Polyester compositions and their products

Abstract

To provide a polyester material that achieves both high impact strength and high flame retardancy. [Solution] Based on the total weight of the polyester composition, the polyester composition comprises 10% to 40% by weight of polyethylene terephthalate, 40% to 50% by weight of polycarbonate, 8% to 18% by weight of flame retardant, 5% to 15% by weight of reinforcing agent, and 0.5% to 3% by weight of processing aid. The present invention further provides products of the polyester composition.

Description

Technical Field

[0001] The present invention relates to a composition and its products, and particularly to a polyester composition and its products.

Background Art

[0002] Existing high-strength (impact strength > 20 kg-cm / cm) polyester materials are inferior in flame retardancy and cannot meet the V0 standard compliant with UL94 standard at a thickness of 1.2 mm. On the other hand, existing flame-retardant grade polycarbonate / recycled polyethylene terephthalate (PC / rPET) alloys cannot be used in the manufacture of products that require high impact strength, such as industrial connectors, accessories for sports equipment, battery cases or electrical enclosures, due to insufficient impact strength.

Summary of the Invention

Problems to be Solved by the Invention

[0003] Existing polyester materials cannot achieve both high impact strength and high flame retardancy. Therefore, developing a polyester material that can achieve both high impact strength and high flame retardancy is an urgent goal for those skilled in the art.

Means for Solving the Problems

[0004] The present invention provides a polyester composition and its products having high impact strength and high flame retardancy.

[0005] One embodiment of the present invention provides a polyester composition. Based on the total weight of the polyester composition, the polyester composition includes 10% to 40% by weight of polyethylene terephthalate, 40% to 50% by weight of polycarbonate, 8% to 18% by weight of a flame retardant, 5% to 15% by weight of a reinforcing agent, and 0.5% to 3% by weight of a processing aid.

[0006] In one embodiment of the present invention, the flame retardant includes a phosphate ester-based flame retardant, and the content of the phosphate ester-based flame retardant is 12% to 18% by weight based on the total weight of the polyester composition.

[0007] In one embodiment of the present invention, the flame retardant comprises a brominated polycarbonate flame retardant and a synergistic agent, and the total content of the brominated polycarbonate flame retardant and the synergistic agent is 8% to 12% by weight, based on the total weight of the polyester composition.

[0008] In one embodiment of the present invention, the weight ratio of the brominated polycarbonate flame retardant to the synergistic agent is 6:1 to 2:1.

[0009] In one embodiment of the present invention, the synergistic agent comprises at least one of antimony trioxide, antimony pentoxide, zinc stannate, zinc oxide, zinc pyrophosphate, and zinc borate.

[0010] In one embodiment of the present invention, the reinforcing agent comprises at least two of the following: ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA), polyolefin elastomer-grafted glycidyl methacrylate (POE-g-GMA), polyethylene-grafted glycidyl methacrylate (PE-g-GMA), polyethylene-grafted methyl acrylate (PE-g-MA), and methyl methacrylate-butadiene-styrene copolymer (MBS).

[0011] In one embodiment of the present invention, the processing aid includes a drip prevention agent, a lubricant, and an antioxidant.

[0012] In one embodiment of the present invention, polyethylene terephthalate includes virgin pellets, recycled pellets, or a combination thereof.

[0013] The polyester composition product of the present invention is manufactured by processing the above polyester composition as engineering plastic particles, wherein the processing step includes injection molding.

[0014] In one embodiment of the present invention, the product simultaneously possesses an impact strength of 20 kg-cm / cm or more and a flame retardancy grade of V0 with a thickness of 1.2 mm in accordance with the UL94 standard.

[0015] In one embodiment of the present invention, the product includes an industrial connector, an accessory for sports equipment, a battery case, and an electrical enclosure. [Effects of the Invention]

[0016] Based on the above, the present invention provides a polyester composition and products thereof that can be used in the manufacture of injection-molded components that achieve both high impact strength and high flame retardancy by using a phosphate ester-based halogen-free flame retardant or a composite halogen-containing flame retardant in combination with a composite reinforcing agent, and can be widely used in products such as industrial connectors, sports equipment accessories, battery cases, and electrical enclosures, and have industrial mass production value. [Modes for carrying out the invention]

[0017] The embodiments of the present invention will be described in detail below. However, these embodiments are merely illustrative, and the present invention is not limited thereto.

