Regenerated thermoplastic resin composition and molded article produced therefrom

Abstract

The regenerated thermoplastic resin composition according to the present invention comprises: about 100 parts by weight of a regenerated thermoplastic resin comprising about 80% to 99% by weight of a regenerated polycarbonate resin and about 1% to 20% by weight of a regenerated polyester resin recovered within 50 km from a coastline; about 0.5 to 20 parts by weight of a rubber-modified aromatic vinyl copolymer resin; about 10 parts by weight to 30 parts by weight of a phosphorus-based flame retardant; and about 0.1 to 1 part by weight of an epoxy ester compound containing an ester group and an epoxy group. The regenerated thermoplastic resin composition is excellent in impact resistance, flowability, flame retardancy, thermal stability, appearance properties, heat resistance, chemical resistance, and a balance between these properties.

Description

Technical Field

[0001] The present invention relates to a recycled thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a recycled thermoplastic resin composition having good properties in terms of impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, and the balance of properties therebetween, and a molded article produced therefrom. Background Art

[0002] With the legislation in the United States and Europe to reduce marine plastic pollution, the demand for environmentally friendly materials by global companies is increasing. Therefore, products with high contents of various recycled materials have been developed as environmentally friendly materials. For example, in 2021, Ocean Bound Plastic (OBP) PET (recycled PET recovered within 50 km from the coastline) was applied as a recycled raw material to products, and in 2022, in addition to typical OBP PET resins and typical recycled polycarbonate resins (R-PCs) collected from sheets, water bottles, etc., IT electronic device models also required the use of recycled polycarbonate resin (ITE-PCM PC) collected from information technology electronic products (ITE) such as mobile phones, laptop computers, and desktop computers, which are difficult to recycle. In particular, due to the revision of EPEAT (Environmental Evaluation of Electrical and Electronic Products in the United States), points can be given for the application of post-consumer materials (ITE-PCM) derived from ITE, so the demand for the application of ITE-PCM is increasing.

[0003] However, since most recycled materials have been processed multiple times and have an unclear origin, the application of high contents of recycled materials can cause problems such as degradation of the thermoplastic resin obtained from the recycled materials and deterioration of the properties of the materials (thermoplastic resin composition and molded product), even if the recycled materials are washed before storage. In particular, OBP (Ocean Bound Plastic) PET and ITE-PCM PC derived from coastal beaches and electronic device components contain a large amount of inorganic metals and foreign substances, leading to degradation of the polymer resin, and there is a high possibility of deterioration of the properties of recycled plastics when applied in excess.

[0004] Therefore, there is a need to develop a recycled thermoplastic resin composition having good properties in terms of impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, and the balance of properties therebetween.

[0005] The background art of the present invention is disclosed in Korean Patent Laid-Open Publication No. 10-2016-0130701, etc. Summary of the Invention

[0006]

Technical Problem

[0007] An object of the present invention is to provide a recycled thermoplastic resin composition having good properties in terms of impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, and the balance of properties therebetween.

[0008] Another object of the present invention is to provide a molded article produced from the recycled thermoplastic resin composition.

[0009] The above and other objects of the present invention can be achieved by the embodiments of the present invention described below.

[0010]

Technical Solution

[0011] 1. One aspect of the present invention relates to a recycled thermoplastic resin composition. The recycled thermoplastic resin composition includes: about 100 parts by weight of a recycled thermoplastic resin, which includes about 80 wt% to about 99 wt% of a recycled polycarbonate resin and about 1 wt% to about 20 wt% of a recycled polyester resin recovered within 50 km from the coastline; about 0.5 parts by weight to about 20 parts by weight of a rubber-modified aromatic vinyl copolymer resin; about 10 parts by weight to about 30 parts by weight of a phosphorus-based flame retardant; and about 0.1 parts by weight to about 1 part by weight of an epoxy ester compound containing an ester group and an epoxy group.

[0012] 2. In Embodiment 1, based on 100 wt% of the total recycled polycarbonate resin, the recycled polycarbonate resin may include about 30 wt% or more of a recycled polycarbonate resin (ITE-PCM PC) recovered from IT electronic products.

[0013] 3. In Embodiment 1 or Embodiment 2, the recycled polycarbonate resin may contain about 0.01 wt% to about 0.5 wt% of metal minerals.

[0014] 4. In Embodiments 1 to 3, the recycled polyester resin may include at least one of ocean-bound plastic (OBP) polyethylene terephthalate, OBP polybutylene terephthalate, and OBP cyclohexanedimethanol terephthalate.

[0015] 5. In Embodiments 1 to 4, the rubber-modified aromatic vinyl copolymer resin may include a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin.

[0016] 6. In Embodiments 1 to 5, the rubber-modified vinyl graft copolymer may be prepared by graft-polymerizing a monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer onto a rubber polymer.

[0017] 7. In Embodiments 1 to 6, the phosphorus-based flame retardant may include at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, and a phosphazene compound.

