WO2012091300A1 - Composition de résine thermoplastique, et article moulé comprenant celle-ci - Google Patents

Composition de résine thermoplastique, et article moulé comprenant celle-ci Download PDF

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Publication number
WO2012091300A1
WO2012091300A1 PCT/KR2011/009040 KR2011009040W WO2012091300A1 WO 2012091300 A1 WO2012091300 A1 WO 2012091300A1 KR 2011009040 W KR2011009040 W KR 2011009040W WO 2012091300 A1 WO2012091300 A1 WO 2012091300A1
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Prior art keywords
thermoplastic resin
resin composition
weight
styrene
parts
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PCT/KR2011/009040
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English (en)
Korean (ko)
Inventor
배수학
송혜경
안성희
이혜진
Original Assignee
제일모직 주식회사
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Priority claimed from KR1020110122562A external-priority patent/KR20120078584A/ko
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Priority to CN2011800626946A priority Critical patent/CN103270107A/zh
Priority to JP2013547292A priority patent/JP2014501314A/ja
Publication of WO2012091300A1 publication Critical patent/WO2012091300A1/fr
Priority to US13/924,900 priority patent/US20130289180A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article comprising the same. More specifically, the present invention provides a thermoplastic resin composition having high flame retardancy, environmentally friendly, improved impact impact strength, flowability (flowability), chemical resistance, thermal stability, and processability, and a molded article including the same.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • PET polyethylene terephthalate
  • ABS and PET with ABS / PET blends themselves, so styrene-acrylonitrile (SAN) copolymers containing epoxy groups should be added.
  • SAN styrene-acrylonitrile
  • the ABS / PET blend itself is not resistant to combustion, and when the spark is ignited by an external ignition factor, the resin itself helps the combustion to continuously spread the fire. Therefore, in the United States and Europe, only flame retardant resins can be used in electrical and electronic products, etc. in order to secure stability against fire such as electrical and electronic products.
  • halogen-based compounds such as polybromodiphenyl ether, tetrabromobisphenol A, brominated substituted epoxy compounds, or chlorinated polyethylene and antimony compounds are used to impart flame retardancy.
  • these flame retardants have the advantage that it is easy to secure flame retardancy and hardly deteriorate in physical properties, but may have a fatal effect on the human body with hydrogen halide gas generated during processing.
  • ABS / PET blend resin composition which is environmentally friendly and improves fluidity, processability, impact strength, chemical resistance and thermal stability while securing flame retardancy using a flame retardant that can replace a halogen-based flame retardant.
  • An object of the present invention is to provide a flame retardant thermoplastic resin composition that is environmentally friendly and has improved flame retardancy, falling impact strength, flowability (flowability), chemical resistance, thermal stability and processability.
  • Another object of the present invention is to provide a molded article molded from the thermoplastic resin composition.
  • thermoplastic resin composition which is one aspect of this invention is a thermoplastic resin composition containing (A) rubber reinforced styrene resin, (B) regenerated polyester resin, (C) vinyl copolymer containing an epoxy group, and (D) phosphorus flame retardant.
  • the regenerated polyester resin is a regenerated polyethylene terephthalate and may be included in 5-35 parts by weight of 100 parts by weight of the base resin consisting of (A) + (B) + (C).
  • the intrinsic viscosity of the regenerated polyethylene terephthalate may be 0.4 g / L-1.5 g / L at 2-chlorophenol solution and 60 ° C.-80 ° C.
  • the composition may further comprise polyethylene terephthalate glycol (PETG).
  • PETG polyethylene terephthalate glycol
  • the phosphorus-based flame retardant may be represented by the following formula (2).
  • the phosphorus flame retardant may be resorcinolbis (2,6-dimethylphenyl) phosphate.
  • composition may further comprise bisphenol-A bis (diphenyl phosphate) (BDP).
  • BDP bisphenol-A bis (diphenyl phosphate)
  • the molded article of the present invention may be molded from the thermoplastic resin composition.
  • the present invention provides a flame retardant thermoplastic resin composition that is environmentally friendly and has improved flame retardancy, falling impact strength, fluidity, chemical resistance, thermal stability and processability.
