Thermoplastic resin composition and molded article formed therefrom
By adjusting the ratio of polyaryl etherketone and polyaryl ethersulfone resin and adding carbon nanotubes and carbon black, the existing resin blends have been solved in terms of poor performance in wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance between them, and the performance improvement and compatibility improvement of the thermoplastic resin composition are achieved.
Patent Information
- Application Number
- CN202380067652.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2022-09-21
- Filing Date
- 2023-09-19
- Publication Date
- 2025-05-13
AI Technical Summary
Existing blends of polyaryl etherketone and polyaryl ethersulfone resins do not perform well in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance between them, and limited compatibility, resulting in significant changes in characteristics in different processing directions.
Appropriate compatibility and properties of the composition are improved by adjusting the component ratio and the average size and void ratio of the additive material by adjusting the component ratio and the average size and void ratio of the additive material.
A thermoplastic resin composition with good characteristics in wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance between them is achieved, and the characteristics change in different processing directions are minimal, and is suitable for semiconductor processing and other fields.
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Abstract
Description
Technical Field
[0001] The present invention relates to a thermoplastic resin composition and a molded article formed from the thermoplastic resin composition. More specifically, the present invention relates to a polyaryletherketone / polyarylethersulfone-based thermoplastic resin composition having excellent properties in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance therebetween, and a molded article formed from the thermoplastic resin composition. Background Art
[0002] Polyaryletherketone (PAEK) resins, such as polyetheretherketone (PEEK) resins, have been used in office automation equipment and automotive applications due to good heat resistance, chemical resistance, rigidity, and fatigue resistance. However, the low impact strength of polyaryletherketone resins limits their use in applications requiring high impact resistance.
[0003] Mixing with polyarylethersulfone (PAES) resin has been used to enhance the impact strength of polyaryletherketone (PAEK) resin. However, due to the limited compatibility between PAEK resin and PAES resin, the blends of PAEK resin and PAES resin may suffer from the degradation of properties such as rigidity and impact strength, and may show significant changes in properties (rigidity, impact strength, etc.) depending on the processing direction (machine direction (MD) and transverse direction (TD)) of the sample, which may limit its application.
[0004] Additionally, blends of polyaryletherketone and polyarylethersulfone resins are required to have improved wear resistance and electrostatic dissipative (ESD) properties for use as resin compositions for semiconductor processing.
[0005] Therefore, there is a need for a thermoplastic resin composition having excellent properties in abrasion resistance, electrostatic discharge dissipation, rigidity, impact resistance and a balance therebetween without reducing the compatibility between polyaryletherketone and polyarylethersulfone resins.
[0006] Background art of the present invention is disclosed in Korean Patent Registration No. 10-2163638, Korean Patent Registration No. 10-1944140, and the like. Summary of the invention
[0007]
Technical issues
[0008] An object of the present invention is to provide a thermoplastic resin composition having good characteristics in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance therebetween.
[0009] Another object of the present invention is to provide a molded article formed from the above-mentioned thermoplastic resin composition.
[0010] The above and other objects of the present invention will become apparent from the following detailed description of the embodiments.
[0011]
Technical solution
[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition includes: about 100 parts by weight of a thermoplastic resin, including about 60 wt% to about 90 wt% of a polyaryletherketone resin and about 10 wt% to about 40 wt% of a polyarylethersulfone resin; about 1 part by weight to about 4 parts by weight of carbon nanotubes; and about 2 parts by weight to about 5 parts by weight of carbon black, wherein the domains (polyarylethersulfone resin) in the matrix (polyaryletherketone resin) have an average size of about 0.5 μm or less as measured by scanning electron microscopy (SEM) at 10,000× and 50,000× magnifications.
[0013] 2. In Embodiment 1, the polyaryletherketone resin may include a repeating unit represented by Formula 1.
[0014] [Formula 1]
[0015]
[0016] 3. In Embodiment 1 or Embodiment 2, the viscosity is measured using a capillary viscometer at a temperature of 400° C. and a time of 1,000 seconds in accordance with ASTM D3835. -1 The polyaryletherketone resin may have a melt viscosity of about 300 Pa·s to about 500 Pa·s, measured at a shear rate of .
[0017] 4. In Embodiments 1 to 3, the polyarylethersulfone resin may include a repeating unit represented by Formula 2.
[0018] [Formula 2]
[0019]
[0020] 5. In Embodiments 1 to 4, the viscometer was used at a temperature of 400° C. and a time of 1,000 seconds in accordance with ASTM D3835. -1 The polyarylethersulfone resin may have a melt viscosity of about 200 Pa·s to about 400 Pa·s, measured at a shear rate of .
