KR102272920B1 - 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 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 in a specific content ratio to the composite composition comprising the composite material, it has excellent surface resistance and exhibits an antistatic effect, while improving moldability, strength, electrical conductivity, thermal stability, etc. It relates to a thermoplastic resin composition having excellent physical properties and a molded article including the same.

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 comprising a carbon-based filler and a molded article comprising the same, and more particularly, to 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 in a specific content ratio to the composite composition comprising the composite material, it has excellent surface resistance and exhibits an antistatic effect, while improving moldability, strength, electrical conductivity, thermal stability, etc. It relates to a thermoplastic resin composition having excellent physical properties and a molded article including the same.

Recently, with the development of electronic product technology, electronic products are miniaturized, highly integrated, and high-performance. Accordingly, in order to prevent electrical damage that may occur during transport and storage of materials such as electronic products and parts, electrically conductive materials are used. .

As used for the above purposes, there are, for example, an electronic component transfer cart, an electronic component transfer pipe coating material, an electronic component tray for thermoforming (IC tray), etc., and transport between manufacturing processes of semiconductor chips and packaging after manufacturing, etc. is being used

The tray or the like has a size and shape determined according to the type and type of the semiconductor chip, and may serve to prevent damage such as an electric shock caused by dust, moisture, etc. to parts on which circuits are printed.

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

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

However, when carbon fiber or carbon black is included, there is a limitation in that it is difficult to improve formability and low sloughing characteristics. In addition, specifically, there is a problem in that the carbon filler content is high, the moldability is deteriorated, and the carbon is smeared.

Therefore, while being a polymer material for electrostatic discharge (ESD) containing a carbon-based filler, a composition that maintains an excellent balance in properties such as moldability, strength, low sloughing, surface resistance, and electrostatic dispersion this is being requested

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 at the same time has excellent physical properties such as moldability, strength, electrical conductivity, and thermal stability, and a thermoplastic resin composition including the same to provide molded products that

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

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

The thermoplastic resin composition according to the present invention exhibits an antistatic effect and also has excellent balance of properties such as moldability, strength, and heat deformation temperature, making it a material for products requiring static discharge characteristics, strength, electrical conductivity, and thermal stability at the same time. can be used appropriately.

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 includes 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(2,3,6-trimethyl-1,4-phenylene)ether A copolymer of 2,3,5-triethyl-1,4-phenylene) ether, or a combination thereof, may be used, more specifically, poly(2,6-dimethyl-1,4-phenylene) A copolymer of ether with 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 and 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 the 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 excessively lower than the above level, rigidity and heat resistance may decrease, and on the contrary, if it is excessively higher than the above level, impact resistance may deteriorate.

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, commonly referred to as HI-polystyrene (HIPS) by taking the initials of High Impact.

HI-polystyrene is a mixture of rubber to improve the fragility of polystyrene, and the impact strength increases as the rubber content increases, while other properties such as tensile strength, heat resistance, light resistance, moldability, and surface gloss are reduced. . In addition, by compounding the rubber, transparency is lost and has a milky opaque characteristic. As a method of mixing 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 styrene monomer and polymerizing it. When a styrene monomer in which rubber is dissolved in advance is polymerized, it becomes a so-called graft polymer having a polystyrene side chain attached to the rubber, and the compatibility between the rubber and polystyrene is increased, and the impact resistance is improved.

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 the 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 the 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 excessively lower than the above level, the impact resistance may be deteriorated. Conversely, if the content of the high-impact polystyrene resin is excessively higher than the above level, the rigidity and heat resistance may decrease.

More specifically, the high-impact polystyrene resin content 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 parts by weight or more. 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 fibrous glass filament focused through a sizing agent may be used.

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 thereof is, for example, 100 μm to 3 mm. , 300 μm to 1 mm, or 500 μm to 1 mm, 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 content of glass fibers in 100 parts by weight of the resin composition is excessively lower than the above level, long-term dimensional stability and bending rigidity may be lowered.

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 or less. may be below.

The thermoplastic resin composition of the present invention also includes a carbon-based composite filler that 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 nanotube may be a single-walled carbon nanotube (SWNT), a multi-walled carbon nanotube (MWNT), or a combination thereof. not limited

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

The thermoplastic resin composition of the present invention includes the carbon-based composite filler in an amount of 7 parts by weight or more, based on 100 parts by weight of the composition. When 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 is not sufficient.

