KR20210050032A - Thermoplastic resin composition for electrostatic discharge comprising carbon-based fillers and molded article comprising the same - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition for electrostatic discharge comprising a carbon-based filler and a molded article comprising the same and, more particularly, to a thermoplastic resin composition and a molded article comprising the same, wherein the thermoplastic resin composition, by adding a combination of carbon nanotubes and conductive carbon black as a carbon-based filler in a specific content ratio to a composite composition containing a thermoplastic polyphenylene ether (PPE) resin, a high-impact polystyrene (HIPS) resin and a glass fiber, has excellent surface resistance to exhibit an antistatic effect, and at the same time is excellent in physical properties such as moldability, strength, electrical conductivity, thermal stability and the like.

Description

Thermoplastic resin composition for electrostatic discharge comprising carbon-based fillers and molded article comprising the same}

The present invention relates to a thermoplastic resin composition for electrostatic discharge including a carbon-based filler and a molded article including the same, and more specifically, a thermoplastic polyphenylene ether (PPE) resin, a high impact polystyrene (HIPS) resin, and a glass fiber. By adding a combination of carbon nanotubes and conductive carbon black as a carbon-based filler to the containing composite composition in a specific content ratio, it has excellent surface resistance and exhibits an antistatic effect, and at the same time, it exhibits an antistatic effect, such as moldability, strength, electrical conductivity, and thermal stability. It relates to a thermoplastic resin composition having excellent physical properties and a molded article including the same.

Recently, due to the development of electronic product technology, electronic products have been miniaturized, highly integrated, and high-performance, and accordingly, electrically conductive materials are used to prevent electrical damage that may occur during transportation and storage of materials such as electronic products and parts. .

Examples of the use of the above applications include electronic parts transfer carts, electronic parts transfer pipe coating materials, and thermoforming electronic parts trays (IC trays). Is being used.

The tray or the like is determined in size and shape according to the type and type of the semiconductor chip, and may serve to prevent damage such as electric shock due to dust, moisture, or the like to a component on which a circuit or the like is printed.

The cart, pipe tray, etc. may include a process of heating to remove moisture during the manufacturing process of parts. For example, since the tray containing the parts may be baked, the material such as the tray is Properties such as heat resistance, stability before and after baking, low distortion, electrostatic dispersion, surface resistance, electrical conductivity, and low sloughing are required.

Conventionally, in order to satisfy the above physical properties, a number of materials using carbon fiber or carbon black have been used.

However, when carbon fibers or carbon black are included, there is a limitation in that it is difficult to improve moldability and low sloughing characteristics. In addition, specifically, there is a problem in that the moldability is inferior due to the high carbon filler content and carbon is buried.

Therefore, a composition that maintains an excellent balance of physical properties such as moldability, strength, low sloughing, surface resistance, and electrostatic dispersion, while being a polymer material for electro-static discharge (ESD) containing a carbon-based filler. Is being demanded.

An object of the present invention is a thermoplastic resin composition comprising a carbon-based filler, which has excellent surface resistance and exhibits an antistatic effect, and also has excellent physical properties such as moldability, strength, electrical conductivity, and thermal stability, and includes the same. It is to provide molded products.

The present invention to solve the above technical problem, (1) a thermoplastic polyphenylene ether resin; (2) high impact polystyrene resin; (3) glass fiber; And (4) a carbon-based composite filler, which is a combination of carbon nanotubes and conductive carbon black, wherein the content of the (4) carbon-based composite filler is 7 parts by weight or more based on a total of 100 parts by weight of the resin composition. It provides a resin composition.

According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

The thermoplastic resin composition according to the present invention exhibits an antistatic effect and has excellent balance of physical properties such as moldability, strength, and heat distortion temperature, and is used as a material for products that simultaneously require electrostatic discharge characteristics, strength, electrical conductivity, and thermal stability. It can be used suitably.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention includes a thermoplastic polyphenylene ether (PPE) resin.

In one embodiment, the thermoplastic polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4- Phenylene) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethyl- Copolymer of 1,4-phenylene) ether and poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether and poly( A copolymer of 2,3,5-triethyl-1,4-phenylene) ether, or a combination thereof, may be used, and more specifically, poly(2,6-dimethyl-1,4-phenylene) A copolymer of ether and poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, or a combination thereof may be used. , More specifically, poly(2,6-dimethyl-1,4-phenylene) ether may be used.