[0018] In a specification, a range expressed as "from one value to another" is a summary expression that avoids listing all values ​​within the range in the specification. Therefore, the description of a particular numerical range includes any value within that range and any smaller numerical range defined by any value within that range, as if the specification were to list any value and a smaller numerical range.

[0019] The present invention provides a polyester composition. The polyester composition comprises polyethylene terephthalate (PET), polycarbonate (PC), a flame retardant, a reinforcing agent, and a processing aid. Based on the total weight of the polyester composition, the PET content is, for example, 10% to 40% by weight, the PC content is, for example, 40% to 50% by weight, the flame retardant content is, for example, 8% to 18% by weight, the reinforcing agent content is, for example, 5% to 15% by weight, and the processing aid content is, for example, 0.5% to 3% by weight. Each component of the polyester composition will be described in detail below.

[0020] Polyethylene terephthalate (PET)

[0021] Polyethylene terephthalate (PET) may include virgin resin pellets, recycled PET pellets (rPET), or a combination thereof. For example, the source of rPET may include recycled pellets for bottles, recycled pellets for film materials (e.g., release film), recycled pellets for textiles, or recycled pellets for other PET products, in order to achieve the goal of introducing recycled materials into the product and to conform to the trends of a circular economy, energy conservation, and carbon reduction. In some embodiments, the source of rPET is mainly recycled pellets for release film. Here, the intrinsic viscosity (IV) of rPET before thickening may be, for example, 0.50 to 0.62 dL / g, and the IV after thickening may be, for example, 0.7 to 0.9 dL / g, and either pre-thickening or post-thickening rPET can be selected as needed. In some embodiments, the PET may contain 10% to 100% by weight of rPET based on the total weight of PET in the polyester composition in order to achieve the goal of low carbon emissions. In some embodiments, the IV value of PET may be, for example, 0.6 to 0.9. If the intrinsic viscosity of the PET resin is less than 0.6, the impact strength of the PET resin may become too low, and the injection-molded product may be weak and brittle. If the intrinsic viscosity of the PET resin exceeds 0.9, the viscosity of the PET resin may become too high, resulting in poor fluidity and making it difficult to apply to injection molding. In some embodiments, the amount of PET added may be, for example, about 20% by weight, 30% by weight, or 35% by weight, based on the total weight of the polyester composition.

[0022] Polycarbonate

[0023] Polycarbonate (PC) may include aliphatic polycarbonate, aromatic polycarbonate, and aliphatic-aromatic polycarbonate, and is not particularly limited. In some embodiments, based on the total weight of the resin composition, the addition amount of PC may be, for example, about 42 wt%, 45 wt% or 49 wt%. In some embodiments, PC may be polycarbonate (PC) with model number A1900 purchased from Formosa Chemicals & Fibre Corporation.

[0024] Halogen-free flame retardant

[0025] The flame retardant can improve the flame resistance performance of the material. The halogen-free flame retardant may include a halogen-free flame retardant so as to meet the Restriction of Hazardous Substances (RoHS) directive of the European Union (EU) and the requirements of halogen-free and non-toxic products. Specific examples of the halogen-free flame retardant may include, for example, phosphate ester-based flame retardants such as triphenyl phosphate (TPP), resorcinol bisphosphate (RDP), bisphenol A di(diphenyl) phosphate (BPAPP), bisphenol A di(dimethyl) phosphate (BBC), resorcinol bis(diphenyl phosphate) (CR-733S), resorcinol bis(di-2,6-dimethylphenyl)) phosphate (PX-200). In some embodiments, based on the total weight of the polyester composition, the addition amount of the halogen-free flame retardant may be about 12 wt% to 18 wt%, for example, about 13.5 wt% or 15 wt%.