[0018] 8. In Embodiments 1 to 7, the epoxy ester compound containing an ester group and an epoxy group may be a compound represented by Formula 1:

[0019] [Formula 1]

[0020]

[0021] wherein R1 and R3 are each independently a C1 to C 10 hydrocarbon group, R2 and R4 are each independently a hydrogen atom or a C1 to C 10 hydrocarbon group, m and n are 0 or 1, and m + n is 1 or 2. Herein, R1 and R2 and R3 and R4 may be connected to each other to form a ring.

[0022] 9. In Embodiments 1 to 8, the recycled thermoplastic resin composition may have a notched Izod impact strength of about 5 kgf·cm / cm to about 40 kgf·cm / cm measured on a 1 / 8" thick sample in accordance with ASTM D256.

[0023] 10. In Embodiments 1 to 9, the recycled thermoplastic resin composition may have a melt flow index (MI) of about 10 g / 10 min to about 45 g / 10 min measured at 260 °C under a load of 2.16 kgf in accordance with ASTM D1238.

[0024] 11. In Embodiments 1 to 10, the recycled thermoplastic resin composition may have a flame retardancy of V-0 or higher measured on a 1.5 mm thick sample by the UL-94 vertical test method.

[0025] 12. In Embodiments 1 to 11, when a 2 g sample of the recycled thermoplastic resin composition prepared in the form of pellets is placed in a glass petri dish having a diameter of 80 mm and the top of the glass petri dish is covered with a glass plate, and then the glass petri dish is heated on a hot plate at 270 °C for 2 hours, the recycled thermoplastic resin composition may have a glass plate weight gain of about 0.01% to about 0.5% calculated according to Equation 1.

[0026] [Equation 1]

[0027] Glass plate weight gain (%) = (weight of the glass plate after heating for 2 hours - initial weight of the glass plate) × 100

[0028] 13. In Embodiments 1 to 12, the recycled thermoplastic resin composition may have a Vicat softening temperature (VST) of about 80 °C to about 120 °C measured in accordance with the ISO 306 evaluation method (B / 50).

[0029] 14. Another aspect of the present invention relates to a molded article. The molded article is produced from a recycled thermoplastic resin composition according to any one of Embodiments 1 to 13.

[0030]

Beneficial Effects

[0031] The present invention provides a thermoplastic resin composition and a molded article produced therefrom, and the thermoplastic resin composition has good properties in terms of impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, balance of properties therebetween, etc. Detailed Embodiments

[0032] Hereinafter, embodiments of the present invention will be described in detail.

[0033] The recycled thermoplastic resin composition according to the present invention includes: (A) a recycled thermoplastic resin, which includes (A1) a recycled polycarbonate resin; (A2) a recycled polyester resin; (B) a rubber-modified aromatic vinyl copolymer resin; (C) a phosphorus-based flame retardant; and (D) an epoxy ester compound.

[0034] When representing a specific numerical range as used herein, "a to b" is defined as "≥a and ≤b".

[0035] (A) Recycled Thermoplastic Resin

[0036] The recycled thermoplastic resin according to the present invention includes (A1) a recycled polycarbonate resin; and (A2) a recycled polyester resin.

[0037] (A1) Recycled Polycarbonate Resin

[0038] The recycled polycarbonate resin according to an embodiment of the present invention is an environment-friendly material and can include any typical recycled polycarbonate resin without limitation. For example, the recycled polycarbonate resin can include post-consumer material PC (PCM PC) recovered from sheets, water bottles, etc., post-consumer material PC (PCM PC) recovered from IT electronic products (ITE-PCM PC), and combinations thereof.

[0039] In some embodiments, based on 100 wt% of the total recycled polycarbonate resin, the recycled polycarbonate resin can include about 30 wt% or more, for example, about 35 wt% to about 95 wt% of the recycled polycarbonate resin (ITE-PCM PC) recovered from IT electronic products. Additionally, based on 100 wt% of the total recycled polycarbonate resin, the recycled polycarbonate resin can include less than about 70 wt%, for example, about 5 wt% to about 65 wt% of the post-consumer material PC (PCM PC) collected from sheets, water bottles, etc. Within these ranges, the recycled thermoplastic resin composition can have better properties in terms of impact resistance, flame retardancy, environmental friendliness, etc.

[0040] In some embodiments, the recycled polycarbonate resin may have a weight average molecular weight (Mw) of about 10,000 g / mol to about 200,000 g / mol, such as about 20,000 g / mol to about 50,000 g / mol, as measured by gel permeation chromatography (GPC). Within this range, the recycled thermoplastic resin composition may have good properties in terms of impact resistance, fluidity (processability), etc.

[0041] In some embodiments, metal minerals (such as calcium (Ca), iron (Fe), etc.) may be present in the recycled polycarbonate in an amount of about 0.01 wt% to about 0.5 wt%, such as about 0.05 wt% to about 0.3 wt%. Within this range, the recycled thermoplastic resin composition may have good impact resistance, flame retardancy, etc.

