Thermoplastic resin composition and article produced therefrom

Abstract

A thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a thermoplastic resin having a melting temperature of 300 °C or higher; about 18-42 parts by weight of needle-like conductive titanium dioxide; and about 4-16 parts by weight of carbon fiber, wherein a weight ratio of the needle-like conductive titanium dioxide to the carbon fiber is about 1.1:1-9:1. The thermoplastic resin composition has excellent electrostatic dissipativity, surface resistance uniformity, rigidity, and balance of these physical properties.

Description

Thermoplastic resin composition and molded article formed therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent electrostatic dissipation properties, surface resistance uniformity, rigidity, and a balance of these physical properties, and a molded article formed therefrom.

[0002]

[0003] In order to use thermoplastic resins as resin compositions for semiconductor processes, it is necessary to improve electrostatic dissipative (ESD) performance. Typically, conductive fillers such as carbon nanotubes, carbon fibers, carbon black, and graphite are applied to the thermoplastic resin to improve the electrostatic dissipative properties of the thermoplastic resin composition, and about 1 × 10 6 About 1 × 10 9 It is made to have a surface resistance value of the level of Ω / sq. However, in order for an existing thermoplastic resin composition to implement a surface resistance value of the above range, a large amount of conductive filler is required.

[0004] However, if an excessive amount of conductive filler is applied, there is a concern that the mechanical properties of the thermoplastic resin composition and the molded product may deteriorate, and the surface resistance may be about 1 × 10 6 As it drops below Ω / sq, it is difficult to secure electrostatic dissipation, and as uniform distribution becomes difficult, problems such as a decrease in surface resistance uniformity occur.

[0005] Therefore, there is a need to develop a thermoplastic resin composition with excellent electrostatic dissipation properties, surface resistance uniformity, rigidity, and a balance of these properties.

[0006] The background technology of the present invention is disclosed in Korean Patent No. 10-1944140, etc.

[0007]

[0008] The purpose of the present invention is to provide a thermoplastic resin composition having excellent electrostatic dissipation properties, surface resistance uniformity, rigidity, and balance of these physical properties.

[0009] Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0010] The above and other objects of the present invention can all be achieved by the present invention described below.

[0011]

[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a thermoplastic resin having a melting temperature of 300°C or higher; about 18 to about 42 parts by weight of needle-like conductive titanium dioxide; and about 4 to about 16 parts by weight of carbon fibers; and is characterized in that the weight ratio of the needle-like conductive titanium dioxide and the carbon fibers is about 1.1:1 to about 9:1.

[0013] 2. In the above 1 specific example, the thermoplastic resin having a melting temperature of 300°C or higher may include at least one of a polyaryl ether ketone resin, a semi-aromatic polyamide resin, and a liquid crystal polymer.

[0014] 3. In the above 1 or 2 specific examples, the polyaryletherketone resin may include a repeating unit represented by the following chemical formula 1.

[0015] [Chemical Formula 1]

[0016]

[0017] 4. In the above 1 to 3 specific examples, the polyaryl ether ketone resin is prepared at a temperature of 400°C and for 1000 sec according to ASTM D3835. -1 The melt viscosity measured by a capillary viscometer under shear rate conditions may be about 100 to about 500 Pa·s.

[0018] 5. In the above 1 to 4 specific examples, the semi-aromatic polyamide resin may include at least one of a repeating unit represented by the following chemical formula 2 and a repeating unit represented by the following chemical formula 3:

[0019] [Chemical Formula 2]

[0020]

[0021] [Chemical Formula 3]

[0022]

[0023] In the above chemical formulas 2 and 3, R1 and R3 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R2 and R4 are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, and n1 and n2 are each independently an integer of 0 to 4.

[0024] 6. In the above 1 to 5 specific examples, the needle-shaped conductive titanium dioxide may have a conductive layer formed on the surface including at least one of antimony-doped tin oxide, phosphorus-doped tin oxide, fluorine-doped tin oxide, copper-doped tin oxide, and cadmium-doped tin oxide.

[0025] 7. In the above 1 to 6 specific examples, the needle-shaped conductive titanium dioxide may have an average diameter of about 100 to about 500 nm and an average length of about 2 to about 10 μm.

[0026] 8. In the above specific examples 1 to 7, the carbon fibers may have an average diameter of about 8 to about 15 μm and an average length of about 0.1 to about 1 mm.

[0027] 9. In the above 1 to 8 specific examples, the thermoplastic resin composition is measured at 20 different locations of a 300 mm × 150 mm × 1 mm sized specimen using a surface resistance measuring device according to ASTM D257, and the average value of the surface resistance calculated therefrom is about 1 × 10 6About 1 × 10 9 It could be Ω / sq.