[0026] Halogen-containing flame retardant / synergist

[0027] The halogen-containing flame retardant may be a composite flame retardant composed of a halogen-containing flame retardant and a synergist in order to achieve the purpose of cost reduction. In some embodiments, the halogen-containing flame retardant may include, for example, a brominated polycarbonate-based flame retardant such as tetrabromocarbonate.

[0028] The synergist may contain at least one of antimony trioxide, antimony pentoxide, zinc stannate, zinc oxide, zinc pyrophosphate, and zinc borate. In some embodiments, the weight ratio of the halogen-containing flame retardant to the synergist is 6:1 to 2:1, such as 5:1 or 4:1. In some embodiments, based on the total weight of the polyester composition, the addition amount of the halogen-containing flame retardant may be about 8 wt% to 12 wt%, such as about 9.5 wt% or 11 wt%. In some embodiments, based on the total weight of the polyester composition, the addition amount of the halogen-containing flame retardant may be about 7 wt% to 10 wt%, such as about 8 wt%. In some embodiments, based on the total weight of the polyester composition, the addition amount of the synergist may be, for example, about 1 wt% to 2 wt%, such as about 1.5 wt%.

[0029] Reinforcing agent

[0030] The reinforcing agent may contain rubber, styrenes, polyolefins, or acrylic esters. In some embodiments, the reinforcing agent is a composite reinforcing agent and may be composed of two or more components. For example, the reinforcing agent may contain at least two of ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA), polyolefin elastomer graft glycidyl methacrylate (POE-g-GMA), polyethylene graft glycidyl methacrylate (PE-g-GMA), polyethylene graft methyl acrylate (PE-g-MA), and methyl methacrylate-butadiene-styrene copolymer (MBS). In some embodiments, based on the total weight of the polyester composition, the addition amount of the reinforcing agent may be about 8 wt%, 10 wt%, or 12 wt%. In some embodiments, the reinforcing agent contains E-MA-GMA and PE-g-MA, and the weight ratio of E-MA-GMA to PE-g-MA is about 0.5:1 to 1.5:1.

[0031] Processing aid

[0032] The processing aid may include, but is not limited to, an anti-dripping agent, a lubricant, and an antioxidant. The anti-dripping agent provides anti-dripping properties during combustion to meet the V0 standard of the UL-94 combustion test standard. The anti-dripping agent is, for example, polytetrafluoroethylene or modified polytetrafluoroethylene. In some embodiments, the amount of anti-dripping agent added may be about 0.1% to 0.5% by weight, for example, about 0.3% by weight, based on the total weight of the polyester composition. In some embodiments, the anti-dripping agent may be an anti-dripping agent of type FS-100 purchased from BANNER INTERNATIONAL CORPORATION.

[0033] The lubricant may include stearates (e.g., zinc stearate, sodium stearate, calcium stearate, etc.), polyethylene wax, siloxane modifiers, or fluororesins (e.g., polytetrafluoroethylene (PTFE)). By introducing a lubricant, friction between materials and between materials and equipment parts can be improved. In this embodiment, the amount of lubricant added may be, for example, about 0.1% to 2% by weight, or about 0.5% or 1% by weight, based on the total weight of the PET polyester material, but is not limited thereto. If the amount of lubricant added is less than 0.1% by weight, the effect of reducing the coefficient of friction may be poor, and the effect of improving the wear resistance of PET may not be significant. If the amount of lubricant added exceeds 2%, the fluidity of the material may become too high, making overflow more likely during injection and potentially making it difficult to control the conditions. Furthermore, excessive addition of lubricant may make the material brittle and reduce its impact strength. In some embodiments, the lubricant may be a lubricant of model number VISCOWAX 115 purchased from WWRC TAIWAN CO., LTD.

[0034] The antioxidant may include hindered phenol antioxidants (e.g., AO-1010, AO-1076, AO-1315, etc.), mixed antioxidants (e.g., B225, B215, B220, B911, etc.), phosphate ester antioxidants (e.g., AO-168, AO-618, TNPP, etc.), composite antioxidants, or combinations thereof. The antioxidant can reduce oxidation of the material during processing and improve the heat resistance and processability of the material. In some embodiments, the antioxidant may include tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxy)phenylpropionate, or combinations thereof. In some embodiments, the amount of antioxidant added based on the total weight of the polyester composition is, for example, about 0.01% to 2% by weight, for example, about 0.5% by weight, 1.0% by weight, or 1.5% by weight. In some embodiments, the antioxidant may be an antioxidant of type B225 purchased from BASF.