[0042] In some embodiments, based on 100 wt% of the total recycled thermoplastic resin, the recycled polycarbonate resin may be present in an amount of about 80 wt% to about 99 wt%, such as about 85 wt% to about 95 wt%. If the content of the recycled polycarbonate resin is less than about 80 wt% based on 100 wt% of the total recycled thermoplastic resin, the recycled thermoplastic resin composition may suffer from deterioration in impact resistance, flame retardancy, environmental friendliness, etc., and if the content of the recycled polycarbonate resin exceeds about 99 wt%, the recycled thermoplastic resin composition may suffer from deterioration in chemical resistance, etc.

[0043] (A2) Recycled polyester resin

[0044] The recycled polyester resin according to one embodiment of the present invention is an environmentally friendly material and includes a recycled polyester resin recovered within 50 km from the coastline.

[0045] In some embodiments, the recycled polyester resin may include ocean-bound plastics (OBP) polyethylene terephthalate (PET), OBP polybutylene terephthalate (PBT), OBP polycyclohexylene dimethylene terephthalate (PCT), OBP polyethylene naphthalate (PEN), OBP polypropylene terephthalate (PTT), combinations thereof, etc. Preferably, the recycled polyester resin includes OBP polyethylene terephthalate, OBP polybutylene terephthalate, and OBP polycyclohexylene dimethylene terephthalate, combinations thereof, etc.

[0046] In some embodiments, the recycled polyester resin may have an intrinsic viscosity [η] of about 0.5 dl / g to about 1.5 dl / g, such as about 0.7 dl / g to about 1.3 dl / g, as measured according to ASTM D2857. Within this range, the recycled thermoplastic resin composition may exhibit good fluidity, molding processability, etc.

[0047] In some embodiments, based on 100 wt% of the total recycled thermoplastic resin, the recycled polyester resin may be present in an amount of about 1 wt% to about 20 wt%, such as about 3 wt% to about 15 wt%. If the content of the recycled polyester resin is less than about 1 wt% based on 100 wt% of the total recycled thermoplastic resin, the recycled thermoplastic resin composition may suffer from deterioration in chemical resistance, and if the content of the recycled polyester resin exceeds about 20 wt%, the recycled thermoplastic resin composition may suffer from deterioration in impact resistance, flame retardancy, etc.

[0048] (B) Rubber-modified aromatic vinyl copolymer resin

[0049] The rubber-modified aromatic vinyl copolymer resin according to an embodiment of the present invention, when applied to a recycled thermoplastic resin together with a phosphorus-based flame retardant and an epoxy ester compound, is used to improve the impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, balance of properties therebetween, etc. of the recycled thermoplastic resin composition, and may include (B1) a rubber-modified vinyl graft copolymer and (B2) an aromatic vinyl copolymer resin.

[0050] (B1) Rubber-modified vinyl graft copolymer

[0051] The rubber-modified vinyl graft copolymer according to an embodiment of the present invention can be prepared by graft polymerizing a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer onto a rubber polymer. For example, the rubber-modified vinyl graft copolymer can be prepared by graft polymerizing a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer (such as a vinyl cyanide monomer, a monomer for imparting processability and heat resistance, or a combination thereof) onto a rubber polymer. The polymerization can be carried out by any suitable polymerization method well known in the art (such as emulsion polymerization, suspension polymerization, etc.). In addition, the rubber-modified vinyl graft copolymer can form a core (rubber polymer)-shell (copolymer of the monomer mixture) structure, but is not limited thereto.

[0052] In some embodiments, the rubber polymer may include, for example, a diene rubber (such as polybutadiene, poly(acrylonitrile-butadiene), etc.), a saturated rubber obtained by hydrogenating a diene rubber, isoprene rubber, C2 to C 10 alkyl (meth)acrylate rubber, C2 to C 10 copolymer of alkyl (meth)acrylate and styrene, ethylene-propylene-diene terpolymer (EPDM), etc. These can be used alone or as a mixture thereof. For example, diene rubber, (meth)acrylate rubber, etc., more specifically, butadiene rubber, butyl acrylate rubber, etc., can be used as the rubber polymer.

[0053] In some embodiments, the rubber polymer (rubber particles) may have an average particle size of about 0.05 μm to about 6 μm, such as about 0.15 μm to about 4 μm, specifically about 0.25 μm to about 3.5 μm. Within this range, the recycled thermoplastic resin composition may have good properties in terms of impact resistance, appearance, etc. Here, the average (z-average) particle diameter of the rubber polymer (rubber particles) can be measured by a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a sieve to remove condensates generated during the polymerization of the rubber polymer, and then a mixed solution of 0.5 g of latex and 30 ml of distilled water is placed in a 1,000 ml flask, and then the flask is filled with distilled water to prepare a sample. Then, 10 ml of the sample is transferred to a quartz cell, and then the average particle diameter of the rubber polymer is measured using a light scattering particle analyzer (Nano-zs, Malvern Limited).