[0021] 6. In embodiments 1 to 5, a melt viscosity ratio of the polyaryletherketone resin to the polyarylethersulfone resin may be in a range of about 1:1 to about 4:1.
[0022] 7. In Embodiments 1 to 6, the carbon nanotubes may have an average diameter of about 3 nm to about 15 nm and an average length of about 10 μm to about 25 μm.
[0023] 8. In embodiments 1 to 7, the carbon black may have an average particle size of about 20 nm to about 50 nm and a void ratio of about 50% to about 90%.
[0024] 9. In embodiments 1 to 8, the thermoplastic resin composition may have a glass transition temperature of about 150° C. to about 170° C. and may exhibit a single glass transition temperature.
[0025] 10. In embodiments 1 to 9, the thermoplastic resin composition may have a weight loss (wear loss) of about 30 mg or less when measured after 1,000 cycles of operation on a sample having a size of 100 mm×100 mm×3.2 mm under a load of 1 kgf and a grinding wheel speed of 60 rpm using an abrasion resistance tester in accordance with ASTM D4060.
[0026] 11. In embodiments 1 to 10, the thermoplastic resin composition may have a surface resistivity of about 1×10 6 Ω / sq to about 1×10 9 Surface resistivity of Ω / sq.
[0027] 12. In embodiments 1 to 11, the thermoplastic resin composition may have a tensile yield strength of about 93 MPa to about 100 MPa and a tensile modulus of about 3.3 GPa to about 4.0 GPa, as measured in accordance with ASTM D638 on a 3.2 mm thick injection molded sample at a crosshead speed of 50 mm / min in the longitudinal direction (MD) of the sample or at a crosshead speed of 50 mm / min in the transverse direction (TD) of the sample, the difference between the tensile yield strength of the injection molded sample in its longitudinal direction and the tensile yield strength in its transverse direction may be less than or equal to about 2 MPa, and the difference between the tensile modulus of the injection molded sample in its longitudinal direction and the tensile modulus in its transverse direction may be less than or equal to about 0.2 GPa.
[0028] 13. In embodiments 1 to 12, the thermoplastic resin composition may have a flexural strength of about 140 MPa to about 150 MPa and a flexural modulus of about 3.2 GPa to about 4.0 GPa, measured in accordance with ASTM D790 on a 3.2 mm thick injection molded sample at a crosshead speed of 2.8 mm / min in the longitudinal direction (MD) of the sample or at a crosshead speed of 2.8 mm / min in the transverse direction (TD) of the sample, the difference between the flexural strength of the injection molded sample in its longitudinal direction and the flexural strength in its transverse direction may be less than or equal to about 2 MPa, and the difference between the flexural modulus of the injection molded sample in its longitudinal direction and the flexural modulus in its transverse direction may be less than or equal to about 0.2 GPa.
[0029] 14. In embodiments 1 to 13, the thermoplastic resin composition may show no breakage when unnotched Izod impact strength is measured in the longitudinal or transverse direction of a 3.2 mm thick injection molded sample in an impact strength test according to ASTM D256.
[0030] 15. Another aspect of the present invention relates to a molded article. The molded article is formed from the thermoplastic resin composition according to Embodiment 1 to Embodiment 14.
[0031]
Beneficial Effects
[0032] Embodiments of the present invention provide a thermoplastic resin composition having excellent characteristics in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance, and a balance therebetween, and a molded article formed therefrom. DETAILED DESCRIPTION
[0033] Hereinafter, embodiments of the present invention will be described in detail.
[0034] The thermoplastic resin composition according to the present invention includes: (A) a polyaryletherketone resin; (B) a polyarylethersulfone resin; (C) carbon nanotubes; and (D) carbon black.
[0035] (A) Polyaryletherketone resin
[0036] The polyaryletherketone resin according to one embodiment of the present invention is used together with a polyarylethersulfone resin, carbon nanotubes and carbon black in a specific content ratio to improve the properties of a thermoplastic resin composition (such as wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and a balance therebetween) without reducing the compatibility between the polyaryletherketone resin and the polyarylethersulfone resin. The polyaryletherketone resin may include a polyaryletherketone resin used in a typical thermoplastic resin composition.
[0037] In some embodiments, the polyaryletherketone resin may include a polyaryletherketone resin including a repeating unit represented by Formula 1 (polyetheretherketone resin, etc.).
[0038] [Formula 1]
[0039]
[0040] In some embodiments, the viscosity is measured using a capillary viscometer at 400°C and 1,000 seconds in accordance with ASTM D3835. -1The polyaryletherketone resin may have a melt viscosity of about 300 Pa·s to about 500 Pa·s, for example, about 310 Pa·s to about 490 Pa·s, measured at a shear rate of . Within this range, the thermoplastic resin composition may have good properties in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance, and a balance therebetween while ensuring good compatibility between the polyaryletherketone resin and the polyarylethersulfone resin.