[0028] 10. In the above 1 to 9 specific examples, the thermoplastic resin composition may have a surface resistance of 20 different locations on a 300 mm × 150 mm × 1 mm sized specimen measured with a surface resistance measuring device according to ASTM D257, and the maximum value of the measured surface resistance divided by the minimum value may be about 100 or less.

[0029] 11. In the above 1 to 10 specific examples, the thermoplastic resin composition may have a yield point tensile strength of about 110 to about 200 MPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection molded specimen according to ASTM D638.

[0030] 12. In the above 1 to 11 specific examples, the thermoplastic resin composition may have a tensile modulus of about 10 to about 25 GPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D638.

[0031] 13. In the above 1 to 12 specific examples, the thermoplastic resin composition may have a flexural strength of about 210 to about 300 MPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection molded specimen according to ASTM D790.

[0032] 14. In the above specific examples 1 to 13, the thermoplastic resin composition may have a flexural modulus of about 5 to about 20 GPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D790.

[0033] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized in that it is formed from a thermoplastic resin composition according to any one of the above-mentioned embodiments 1 to 14.

[0034]

[0035] The present invention has the effect of providing a thermoplastic resin composition having excellent electrostatic dissipation properties, surface resistance uniformity, rigidity, and balance of these physical properties, and a molded article formed therefrom.

[0036]

[0037] Hereinafter, the present invention will be described in detail as follows.

[0038] A thermoplastic resin composition according to the present invention comprises (A) a thermoplastic resin having a melting temperature of 300°C or higher; (B) needle-shaped conductive titanium dioxide; and (C) carbon fiber.

[0039]

[0040] (A) Thermoplastic resin with a melting temperature of 300°C or higher

[0041] According to one specific example of the present invention, a thermoplastic resin having a melting temperature of 300°C or higher can be applied together with needle-shaped conductive titanium dioxide and carbon fibers in specific contents and content ratios to improve electrostatic dissipation properties, surface resistance uniformity, rigidity, and physical property balance thereof of the thermoplastic resin composition, and a thermoplastic resin having a melting temperature of 300°C or higher can be used without limitation. When the melting temperature of the thermoplastic resin is lower than 300°C, there is a concern that the heat resistance of the thermoplastic resin composition may deteriorate.

[0042] In a specific example, the thermoplastic resin having a melting temperature of 300°C or higher may include, but is not limited to, polyaryletherketone resin, semi-aromatic polyamide resin, liquid crystal polymer, polysulfone resin, polyetherimide resin, polyarylate resin, polyphenylene sulfide resin, polyetherimide resin, and combinations thereof. For example, the thermoplastic resin having a melting temperature of 300°C or higher may include polyaryletherketone resin, semi-aromatic polyamide resin, and / or liquid crystal polymer.

[0043] In a specific example, the polyaryl ether ketone resin may be a polyaryl ether ketone resin having a melting temperature of 300°C or higher, which is used in a typical thermoplastic resin composition.

[0044] In a specific example, the polyaryl ether ketone resin may be a polyaryl ether ketone resin (e.g., polyether ether ketone resin) containing a repeating unit represented by the following chemical formula 1.

[0045] [Chemical Formula 1]

[0046]

[0047] In a specific example, the polyaryl ether ketone resin is prepared at a temperature of 400°C and for 1000 sec according to ASTM D3835. -1 The melt viscosity measured by a capillary viscometer under shear rate conditions may be about 100 to about 500 Pa·s, for example, about 110 to about 490 Pa·s. Within this range, the thermoplastic resin composition may have excellent heat resistance, rigidity, processability, and a balance of these physical properties.

[0048] In a specific example, the semi-aromatic polyamide resin may be a semi-aromatic polyamide resin having a melting temperature of 300°C or higher, which is used in a typical thermoplastic resin composition.

[0049] In a specific example, the semi-aromatic polyamide resin may include at least one of a repeating unit represented by the following chemical formula 2 and a repeating unit represented by the following chemical formula 3.

[0050] [Chemical Formula 2]

[0051]

[0052] [Chemical Formula 3]

[0053]

[0054] In the above chemical formulas 2 and 3, R1 and R3 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R2 and R4 are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, and n1 and n2 are each independently an integer of 0 to 4.

[0055] In a specific example, the semi-aromatic polyamide resin may be prepared by reacting a dicarboxylic acid component including terephthalic acid or an alkyl ester thereof, which is substituted or unsubstituted with a phenyl group as R1, and / or isophthalic acid or an alkyl ester thereof, which is substituted or unsubstituted with a phenyl group as R3; and an aliphatic diamine component including a linear or branched alkylene group having 6 to 12 carbon atoms (1,6-hexanediamine (hexamethylene diamine: HMDA), 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, etc.)) according to a known polymerization method.

[0056] In a specific example, the semi-aromatic polyamide resin may have a glass transition temperature measured by differential scanning calorimetry (DSC) of about 100 to about 150°C, for example, about 120 to about 140°C. Within this range, the thermoplastic resin composition may have excellent heat resistance, processability, and balance of physical properties thereof.