  • Specimen made of a thermoplastic resin composition of one aspect of the present invention may have a falling dart impact (FDI) of 15J-55J.
  • Falling impact strength can be measured by a conventional method.
  • a pellet made of a thermoplastic resin composition may be injected to obtain a square specimen having a thickness of 3.2 mm x width of 80 mm, and a drop weight may be dropped to convert crack generation energy from a height at which cracks are generated. have.
  • the falling ball impact strength may preferably be 35J-50J.
  • MI of the thermoplastic resin composition may be 25 g / 10 minutes to 40 g / 10 minutes.
  • Melt index can be measured by a conventional method. For example, it can measure in 220 degreeC and 10 kg conditions based on ASTMD1238.
  • the chemical resistance of the thermoplastic resin composition may be 1.0-2.0%. Chemical resistance can be measured by a conventional method.
  • Figure 1 shows an embodiment of a quarter elliptic jig model for evaluating the chemical resistance according to the present invention. A specimen of the same model as in FIG. 1 is injected. Cut the specimen to 15 mm thick and apply chemicals. Allow to stand at 25 ° C. for 72 hours and determine the location of the crack that occurred after removal of chemicals. The critical strain ( ⁇ ) is calculated according to Equation 1 below. The critical strain is evaluated according to the evaluation criteria of Table 2 below.
  • A is the length of the major axis of the elliptical jig model
  • b is the length of the minor axis of the elliptical jig model
  • t is the thickness of the specimen
  • x is from the vertical intersection of the location of the crack in the elliptical jig model and the long axis of the elliptical jig model
  • Distance to center of elliptical jig model
  • the thermoplastic resin composition may have a yellow index change ( ⁇ YI) of 10-20 when the specimen made of the composition is left at 250 ° C. for 10 minutes.
  • ⁇ YI yellow index change
  • specimens made from the compositions of the present invention can provide high temperature retention thermal stability.
  • the change in yellowness index related to thermal stability can be measured by a conventional method.
  • the specimen can be obtained by injecting in a cylinder having a molding temperature of 250 ° C. for 10 minutes. It can be obtained from the difference of the yellow index measured according to ASTM D1925 for each specimen obtained before and after the retention.
  • the thermal stability-related yellow index change ( ⁇ YI) may be 10-15.
  • the thermoplastic resin composition may have an Izod impact strength of 11 kgf ⁇ cm / cm or more measured in accordance with ASTM D256 at a 1/4 ′′ thickness of the specimen prepared from the composition.
  • thermoplastic resin composition may have a flame retardancy of more than V-2 measured by UL 94 VB for the specimen prepared from the composition.
  • thermoplastic resin composition of the present invention is excellent in all of impact resistance, fluidity, chemical resistance, thermal stability and flame retardancy.
  • thermoplastic resin composition of the present invention may include a rubber-reinforced styrene resin, a regenerated polyester resin, a vinyl copolymer including an epoxy group, and a phosphorus flame retardant.
  • the rubber-reinforced styrene resin is a polymer in which a rubbery polymer is dispersed in the form of particles in a matrix composed of an aromatic vinyl copolymer. It is prepared by adding and polymerizing an aromatic vinyl monomer and a vinyl monomer copolymerizable with the aromatic vinyl monomer in the presence of a rubbery polymer.
  • Examples of rubber-reinforced styrene resins include acrylonitrile-butadiene-styrene copolymer resins (ABS), acrylonitrile-acrylic rubber-styrene copolymer resins (AAS), acrylonitrile-ethylenepropylene rubber-styrene copolymer resins ( AES) etc. can be mentioned.
  • ABS acrylonitrile-butadiene-styrene copolymer resins
  • AAS acrylonitrile-acrylic rubber-styrene copolymer resins
  • AES acrylonitrile-ethylenepropylene rubber-styrene copolymer resins
  • the rubber-reinforced styrene resin can be produced by a known polymerization method including emulsion polymerization, suspension polymerization, bulk polymerization and the like.
  • Styrene-based graft copolymer resin alone or styrene-based graft copolymer resin and styrene-based copolymer resin can be prepared by mixing and extruding.
  • the extrusion temperature is not limited but may be 210 ° C.