[0041] In some embodiments, the polyaryletherketone resin may be present in an amount of 60 wt% to about 90 wt%, for example, about 60 wt% to about 85 wt%, based on the total weight of the thermoplastic resin including the polyaryletherketone resin and the polyarylethersulfone resin. If the content of the polyaryletherketone resin is less than about 60 wt% based on the total weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of compatibility, electrostatic discharge dissipation, rigidity, and impact resistance of the polyaryletherketone resin and the polyarylethersulfone resin, and may exhibit significant changes in properties (rigidity and impact resistance, etc.) according to the processing direction (longitudinal direction (MD) and transverse direction (TD)) of the sample. If the content of the polyaryletherketone resin exceeds about 90 wt% based on the total weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of compatibility, rigidity, and impact resistance of the polyaryletherketone resin and the polyarylethersulfone resin, and may exhibit significant changes in properties (rigidity and impact resistance, etc.) according to the processing direction (longitudinal direction (MD) and transverse direction (TD)) of the sample.
[0042] (B) Polyarylethersulfone resin
[0043] The polyarylethersulfone resin according to one embodiment of the present invention is used together with a polyaryletherketone resin, carbon nanotubes and carbon black in a specific content ratio to improve the properties of a thermoplastic resin composition, such as wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and a balance therebetween, without reducing the compatibility between the polyaryletherketone resin and the polyarylethersulfone resin. The polyarylethersulfone resin may include a polyarylethersulfone resin used in a typical thermoplastic resin composition.
[0044] In some embodiments, the polyarylethersulfone resin may include a polyarylethersulfone resin including a repeating unit represented by Formula 2 (polyphenylsulfone resin, etc.).
[0045] [Formula 2]
[0046]
[0047] In some embodiments, the viscosity is measured using a capillary viscometer at 400°C and 1,000 seconds in accordance with ASTM D3835. -1The polyarylethersulfone resin may have a melt viscosity of about 200 Pa·s to about 400 Pa·s, for example, about 210 Pa·s to about 390 Pa·s, measured at a shear rate of . Within this range, the thermoplastic resin composition may have good properties in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance, and a balance therebetween while ensuring good compatibility between the polyaryletherketone resin and the polyarylethersulfone resin.
[0048] In some embodiments, the melt viscosity ratio of the polyaryletherketone resin to the polyarylethersulfone resin may be in the range of about 1: 1 to about 4: 1, for example, about 1.05: 1 to about 2.5: 1. Within this range, good compatibility between the polyaryletherketone resin and the polyarylethersulfone resin may be ensured, whereby the domain (polyarylethersulfone resin) in the matrix (polyaryletherketone resin) may have an average size of about 0.5 μm or less, and the thermoplastic resin composition may exhibit a single glass transition temperature, may have good properties in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance, etc., and may exhibit minimal variation in properties (rigidity, impact resistance, etc.) according to the processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0049] In some embodiments, the polyarylethersulfone resin may be present in an amount of about 10 wt % to about 40 wt %, for example, about 15 wt % to about 40 wt %, based on the total weight of the thermoplastic resin including the polyaryletherketone resin and the polyarylethersulfone resin. If the content of the polyarylethersulfone resin is less than about 10 wt % based on the total weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, rigidity, and impact resistance, and may exhibit significant changes in properties (rigidity, impact resistance, etc.) according to the processing directions (machine direction (MD) and transverse direction (TD)) of the sample. If the content of the polyarylethersulfone resin exceeds about 40 wt % based on the total weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, electrostatic discharge dissipation, rigidity, impact resistance, etc., and may show significant changes in properties (rigidity, impact resistance, etc.) depending on the processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0050] (C) Carbon nanotubes
[0051] The carbon nanotubes according to one embodiment of the present invention are used together with polyaryletherketone resin, polyarylethersulfone resin and carbon black in a specific content ratio to improve the properties of the thermoplastic resin composition, such as wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance therebetween, without reducing the compatibility between the polyaryletherketone resin and the polyarylethersulfone resin. For example, the carbon nanotubes may include single-layer carbon nanotubes, double-layer carbon nanotubes, multi-layer carbon nanotubes, bundled carbon nanotubes, etc.
