JPS61272267A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition of high functionality approaching ceramics, especially of both outstanding wear resistance and hardness, for use in structural members, electric and electronic parts, by incorporating thermoplastic resin with silicon nitride and a silane-based coupling agent for silicon nitride. CONSTITUTION:The objective composition can be obtained by incorporating (A) a thermoplastic resin such as ABS resin or styrene resin with (B) 10-80 inner wt% of silicon nitride with a granular size <=100 (pref. <=50)mum, pref. of inexpensive beta-type or low alpha-type and (C) 0.5-3 outer wt% based on the component (B) of a silane coupling agent for silicon nitride, (e.g., 3-aminopropyl triethoxysilane). The process is pref. as follows: the components (B) and (C) are premixed each other followed by blending the component (A) and, if needed, various filler, releasing agent, colorant, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is particularly useful as a structural member, and is particularly useful as a wiring component,
This relates to thermoplastic resin compositions that can be used for electrical parts, electronic parts, etc., and its purpose is to improve surface hardness, wear resistance,
The objective is to provide various functions such as bending strength, bending elasticity, dimensional stability, heat resistance, electrical insulation, and thermal conductivity all at once.

[Conventional technology]

Conventionally, thermoplastic resins include general-purpose plastics and engineering plastics called engineering plastics or super engineering plastics, and although the latter have been improved in functionality, they naturally have their limits. On the other hand, in the field of ceramics, oxide-based general-purpose ceramics and non-oxide-based ceramics such as depressions and carbides are attracting attention as engineering ceramics, but commercializing them requires a great deal of equipment and experience. is necessary.

[Problem that the invention seeks to solve]

As a result of various studies aimed at improving the high functionality of plastics that is closer to that of ceramics, especially the abrasion resistance and high hardness that were extremely difficult to achieve with conventional engineering plastics, the inventors of the present invention found that they could replace conventional fillers. The present invention was completed based on the discovery that it is sufficient to use silicon nitride and a surface treatment agent for silicon nitride in addition to conventional fillers.

[Means for solving problems]

The present invention is a thermoplastic resin composition containing silicon nitride and a silane-based surface treatment agent for silicon nitride.

Hereinafter, the present invention will be explained in more detail.

There are two types of silicon nitride: α-type and β-type. In the present invention, the same degree of effectiveness can be obtained using either form, so the inexpensive β-type or low-α type silicon nitride is used. It is desirable to use Further, from the viewpoints of crosstalk, filling properties, and moldability, the particle size is desirably 100 μm or less, particularly 50 μm or less.

The filling amount of silicon nitride is about 10 to 85 inches on the inside weight of the thermoplastic resin, but in order to improve dimensional stability, abrasion resistance, heat resistance, and thermal conductivity, it is necessary to fill the thermoplastic resin with 20 to 75 inches on the surface. 10 to 7 for improving hardness, bending strength, and bending elastic modulus
It is desirable to set it to 5%. If the amount is less than 10%, the effect of improving various functions will be small, and if the amount is more than 85%, crosstalk, filling properties, and moldability will deteriorate. In addition to the above-mentioned functions, it has been difficult to improve wear resistance and high hardness with conventional engineering plastics.

Surface treatment agents for silicon nitride are necessary to promote the effects of imparting the various functions described above, and include silane-based, titanate-based,
Although aluminate-based and poran-based compounds are used, silane-based compounds are preferred in the present invention because they exhibit a large promoting effect.

Examples of silane compounds include 3-(2-aminoethyl)aminopropyltrimethoxysilane, 6-aminoprogyltriethoxysilane, 6-gelisidoxyzologyltrimethoxysilane, 6-chlorozolopyltrimethoxysilane, and 3-methacrylate. Roxypropyltrimethoxysilane, 3-mercazotoprotrimethoxysilane, etc.
can be given.

The amount of the silane-based surface treatment agent for silicon nitride used is preferably 0.5 to 3% by weight based on the silicon nitride for external machining, and within this range, the smaller the particle size of the silicon nitride, the larger the amount required to be added. There is a tendency to

A more preferable usage amount is 0.7 to 1.0% by weight.

Thermoplastic resins used in the present invention include AB8 resin, styrene resin, divinyl chloride resin, polyamide resin such as nylon 6, nylon 66, and nylon 12, propylene resin, ethylene resin, fluororesin, - Remethacrylate resin, aramid resin, polyphenylene sulfide (PP8), polyethylene terephthalate) (P
ET), polybutylene terephthalate (I'BT), /
Rifuenylene Odot IF (PI'O), polycarbonate (FO), polyetheretherketone (PI'O), polycarbonate (FO), polyetheretherketone (PI'O),
IiE! K), polyacetal (I'OM),
Polysal 7one (P day), polyether sulfone (I
It is one or more selected from IKB), etc., and modified products thereof, and can be used regardless of powder form or granule form (pellet form).