[0054] In some embodiments, based on 100 wt% of the rubber-modified vinyl graft copolymer, the rubber polymer may be present in an amount of about 20 wt% to about 80 wt%, such as about 25 wt% to about 70 wt%, and based on 100 wt% of the rubber-modified vinyl graft copolymer, the monomer mixture may be present in an amount of about 20 wt% to about 80 wt%, such as about 30 wt% to about 75 wt%. Within these ranges, the recycled thermoplastic resin composition may have good properties in terms of impact resistance, heat resistance, processability, appearance, etc.

[0055] In some embodiments, the aromatic vinyl monomer may be graft copolymerized with the rubber polymer and may include, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc., but is not limited thereto. These may be used alone or as a mixture thereof. Based on 100 wt% of the monomer mixture, the aromatic vinyl monomer may be present in an amount of about 10 wt% to about 90 wt%, such as about 20 wt% to about 80 wt%. Within this range, the recycled thermoplastic resin composition may have good processability, impact resistance, etc.

[0056] In some embodiments, the vinyl cyan monomer may be copolymerized with the aromatic vinyl monomer and may include, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. These may be used alone or as a mixture thereof. For example, acrylonitrile, methacrylonitrile, etc. may be used as the vinyl cyan monomer. In addition, monomers for imparting processability and heat resistance may include (meth)acrylic acid, C1 to C 10 alkyl (meth)acrylate, maleic anhydride, N-substituted maleimide, etc.

[0057] In some embodiments, the rubber-modified vinyl graft copolymer may include, for example, a copolymer (g-ABS) prepared by grafting styrene monomer as an aromatic vinyl compound and acrylonitrile monomer as a vinyl cyanide compound onto a butadiene rubber polymer, a copolymer (g-MBS) prepared by grafting styrene monomer as an aromatic vinyl compound and methyl methacrylate as a monomer for imparting processability and heat resistance onto a butadiene rubber polymer, a copolymer (g-MABS) prepared by grafting styrene monomer, acrylonitrile monomer, and methyl methacrylate onto a butadiene rubber polymer, an acrylate-styrene-acrylonitrile graft copolymer (g-ASA) prepared by grafting styrene monomer as an aromatic vinyl compound and acrylonitrile monomer as a vinyl cyanide compound onto a butyl acrylate rubber polymer, and the like. For example, g-ABS, g-MBS, etc. may be used.

[0058] In some embodiments, based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the rubber-modified vinyl graft copolymer may be present in an amount of about 20 wt% to about 80 wt%, for example, about 25 wt% to about 75 wt%. Within this range, the recycled thermoplastic resin composition may have good impact resistance, chemical resistance, etc.

[0059] (B2) Aromatic vinyl copolymer resin

[0060] The aromatic vinyl copolymer resin according to an embodiment of the present invention may be the aromatic vinyl copolymer resin used in typical rubber-modified aromatic vinyl copolymer resins. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.

[0061] In some embodiments, the aromatic vinyl copolymer resin may be prepared by mixing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, and then polymerizing the mixture. Here, the polymerization may be carried out by any suitable polymerization method well known in the art (such as emulsion polymerization, suspension polymerization, etc.).

[0062] In some embodiments, the aromatic vinyl monomer may include, for example, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. These may be used alone or as a mixture thereof. Based on 100 wt% of the total aromatic vinyl copolymer resin, the aromatic vinyl monomer may be present in an amount of about 10 wt% to about 95 wt%, for example, about 20 wt% to about 90 wt%. Within this range, the recycled thermoplastic resin composition may have good impact resistance, fluidity, etc.

[0063] In some embodiments, the monomers copolymerizable with the aromatic vinyl monomer may include at least one of vinyl cyanide monomers and alkyl (meth)acrylate monomers. For example, the monomers copolymerizable with the aromatic vinyl monomer may include vinyl cyanide monomers, or may include vinyl cyanide monomers and alkyl (meth)acrylate monomers.

[0064] In some embodiments, the vinyl cyanide monomers may include, for example, acrylonitrile, methacrylonitrile, ethylacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, etc. These may be used alone or as a mixture thereof. For example, the vinyl cyanide monomers may include, for example, acrylonitrile, methacrylonitrile, etc.

[0065] In some embodiments, the alkyl (meth)acrylate monomers may include, for example, (meth)acrylic acid and / or C1 to C 10 alkyl (meth)acrylate. These may be used alone or as a mixture thereof. For example, the alkyl (meth)acrylate monomers may include methyl methacrylate, methyl acrylate, etc.

[0066] In some embodiments, based on 100 wt% of the aromatic vinyl copolymer resin, the monomers copolymerizable with the aromatic vinyl monomer may be present in an amount of about 5 wt% to about 90 wt%, for example about 10 wt% to about 80 wt%. Within this range, the recycled thermoplastic resin composition may have good impact resistance, fluidity, etc.