[0052] In some embodiments, the carbon nanotubes may have an average diameter of about 3 nm to about 15 nm, for example, about 5 nm to about 13 nm (measured by a transmission electron microscope (TEM)), and an average length of about 10 μm to about 25 μm, for example, about 12 μm to about 20 μm (measured by a scanning electron microscope (SEM)). Within these ranges, the thermoplastic resin composition may have good properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, wear resistance, and electrostatic discharge dissipation, and may exhibit minimal changes in properties (rigidity and impact resistance, etc.) according to the processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0053] In some embodiments, the amount of carbon nanotubes present relative to about 100 parts by weight of the thermoplastic resin may be about 1 part by weight to about 4 parts by weight, for example, about 1.5 parts by weight to about 3 parts by weight. If the content of carbon nanotubes is less than about 1 part by weight relative to about 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of compatibility between polyaryletherketone resin and polyarylethersulfone resin, electrostatic discharge dissipation, rigidity and impact resistance, and may show significant changes in properties (rigidity and impact resistance, etc.) according to the processing direction (longitudinal direction (MD) and transverse direction (TD)) of the sample. If the content of carbon nanotubes exceeds about 4 parts by weight relative to about 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of electrostatic discharge dissipation, etc.
[0054] (D) Carbon black
[0055] Carbon black according to one embodiment of the present invention is used with polyaryletherketone resin, polyarylethersulfone resin and carbon nanotube in a specific content ratio to improve the properties of thermoplastic resin composition, such as wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and balance therebetween, without reducing the compatibility between polyaryletherketone resin and polyarylethersulfone resin. Carbon black may include conductive carbon black used in typical thermoplastic resin composition.
[0056] In some embodiments, the carbon black may have an average particle size of about 20 nm to about 50 nm, for example, about 25 nm to about 45 nm, and a void fraction of about 50% to about 90%, for example, about 65% to about 85%, as measured by a transmission electron microscope (TEM). Within these ranges, the thermoplastic resin composition may have good properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, wear resistance, and electrostatic discharge dissipation, and may exhibit minimal variation in properties (rigidity and impact resistance, etc.) according to the processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0057] In some embodiments, the carbon black may be present in an amount of about 2 parts by weight to about 5 parts by weight, for example, about 2.5 parts by weight to about 4 parts by weight, relative to about 100 parts by weight of the thermoplastic resin. If the content of carbon black is less than about 2 parts by weight relative to about 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of electrostatic discharge dissipation, etc. If the content of carbon black exceeds about 5 parts by weight relative to about 100 parts by weight of the thermoplastic resin, the thermoplastic resin composition may have poor properties in terms of wear resistance and electrostatic discharge dissipation, etc.
[0058] In some embodiments, the weight ratio of carbon nanotubes to carbon black may be in the range of about 1:0.5 to about 1:3, for example, about 1:1 to about 1:2. Within this range, the thermoplastic resin composition may have further improved properties in terms of wear resistance and electrostatic discharge dissipation.
[0059] An embodiment of the thermoplastic resin composition according to the present invention may further include additives used in typical thermoplastic resin compositions. The additives may include, for example, flame retardants, fillers, antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, thermal stabilizers, UV stabilizers, pigments, dyes, and mixtures thereof. Relative to about 100 parts by weight of the thermoplastic resin, the additive may optionally be present in an amount of about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 20 parts by weight.
[0060] In the thermoplastic resin composition according to the present invention, the domains (polyarylethersulfone resin) in the matrix (polyaryletherketone resin) may have an average size of 0.5 μm or less (including the case where no domains are visible) as measured by a scanning electron microscope (SEM) at magnifications of 10,000× and 50,000×. If the average size of the domains exceeds about 0.5 μm, the thermoplastic resin composition may have poor properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, rigidity, impact resistance, etc., and may show significant changes in properties (rigidity, impact resistance, etc.) according to the processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0061] In some embodiments, the thermoplastic resin composition may have a glass transition temperature of about 150° C. to about 170° C., for example, about 150° C. to about 165° C., and may exhibit a single glass transition temperature. Within this range, the thermoplastic resin composition may have good properties in terms of rigidity and impact resistance, etc., without reducing the compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, and may exhibit minimal changes in properties (rigidity and impact resistance, etc.) according to the processing directions (longitudinal direction (MD) and transverse direction (TD)) of the sample. Here, "single glass transition temperature" means that only one peak is observed in a graph of tan δ versus temperature obtained by measuring the modulus of a sample of the thermoplastic resin composition using a dynamic mechanical analyzer (model: Q800, manufacturer: TA Instruments Inc.) under conditions of a strain of 2.5%, a frequency of 1 Hz, and a heating rate of 5° C. / min.
[0062] One embodiment of the thermoplastic resin composition according to the present invention can be prepared in the form of pellets by mixing the aforementioned components, followed by melt extrusion at a temperature of about 350 to about 450° C., for example, about 380 to about 420° C. in a typical twin-screw extruder.