To mix silicon nitride, silicon snow silane surface treatment agent, and thermoplastic resin, they can be mixed by putting them all at once into a mixer, but first, silicon nitride and silicon nitride silane surface treatment agent are mixed. It is preferable to mix the above and then add the thermoplastic resin to the mixture, from the viewpoint of uniform dispersion and wettability between silicon nitride and the thermoplastic resin.

The thermoplastic resin composition of the present invention includes calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, calcium silicate, Merck, clay, mica, glass balloon, crow heather, amorphous silica, crystalline silica, and alumina. , silicon carbide, zirconia, boron nitride, aluminum nitride, and other lightning reinforcement materials, fibers, mold release agents, colorants, antioxidants, dispersants, and other components may be used as appropriate, as required.

The thermoplastic resin composition of the present invention can be applied to all conventional uses using thermoplastic resins. For example, parts that utilize mechanical properties such as surface hardness, wear resistance, bending strength, and flexural modulus include gears, cams, and bearings, and various parts that utilize dimensional stability. For structural members of optical lenses and barrels of optical lenses, insulation,
For example, materials that utilize thermal conductivity, heat resistance, and dimensional stability are suitable for use as fillers and protective materials for dissipating heat generated from electrical and electronic components such as semiconductor chips and resistors. .

The following is a more detailed explanation using examples [Example] Example 1 Mixing silicon nitride and a silane-based surface treatment agent of 1% by weight of silicon nitride by external grinding based on silicon nitride using an omnimixer. Next, nylon 6 was added, mixed and mixed, and then ground to obtain a thermoplastic resin composition. This was put into a mold and hot press molded to obtain a flat plate-shaped product with dimensions of 170 x 170 x 3x*.

Various physical properties of this molded article were measured. The result is the first
Shown in the table.

For comparison, tests were conducted in the case where silicon nitride was not added (Experiment 46) and the case where a silane-based surface treatment agent for silicon nitride was not added (Experiment 47).

The materials used in the Examples and Comparative Examples and the methods for measuring physical properties are as follows.

Materials 0 Silicon silicide...β type, purity 99 weight ratio, particle size 44μ or less (Denki Kagaku Kogyo Co., Ltd. part name [8N-BJ) 0 Nitride, silicon silane surface treatment agent...3-aminoprot Lutriethoxysilane (trade name: Sila Ace 8330J, manufactured by Chisso Corporation) 0 Nylon 6...trade name, r1011FJ, manufactured by Ube Industries, Ltd.
Physical property measurement method: 0 Rock hardness: Measured according to J-8K 7202.

0 bending strength..., measured according to rxsx 7203.

Distance between fulcrums: 60n Loading speed: 2 tm/m1n O bending elastic modulus: Measured according to J Engineering EIK 7203.

0 Thermal deformation intensity [HDT] ・Measured in accordance with 6911 for T-work 8.

Bending crab 18-5 k! ! f/am20 maximum deflection: Measured according to J Engineering E1m 7203.

Example 2 As a thermoplastic resin, PP8 (trade name [Rydon'-4J, manufactured by Phillips Petroleum Co., Ltd.] was used; as a silane-based surface treatment agent for silicon nitride, 3-chloropropyltrimethoxysilane (trade name, manufactured by Chisso Corporation, [Sila Ace 8620J and silicon nitride) was used. A molded product was prepared using the same material as in Example 1, and the thermal conductivity, amount of wear, molding shrinkage rate, and coefficient of linear expansion were measured.

The results are shown in Table 2.

For comparison, when silicon nitride is not mixed (experiment/161
3) and the case in which a silane-based surface treatment agent for silicon nitride was not added (Experiment 414) were tested.

Physical property measurement method 0 Thermal conductivity...Heat conduction vehicle measuring device (Agne Co., Ltd. "AB"
C-To-1 type) at a temperature of 20° C. by the temperature gradient method.

0 wear amount: Measured according to J Engineering INK 7204K.

Type of wear wheel: O8-17 Number of revolutions: 1.000 times Load = 1kl! O Molding shrinkage rate: The ratio of the amount of shrinkage of the molded product immediately after molding to the mold dimensions was measured.

A: Mold dimensions B: Molded product dimensions 0 linear expansion coefficient: Measured using a Takashi Manufacturing Co., Ltd. device [TMA J] at a temperature of 20 to 80° C. and a load of 2 g.

〔Effect of the invention〕

The thermoplastic resin composition of the present invention has surface hardness, abrasion resistance,
It has excellent physical properties such as bending strength, bending elasticity, dimensional stability, heat resistance, electrical insulation, and thermal conductivity, and is used as structural members and electronic/electrical parts.

In particular, it has been difficult to improve wear resistance and high hardness with conventional engineering plastics.

Claims (1)

[Claims] (1) Thermoplastic resin composition containing silicon nitride and a silane-based surface treatment agent for silicon nitride