The degree of polymerization of the thermoplastic polyphenylene ether resin is not particularly limited, but considering the thermal stability or workability of the resin composition, it may be appropriate that the intrinsic viscosity measured in a chloroform solvent at 25° C. is 0.2 to 0.8.

In one embodiment, the thermoplastic resin composition of the present invention may include 30 to 75 parts by weight of a thermoplastic polyphenylene ether resin based on 100 parts by weight of the composition. If the content of the thermoplastic polyphenylene ether resin in 100 parts by weight of the resin composition is too low than the above level, rigidity and heat resistance may be deteriorated. Conversely, if it is too high than the above level, impact resistance may be deteriorated.

More specifically, the content of the thermoplastic polyphenylene ether resin in 100 parts by weight of the thermoplastic resin composition of the present invention may be 35 parts by weight or more, 40 parts by weight or more, or 45 parts by weight or more, and also 70 parts by weight or less, 65 parts by weight or less. Or 60 parts by weight or less.

The thermoplastic resin composition of the present invention also includes a high impact polystyrene (HIPS) resin.

High-impact polystyrene is an impact-resistant polystyrene, which takes the acronym of High Impact and is commonly referred to as HI-polystyrene (HIPS).

HI-polystyrene is a rubber compounded to improve the fragility of polystyrene, and its impact strength increases as the rubber content increases, while other properties such as tensile strength, heat resistance, light resistance, moldability, and surface gloss decrease. . In addition, by blending rubber, transparency is lost and it has a milky white opaque characteristic. As a method of blending rubber with polystyrene, there is a method of mechanically blending rubber and polystyrene or mixing them in a latex form, or a method of dissolving rubber in a styrene monomer for polymerization. When the styrene monomer in which rubber is dissolved in advance is polymerized, the rubber becomes a so-called graft polymer having polystyrene side chains, and the compatibility between the rubber and polystyrene increases, thereby improving impact resistance.

In one embodiment, as the high-impact polystyrene resin included in the thermoplastic resin composition of the present invention, a high-impact polystyrene resin prepared by such a grafting method may be used.

In one embodiment, the thermoplastic resin composition of the present invention may include 10 to 50 parts by weight of a high-impact polystyrene resin based on 100 parts by weight of the composition. If the content of the high-impact polystyrene resin in 100 parts by weight of the resin composition is too low than the above level, the impact resistance may deteriorate, and if it is too high than the above level, the stiffness and heat resistance may be deteriorated.

More specifically, the content of the high-impact polystyrene resin in 100 parts by weight of the thermoplastic resin composition of the present invention may be 12 parts by weight or more, 25 parts by weight or more, or 20 parts by weight or more, and also 45 parts by weight or less, 40 parts by weight or less, or 35 It may be less than or equal to parts by weight.

The thermoplastic resin composition of the present invention also includes glass fibers.

In one embodiment, as the glass fiber, a fiber glass filament may be collected through a sizing agent.

In one embodiment, the average diameter of the glass fibers may be, for example, 1 to 50 µm, 3 to 30 µm, or 3 to 20 µm, and the average length is, for example, 100 µm to 3 mm , 300 μm to 1 mm, or 500 μm to 1 mm may be, but is not limited thereto.

In one embodiment, the thermoplastic resin composition of the present invention may contain 1 to 20 parts by weight of glass fibers based on 100 parts by weight of the composition. If the glass fiber content in 100 parts by weight of the resin composition is too low than the above level, long-term dimensional stability and bending stiffness may be deteriorated. Conversely, if it is too high than the above level, the glass fiber may protrude to the surface during injection molding.

More specifically, the glass fiber content in 100 parts by weight of the thermoplastic resin composition of the present invention may be 2 parts by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and also 18 parts by weight or less, 15 parts by weight or less, or 10 parts by weight. It can be below.

The thermoplastic resin composition of the present invention also includes a carbon-based composite filler, which is a combination of carbon nanotubes and conductive carbon black.

As the carbon nanotubes, carbon nanotubes commonly used in this field may be used without limitation. For example, the carbon nanotubes may be single-walled carbon nanotubes (SWNTs), multi-walled carbon nanotubes (MWNTs), or a combination thereof. Not limited.

Unlike general carbon black, the conductive carbon black has a long chain structure. When added to a polymer resin, the particles form a chain structure to conduct electricity, or pi electrons jump between the carbon black particles to conduct conductivity. It is known that pi electrons jump when the distance between carbon black particles is 100 Å or less. Therefore, when the dispersion of the conductive carbon black is excellent and the particles are small, the distance between the carbon black particles is shortened, thereby increasing the role of the conductive path.