[0057] In addition, the semi-aromatic polyamide resin may have an intrinsic viscosity [η] of about 0.7 to about 1.2 dL / g, for example, about 0.8 to about 1.0 dL / g, measured at 25°C using an Ubbelohde viscometer after being dissolved in a concentrated sulfuric acid solution (98%) at a concentration of 0.5 g / dL. Within this range, the thermoplastic resin composition may have excellent heat resistance, rigidity, processability, etc.

[0058] In a specific example, the liquid crystalline polymer (LCP) has a melting temperature of 300°C or higher and exhibits an anisotropic melt phase. Thermotropic liquid crystal polymers such as liquid crystal polyesteramide and liquid crystal polyester can be used. Here, the anisotropic melt phase of the liquid crystal polymer can be confirmed by a method of a conventional polarization system using a right-angle polarizer. For example, a sample on a Leitz heating plate under a nitrogen atmosphere can be observed with a Leitz polarization microscope.

[0059] In specific embodiments, the liquid crystal polymer may include repeating units of aromatic oxycarbonyl, aromatic dicarbonyl, aromatic dioxy, aromatic aminooxy, aromatic aminocarbonyl, aromatic diamino, aromatic oxydicarbonyl, aliphatic dioxy, or combinations thereof.

[0060] In specific embodiments, the liquid crystal polymer comprising the repeating units described above may include both those that provide an anisotropic melt phase and those that do not, depending on the structural elements of the polymer and the ratio and arrangement distribution of the elements. The liquid crystal polymer used in the present invention exhibits an anisotropic melt phase.

[0061] In specific embodiments, examples of monomers providing aromatic oxycarbonyl repeating units are 4-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxybiphenyl-4-carboxylic acid, 3'-hydroxybiphenyl-4-carboxylic acid, 4'-hydroxybiphenyl-3-carboxylic acid, and alkyl-, alkoxy- or halogen-substituted derivatives thereof, and ester-forming derivatives such as acyl derivatives, ester derivatives and acyl halides thereof. Of the above, 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred in terms of easier control of the properties and melting temperature of the resulting liquid crystal polymer.

[0062] In specific embodiments, examples of monomers providing aromatic dicarbonyl repeating units are aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, and alkyl-, alkoxy- or halogen-substituted derivatives thereof, and ester derivatives thereof, ester-forming derivatives such as acid halides. Among the above, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of easier control of the mechanical properties, heat resistance, melting temperature and molding properties of the resulting liquid crystal polymer.

[0063] In specific embodiments, examples of monomers providing aromatic dioxy repeating units are aromatic diols such as hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, and ester-forming derivatives such as alkyl-, alkoxy-, or halogen-substituted derivatives, and acyl derivatives thereof. Among the above, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of good reactivity during the polymerization process and good properties of the resulting liquid crystal polymer blend.

[0064] In specific embodiments, examples of monomers providing aromatic aminooxy repeating units are aromatic hydroxyamines such as p-aminophenol, m-aminophenol, N-acetyl-4-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, 8-amino-2-naphthol, 4-amino-4'-hydroxybiphenyl, and ester-forming derivatives such as alkyl-, alkoxy- or halogen-substituted derivatives and acyl derivatives thereof, and amide-forming derivatives such as N-acyl derivatives thereof.

[0065] In specific embodiments, examples of monomers providing aromatic diamino repeating units are aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene and amide forming derivatives such as alkyl-, alkoxy- or halogen-substituted derivatives, and N-acyl derivatives thereof.

[0066] In specific embodiments, examples of monomers providing aromatic aminocarbonyl repeating units are aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid and alkyl-, alkoxy- or halogen-substituted derivatives thereof, and ester-forming derivatives such as acyl derivatives, ester derivatives and acid halides thereof, and amide-forming derivatives such as N-acyl derivatives thereof.

[0067] In specific embodiments, examples of monomers providing aromatic oxydicarbonyl repeating units are hydroxy-aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, and alkyl-, alkoxy- or halogen-substituted derivatives thereof, and ester-forming derivatives such as acyl derivatives, ester derivatives and acyl halides thereof.

[0068] In specific embodiments, examples of monomers providing aliphatic dioxy repeating units include aliphatic diols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and acyl derivatives thereof. In addition, a liquid crystal polymer having aliphatic dioxy repeating units can be obtained by reacting a polyester having aliphatic dioxy repeating units such as polyethylene terephthalate or polybutylene terephthalate with the aromatic oxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyamine, aromatic aminocarboxylic acid, aromatic diamine or acyl derivative, ester derivative or acid halide thereof.