  • the rubber-reinforced styrene resin may be manufactured by only one step reaction process without separately preparing the styrene graft copolymer resin and the styrene copolymer resin.
  • blend in consideration of each compatibility.
  • the rubber content is preferably included in 5-30% by weight of the total resin.
  • Styrene-based graft copolymer resin of the rubber-reinforced styrenic resin may be 20-100% by weight, styrene-based copolymer resin may be blended in 0-80% by weight.
  • the mixture of 40-60 weight% of styrene graft copolymer resins and 40-60 weight% of styrene copolymer resins can be extruded and used.
  • the styrene graft copolymer resin may be prepared by adding and polymerizing an aromatic vinyl monomer capable of graft polymerization and a monomer copolymerizable with the aromatic vinyl monomer to a rubbery polymer.
  • the rubbery polymer examples include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene rubber, isoprene rubber, chloroprene rubber, butyl acrylate and the like.
  • diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), saturated rubbers in which hydrogen is added to the diene rubber, isoprene rubber, chloroprene rubber, butyl acrylate and the like.
  • EPDM ethylene / propylene / diene monomer terpolymer
  • polybutadiene rubber is preferable among diene rubbers.
  • the rubbery polymer is suitably 5-65% by weight in the styrenic graft copolymer resin.
  • the average size of the rubbery particles may be 0.1 ⁇ m-4 ⁇ m.
  • Aromatic vinyl monomers capable of graft polymerization in rubbery polymers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para-t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene and dichlorostyrene. , Dibromostyrene, vinyl naphthalene, and the like. Preferably styrene is preferred.
  • the aromatic vinyl monomer may be 30 to 94% by weight of the styrenic graft copolymer resin.
  • Examples of the monomer copolymerizable with the aromatic vinyl monomer include unsaturated nitrile, such as saturated nitrile, acrylonitrile or methacrylonitrile, or a mixture of two or more thereof. Preferably acrylonitrile is preferred.
  • the copolymerizable monomer may be 1-20% by weight of the styrene-based graft copolymer resin. Preferably it may be 10-20% by weight.
  • monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be further added. These monomers may be added at 0-15% by weight in the copolymer resin.
  • the styrene copolymer resin may be prepared by polymerizing the aromatic vinyl monomer mentioned in the manufacture of the graft copolymer and a monomer copolymerizable with the aromatic vinyl monomer.
  • the aromatic vinyl monomers used in the styrene copolymer resins include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para-t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, Dibromostyrene, vinyl naphthalene, and the like.
  • styrene is preferred.
  • the aromatic vinyl monomer is suitably 60 to 90% by weight of the styrene copolymer resin. Preferably, it may be 70-80% by weight.
  • Monomers copolymerizable with the aromatic vinyl monomers include unsaturated nitrile compounds such as saturated nitrile, acrylonitrile or methacrylonitrile, or mixtures of two or more thereof. Preferably acrylonitrile is preferred.
  • the copolymerizable monomer may be 10-40% by weight of the styrene-based copolymer resin. Preferably it may be 20-30% by weight.
  • Monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide, may be further added to the styrene copolymer resin for processability and heat resistance. These monomers can be added at 0-15% by weight in the copolymer resin.
  • the rubber-reinforced styrenic resin may be included as 40-90 parts by weight of 100 parts by weight of the basic resin (A) + (B) + (C) consisting of a rubber-reinforced styrene-based resin, a recycled polyester resin and a vinyl copolymer comprising an epoxy group.
  • A basic resin
  • B B
  • C vinyl copolymer comprising an epoxy group.
  • the recycled polyester resin may include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or an alloy thereof.
  • PET polyethylene terephthalate
  • Preferably recycled PET can be used.
  • PET can be prepared by removing foreign matter from a PET source.
  • PET sources include, but are not limited to, conventional discarded plastic containers, polyester extruded products or injection molded products, including, but not limited to bottled water or soft drink containers.
  • Foreign material can be removed by washing the PET source with caustic soda water or the like.
  • the PET source may be milled and the milled PET may be reextruded.
  • the foreign matter content of the PET source or recycled PET is determined by inserting the prepared pellets or pulverized PET into a polyimide film and placing it in a 250 ° C. presser to make a disc film having a thickness of about 0.5 mm, and the number of foreign substances generated.