The thermoplastic resin composition of the present invention contains the carbon-based composite filler in an amount of 7 parts by weight or more, based on 100 parts by weight of the composition. If the content of the carbon-based composite filler in 100 parts by weight of the resin composition is less than 7 parts by weight, the electrostatic discharge effect will not be sufficient.

There is no particular limitation on the upper limit of the content of the carbon-based composite filler in the thermoplastic resin composition of the present invention, but in terms of flame retardancy, fluidity, and impact strength of the composition, it is appropriate that it is 25 parts by weight or less based on 100 parts by weight of the composition.

More specifically, the content of the carbon-based composite filler in 100 parts by weight of the thermoplastic resin composition of the present invention may be 8 parts by weight or more, 9 parts by weight or more, or 10 parts by weight or more, and also 22 parts by weight or less, 20 parts by weight or less, or 18 It may be less than or equal to parts by weight.

In one embodiment, the content of carbon nanotubes in 100 parts by weight of the thermoplastic resin composition of the present invention may be 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, or 3 parts by weight or more, and also 10 parts by weight. It may be parts by weight or less, 8 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less.

In one embodiment, the conductive carbon black content in 100 parts by weight of the thermoplastic resin composition of the present invention may be 2 parts by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and also 20 parts by weight or less, 18 parts by weight or less, or 16 parts by weight. It may be less than or equal to part.

In addition to the above components, the thermoplastic resin composition of the present invention may further include one or more additives commonly used in the thermoplastic resin composition, for example, a light stabilizer, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, a pigment, a dye, and It may include one or more of general carbon black.

In one embodiment, the light stabilizer is 2-(2'-hydroxyphenyl)-benzotriazole, 2-hydroxy-benzophenone, 2-(2'-hydroxy-5'-octylphenyl)benzotria Sol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(4,6-diphenyl-1,3,5-tri Azin-2-yl)-5-hexyloxy-phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol or 2,2' -Methylenebis(6-(2H-benzotriazol-2-yl))-4-(1,1,3,3-tetramethylbutyl)phenol and the like can be used.

In one embodiment, as the heat stabilizer, bisphenol A epoxy resin, monocarbodiimide, polycarbodiimide, or the like may be used.

In one embodiment, the antioxidant is tris(nonylphenyl)phosphite, (2,4,6-tri-tert-butylphenyl)(2-butyl-2-ethyl-1,3-propanediol)phosphite , Tris(2,4-dibutylphenyl)phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butyl-4-methylphenyl) Organophosphorous antioxidants such as pentaerythritol diphosphite or distearyl pentaerythritol diphosphite, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) pro Phenolic antioxidants such as cypionate or octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis(3-dodecylthiopropio) Thioester-based antioxidants such as nate) may be used.

In one embodiment, as the nucleating agent, talc, mica, silicate, ionomer, sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and the like may be used.

In one embodiment, as the lubricant, a long chain ester of pentaerythritol or stearyl stearate may be used.

According to another aspect of the present invention, there is provided a molded article comprising the thermoplastic resin composition of the present invention.

In one embodiment, the molded article of the present invention may be manufactured by extrusion, casting, blow molding, or injection molding the melt of the thermoplastic resin composition of the present invention.

In one embodiment, the molded article of the present invention may be an electronic component transfer cart, an electronic component transfer pipe coating material, or an electronic component tray for thermoforming.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[ Example ]

Components used in Examples and Comparative Examples of the present invention are as follows, and the contents of each component are as described in Tables 1 and 2.

PPE: Thermoplastic polyphenylene ether resin (poly(2,6-dimethyl-1,4-phenylene) ether) (PX-100F, Mitsubishi Chemical)

HIPS: High impact polystyrene resin () (HI425TVL, Kumho Petrochemical)

GF: Glass fiber (910-10P*, Owen Corning Korea)

CNT(1): Multi-walled carbon nanotubes, 99.9% purity (LG Chemical)

CNT(2): Multi-walled carbon nanotube, 99% purity (Nanocyl)

CB: Conductive carbon black (Unipetrol)

CF: carbon fiber

Other additives: Talc (KCP04), antioxidant (IRG168, 412S), release agent (PETS AHS)

The thermoplastic resin compositions of Examples 1 to 7 and the thermoplastic resin compositions of Comparative Examples 1 to 7 were prepared by mixing the components shown in Tables 1 and 2 in the amounts described. Subsequently, extrusion of each of the prepared thermoplastic resin compositions was performed using a 32 pie twin-screw extruder under conditions of 230°C to 250°C and 200 rpm to 250 rpm, and an injection machine having a clamping force of 100 tons to 200 tons under the same temperature conditions. An injection specimen was prepared by using.