[0067] In some embodiments, the aromatic vinyl copolymer resin may have a weight average molecular weight (Mw) of about 10,000 g / mol to about 300,000 g / mol, for example about 15,000 g / mol to about 150,000 g / mol, measured by gel permeation chromatography (GPC). Within this range, the recycled thermoplastic resin composition may have good mechanical strength, plasticity, etc.

[0068] In some embodiments, based on 100 wt% of the rubber-modified aromatic vinyl copolymer resin, the aromatic vinyl copolymer resin may be present in an amount of about 20 wt% to about 80 wt%, for example about 25 wt% to about 75 wt%. Within this range, the recycled thermoplastic resin composition may have good fluidity, chemical resistance, etc.

[0069] In some embodiments, relative to about 100 parts by weight of the recycled thermoplastic resin, the rubber-modified aromatic vinyl copolymer resin may be present in an amount of about 0.5 to about 20 parts by weight, such as about 1 to about 15 parts by weight. If the content of the rubber-modified aromatic vinyl copolymer resin is less than about 0.5 parts by weight, the recycled thermoplastic resin composition may suffer from deterioration in impact resistance, and if the content of the rubber-modified aromatic vinyl copolymer resin exceeds about 20 parts by weight, the recycled thermoplastic resin composition may suffer from deterioration in flame retardancy, heat resistance, etc.

[0070] (C) Phosphorus-based flame retardant

[0071] The phosphorus-based flame retardant according to an embodiment of the present invention, when applied to the recycled thermoplastic resin together with the rubber-modified aromatic vinyl copolymer resin and the epoxy ester compound, is used to improve the impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, and property balance of the recycled thermoplastic resin composition, and may include phosphorus-based flame retardants used in typical thermoplastic resin compositions. For example, the phosphorus-based flame retardant may include phosphate ester compounds, phosphonate ester compounds, phosphinate ester compounds, phosphine oxide compounds, phosphazene compounds, and metal salts thereof. These may be used alone or as a mixture thereof.

[0072] In some embodiments, the phosphorus-based flame retardant may include aromatic phosphate ester compounds. The aromatic phosphate ester compounds include, for example, diaryl phosphates (such as diphenyl phosphate), triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(2,6-dimethylphenyl) phosphate, tris(2,4,6-trimethylphenyl) phosphate, tris(2,4-di-tert-butylphenyl) phosphate, tris(2,6-dimethylphenyl) phosphate, bisphenol A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), resorcinol bis[bis(2,6-dimethylphenyl) phosphate], resorcinol bis[bis(2,4-(di-tert-butylphenyl) phosphate], hydroquinone bis[bis(2,6-dimethylphenyl) phosphate], hydroquinone bis[bis(2,4-di-tert-butylphenyl) phosphate], etc., but are not limited thereto. These may be used alone or as a mixture thereof. In addition, the aromatic phosphate ester compound may be an oligomer type bisphenol A diphosphate ester, etc.

[0073] In some embodiments, relative to about 100 parts by weight of the recycled thermoplastic resin, the phosphorus-based flame retardant may be present in an amount of about 10 parts by weight to about 30 parts by weight, such as about 12 parts by weight to about 22 parts by weight. If the content of the phosphorus-based flame retardant is less than about 10 parts by weight relative to about 100 parts by weight of the recycled thermoplastic resin, the recycled thermoplastic resin composition may suffer from deterioration in fluidity, flame retardancy, etc., and if the content of the phosphorus-based flame retardant exceeds about 30 parts by weight, the recycled thermoplastic resin composition may suffer from deterioration in impact resistance, yield (sudden increase in melt flow index), heat resistance, chemical resistance, etc.

[0074] (D) Epoxy ester compound

[0075] The epoxy ester compound containing an ester group and an epoxy group according to one embodiment of the present invention, when applied to a recycled thermoplastic resin together with a rubber-modified aromatic vinyl copolymer resin and a phosphorus-based flame retardant, is used to improve the impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, etc. of the recycled thermoplastic resin composition, and may include, for example, a compound represented by Formula 1.

[0076] [Formula 1]

[0077]

[0078] In Formula 1, R1 and R3 are each independently a C1 to C 10 hydrocarbon group, R2 and R4 are each independently a hydrogen atom or a C1 to C 10 hydrocarbon group, m and n are 0 or 1, and m + n is 1 or 2. Here, R1 and R2 and R3 and R4 may be connected to each other to form a ring.

[0079] In some embodiments, the epoxy ester compound containing an ester group and an epoxy group may include compounds represented by Formula 1a to Formula 1c, but is not limited thereto.

