and / or (c) siliceous filler, and (d) silane compound in the present invention is generally (a) 100.
The total amount of (a) and (c) is 500 parts by weight or less, preferably 300 parts by weight or less, and (d) 0.01 to 10 parts by weight to 100 parts by weight of the total of (a) and (c). , Preferably 0.3 to 5 parts by weight. In addition, as a method for preparing the composition by (a) to (d), (i) and / or (c) is treated with (d) and then heat-treated as it is or at a decomposition temperature of (d) or lower. Then, the method of melt-mixing with (a) is generally used, but the method is not limited to this. A method of simultaneously mixing (a) to (d), a method of mixing (d) with (a) After that, a method of mixing with (a) and / or (c) can be arbitrarily selected. Further, an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, a coloring agent, an ultraviolet absorber, a coupling agent, and another kind of polymer can be added and blended within a range that does not impair the object of the present invention.

(Effects of the Invention) The resin composition according to the present invention has excellent strength characteristics and electric characteristics when absorbing moisture, and therefore, a sealing material for electronic parts,
It is very useful as a substrate for printed wiring boards and as a connector for various electrical component instruments.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples. Example Chubu,
All percentages are by weight.

Examples 1-5, Comparative Examples 1-4 Ryton V-1 (Made by Philippe Spestrian Arm Co., Ltd.
Table 1 for PPS, [η] 0.15), fillers and silane compounds.
After mixing at the ratio shown in, melt-kneading with an extruder and pelletizing.
Turned into 3 ounce injection molding machine (cylinder temperature 3
Mold the test piece at 20 ℃, mold temperature 150 ℃,
The physical properties were measured. Clearly the molded article according to the invention is mechanical
It also exhibits excellent electric characteristics when absorbing moisture.

Examples 6-10, Comparative Examples 5-8 Ryton (PP manufactured by Philippe Petroleum)
S), the filler and the silane compound are mixed in the ratio shown in Table-2.
After combining, they were melt-kneaded and pelletized by an extruder. this
3 ounce injection molding machine (cylinder temperature 320 ℃, mold temperature
The test piece was molded at a temperature of 150 ° C.) and the physical properties were measured.

Claims (1)

[Claims] 1. A polyphenylene sulfide resin, a fibrous filler and / or another siliceous filler, a silane compound having at least two unsaturated double bonds in one molecule, and / or at least one molecule. A polyphenylene sulfide resin composition comprising a non-hydrochloric silane compound having one unsaturated double bond and at least one amino group.