  • the composition may further comprise polyethylene terephthalate glycol (PETG).
  • PETG may be included in an amount of 50-100 parts by weight based on 100 parts by weight of recycled PET. Within this range, the fluidity and impact strength of the resin composition can be improved. Preferably it may be included in 50-70 parts by weight. PETG may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C) consisting of a rubber-reinforced styrene resin, a recycled polyester resin and a vinyl copolymer comprising an epoxy group. Preferably it may be included in 2-7 parts by weight.
  • the recycled polyester resin may have an intrinsic viscosity of 0.4 g / L-1.5 g / L, preferably 0.7 g / L-1.0 g / L, measured at 2-chlorophenol solution and at 60 ° C.-80 ° C. Within this range, fluidity and processability of the composition may be good.
  • the recycled polyester resin may be included as 5-35 parts by weight of 100 parts by weight of the base resin (A) + (B) + (C) composed of a rubber-reinforced styrene resin, a recycled polyester resin and a vinyl copolymer comprising an epoxy group. have. If it is less than 5 parts by weight, the chemical resistance and falling impact strength values are not good. If it is more than 35 weight part, since the recycled polyester resin is a crystalline resin, the fluidity of the resin composition may not be good. Preferably it may be included in 10-35 parts by weight, more preferably 10-15 parts by weight.
  • the vinyl copolymer including an epoxy group is a resin produced by copolymerizing a monomer mixture composed of an unsaturated epoxy monomer containing a epoxy group and a vinyl monomer to polymerize an unsaturated epoxy group in a styrene copolymer.
  • the monomer mixture preferably consists of 0.001-5 mol% of unsaturated epoxy monomers containing epoxy groups and 99.999-95 mol% of vinyl monomers.
  • the unsaturated epoxy monomer may be represented by the following formula (1).
  • R1, R2, R3, R6, R7 and R8 are each of H6-C14 substituted with H, C1-12 alkyl or unsaturated alkyl group, C6-C14 aryl group, C1-12 saturated or unsaturated alkyl group
  • R 4 and R 5 are each C 1 -C 12 alkylene, C 6 -C 14 arylene, or C 1 -C 14 arylene group substituted with C 1-12 saturated or unsaturated alkyl group
  • unsaturated epoxy monomers examples include glycidyl methacrylate, glycidyl acrylate, epoxy alkyl acrylate, allyl glycidyl ether, aryl glycidyl ether, butadiene monooxide, vinyl glycidyl ether, glycidyl Itaconate and the like, but are not limited thereto.
  • An unsaturated epoxy compound can be used individually or in mixture of 2 or more types.
  • the unsaturated epoxy monomer may be added at 0.001-5 mol%, preferably 1-3 mol% in the mixture of the monomers constituting the vinyl copolymer including the epoxy group. Within this range, the impact strength improving effect is good and no gelation phenomenon occurs during extrusion.
  • the vinyl monomer includes an aromatic vinyl monomer and a monomer polymerizable with the aromatic vinyl monomer.
  • Aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, para-t-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. May be used, but is not limited thereto.
  • the aromatic vinyl monomers may be used alone or in a mixture thereof.
  • the monomer capable of polymerizing the aromatic vinyl monomer and the monomer may be saturated nitrile or unsaturated nitrile such as acrylonitrile or methacrylonitrile or a mixture of two or more thereof.
  • acrylonitrile is preferred.
  • the vinyl monomer may be added at 99.999-95 mol%, preferably 97-99 mol% in the mixture of monomers constituting the vinyl copolymer including the epoxy group. Within this range, the chemical resistance is excellent and the flowability is good.
  • the vinyl copolymer including an epoxy group is 5-25 weight in 100 parts by weight of the basic resin (A) + (B) + (C) composed of a rubber-reinforced styrene resin, a recycled polyester resin and a vinyl copolymer containing an epoxy group. It can be included as a wealth. Within the above range, the fluidity of the resin composition may not be lowered and compatibility may be good. Preferably it may be included in 5-15 parts by weight.
  • Phosphorus-based flame retardant is added to increase the flame retardancy of the resin composition.