[0080] [Formula 1a]

[0081]

[0082] [Formula 1b]

[0083]

[0084] [Formula 1c]

[0085]

[0086] In some embodiments, relative to about 100 parts by weight of the recycled thermoplastic resin, the epoxy ester compound may be present in an amount of about 0.1 part by weight to about 1 part by weight, such as about 0.2 part by weight to about 0.9 part by weight. If the content of the epoxy ester compound is less than about 0.1 part by weight relative to about 100 parts by weight of the recycled thermoplastic resin, the recycled thermoplastic resin composition may suffer from deterioration in thermal stability, appearance, etc., and if the content of the epoxy ester compound exceeds about 1 part by weight, the recycled thermoplastic resin composition may suffer from deterioration in impact resistance, flame retardancy, thermal stability, etc.

[0087] The recycled thermoplastic resin composition according to an embodiment of the present invention may further include additives used in typical thermoplastic resin compositions. The additives may include antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, mixtures thereof, etc., but are not limited thereto. Relative to about 100 parts by weight of the recycled thermoplastic resin, the additives may be present in an amount of about 0.001 part by weight to about 40 parts by weight, such as about 0.1 part by weight to about 10 parts by weight.

[0088] The recycled thermoplastic resin composition according to an embodiment of the present invention can be prepared in the form of pellets by mixing the foregoing components and then melt-extruding at about 220 °C to about 300 °C, such as about 230 °C to about 270 °C, using a typical twin-screw extruder.

[0089] In some embodiments, the recycled thermoplastic resin composition may have a notched Izod impact strength of about 5 kgf·cm / cm to about 40 kgf·cm / cm, such as about 5 kgf·cm / cm to about 35 kgf·cm / cm, measured on a 1 / 8" thick sample in accordance with ASTM D256.

[0090] In some embodiments, the recycled thermoplastic resin composition may have a melt flow index (MI) of about 10 g / 10 min to about 45 g / 10 min, such as about 11 g / 10 min to about 40 g / 10 min, measured at 260 °C under a load of 2.16 kgf in accordance with ASTM D1238.

[0091] In some embodiments, the recycled thermoplastic resin composition may have a flame retardancy of V-0 or higher measured on a 1.5 mm thick sample by the UL-94 vertical test method.

[0092] In some embodiments, a sample of the regenerated thermoplastic resin composition prepared in the form of pellets with a weight of 2 g is placed in a glass Petri dish with a diameter of 80 mm, and the top of the glass Petri dish is covered with a glass plate. Subsequently, after heating the glass Petri dish on a hot plate at 270 °C for 2 hours, the regenerated thermoplastic resin composition may have a glass plate weight gain of about 0.01% to about 0.5%, for example, about 0.01% to about 0.4%, calculated according to Equation 1.

[0093] [Equation 1]

[0094] Glass plate weight gain (%) = (weight of the glass plate after heating for 2 hours - initial weight of the glass plate) × 100

[0095] In some embodiments, the regenerated thermoplastic resin composition may have a Vicat softening temperature (VST) of about 80 °C to about 120 °C, for example, about 83 °C to about 110 °C, measured according to the ISO 306 evaluation method (B / 50).

[0096] The molded article according to the present invention is produced from the regenerated thermoplastic resin composition described above. The regenerated thermoplastic resin composition can be prepared in the form of pellets. The prepared pellets can be produced into various molded articles (products) by various molding methods (such as injection molding, extrusion, vacuum molding, casting, etc.). These molding methods are well known to those skilled in the art of the present invention. By applying a high content of recycled raw materials, the molded article has good properties in terms of impact resistance, fluidity, flame retardancy, thermal stability, appearance, heat resistance, chemical resistance, balance of properties therebetween, etc., and is therefore useful as an external material for electrical and electronic products (such as IT electronic devices, etc.).

[0097]

Mode of Invention

[0098] Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and should not be construed as limiting the present invention in any way.

[0099] Examples

[0100] Details of the components used in the examples and comparative examples are as follows.

[0101] (A) Regenerated thermoplastic resin

[0102] (A1) Regenerated polycarbonate resin

[0103] (A1-1) Use of regenerated polycarbonate resin (PCM PC, manufacturer: NingboTopcentral, product name: PC-T105A) collected from sheets, water bottles, etc.

[0104] (A1-2) Use recycled polycarbonate resin (ITE-PCM PC, manufacturer: NingboTopcentral, product name: PC-IT3020BTL) collected from IT electronic products.

[0105] (A2) Recycled polyester resin

[0106] Use recycled polyethylene terephthalate (OBP PET, manufacturer: Lavergne, product name: VYPET VNT-108HS) recovered within 50 km from the coastline.

[0107] (B) Rubber-modified aromatic vinyl copolymer resin

[0108] Use a mixture of (B1) 30 wt% of a rubber-modified aromatic vinyl graft copolymer and (B2) 70 wt% of an aromatic vinyl copolymer resin.

[0109] (B1) Use a rubber-modified vinyl graft copolymer (g-MBS, manufacturer: Arkema, product name: Arkema E920) prepared by graft copolymerizing a monomer mixture including styrene and methyl methacrylate onto butadiene rubber having an average particle size of 0.15 μm.