The upper limit of the content of the carbon-based composite filler in the thermoplastic resin composition of the present invention is not particularly limited, 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 parts by weight or more. It may be less than or equal to parts by weight.

In one embodiment, the carbon nanotube content 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 or more. 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 or less. may be less than or equal to

The thermoplastic resin composition of the present invention may further include one or more additives commonly used in the thermoplastic resin composition in addition to the above components, 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 includes 2-(2'-hydroxyphenyl)-benzotriazole, 2-hydroxy-benzophenone, 2-(2'-hydroxy-5'-octylphenyl)benzotriazole 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 etc. can be used.

In one embodiment, as the heat stabilizer, bisphenol A epoxy resin, monocarbodiimide or polycarbodiimide 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 cionate 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, the nucleating agent may include talc, mica, silicate, ionomer, sodium 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, and the like.

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 including 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 of a 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 thereto.

[ Example ]

The components used in Examples and Comparative Examples of the present invention are as follows, and the content of each component is 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, purity 99.9% (LG Chem)

CNT(2): multi-walled carbon nanotubes, purity 99% (Nanocyl)

CB: Conductive Carbon Black (Unipetrol)

CF: carbon fiber

Other additives: Talc (KCP04), antioxidants (IRG168, 412S), mold release agents (PETS AHS)

By mixing the components shown in Tables 1 and 2 in the amounts described, the thermoplastic resin compositions of Examples 1 to 7 and the thermoplastic resin compositions of Comparative Examples 1 to 7 were prepared. Thereafter, extrusion was performed on each of the above-prepared thermoplastic resin compositions using a 32-pi 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. was used to prepare an injection specimen.

In the case of injection specimens for measuring mechanical properties, injection specimens meeting each ISO standard were prepared to be suitable for measuring tensile strength and flexural strength.

[Table 1]

[Table 2]

[Evaluation of physical properties]

(1) surface resistance

The surface resistance of the injection specimens prepared from 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 result measured by the instrument is ^{displayed as 10 x} numbers, and it can be confirmed that the surface resistance is low when the order of the surface resistance is low.

(2) dispersibility

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

(3) Machinability

In the process of manufacturing an injection specimen using the thermoplastic resin composition 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, etc. The degree was evaluated in five steps as follows.

- Very good: no problems mentioned above during extrusion

- Excellent: A state in which the above-mentioned problems exist slightly during extrusion, but there are no problems in production

- Good: The above-mentioned problems exist during extrusion, but there are no problems in production

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

- Very poor: The overall problem such as gas generation, swell phenomenon, and raw material input during extrusion is so serious that production is difficult.

(4) Tensile strength

The tensile strength of the injection specimens prepared from the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 was measured according to ISO.

(5) Flexural strength

Flexural strength was measured in accordance with ISO for the injection 　 specimens prepared from the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7.

(6) heat deflection temperature

The heat deflection temperature was measured according to ISO for the injection 　 specimens prepared from the thermoplastic resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7.

[Table 3]

[Table 4]

As shown in Table 3, the thermoplastic resin compositions of Examples according to the present invention were all excellent in processability, excellent in surface resistance, dispersibility and mechanical properties, and it can be confirmed that the thermal deformation temperature was 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 up to a target level. was not reached and mechanical properties were severely deteriorated, Comparative Example 4 had very poor dispersibility and extrusion and injection processing was impossible, Comparative Example 5 had poor surface resistance and mechanical properties, and Comparative Example 6 had dispersibility and mechanical properties was severely deteriorated, 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)

Based on a total of 100 parts by weight of the resin composition,
(1) 45 to 60 parts by weight of a thermoplastic polyphenylene ether resin;
(2) 20 to 25 parts by weight of a high-impact polystyrene resin;
(3) 5 to 10 parts by weight of glass fiber; and
(4) a carbon-based composite filler that is a combination of 1 to 5 parts by weight of carbon nanotubes and 5 to 15 parts by weight of conductive carbon black;
(4) the content of the carbon-based composite filler is 8 parts by weight or more, based on 100 parts by weight of the total resin composition,
Does not contain carbon fiber,
Thermoplastic resin composition. The method according to 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, 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 Lene)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. The thermoplastic resin composition according to claim 1, wherein the high-impact polystyrene resin is a high-impact polystyrene resin produced by a grafting 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 general carbon black. A molded article comprising the thermoplastic resin composition of any one of claims 1 to 5. 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.