[0063] In some embodiments, the thermoplastic resin composition may have a weight loss (wear loss) of about 30 mg or less, e.g., about 10 to about 25 mg, measured after 1,000 cycles of operation on a sample having a size of 100 mm×100 mm×3.2 mm under conditions of a load of 1 kgf and a grinding wheel speed of 60 rpm using an abrasion resistance tester in accordance with ASTM D4060.
[0064] In some embodiments, the thermoplastic resin composition may have a surface resistivity of about 1×10 6 Ω / sq to about 1×10 9 Ω / sq, for example, about 2×10 6 Ω / sq to about 1×10 9 Surface resistivity of Ω / sq.
[0065] In some embodiments, the thermoplastic resin composition may have a tensile yield strength of about 93 MPa to about 100 MPa, e.g., about 95 MPa to about 99 MPa, and a tensile modulus of about 3.3 GPa to about 4.0 GPa, e.g., about 3.4 GPa to about 3.9 GPa, as measured in accordance with ASTM D638 on a 3.2 mm thick injection molded specimen at a crosshead speed of 50 mm / min in the machine direction (MD) of the specimen.
[0066] In some embodiments, the thermoplastic resin composition can have a tensile yield strength of about 93 MPa to about 100 MPa, e.g., about 95 MPa to about 99 MPa, and a tensile modulus of about 3.3 GPa to about 4.0 GPa, e.g., about 3.4 GPa to about 3.9 GPa, as measured in accordance with ASTM D638 on a 3.2 mm thick injection molded specimen at a crosshead speed of 50 mm / min in the transverse direction (MD) of the specimen.
[0067] In some embodiments, the difference between the tensile yield strength of the thermoplastic resin composition in the longitudinal direction of the injection molded sample and the tensile yield strength in the transverse direction of the injection molded sample may be about 2 MPa or less, and the difference between the tensile modulus of the thermoplastic resin composition in the longitudinal direction of the injection molded sample and the tensile modulus in the transverse direction of the injection molded sample may be about 0.2 GPa or less.
[0068] In some embodiments, the thermoplastic resin composition may have a flexural strength of about 140 MPa to about 150 MPa, e.g., about 141 MPa to about 149 MPa, and a flexural modulus of about 3.2 GPa to about 4.0 GPa, e.g., about 3.3 GPa to about 3.8 GPa, measured in accordance with ASTM D790 on a 3.2 mm thick injection molded sample at a crosshead speed of 2.8 mm / min in the machine direction (MD) of the sample.
[0069] In some embodiments, the thermoplastic resin composition may have a flexural strength of about 140 MPa to about 150 MPa, e.g., about 141 MPa to about 149 MPa, and a flexural modulus of about 3.2 GPa to about 4.0 GPa, e.g., about 3.3 GPa to about 3.8 GPa, measured according to ASTM D790 on a 3.2 mm thick injection molded sample at a crosshead speed of 2.8 mm / min in the transverse direction (TD) of the sample.
[0070] In some embodiments, the difference between the flexural strength of the thermoplastic resin composition in the longitudinal direction of the injection molded sample and the flexural strength in the transverse direction of the injection molded sample may be about 2 MPa or less, and the difference between the tensile modulus of the thermoplastic resin composition in the longitudinal direction of the injection molded sample and the tensile modulus in the transverse direction of the injection molded sample may be about 0.2 GPa or less.
[0071] In some embodiments, the thermoplastic resin composition may exhibit no breakage when unnotched Izod impact strength is measured in the machine direction (MD) of an injection molded sample on a 3.2 mm thick injection molded sample in an impact strength test according to ASTM D256.
[0072] In some embodiments, the thermoplastic resin composition may exhibit no breakage when unnotched Izod impact strength is measured in the transverse direction (TD) of the injection molded sample on a 3.2 mm thick injection molded sample in an impact strength test according to ASTM D256.
[0073] The molded product according to the present invention is formed by the above-mentioned thermoplastic resin composition. The thermoplastic resin composition can be prepared into a pellet form. The prepared pellets can be manufactured into various molded products (articles) by various molding methods (such as injection molding, extrusion, vacuum molding and casting, etc.). These molding methods are well known to those of ordinary skill in the field to which the present invention belongs. The molded product has good properties in terms of wear resistance, electrostatic discharge dissipation, rigidity, impact resistance and the balance between them, without reducing the compatibility between polyaryletherketone resin and polyarylethersulfone resin, and shows the minimum change of properties (rigidity and impact resistance, etc.) according to the processing direction (longitudinal (MD) and transverse (TD)) of the sample. Accordingly, the molded product is used as a material for semiconductor wafer cleaning equipment (such as wafer suction cups and suction cup pins), semiconductor wafer transmission equipment (such as wafer carriers and front-opening wafer transfer boxes (FOUPs)), semiconductor fixing equipment (such as fixing rings) and semiconductor wafer chip fixing and post-processing equipment (such as trays and molds).