[0110] (B2) Use a SAN resin (weight average molecular weight: about 90,000 g / mol) polymerized from a mixture of 75 wt% of styrene and 25 wt% of acrylonitrile.

[0111] (C) Phosphorus-based flame retardant

[0112] Use an oligomer type bisphenol A diphosphate (bisphenol A diphosphate, manufacturer: Yoke Chemical, product name: YOKE BDP).

[0113] (D) Epoxy ester compound containing an ester group and an epoxy group

[0114] Use the compound represented by Formula 1a.

[0115] [Formula 1a]

[0116]

[0117] Examples 1 to 12 and Comparative Examples 1 to 8

[0118] Mix the foregoing components in the amounts listed in Tables 1, 2, and 3, and then extrude at 250 °C to prepare a thermoplastic resin composition in the form of pellets. Here, extrusion is carried out using a twin-screw extruder (L / D: 44, diameter: 45 mm). Dry the prepared pellets at about 80 °C for about 4 hours or longer, and then perform injection molding using a 6-ounce injection molding machine (molding temperature: about 270 °C, mold temperature: about 120 °C) to prepare samples. Evaluate the following properties of the prepared samples, and the results are shown in Tables 1, 2, and 3.

[0119] Characteristic evaluation

[0120] (1) Notched Izod impact strength (unit: kgf·cm / cm): Measure the notched Izod impact strength on 1 / 8"-thick samples in accordance with ASTM D256.

[0121] (2) Melt flow index (unit: g / 10 min): Measure the melt flow index (MI) at 260 °C under a load of 2.16 kgf in accordance with ASTM D1238.

[0122] (3) Flame retardancy: Measure the flame retardancy on 1.5-mm-thick samples by the UL-94 vertical test method.

[0123] (4) Thermal stability and appearance: Place 2 g of the sample prepared in the form of pellets in a glass petri dish with a diameter of 80 mm, cover the top of the glass petri dish with a glass plate, and then heat the glass petri dish on a hot plate at 270 °C for 2 hours. Thereafter, calculate the weight gain of the glass plate (gas generation amount, unit: %) according to Equation 1.

[0124] [Equation 1]

[0125] Weight gain of glass plate (%) = (weight of glass plate after heating for 2 hours - initial weight of glass plate) × 100

[0126] (5) Heat resistance: Measure the Vicat softening temperature (VST, unit: °C) in accordance with ISO 306 method (B / 50).

[0127] (6) Chemical resistance: Apply 0.5 mL of the liquid extracted from a cleaning wipe (manufacturer: PDI, product name: Super P Sani-cloth AFIII) to 10 1 / 8"-thick Type I tensile samples prepared in accordance with ASTM D638, then place these samples in a 1.0% strain curvature fixture for 1 hour, and count the number of cracked samples.

[0128] [Table 1]

[0129]

[0130] *Parts by weight: based on about 100 parts by weight of (A) recycled thermoplastic resin

[0131] [Table 2]

[0132]

[0133]

[0134] *Parts by weight: based on about 100 parts by weight of (A) recycled thermoplastic resin

[0135] [Table 3]

[0136]

[0137] *Parts by weight: based on about 100 parts by weight of (A) recycled thermoplastic resin

[0138] As can be seen from the above results, the recycled thermoplastic resin composition according to the present invention is environmentally friendly by using recycled raw materials, and has good properties in terms of impact resistance (notched Izod impact strength), fluidity (melt flow index), flame retardancy (flame retardant grade), thermal stability and appearance (weight gain of glass plate), heat resistance (VST), chemical resistance, and the balance of properties therebetween.

[0139] On the contrary, it can be seen that the thermoplastic resin composition of Comparative Example 1 prepared by using an excessive amount of recycled polycarbonate resin and an insufficient amount of recycled polyester resin suffers from deterioration in chemical resistance and the like, and the thermoplastic resin composition of Comparative Example 2 prepared by using an insufficient amount of recycled polycarbonate resin and an excessive amount of recycled polyester resin suffers from deterioration in impact resistance, flame retardancy and the like. It can be seen that the thermoplastic resin composition of Comparative Example 3 prepared by using an insufficient amount of rubber-modified aromatic vinyl copolymer resin suffers from deterioration in impact resistance and the like, and the thermoplastic resin composition of Comparative Example 4 prepared by using an excessive amount of rubber-modified aromatic vinyl copolymer resin suffers from deterioration in flame retardancy, heat resistance and the like. It can be seen that the thermoplastic resin composition of Comparative Example 5 prepared by using an insufficient amount of phosphorus-based flame retardant suffers from deterioration in fluidity and flame retardancy, and the thermoplastic resin composition of Comparative Example 6 prepared by using an excessive amount of phosphorus-based flame retardant suffers from deterioration in impact resistance, heat resistance, chemical resistance and the like, as well as deterioration in yield due to a rapid increase in melt flow index. In addition, it can be seen that the thermoplastic resin composition of Comparative Example 7 prepared by using an insufficient amount of epoxy ester compound suffers from deterioration in thermal stability and appearance, and the thermoplastic resin composition of Comparative Example 8 prepared by using an excessive amount of epoxy ester compound suffers from deterioration in impact resistance and flame retardancy.