[0069] In specific embodiments, the liquid crystal polymer may have a thioester bond, provided that the bond does not impair the purpose of the present invention. Examples of monomers providing a thioester bond include mercapto-aromatic carboxylic acid, aromatic dithiol, and hydroxy-aromatic thiol. The proportion of such additional monomers based on the total amount of monomers providing aromatic oxycarbonyl, aromatic dicarbonyl, aromatic dioxy, aromatic aminooxy, aromatic diamino, aromatic oxy dicarbonyl, and aliphatic dioxy repeating units is preferably about 10 mol% or less.

[0070] Among the above, the preferred liquid crystal polymer used in the present invention is one that includes an aromatic oxycarbonyl repeating unit including a 4-oxybenzoyl repeating unit and / or a 6-oxy-2-naphthoyl repeating unit.

[0071] In specific embodiments, examples of preferred liquid crystal polymers comprising 4-oxybenzoyl and / or 6-oxy-2-naphthoyl repeating units may include:

[0072] 1) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid copolymer,

[0073] 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer,

[0074] 3) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl copolymer,

[0075] 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer,

[0076] 5) 4-hydroxybenzoic acid / terephthalic acid / hydroquinone copolymer,

[0077] 6) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer,

[0078] 7) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer,

[0079] 8) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / N-acetyl-4-aminophenol copolymer

[0080] 9) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer,

[0081] 10) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer,

[0082] 11) 4-hydroxybenzoic acid / 2,6-naphthalene dicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer,

[0083] 12) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone copolymer,

[0084] 13) 4-hydroxybenzoic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone copolymer,

[0085] 14) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone copolymer,

[0086] 15) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer,

[0087] 16) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer,

[0088] 17) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer,

[0089] 18) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer,

[0090] 19) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer,

[0091] 20) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer,

[0092] 21) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer,

[0093] 22) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol copolymer, and

[0094] 23) 4-Hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer.

[0095] Among the above, copolymers of 1), 8), 9) and 13) are preferable from the viewpoint of the formability and mechanical properties of the polymer.

[0096] In a specific embodiment, the liquid crystal polymer may be a polymer blend comprising two or more liquid crystal polymers for the purpose of increasing the fluidity of the polymer during molding.

[0097] In specific embodiments, the method for producing the liquid crystal polymer is not limited, and any method known in the art may be utilized. For example, conventional polycondensation methods such as slurry polymerization and melt acid decomposition, which produce polymers by forming ester and / or amide bonds among the monomer elements described above, may be utilized.

[0098] In specific embodiments, the above-described melt acid decomposition method is preferably used for the production of liquid crystal polymers. In this method, the monomers are heated to form a molten solution, and then the solution is reacted to form a molten polymer. The final step of this method may be performed under vacuum to facilitate the removal of volatile byproducts such as acetic acid or water.

[0099] In a specific embodiment, the slurry polymerization method is characterized in that the monomer is reacted in a heat-exchange fluid to produce a solid-state polymer in the form of a suspension in the heat-exchange liquid medium.

[0100] In a specific embodiment, in either the melt acid decomposition method or the slurry polymerization method, the polymerizing monomer may be in the form of a lower acyl derivative obtained by acylating a hydroxyl group and / or an amino group. The lower acyl group may have 2 to 5 carbon atoms, for example, 2 to 3 carbon atoms. Preferably, an acetylated monomer is used in the reaction.

[0101] In specific embodiments, the lower acyl derivative of the monomer may be prepared by independently acylating the monomer previously, or may be produced in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the preparation of the liquid crystal polymer.

[0102] In a specific embodiment, in either the molten acid cracking method or the slurry polymerization method, a catalyst may be utilized in the reaction if desired.

[0103] In specific embodiments, examples of catalysts include organotin compounds such as dialkyl tin oxides (e.g., dibutyl tin oxide) and diaryl tin oxides; antimony trioxide; titanium dioxide; organotin compounds such as alkoxy titanium silicates and titanium alkoxides; alkali or alkaline earth metal salts of carboxylic acids such as potassium acetate; salts of inorganic acids (e.g., K2SO4); and gaseous acid catalysts such as Lewis acids (e.g., BF3) and hydrogen halides (e.g., HCl).

[0104] In specific examples, when a catalyst is used, the amount of catalyst added to the reaction may be from about 10 to about 1,000 ppm, for example from about 20 to about 200 ppm, based on the total amount of monomers.

[0105] In a specific example, the liquid crystal polymer may be obtained from a reaction vessel in which it is polymerized in a molten state and then processed to produce pellets, flakes or powder.

[0106] In specific embodiments, the liquid crystal polymer in the form of pellets, flakes, or powder may be heated to a substantially solid state, if desired, under vacuum or an inert gas atmosphere such as nitrogen or helium. The heat treatment temperature may be from about 260 to about 350°C, for example from about 280 to about 320°C.