[0074]
Invention Mode
[0075] Next, the present invention will be described in more detail with reference to some examples. However, it should be noted that these examples are provided for illustration only and are not to be construed as limiting the present invention in any way.
[0076] Example
[0077] The details of the components used in Examples and Comparative Examples are as follows:
[0078] (A) Polyaryletherketone resin
[0079] (A1) Polyetheretherketone resin (melt viscosity: 470 Pa·s, product name: 650G, manufacturer: Victrex Plc) was used.
[0080] (A2) Polyetheretherketone resin (melt viscosity: 350 Pa·s, product name: 450G, manufacturer: Victrex Plc) was used.
[0081] (A3) A polyetheretherketone resin (melt viscosity: 150 Pa·s, product name: KT880, manufacturer: Solvay SA) is used.
[0082] (A4) Polyetheretherketone resin (melt viscosity: 90 Pa·s, product name: 90G, manufacturer: Victrex Plc) was used.
[0083] (B) Polyarylethersulfone resin
[0084] (B1) A polyphenylsulfone resin (melt viscosity: 230 Pa·s, product name: Ultrason P2010, manufacturer: BASF SE) was used.
[0085] (B2) A polyphenylsulfone resin (melt viscosity: 320 Pa·s, product name: Ultrason P3010, manufacturer: BASF SE) was used.
[0086] (B3) A polyphenylsulfone resin (melt viscosity: 360 Pa·s, product name: Radel 5100, manufacturer: Solvay SA) was used.
[0087] (C) Carbon nanotubes
[0088] Carbon nanotubes (product name: Lucan BT1003M, manufacturer: LG Chemical) were used.
[0089] D) Carbon black
[0090] Carbon black (product name: KetjenBlack EC-600JD, manufacturer: Lion Specialty Chemicals) was used.
[0091] Examples 1 to 11 and Comparative Examples 1 to 9
[0092] The aforementioned components were mixed in the amounts listed in Table 1, Table 2, Table 3 and Table 4, and then extruded at 400°C to prepare a thermoplastic resin composition in the form of pellets. Here, a twin-screw extruder (L / D: 40, Φ: 45 mm) was used for extrusion. The prepared pellets were dried at 100°C for 4 hours or more, and then injection molded using a 6 ounce (oz.) injection molding machine (molding temperature: 400°C, mold temperature: 150°C) to prepare a sample. The following properties of the prepared samples were evaluated. The results are shown in Table 1, Table 2, Table 3 and Table 4.
[0093] Characteristic evaluation
[0094] (1) Average domain size (unit: μm): After coating the sample with platinum, the size of each domain (polyarylethersulfone resin) in the matrix (polyaryletherketone resin) was measured at magnifications of 10,000× and 50,000× using a data input tool of a scanning electron microscope (SEM, model name: S-4800, manufacturer: Hitachi High-Tech.), and the obtained values were then averaged.
[0095] (2) Glass transition temperature (unit: °C): After measuring the modulus of the sample using a dynamic mechanical analyzer (model name: Q800, manufacturer: TA Instruments Inc.) under the conditions of 2.5% strain, 1 Hz frequency and 5 °C / min heating rate, the temperature corresponding to the peak in the curve graph of tan δ versus temperature was determined as the glass transition temperature of the sample.
[0096] (3) Wear resistance: According to ASTM D4060, using an abrasion resistance tester (model name: 5135, manufacturer: Taber Industries, grinding wheel: CS-17), the weight loss (wear loss, unit: mg) of a sample having a size of 100 mm×100 mm×3.2 mm was measured after 1000 cycles of operation under the conditions of a load of 1 kgf and a grinding wheel speed of 60 rpm.
[0097] (4) Surface resistivity (unit: Ω / sq): Surface resistivity was measured on a 1 mm thick sample using a surface resistivity meter (model name: 152-1, manufacturer: TREK) in accordance with ASTM D257.
[0098] (5) Tensile yield strength (unit: MPa) and tensile modulus (unit: GPa): The tensile yield strength and tensile modulus were measured in accordance with ASTM D638 on 3.2 mm thick injection molded specimens (dimensions: 150 mm×150 mm×3.2 mm) at a crosshead speed of 50 mm / min in the machine direction (MD) of the specimen or at a crosshead speed of 50 mm / min in the transverse direction (TD) of the specimen.
[0099] (6) Flexural strength (unit: MPa) and flexural modulus (unit: GPa): The flexural strength and flexural modulus were measured on 3.2 mm thick injection molded specimens in accordance with ASTM D790 at a crosshead speed of 50 mm / min in the machine direction (MD) of the specimen or at a crosshead speed of 50 mm / min in the transverse direction (TD) of the specimen.