  • Phosphorus-based flame retardant may be represented by the structure of the following formula (2).
  • R3, R4 and R5 are the same or different and are hydrogen or an alkyl group of C1-C4,
  • X is an aryl group of C6-C20 or an C6-C20 aryl group substituted with an alkyl group of C1-C4, and
  • n is from 0 to Is an integer of 4)
  • X may preferably be derived from dialcohol of resorcinol, hydroquinol or bisphenol A.
  • n 1, resorcinol bis (diphenyl) phosphate, resorcinol bis (2,6-dimethylphenyl) phosphate, resorcinol bis (2,4-dibutylbutylphenyl) phosphate, hydroquinol bis ( 2,6-dimethylphenyl) phosphate, hydroquinolbis (2,4-dibutylbutylphenyl) phosphate, and the like.
  • Phosphorus-based flame retardants can be applied alone or in mixtures.
  • the phosphorus flame retardant may be resorcinolbis (2,6-dimethylphenyl) phosphate. More preferably, bisphenol-A (diphenyl phosphate) (BDP) is added to resorcinol bis (2,6-dimethylphenyl) phosphate and used together. If bisphenol-A (diphenyl phosphate) is used together, the flame retardancy may be better at the same content.
  • Resorcinolbis (2,6-dimethylphenyl) phosphate: bisphenol-A (diphenyl phosphate) (BDP) may be used in a weight ratio of 1: 0.5 to 1: 2.
  • the phosphorus flame retardant may be included in an amount of 1 to 15 parts by weight based on 100 parts by weight of the base resin (A) + (B) + (C) composed of a rubber modified styrene resin, a recycled polyester resin, and a vinyl copolymer including an epoxy group. . Within this range, the flame retardancy and fluidity of the resin composition can be improved. Preferably it may be included in 1-6 parts by weight.
  • the resin composition includes additives such as flame retardants, lubricants, mold release agents, antistatic agents, dispersants, antidropping agents, impact modifiers, antioxidants, plasticizers, heat stabilizers, light stabilizers, weather stabilizers, compatibilizers, pigments, dyes, inorganic fillers, and mixtures thereof. It may further include in the usual range.
  • the resin composition can be produced by a known method.
  • the component or the component and the additive may be mixed, and then melt-extruded in an extruder and manufactured in pellet form.
  • the molded article of the present invention may be prepared from the thermoplastic resin composition. Methods for producing molded articles from resin compositions are known to those skilled in the art. Examples of the molded article include internal and external parts of the electric and electronic products, but are not limited thereto.
  • SAN styrene / acrylonitrile copolymer resin
  • PET Polyethylene terephthalate
  • Polyethylene terephthalate collected from general bottled water and soft drink containers requires caustic soda water to remove foreign substances through organic and inorganic cleaning processes, and to remove foreign substances, re-extrude the crushed PET.
  • Recycled PET can be obtained. Determination of how much foreign matter is contained in the pellet or crushed PET 10g between the polyimide film and put into a press maintained at 250 °C to determine the number of foreign substances generated in the pancake having a thickness of about 0.5mm.
  • Polyethylene terephthalate (A1100, Anychem) was reextruded at 250 ° C. to produce regenerated polyethylene terephthalate.
  • the inherent viscosity of the produced regenerated polyethylene terephthalate was 0.75 g / L as measured at 2-chlorophenol solution and 70 ° C.
  • styrene-acrylonitrile copolymer resin 120 parts by weight of deionized water, 0.2 parts by weight of azobisisobutyronitrile, 0.4 parts by weight of tricalcium phosphate, 100 parts by weight of a monomer mixture consisting of 1 mol% glycidyl methacrylate, 80 mol% styrene and 19 mol% acrylonitrile 0.2 parts by weight of octyl mercaptan was added. After heating up to 80 ° C. for 60 minutes, the mixture was maintained at 80 ° C. for 180 minutes to prepare a styrene-acrylonitrile copolymer resin including an epoxy group. It was washed with water, dehydrated and dried to prepare a styrene-acrylonitrile copolymer resin (SAN with epoxy) containing a powdered epoxy group.