[0035] Performance additives

[0036] In some embodiments, the polyester composition may further contain performance additives to provide various additional properties. For example, the polyester composition may further contain a UV absorber to provide UV absorption properties.

[0037] The present invention provides a product that can be manufactured by further processing the above polyester composition as engineering plastic particles, the processing step of which may include injection molding. It can be used in products such as industrial connectors, accessories for sports equipment, battery cases, and electrical enclosures.

[0038] In some embodiments, PET, PC, flame retardants, reinforcing agents, and processing aids are first uniformly mixed in proportions, then melt-extruded in an extruder, and subsequently cooled in water to form pellets, thereby forming engineering plastic particles. By injection molding these engineering plastic particles, injection-molded components with high impact strength and high flame retardancy can be formed, which can be applied to products such as industrial connectors, sports equipment accessories, battery cases, and electrical enclosures.

[0039] The polyester composition and its products of the present invention will be described in detail below with reference to experimental examples. However, the following experimental examples are not intended to limit the present invention.

[0040] Experimental example

[0041] To demonstrate that the polyester composition presented in this invention possesses excellent impact strength, mechanical strength, and good flame retardancy, the following specific experimental examples were prepared.

[0042] rPET, PC, flame retardant, reinforcing agent, and processing aid were uniformly mixed according to the specified ratios, then melted in a twin-screw extruder at a processing temperature of approximately 245-280°C, and then standard test specimens for mechanical property and flame retardancy testing were injected using an injection molding machine (mold temperature approximately 40°C).

[0043] Test method

[0044] Impact strength: Tests were conducted according to the ASTM D256 standard. The obtained value (unit: kg-cm / cm) represents the total energy that the test specimen can withstand at the time of fracture. A higher value indicates a higher impact strength (or resistance strength) that the test specimen can withstand.

[0045] Tensile Strength: Tests were conducted according to the ASTM D638 standard. The obtained value (in MPa) represents the total energy that the test specimen can withstand under tensile deformation; a higher value indicates a higher tensile strength that the test specimen can withstand.

[0046] Bending strength: Tests were conducted according to the ASTM D790 standard. The obtained values ​​(in MPa) represent the resistance of the test specimen to bending deformation; a higher value indicates a higher bending strength that the test specimen can withstand.

[0047] Flexural modulus: Tested according to ASTM D790 standard. The obtained value (unit: MPa) represents the total energy for the bending deformation of the test specimen; a higher value indicates higher stiffness of the test specimen.

[0048] Heat Distortion Temperature (HDT): Tested at 0.45 MPa according to ASTM D648 standard. The obtained value (in °C) represents the resistance of the test specimen to heat deformation; a higher value indicates higher heat resistance of the test specimen.

[0049] Flame retardancy: Tested according to UL94 standards. The test specimen thickness was 1.2 mm. Flame retardancy grade V0 indicates that the fire was extinguished within 10 seconds and there were no drips. V1 indicates that the fire was extinguished within 30 seconds and there were no drips. V2 indicates that the fire was extinguished within 30 seconds and there was a possibility of cotton ignition due to drips.

[0050] The component ratios and test results of the polyester compositions of Examples 1-2 and Comparative Examples 1-6 are shown in Tables 1 and 2 below. Here, all component ratios are in weight percent.

[0051] [Table 1]

[0052] [Table 2]

[0053] Formulation information in Table 1 and Table 2: PC: Model number A1900, purchased from Formosa Chemicals & Fibre Corporation. rPET: Model number 6EX01, purchased from Nan Ya Plastics Corporation. IV is 0.85. Drip-preventing agent: Model number FS-100, purchased from BANNER INTERNATIONAL CORPORATION. Lubricant: Model number VISCOWAX 115, purchased from WWRC TAIWAN CO., LTD. Antioxidant: Model number B225, purchased from BASF.