[0100] (7) Unnotched Izod impact strength (unit: kgf·cm / cm): Unnotched Izod impact strength was measured on 3.2 mm thick injection molded specimens in the machine direction (MD) or in the transverse direction (TD) of the specimen in accordance with ASTM D256. (NB: no break)
[0101] Table 1
[0102]
[0103] * Parts by weight: Parts by weight relative to 100 parts by weight of thermoplastic resin (A+B)
[0104] Table 2
[0105]
[0106] * Parts by weight: Parts by weight relative to 100 parts by weight of thermoplastic resin (A+B)
[0107] Table 3
[0108]
[0109] * Parts by weight: Parts by weight relative to 100 parts by weight of thermoplastic resin (A+B)
[0110] Table 4
[0111]
[0112] * Parts by weight: Parts by weight relative to 100 parts by weight of thermoplastic resin (A+B)
[0113] From the above results, it can be seen that the thermoplastic resin composition according to the present invention exhibits good compatibility between the polyaryletherketone resin (matrix) and the polyarylethersulfone resin (domain), which is demonstrated by an average domain size of 0.5 μm or less. In addition, the thermoplastic resin composition according to the present invention has good properties in terms of wear resistance, electrostatic discharge dissipation (surface resistivity), rigidity (tensile yield strength, tensile modulus, flexural strength and flexural modulus) and impact resistance (unnotched Izod impact strength), and exhibits uniform properties in different processing directions (machine direction (MD) and transverse direction (TD)) of the sample.
[0114] On the contrary, the thermoplastic resin composition of Comparative Example 1 (in which the content of the polyaryletherketone resin is less than the range according to the present invention and the content of the polyarylethersulfone resin exceeds the range according to the present invention) has poor properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, electrostatic discharge dissipation (ESD exceeds the upper limit according to the present invention), rigidity and impact resistance, and shows significant changes in properties (rigidity and impact resistance, etc.) according to the machine directions (MD and TD) of the sample; the thermoplastic resin composition of Comparative Example 2 (in which the content of the polyaryletherketone resin exceeds the range according to the present invention and the content of the polyarylethersulfone resin is less than the range according to the present invention) has poor properties in terms of compatibility between the polyaryletherketone resin and the polyarylethersulfone resin, rigidity and impact resistance. The thermoplastic resin composition of Comparative Example 3 (wherein the content of carbon nanotubes is less than the range according to the present invention) has poor characteristics in terms of compatibility between polyaryletherketone resin and polyarylethersulfone resin, electrostatic discharge dissipation (ESD exceeds the upper limit according to the present invention), rigidity and impact resistance, and exhibits significant changes in characteristics (rigidity and impact resistance, etc.) in terms of the processing direction (MD and TD) of the sample; and the thermoplastic resin composition of Comparative Example 4 (wherein the content of carbon nanotubes exceeds the range according to the present invention) has poor characteristics in terms of electrostatic discharge dissipation (ESD is less than the lower limit according to the present invention). Here, low surface resistivity increases the risk of damaging electronic components due to external static electricity or external electricity. In addition, the thermoplastic resin composition of Comparative Example 5 (wherein the content of carbon black is less than the range according to the present invention) has poor characteristics in terms of electrostatic discharge dissipation (ESD exceeds the upper limit according to the present invention); and the thermoplastic resin composition of Comparative Example 6 (wherein the content of carbon black exceeds the range according to the present invention) has poor characteristics in terms of wear resistance and electrostatic discharge dissipation (ESD is less than the lower limit according to the present invention). In addition, the thermoplastic resin compositions of Comparative Examples 7 to Comparative Examples 9 (wherein the average size of the domain (polyarylethersulfone resin) in the matrix (polyaryletherketone resin) exceeds 0.5 μm) have poor characteristics in terms of compatibility between polyaryletherketone resin and polyarylethersulfone resin, electrostatic discharge dissipation (ESD exceeds the upper limit according to the present invention), rigidity and impact resistance, and exhibit significant changes in characteristics (rigidity and impact resistance, etc.) according to the processing directions (MD and TD) of the samples.
[0115] Although some embodiments have been described herein, it will be appreciated by those skilled in the art that various modifications, changes and variations may be made without departing from the spirit and scope of the present invention. Therefore, it should be understood that these embodiments are provided only for illustration and cannot be interpreted as limiting the present invention in any way. The scope of the present invention should be limited by the appended claims, rather than by the foregoing description, and the claims and their equivalents are intended to cover these modifications, etc. that fall within the scope of the present invention.