[0107] In a specific embodiment, the liquid crystal polymer may have a crystalline melting temperature (Tm) of about 300 to about 360°C as determined by differential scanning calorimetry. A method for determining the crystalline melting temperature is as follows:

[0108] A differential scanning calorimeter (DSC) Exstar 6000 (Seiko Instruments Inc., Chiba, Japan) or the same type of DSC device is used. The liquid crystal polymer sample to be observed is heated from room temperature at a rate of 20°C / min to measure the endothermic peak (Tm1). The sample is then maintained at a temperature 20 to 50°C higher than Tm1 for 10 minutes. The sample is then cooled to room temperature at a rate of 10°C / min and heated again at a rate of 10°C / min. The endothermic peak found at the final stage is recorded as the crystalline melting temperature (Tm) of the liquid crystal polymer sample.

[0109]

[0110] (B) Bed-type conductive titanium dioxide

[0111] According to one specific example of the present invention, needle-shaped conductive titanium dioxide (TiO2) is applied in a specific content and content ratio together with carbon fibers and the like to a thermoplastic resin having a melting temperature of 300°C or higher, thereby improving the electrostatic dissipation property, surface resistance uniformity, rigidity, and physical property balance of the thermoplastic resin composition.

[0112] In a specific example, the needle-shaped conductive titanium dioxide may be a commercially available product without limitation, and may have a conductive layer formed on the surface including at least one of antimony-doped tin oxide, phosphorus-doped tin oxide, fluorine-doped tin oxide, copper-doped tin oxide, and cadmium-doped tin oxide.

[0113] In a specific example, the needle-shaped conductive titanium dioxide may have an average diameter of about 100 to about 500 nm as measured by a transmission electron microscope (TEM), and an average length of about 2 to about 10 μm as measured by a scanning electron microscope (SEM). Within this range, the thermoplastic resin composition may have excellent electrostatic dissipative properties, surface resistance uniformity, rigidity, and the like.

[0114] In a specific example, the needle-shaped conductive titanium dioxide may be included in an amount of about 18 to about 42 parts by weight, for example, about 20 to about 40 parts by weight, based on about 100 parts by weight of the thermoplastic resin having a melting temperature of 300°C or higher. If the content of the needle-shaped conductive titanium dioxide is less than about 18 parts by weight based on about 100 parts by weight of the thermoplastic resin having a melting temperature of 300°C or higher, there is a concern that the electrostatic dissipation property, surface resistance uniformity, rigidity, etc. of the thermoplastic resin composition may be deteriorated, and if it exceeds about 42 parts by weight, there is a concern that the electrostatic dissipation property, processability, etc. of the thermoplastic resin composition may be deteriorated.

[0115]

[0116] (C) Carbon fiber

[0117] According to one specific example of the present invention, carbon fiber is applied in a specific amount and content ratio together with needle-shaped conductive titanium dioxide, etc., to a thermoplastic resin having a melting temperature of 300°C or higher, thereby improving electrostatic dissipation properties, surface resistance uniformity, rigidity, and physical property balance of the thermoplastic resin composition. Carbon fibers used in conventional thermoplastic resin compositions can be applied.

[0118] In a specific example, the carbon fibers may have an average diameter of about 8 to about 15 μm, for example, about 9 to about 13 μm, as measured by an optical microscope, and an average length of about 0.1 to about 1 mm, for example, about 0.12 to about 0.9 mm. Within this range, the thermoplastic resin composition may have excellent electrostatic dissipative properties, surface resistance uniformity, rigidity, and the like.

[0119] In a specific example, the carbon fiber may be included in an amount of about 4 to about 16 parts by weight, for example, about 5 to about 15 parts by weight, relative to about 100 parts by weight of the thermoplastic resin having a melting temperature of 300°C or higher. If the content of the carbon fiber is less than about 4 parts by weight relative to about 100 parts by weight of the thermoplastic resin having a melting temperature of 300°C or higher, there is a concern that the electrostatic dissipation property, rigidity, surface resistance uniformity, etc. of the thermoplastic resin composition may be deteriorated, and if it exceeds about 16 parts by weight, there is a concern that the electrostatic dissipation property, processability, etc. of the thermoplastic resin composition may be deteriorated.

[0120] In a specific example, the weight ratio of the needle-shaped conductive titanium dioxide and the carbon fiber may be from about 1.1:1 to about 9:1, for example from about 1.3:1 to about 8:1. In this range, the electrostatic dissipation property, surface resistance uniformity, rigidity, and the balance of their physical properties of the thermoplastic resin composition may be more excellent.

[0121]

[0122] A thermoplastic resin composition according to one specific example of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of the additives include flame retardants, fillers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, heat stabilizers, ultraviolet stabilizers, pigments, dyes, and mixtures thereof. When the additives are used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 20 parts by weight, based on about 100 parts by weight of the thermoplastic resin having a melting temperature of 300°C or higher.

[0123]

[0124] A thermoplastic resin composition according to one specific example of the present invention may be in the form of pellets obtained by mixing the above components and melt-extruding them at about 300 to about 450°C, for example, about 310 to about 400°C, using a conventional twin-screw extruder.