In the case of an injection specimen for measuring mechanical properties, an injection specimen conforming to each ISO standard was prepared so as to be suitable for measuring tensile strength and flexural strength.

[Table 1]

[Table 2]

[Physical property evaluation]

(1) surface resistance

The surface resistance of the injection specimens made of the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was measured using HirestaUX equipment and LorestGX equipment of Mitsybushi Chemical Analytech. The results measured by the device are ^{displayed as 10 x} values, and if the order of the surface resistance is low, it can be confirmed that the surface resistance is low.

(2) dispersibility

The carbon material 　 dispersibility of the injection 　 specimens prepared with the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was measured using a CM-M6 Spectrophotometer of Minolta. The lower the dispersibility 　 value is, the higher the dispersibility of the carbon material 　.

(3) processability

In the process of manufacturing an injection specimen using the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7, the overall processability is excellent in consideration of whether gas is generated during extrusion or injection, swell phenomenon, and constant input of raw materials. The degree was evaluated in 5 steps as follows.

-Very good: No problem at all during extrusion

-Excellent: The above-described problem exists minutely during extrusion, but there is no problem at all in production

-Good: The above-described problem exists during extrusion, but there is no problem in production

-Poor: The above-described problem exists during extrusion, and there is a problem in production, especially due to the severe swell phenomenon.

-Very poor: Production is difficult because the overall problem such as gas generation during extrusion, swell phenomenon, and raw material input is too serious.

(4) Tensile strength

Tensile strength was measured according to ISO for injection specimens made of the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7.

(5) flexural strength

The flexural strength of the extruded specimens made of the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was measured according to ISO.

(6) Heat deflection temperature

The heat deflection temperature was measured based on ISO for the injection specimens made of the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7.

[Table 3]

[Table 4]

As shown in Table 3, it can be seen that all of the thermoplastic resin compositions of the examples according to the present invention have excellent processability, excellent surface resistance, dispersibility, and mechanical properties, and that the heat deflection temperature is also kept constant.

On the other hand, as shown in Table 4, Comparative Example 1 had very poor dispersibility, Comparative Example 2 had very poor processability and dispersibility, and mechanical properties were also severely deteriorated, and Comparative Example 3 had a surface resistance to a target level. And mechanical properties were severely degraded, and Comparative Example 4 had very poor dispersibility and extrusion and injection processing were not possible, Comparative Example 5 had poor surface resistance and mechanical properties, and Comparative Example 6 had dispersibility and mechanical properties. This was severely lowered and the heat deflection temperature was also low. In Comparative Example 7, the surface resistance did not reach the target level, the dispersibility and mechanical properties were severely deteriorated, and the heat deflection temperature was also low.

Claims (7)

(1) thermoplastic polyphenylene ether resin;
(2) high impact polystyrene resin;
(3) glass fiber; And
(4) a carbon-based composite filler that is a combination of carbon nanotubes and conductive carbon black; and,
The content of the (4) carbon-based composite filler is 7 parts by weight or more, based on a total of 100 parts by weight of the resin composition,
Thermoplastic resin composition. The method of claim 1, wherein the thermoplastic polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene) ether, and poly( 2,6-dipropyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-propyl-1,4-phenyl Ren) ether, poly(2-ethyl-6-propyl-1,4-phenylene) ether, poly(2,6-diphenyl-1,4-phenylene) ether, poly(2,6-dimethyl-1 Copolymer of ,4-phenylene) ether and poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether and poly(2) A copolymer of ,3,5-triethyl-1,4-phenylene) ether, or a combination thereof may be used, and more specifically, poly(2,6-dimethyl-1,4-phenylene) ether And poly(2,3,6-trimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, or a combination thereof, a thermoplastic resin composition . The thermoplastic resin composition according to claim 1, wherein the high-impact polystyrene resin is a high-impact polystyrene resin produced by a graft method. The thermoplastic resin composition according to claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes, multi-walled carbon nanotubes, or a combination thereof. The thermoplastic resin composition of claim 1, further comprising at least one additive selected from a light stabilizer, a heat stabilizer, an antioxidant, a nucleating agent, a lubricant, a pigment, a dye, and a general carbon black. A molded article comprising the thermoplastic resin composition of claim 1. The molded article according to claim 6, which is an electronic component transfer cart, an electronic component transfer pipe coating material, or an electronic component tray for thermoforming.