[0140] Although some embodiments have been described herein, those skilled in the art will understand that various modifications, changes, and variations can be made without departing from the spirit and scope of the present invention. Therefore, it should be understood that these embodiments are provided for illustrative purposes only and are not to be construed as limiting the present invention in any way. The scope of the present invention should be defined by the appended claims rather than by the foregoing description, and the claims and their equivalents are intended to cover such modifications and the like that fall within the scope of the present invention.

Claims

1. A recycled thermoplastic resin composition, comprising: About 100 parts by weight of a recycled thermoplastic resin, which comprises about 80 wt% to about 99 wt% of a recycled polycarbonate resin and about 1 wt% to about 20 wt% of a recycled polyester resin recovered within 50 km from the coastline; About 0.5 parts by weight to about 20 parts by weight of a rubber-modified aromatic vinyl copolymer resin; About 10 parts by weight to about 30 parts by weight of a phosphorus-based flame retardant; and About 0.1 parts by weight to about 1 part by weight of an epoxy ester compound containing an ester group and an epoxy group.

2. The recycled thermoplastic resin composition according to claim 1, wherein based on 100 wt% of the total recycled polycarbonate resin, the recycled polycarbonate resin comprises about 30 wt% or more of a recycled polycarbonate resin (ITE-PCM PC) recovered from IT electronic products.

3. The recycled thermoplastic resin composition according to claim 1 or claim 2, wherein the recycled polycarbonate resin contains about 0.01 wt% to about 0.5 wt% of metal minerals.

4. The recycled thermoplastic resin composition according to any one of claims 1 to 3, wherein the recycled polyester resin comprises at least one of ocean-bound plastic (OBP) polyethylene terephthalate, OBP polybutylene terephthalate, and OBP cyclohexanedimethanol terephthalate.

5. The recycled thermoplastic resin composition according to any one of claims 1 to 4, wherein the rubber-modified aromatic vinyl copolymer resin comprises a rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin.

6. The recycled thermoplastic resin composition according to claim 5, wherein the rubber-modified vinyl graft copolymer is prepared by graft polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer onto a rubber polymer.

7. The recycled thermoplastic resin composition according to any one of claims 1 to 6, wherein the phosphorus-based flame retardant comprises at least one of a phosphate ester compound, a phosphonate ester compound, a phosphinate ester compound, a phosphine oxide compound, and a phosphazene compound.

8. The recycled thermoplastic resin composition according to any one of claims 1 to 7, wherein the epoxy ester compound containing an ester group and an epoxy group comprises a compound represented by Formula 1: [Formula 1] wherein R1 and R3 are each independently a C1 to C 10 hydrocarbyl group, R2 and R4 are each independently a hydrogen atom or a C1 to C 10 hydrocarbyl group, m and n are 0 or 1, and m + n is 1 or 2. Herein, R1 and R2 and R3 and R4 are connected to each other to form a ring.

9. The recycled thermoplastic resin composition according to any one of claims 1 to 8, wherein the recycled thermoplastic resin composition has a notched Izod impact strength of about 5 kgf·cm / cm to about 40 kgf·cm / cm measured on a 1 / 8" thick sample according to ASTM D256.

10. The recycled thermoplastic resin composition according to any one of claims 1 to 9, wherein the recycled thermoplastic resin composition has a melt flow index (MI) of about 10 g / 10 min to about 45 g / 10 min measured at 260 °C under a load of 2.16 kgf according to ASTM D1238.

11. The recycled thermoplastic resin composition according to any one of claims 1 to 10, wherein the recycled thermoplastic resin composition has a flame retardancy of V-0 or higher measured on a 1.5 mm thick sample by the UL-94 vertical test method.

12. The recycled thermoplastic resin composition according to any one of claims 1 to 11, wherein a sample of 2 g of the recycled thermoplastic resin composition prepared in the form of pellets is placed in a glass petri dish having a diameter of 80 mm, and the top of the glass petri dish is covered with a glass plate, and then after heating the glass petri dish at 270 °C on a hot plate for 2 hours, the recycled thermoplastic resin composition has a glass plate weight gain of about 0.01% to about 0.5% calculated according to Equation 1: [Equation 1] Glass plate weight gain (%) = (weight of the glass plate after heating for 2 hours - initial weight of the glass plate) × 100.

13. The recycled thermoplastic resin composition according to any one of claims 1 to 12, wherein the recycled thermoplastic resin composition has a Vicat softening temperature (VST) of about 80 °C to about 120 °C measured according to the ISO 306 evaluation method (B / 50).

14. A molded article produced from the recycled thermoplastic resin composition according to any one of claims 1 to 13.

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