[0125] In a specific example, the thermoplastic resin composition is measured at 20 different locations on a 300 mm × 150 mm × 1 mm sized specimen using a surface resistance measuring device according to ASTM D257, and the average value of the surface resistance calculated therefrom is about 1 × 10 6 About 1 × 10 9 Ω / sq, for example, about 1.1 × 10 6 About 9 × 10 8 It could be Ω / sq.

[0126] In a specific example, the thermoplastic resin composition may have a surface resistance of 20 different locations on a 300 mm × 150 mm × 1 mm sized specimen measured with a surface resistance measuring device according to ASTM D257, and the maximum value of the measured surface resistance divided by the minimum value may be about 100 or less, for example, about 95 or less.

[0127] In a specific example, the thermoplastic resin composition may have a yield point tensile strength of about 110 to about 200 MPa, for example, about 115 to about 195 MPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D638.

[0128] In a specific example, the thermoplastic resin composition may have a tensile modulus of about 10 to about 25 GPa, for example, about 10 to about 23 GPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D638.

[0129] In a specific example, the thermoplastic resin composition may have a flexural strength of about 210 to about 300 MPa, for example, about 210 to about 290 MPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D790.

[0130] In a specific example, the thermoplastic resin composition may have a flexural modulus of about 5 to about 20 GPa, for example, about 6 to about 18 GPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D790.

[0131]

[0132] A molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition can be manufactured in the form of pellets, and the manufactured pellets can be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention pertains. Since the molded article has excellent static dissipative properties, surface resistance uniformity, rigidity, and physical property balance thereof, it is useful as a material for semiconductor wafer cleaning equipment such as wafer chucks and chuck pins, semiconductor wafer transport equipment such as wafer carriers and FOUPs, semiconductor fixing equipment such as retaining rings, and semiconductor wafer chip fixing and post-processing equipment such as trays and dies.

[0133]

[0134] Hereinafter, the present invention will be described in more detail through examples; however, these examples are for the purpose of explanation only and should not be construed as limiting the present invention.

[0135]

[0136] Example

[0137] Below, the specifications of each component used in the examples and comparative examples are as follows.

[0138] (A) Thermoplastic resin

[0139] (A1) Polyether ether ketone resin (manufacturer: Victrex, product name: 150P, melting temperature: 340℃) was used.

[0140] (A2) Polyphthalamide resin (manufacturer: Solvay, product name: Amodel 1004, melting temperature: 310℃) was used.

[0141] (A3) Liquid crystal polymer (Manufacturer: Seyang Polymer, Product name: L, Melting temperature: 340℃) was used.

[0142] (B) Conductive titanium dioxide

[0143] A bed-type conductive titanium dioxide (manufacturer: Ishihara, product name: FT-3000) was used.

[0144] (C) Carbon fiber

[0145] Carbon fiber (Manufacturer: Taeyoung Metal, Product Name: T70-PU) was used.

[0146]

[0147] Examples 1 to 11 and Comparative Examples 1 to 6

[0148] After adding each of the above components in the contents as shown in Tables 1, 2, and 3 below, pellets were manufactured by extrusion at about 380°C (polyetheretherketone resin (A1)), about 320°C (polyphthalamide resin (A2)), or about 345°C (liquid crystal polymer (A3)) depending on the type of thermoplastic resin. The extrusion was performed using a twin-screw extruder with L / D=40 and a diameter of 45 mm, and the manufactured pellets were dried at about 100°C for about 4 hours or more, and then injected using a 6 oz injection molding machine (molding temperature: about 400°C, mold temperature: about 150°C) to manufacture specimens. The physical properties of the manufactured specimens were evaluated by the following methods, and the results are shown in Tables 1, 2, and 3 below.

[0149]

[0150] Method of measuring physical properties

[0151] (1) Average surface resistance (unit: Ω / sq): In accordance with ASTM D257, the surface resistance of 20 different locations on a 300 mm × 150 mm × 1 mm sized specimen was measured using a surface resistance meter (manufacturer: Trek, device name: Resistance Meter 152-1), and the average surface resistance was calculated from this.

[0152] (2) Surface resistance uniformity evaluation: According to ASTM D257, the surface resistance of 20 different locations of a 300 mm × 150 mm × 1 mm sized specimen was measured using a surface resistance meter (manufacturer: Trek, device name: Resistance Meter 152-1). Then, the surface resistance uniformity was evaluated by dividing the maximum value of the measured surface resistance by the minimum value (maximum surface resistance ÷ minimum surface resistance) (100 or less was considered excellent).

[0153] (3) Yield point tensile strength and tensile modulus (unit: MPa and GPa): According to ASTM D638, the yield point tensile strength and tensile modulus of a 3.2 mm thick injection molded specimen (150 mm × 150 mm × 3.2 mm) were measured at a speed of 50 mm / min, respectively.