  • SAN with epoxy styrene-acrylonitrile copolymer resin
  • Resorcinol bis (2,6-dimethylphenyl) phosphate (PX200, Nippon Shoh Chemical) was used as a phosphorus flame retardant.
  • each component was added in the content (unit: parts by weight) described in Table 1 below.
  • the resulting mixture was extruded at 240 ° C., screw speed 250 rpm, and mixture feed rate 60 kg / hr in a conventional twin screw extruder to prepare pellets.
  • the prepared pellets were dried at 80 ° C. for 2 hours, and then, specimens were prepared at a molding temperature of 180 ° C. and a mold temperature of 40 ° C. in a 6 oz injection machine.
  • Falling impact strength It is evaluated according to ASTM D3763. The height of the cracks is evaluated by dropping the drop weight having a weight of 4.0 kg and a hemispherical diameter of 12.5 mm for each of the prepared square specimens (thickness 3.2 mm x width 80 mm). The height at which cracks are generated is converted into energy to determine the fall impact strength.
  • MI Melt index
  • A is the length of the major axis of the elliptical jig model
  • b is the length of the minor axis of the elliptical jig model
  • t is the thickness of the specimen
  • x is from the vertical intersection of the location of the crack in the elliptical jig model and the long axis of the elliptical jig model
  • Distance to center of elliptical jig model
  • the specimen was obtained by injecting in a cylinder at 250 ° C. for 10 minutes using an injection machine.
  • the yellow index is measured according to ASTM D1925 with CONICA & Minolta (model CM-3600d) for each specimen before and after the retention and the change in yellow index ( ⁇ YI) is evaluated therefrom.
  • Izod impact strength rated according to ASTM D256 at 1/4 "thickness.
  • thermoplastic resin composition of the present invention comprising 5-35 parts by weight of recycled PET in a thermoplastic resin composition comprising an ABS resin, a recycled PET, a SAN resin including an epoxy group, and a phosphorus-based flame retardant has a falling impact strength. It can be seen that the flow, chemical resistance, thermal stability, flame retardancy, etc. were all excellent (see Example 1-3). In particular, the composition further comprising PETG in the thermoplastic resin composition of the present invention further improved the impact strength and flowability (see Example 4). In addition, the flame retardancy was further improved when BDP was further included together with resorcinol bis (2,6-dimethylphenyl) phosphate in the thermoplastic resin composition of the present invention (see Example 5).
  • compositions containing less than 5 parts by weight or more than 35 parts by weight of recycled PET did not have good impact strength, flowability, chemical resistance, and thermal stability (see Comparative Example 1-2).
  • the composition including the bromine-based flame retardant / antimony trioxide system instead of the phosphorus-based flame retardant greatly reduces the impact strength and thermal stability due to decomposition of the PET resin by antimony trioxide (see Comparative Example 3).

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention concerne une composition de résine thermoplastique et un article moulé comprenant celle-ci. Plus particulièrement, la présente invention concerne une composition de résine thermoplastique qui est hautement ignifuge et écologique, et qui améliore la résistance à l'impact d'une chute de bille, la coulabilité (fluidité), la résistance chimique, la stabilité thermique, et l'aptitude au traitement. L'invention concerne en outre un article moulé comprenant la composition de résine thermoplastique.
PCT/KR2011/009040 2010-12-30 2011-11-24 Composition de résine thermoplastique, et article moulé comprenant celle-ci WO2012091300A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2011800626946A CN103270107A (zh) 2010-12-30 2011-11-24 热塑性树脂组合物及包含其的模制品
JP2013547292A JP2014501314A (ja) 2010-12-30 2011-11-24 熱可塑性樹脂組成物及びこれを含む成形品
US13/924,900 US20130289180A1 (en) 2010-12-30 2013-06-24 Thermoplastic Resin Composition and Molded Article Including Same

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KR10-2010-0139712 2010-12-30
KR20100139712 2010-12-30
KR10-2011-0122562 2011-11-22
KR1020110122562A KR20120078584A (ko) 2010-12-30 2011-11-22 열가소성 수지 조성물 및 이를 포함하는 성형품

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CN112679900A (zh) * 2020-12-18 2021-04-20 金发科技股份有限公司 一种高性能aes/回收pet/回收pctg复合材料及其制备方法和应用

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