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EP-3858915-B1 - THERMOPLASTIC RESIN COMPOSITION AND MOLDED PRODUCT USING SAME

EP3858915B1EP 3858915 B1EP3858915 B1EP 3858915B1EP-3858915-B1

Inventors

  • HWANG, Donggeun
  • Choi, Woojin
  • KWON, KEEHAE
  • KIM, Younghyo

Dates

Publication Date
20260513
Application Date
20190920

Claims (14)

  1. A thermoplastic resin composition, comprising 100 parts by weight of a base resin comprising: (A) 20 wt% to 30 wt% of an acrylonitrile-butadiene-styrene graft copolymer wherein the average particle diameter of rubber polymer particles is 200 nm to 350 nm; (B) 15 wt% to 25 wt% of a branched styrene-acrylonitrile copolymer; (C) 25 wt% to 35 wt% of an acrylonitrile-butadiene-styrene copolymer resin wherein the average particle diameter of a rubber polymer is 1000 nm to 5000 nm; and (D) 10 wt% to 40 wt% of an alpha-methylstyrene-styrene-acrylonitrile copolymer having a weight average molecular weight of 50,000 g/mol to 250,000 g/mol, (E) 20 parts by weight to 30 parts by weight of a brominated epoxy resin, (F) 2 parts by weight to 8 parts by weight of antimony trioxide, (G) 1 part by weight to 5 parts by weight of a chlorinated polyethylene resin, and (H) 3 parts by weight to 6 parts by weight of a super high molecular-weight styrene-acrylonitrile copolymer having a weight average molecular weight of greater than or equal to 1,000,000 g/mol, wherein the average particle diameter is a Z-average particle diameter measured using a dynamic light scattering particle size analyzer.
  2. The thermoplastic resin composition of claim 1, wherein the (A) acrylonitrile-butadiene-styrene graft copolymer wherein the average particle diameter of rubber polymer particles is 200 nm to 350 nm has a core-shell structure comprising a core of a butadiene-based rubber polymer component, and a shell formed by a graft copolymerization reaction of acrylonitrile and styrene to the rubber polymer around the core.
  3. The thermoplastic resin composition of claim 1 or claim 2, wherein the (B) branched styrene-acrylonitrile copolymer has a polydispersity index (PDI) of greater than or equal to 3.
  4. The thermoplastic resin composition of any one of claim 1 to claim 3, wherein the (C) acrylonitrile-butadiene-styrene copolymer resin wherein the average particle diameter of a rubber polymer is 1000 nm to 5000 nm comprises a dispersed phase of a core-shell structure comprising a core of a butadiene-based rubber polymer and a shell formed by graft polymerization of acrylonitrile and styrene on the core, and a continuous phase including an unbranched linear stryene-acrylonitrile.
  5. The thermoplastic resin composition of claim 4, wherein based on 100 wt% of the acrylonitrile-butadiene-styrene copolymer resin, the dispersed phase of a core-shell structure is included in an amount of 10 wt% to 20 wt%, and the continuous phase including the styrene-acrylonitrile copolymer is included in an amount of 80 wt% to 90 wt%.
  6. The thermoplastic resin composition of any one of claim 1 to claim 5, wherein the (D) alpha-methylstyrene-styrene-acrylonitrile copolymer is a copolymer of a monomer mixture comprising 50 wt% to 80 wt% of alpha-methylstyrene, 10 wt% to 50 wt% of acrylonitrile, and more than 0 wt% and equal to or less than 40 wt% of styrene.
  7. The thermoplastic resin composition of any one of claim 1 to claim 6, wherein the (H) super high molecular-weight styrene-acrylonitrile copolymer having a weight average molecular weight of greater than or equal to 1,000,000 g/mol has a weight average molecular weight of 5,000,000 g/mol to 10,000,000 g/mol.
  8. The thermoplastic resin composition of any one of claim 1 to claim 7, wherein the (E) brominated epoxy resin has a weight average molecular weight of 800 g/mol to 12,000 g/mol.
  9. The thermoplastic resin composition of any one of claim 1 to claim 8, wherein based on 100 wt% of the (G) chlorinated polyethylene resin, chlorine is included in an amount of 28 wt% to 40 wt%.
  10. The thermoplastic resin composition of any one of claim 1 to claim 9, wherein the thermoplastic resin composition further comprises at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, an antioxidant, an ultraviolet stabilizer, an antistatic agent, a pigment, and a dye.
  11. A molded product using a thermoplastic resin composition of any one of claims 1 to 10.
  12. The molded product of claim 11, wherein a Vicat softening temperature is greater than or equal to 96 °C as measured under conditions of a 5 kg load and a temperature increase rate of 50 °C/h according to ISO 306 B50.
  13. The molded product of claim 11 or claim 12, wherein flame retardancy is V-1 grade or higher, measured according to UL94 standards.
  14. The molded product of any one of claim 11 to claim 13, wherein glossiness is 60 GU or less as measured at 60° according to ASTM D523.