[0154] (4) Flexural strength and flexural modulus (unit: MPa and GPa): According to ASTM D790, the flexural strength and flexural modulus of 3.2 mm thick injection molded specimens were measured at a speed of 2.8 mm / min, respectively.

[0155]

[0156] Example 12345 (A1) (weight part) 100 100 100 100 100 (A2) (weight part)----- (A3) (weight part)----- (B) (weight part) 20 30 40 30 30 (C) (weight part) 10 10 10 5 15 (B): (C) (weight ratio) 2:13:14:16:12:1 Average surface resistance (Ω / sq) 4.1 × 10 8 2.9×10 7 3.1×10 6 1.3×10 8 6.2×10 6 Maximum surface resistance (Ω / sq) 1.6×10 9 1.6×10 8 1.2×10 7 6.3×10 8 2.8×10 7 Minimum surface resistance (Ω / sq)2.1×10 7 4.2×10 6 8.9×10 5 7.6×106 2.7×10 6 Surface resistance uniformity evaluation 76.238.113.582.910.4 Yield point tensile strength (MPa) 124141155123165 Tensile modulus (GPa) 13.815.818.313.118.6 Flexural strength (MPa) 227242265223262 Flexural modulus (GPa) 9.211.413.88.115.3

[0157]

[0158] Example 67891011(A1) (parts by weight)--100100100100(A2) (parts by weight)100-----(A3) (parts by weight)-100----(B) (parts by weight)303040204020(C) (parts by weight)1010515155(B):(C) (weight ratio)3:13:18:11.3:12.7:14:1 Average surface resistance (Ω / sq)2.1×10 7 3.6×10 7 3.7×10 7 3.4×10 7 1.4×10 6 5.7×10 8 Maximum surface resistance (Ω / sq) 1.7×10 8 2.1×10 8 2.1×10 8 2.6×10 8 2.1×10 6 2.3×10 9 Minimum surface resistance (Ω / sq)8.4×10 6 4.5×10 6 2.9×10 6 6.2×10 6 1.1×10 6 2.5×10 7 Surface resistance uniformity evaluation 20.246.772.441.91.992.0 Yield point tensile strength (MPa) 150142135144188111 Tensile modulus (GPa) 16.116.115.316.121.110.8 Flexural strength (MPa) 251246238245289212 Flexural modulus (GPa) 11.911.610.113.218.06.5

[0159]

[0160] Comparative Example 123456 (A1) (weight part) 100100100100100100 (A2) (weight part)------ (A3) (weight part)------ (B) (weight part) 154530301842 (C) (weight part) 1010318184 (B): (C) (weight ratio) 1.5:14.5:110:11.7:11:110.5:1 Average surface resistance (Ω / sq) 1.6×10 9 8.9×10 5 9.5×10 10 7.9×10 4 8.2×10 5 1.5×10 9 Maximum surface resistance (Ω / sq) 1.3×10 10 3.9×10 6 2.1×10 11 2.1×10 5 5.1×10 7 1.3×10 10 Minimum surface resistance (Ω / sq) 4.9×10 7 3.5×10 5 1.8×10 10 3.1×10 4 2.9×10 5 8.9×10 7 Surface resistance uniformity evaluation 265.3 11.1 11.7 6.8 175.9 146.1 Yield point tensile strength (MPa) 115 16 398 198 150 116 Tensile modulus (GPa) 12.3 19.26 23.6 18 10.6 Flexural strength (MPa) 220 28 1189 295 260 211 Flexural modulus (GPa) 8.2 14.9 4.2 19.5 15.16.5

[0161]

[0162] From the above results, it can be seen that the thermoplastic resin composition of the present invention has excellent electrostatic dissipation properties (average surface resistance), surface resistance uniformity (maximum surface resistance ÷ minimum surface resistance), rigidity (yield point tensile strength, tensile modulus, flexural strength, flexural modulus), and a balance of these physical properties.

[0163] On the other hand, in the case of Comparative Example 1, where a small amount of needle-like conductive titanium dioxide was applied, it can be seen that static dissipation property, surface resistance uniformity, etc. were deteriorated, and in the case of Comparative Example 2, where an excessive amount of needle-like conductive titanium dioxide was applied, it can be seen that static dissipation property, etc. were deteriorated. In the case of Comparative Example 3, where a small amount of carbon fiber was applied, it can be seen that static dissipation property, rigidity, etc. were deteriorated, and in the case of Comparative Example 4, where an excessive amount of carbon fiber was applied, it can be seen that static dissipation property, etc. were deteriorated. In addition, even when the contents of needle-like conductive titanium dioxide and carbon fiber are within the scope of the present invention, in the case of Comparative Example 5, where the weight ratio of needle-like conductive titanium dioxide and carbon fiber is less than the scope of the present invention, it can be seen that static dissipation property, surface resistance uniformity, etc. were deteriorated, and in the case of Comparative Example 6, where the weight ratio of needle-like conductive titanium dioxide and carbon fiber exceeds the scope of the present invention, it can be seen that static dissipation property, surface resistance uniformity, etc. were deteriorated.