[0054] As can be seen from the test results in Table 1, the polyester compositions of Examples 1 and 2 both satisfy the components and proportions presented in the present invention and exhibit good impact strength and flame retardancy, simultaneously having an impact strength of 20 kg-cm / cm or more and a flame retardancy grade V0 at a thickness of 1.2 mm in accordance with the UL94 standard. The polyester composition of Comparative Example 1 has a polycarbonate content that is higher than the range presented in the present invention and a flame retardant content that is lower than the range presented in the present invention, resulting in inferior flame retardancy. The polyester composition of Comparative Example 2 has a flame retardant content that is higher than the range presented in the present invention, resulting in inferior impact strength.

[0055] As can be seen from the test results in Table 2, Comparative Example 3, which uses only a single reinforcing agent, is inferior in flame retardancy compared to Example 1. Comparative Example 4, which uses only a single reinforcing agent, is inferior in flame retardancy compared to Example 2. Comparative Example 5, which uses a single reinforcing agent and phosphazene as a halogen-free flame retardant, achieves V0 grade flame retardancy, but its impact strength is insufficient compared to Example 1. Comparative Example 6, which uses a single reinforcing agent and uses decabromodiphenylethane and antimony trioxide as halogen-containing flame retardants, achieves V0 grade flame retardancy, but its impact strength is insufficient compared to Example 2.

[0056] In summary, the polyester composition of the present invention can be used in the manufacture of injection-molded components that achieve both high impact strength and high flame retardancy by using a specific proportion of a phosphate ester-based halogen-free flame retardant or a specific proportion of a composite halogen-containing polycarbonate-based flame retardant in combination with a specific proportion of a composite reinforcing agent. [Industrial applicability]

[0057] The polyester composition of the present invention can be widely used in products such as industrial connectors, accessories for sports equipment, battery cases, and electrical enclosures, and has industrial mass production value.

Claims

1. A polyester composition, Based on the total weight of the aforementioned polyester composition, 10% to 40% by weight of polyethylene terephthalate, 40% to 50% polycarbonate by weight, 8% to 18% by weight of flame retardant, 5% to 15% by weight of a reinforcing agent, 0.5% to 3% by weight of processing aids, A polyester composition containing the following:

2. The flame retardant comprises a phosphate ester-based flame retardant, and the content of the phosphate ester-based flame retardant is 12% to 18% by weight, based on the total weight of the polyester composition. The polyester composition according to claim 1.

3. The flame retardant comprises a brominated polycarbonate flame retardant and a synergistic agent, and the total content of the brominated polycarbonate flame retardant and the synergistic agent is 8% to 12% by weight, based on the total weight of the polyester composition. The polyester composition according to claim 1.

4. The weight ratio of the brominated polycarbonate flame retardant to the synergistic agent is 6:1 to 2:

1. The polyester composition according to claim 3.

5. The synergistic agent comprises at least one of antimony trioxide, antimony pentoxide, zinc stannate, zinc oxide, zinc pyrophosphate, and zinc borate. The polyester composition according to claim 3.

6. The reinforcing agent comprises at least two of the following: ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MA-GMA), polyolefin elastomer-grafted glycidyl methacrylate (POE-g-GMA), polyethylene-grafted glycidyl methacrylate (PE-g-GMA), polyethylene-grafted methyl acrylate (PE-g-MA), and methyl methacrylate-butadiene-styrene copolymer (MBS). The polyester composition according to claim 1.

7. The processing aid includes an anti-dripping agent, a lubricant, and an antioxidant. The polyester composition according to claim 1.

8. The polyethylene terephthalate includes virgin pellets, recycled pellets, or a combination thereof. The polyester composition according to claim 1.

9. A polyester composition product manufactured by processing the polyester composition described in any one of claims 1 to 8 as engineering plastic particles, The aforementioned processing step includes injection molding. product.

10. It has an impact strength of 20 kg-cm / cm or more and a thickness of 1.2 mm that conforms to the UL94 standard, and simultaneously possesses flame retardancy grade V0. The product according to claim 9.

11. Including industrial connectors, sports equipment accessories, battery cases, and electrical enclosures, The product according to claim 9.

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