Description

BACKGROUND OF THE INVENTION (a) Field of the Invention A thermoplastic resin composition and a molded product using the same are disclosed. (b) Description of the Related Art Styrene-based resins represented by acrylonitrile-butadiene-styrene copolymer (ABS) resins are widely used in automobiles, home appliances, and OA devices due to excellent moldability, mechanical properties, appearance, secondary workability, and the like. Molded products using the styrene-based resins may be widely applied to various products requiring painting/non-painting, for example, interior/exterior materials for automobiles and the like. Recently, in Europe and elsewhere, a flame retardant standard for the interior/exterior materials for automobiles tends to be more reinforced in order to prevent damage to people caused by automobile fire accidents. For example, in Europe, like Regulation No. 118-03 and the like, a more reinforced flame retardant standard than the previous one is demanded. Therefore, there is a need to develop a styrene-based resin capable of maintaining low lightness and excellent appearance while satisfying the reinforced flame retardant standard. US 5,965,665 discloses a low gloss thermoplastic resin composition containing a rubber modified thermoplastic resin, a gel polymer and a low molecular weight polyolefin polymer which provides low surface gloss properties and improved impact properties. US 4,404,323 discloses a heat resistant polymer composition based on one or more graft copolymers of styrene and acrylonitrile on a rubber and a copolymer of alpha-methylstyrene and acrylonitrile. SUMMARY OF THE INVENTION [Technical Problem] A thermoplastic resin composition that satisfies a reinforced flame retardant standard while maintaining excellent low lightness and appearance, and a molded product using the same, are provided. [Technical Solution] According to an embodiment, a thermoplastic resin composition includes 100 parts by weight of a base resin that includes (A) 20 wt% to 30 wt% of an acrylonitrile-butadiene-styrene graft copolymer wherein the average particle diameter of rubber polymer particles is 200 nm to 350 nm; (B) 15 wt% to 25 wt% of a branched styrene-acrylonitrile copolymer; (C) 25 wt% to 35 wt% of an acrylonitrile-butadiene-styrene copolymer resin wherein the average particle diameter of a rubber polymer is 1000 nm to 5000 nm; and (D) 10 wt% to 40 wt% of an alpha-methylstyrene-styrene-acrylonitrile copolymer having a weight average molecular weight of 50,000 g/mol to 250,000 g/mol, (E) 20 parts by weight to 30 parts by weight of a brominated epoxy resin, (F) 2 parts by weight to 8 parts by weight of antimony trioxide, (G) 1 part by weight to 5 parts by weight of a chlorinated polyethylene resin, and (H) 3 parts by weight to 6 parts by weight of a super high molecular-weight styrene-acrylonitrile copolymer having a weight average molecular weight of greater than or equal to 1,000,000 g/mol, wherein the average particle diameter is a Z-average particle diameter measured using a dynamic light scattering particle size analyzer. The (A) acrylonitrile-butadiene-styrene graft copolymer wherein the average particle diameter of rubber polymer particles is 200 nm to 350 nm may have a core-shell structure including a core of a butadiene-based rubber polymer, and a shell formed by graft polymerization of acrylonitrile and styrene on the core. The (B) branched styrene-acrylonitrile copolymer may have a polydispersity index (PDI) of greater than or equal to 3. The (C) acrylonitrile-butadiene-styrene copolymer resin wherein the average particle diameter of a rubber polymer is 1000 nm to 5000 nm may include a dispersed phase of a core-shell structure including a core of a butadiene-based rubber polymer and a shell formed by graft polymerization of acrylonitrile and styrene on the core, and a continuous phase including a stryene-acrylonitrile. The styrene-acrylonitrile copolymer constituting the styrene-acrylonitrile copolymer continuous phase may be an unbranched linear styrene-acrylonitrile copolymer. Based on 100 wt% of an acrylonitrile-butadiene-styrene copolymer resin having an average particle diameter of (C) from 1000 nm to 5000 nm, the dispersed phase of the core-shell structure may be included in an amount of 10 wt% to 20 wt% and the styrene-acrylonitrile copolymer continuous phase may be included in an amount of 80 wt% to 90 wt%. The (D) alpha-methylstyrene-styrene-acrylonitrile copolymer may be a copolymer of a monomer mixture including 50 wt% to 80 wt% of alpha-methylstyrene, 10 wt% to 50 wt% of acrylonitrile, and 0 wt% to 40 wt% of styrene. The (H) super high molecular-weight styrene-acrylonitrile copolymer having a weight average molecular weight of greater than or equal to 1,000,000 g/mol may have a weight average molecular weight of 5,000,000 g/mol to 10,000,000 g/mol. The (E) brominated epoxy resin may have a weight average molecular weight of 800 g/mol to 12,000 g/mol. Based on 100 wt% of the