[0164]

[0165] The present invention has been described with reference to exemplary embodiments. Those skilled in the art will appreciate that the present invention can be implemented in modified forms without departing from its essential characteristics. Therefore, the disclosed embodiments should be considered illustrative rather than limiting. The scope of the present invention is set forth in the claims, not the foregoing description, and all differences within the scope equivalent thereto should be construed as being encompassed by the present invention.

Claims

1. About 100 parts by weight of a thermoplastic resin having a melting temperature of 300°C or higher; About 18 to about 42 parts by weight of a conductive titanium dioxide; and Containing about 4 to about 16 parts by weight of carbon fiber; A thermoplastic resin composition characterized in that the weight ratio of the above-mentioned needle-shaped conductive titanium dioxide and the above-mentioned carbon fiber is about 1.1:1 to about 9:

1.

2. A thermoplastic resin composition according to claim 1, wherein the thermoplastic resin having a melting temperature of 300°C or higher comprises at least one of a polyaryl ether ketone resin, a semi-aromatic polyamide resin, and a liquid crystal polymer.

3. A thermoplastic resin composition according to claim 2, wherein the polyaryl ether ketone resin comprises a repeating unit represented by the following chemical formula 1. [Chemical Formula 1] 4. In the second or third paragraph, the polyaryl ether ketone resin is prepared at a temperature of 400°C and for 1000 sec according to ASTM D3835. -1 A thermoplastic resin composition characterized in that the melt viscosity measured by a capillary viscometer under shear rate conditions is about 100 to about 500 Pa·s.

5. A thermoplastic resin composition according to any one of claims 2 to 4, wherein the semi-aromatic polyamide resin comprises at least one of a repeating unit represented by the following chemical formula 2 and a repeating unit represented by the following chemical formula 3: [Chemical Formula 2] [Chemical Formula 3] In the above chemical formulas 2 and 3, R1 and R3 are each independently a hydrocarbon group having 1 to 6 carbon atoms or a halogen atom, R2 and R4 are each independently a linear or branched alkylene group having 6 to 12 carbon atoms, and n1 and n2 are each independently an integer of 0 to 4.

6. A thermoplastic resin composition according to any one of claims 1 to 5, wherein the needle-shaped conductive titanium dioxide has a conductive layer formed on the surface thereof, the conductive layer comprising at least one of antimony-doped tin oxide, phosphorus-doped tin oxide, fluorine-doped tin oxide, copper-doped tin oxide, and cadmium-doped tin oxide.

7. A thermoplastic resin composition according to any one of claims 1 to 6, wherein the needle-shaped conductive titanium dioxide has an average diameter of about 100 to about 500 nm and an average length of about 2 to about 10 ㎛.

8. A thermoplastic resin composition according to any one of claims 1 to 7, wherein the carbon fibers have an average diameter of about 8 to about 15 ㎛ and an average length of about 0.1 to about 1 mm.

9. In any one of the first to eighth clauses, the thermoplastic resin composition is a thermoplastic resin composition in which the surface resistance of 20 different locations of a 300 mm × 150 mm × 1 mm sized specimen is measured using a surface resistance measuring device according to ASTM D257, and the average value of the surface resistance calculated therefrom is about 1 × 10 6 About 1 × 10 9 A thermoplastic resin composition characterized by having a density of Ω / sq.

10. A thermoplastic resin composition according to any one of claims 1 to 9, characterized in that the thermoplastic resin composition is a thermoplastic resin composition in which the maximum value of the measured surface resistance divided by the minimum value is about 100 or less, after measuring the surface resistance at 20 different locations of a specimen measuring 300 mm × 150 mm × 1 mm in size using a surface resistance measuring device according to ASTM D257.

11. A thermoplastic resin composition according to any one of claims 1 to 10, characterized in that the thermoplastic resin composition has a yield point tensile strength of about 110 to about 200 MPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection molded specimen according to ASTM D638.

12. A thermoplastic resin composition according to any one of claims 1 to 11, characterized in that the thermoplastic resin composition has a tensile modulus of about 10 to about 25 GPa, measured at a speed of 50 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D638.

13. A thermoplastic resin composition according to any one of claims 1 to 12, characterized in that the thermoplastic resin composition has a flexural strength of about 210 to about 300 MPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection molded specimen according to ASTM D790.

14. A thermoplastic resin composition according to any one of claims 1 to 13, characterized in that the thermoplastic resin composition has a flexural modulus of about 5 to about 20 GPa, measured at a speed of 2.8 mm / min using a 3.2 mm thick injection-molded specimen according to ASTM D790.

15. A molded product characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 14.

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