Claims
1. A thermoplastic resin composition comprising: About 100 parts by weight of a thermoplastic resin, including about 60 wt % to about 90 wt % of a polyaryletherketone resin and about 10 wt % to about 40 wt % of a polyarylethersulfone resin; From about 1 part by weight to about 4 parts by weight of carbon nanotubes; and about 2 parts by weight to about 5 parts by weight of carbon black, Wherein the domains (the polyarylethersulfone resin) in the matrix (the polyaryletherketone resin) have an average size of about 0.5 μm or less as measured by scanning electron microscopy (SEM) at magnifications of 10,000× and 50,000×.
2. The thermoplastic resin composition according to claim 1, wherein the polyaryletherketone resin comprises a repeating unit represented by Formula 1, [Formula 1] 3. The thermoplastic resin composition according to claim 1 or 2, wherein the viscosity is measured using a capillary viscometer at a temperature of 400°C and a flow rate of 1,000 seconds in accordance with ASTM D3835. -1 The polyaryletherketone resin has a melt viscosity of about 300 Pa·s to about 500 Pa·s when measured at a shear rate of about 1.5 %.
4. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyarylethersulfone resin comprises a repeating unit represented by Formula 2, [Formula 2] 5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the viscosity is measured using a capillary viscometer at a temperature of 400°C and a flow rate of 1,000 seconds in accordance with ASTM D3835. -1 The polyarylethersulfone resin has a melt viscosity of about 200 Pa·s to about 400 Pa·s when measured at a shear rate of . 6 . The thermoplastic resin composition according to claim 1 , wherein a melt viscosity ratio of the polyaryletherketone resin to the polyarylethersulfone resin is in the range of about 1:1 to about 4:
1. 7 . The thermoplastic resin composition according to claim 1 , wherein the carbon nanotubes have an average diameter of about 3 nm to about 15 nm and an average length of about 10 μm to about 25 μm. 8 . The thermoplastic resin composition according to claim 1 , wherein the carbon black has an average particle size of about 20 nm to about 50 nm and a void fraction of about 50% to about 90%. 9 . The thermoplastic resin composition according to claim 1 , wherein the thermoplastic resin composition has a glass transition temperature of about 150° C. to about 170° C. and exhibits a single glass transition temperature.
10. The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic resin composition has a weight loss (wear loss) of about 30 mg or less when measured after 1,000 cycles of operation on a sample having a size of 100 mm×100 mm×3.2 mm under the conditions of a load of 1 kgf and a grinding wheel speed of 60 rpm using an abrasion resistance tester in accordance with ASTM D4060.
11. The thermoplastic resin composition according to any one of claims 1 to 10, wherein the thermoplastic resin composition has a surface resistivity of about 1×10 6 Ω / sq to about 1×10 9 Surface resistivity of Ω / sq.
12. The thermoplastic resin composition according to any one of claims 1 to 11, wherein the thermoplastic resin composition has a tensile yield strength of about 93 MPa to about 100 MPa and a tensile modulus of about 3.3 GPa to about 4.0 GPa, measured according to ASTM D638 on a 3.2 mm thick injection molded sample at a crosshead speed of 50 mm / min in the machine direction (MD) of the injection molded sample or at a crosshead speed of 50 mm / min in the transverse direction (TD) of the injection molded sample, the difference between the tensile yield strength of the injection molded sample in the machine direction thereof and the tensile yield strength in the transverse direction thereof is less than or equal to about 2 MPa, and the difference between the tensile modulus of the injection molded sample in the machine direction thereof and the tensile modulus in the transverse direction thereof is less than or equal to about 0.2 GPa.
13. The thermoplastic resin composition according to any one of claims 1 to 12, wherein the thermoplastic resin composition has a flexural strength of about 140 MPa to about 150 MPa and a flexural modulus of about 3.2 GPa to about 4.0 GPa, measured according to ASTM D790 on a 3.2 mm thick injection molded sample at a crosshead speed of 2.8 mm / min in the machine direction (MD) of the injection molded sample or at a crosshead speed of 2.8 mm / min in the transverse direction (TD) of the injection molded sample, the difference between the flexural strength of the injection molded sample in the machine direction thereof and the flexural strength in the transverse direction thereof is less than or equal to about 2 MPa, and the difference between the flexural modulus of the injection molded sample in the machine direction thereof and the flexural modulus in the transverse direction thereof is less than or equal to about 0.2 GPa.
14. The thermoplastic resin composition according to any one of claims 1 to 13, wherein in an impact strength test according to ASTM D256, the thermoplastic resin composition shows no breakage when unnotched Izod impact strength is measured in the longitudinal direction or the transverse direction of a 3.2 mm thick injection molded sample.
15. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 14.
Citation Information
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