WO2021137490A1 - Composition de résine thermoplastique et produit moulé formé à partir de celle-ci - Google Patents

Composition de résine thermoplastique et produit moulé formé à partir de celle-ci Download PDF

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Publication number
WO2021137490A1
WO2021137490A1 PCT/KR2020/018721 KR2020018721W WO2021137490A1 WO 2021137490 A1 WO2021137490 A1 WO 2021137490A1 KR 2020018721 W KR2020018721 W KR 2020018721W WO 2021137490 A1 WO2021137490 A1 WO 2021137490A1
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resin composition
thermoplastic resin
weight
parts
rubber
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PCT/KR2020/018721
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English (en)
Korean (ko)
Inventor
이진성
권영철
오현지
이기림
이범희
정현택
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롯데케미칼 주식회사
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Publication of WO2021137490A1 publication Critical patent/WO2021137490A1/fr

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    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, low flammability, impact resistance, and the like, and a molded article formed therefrom.
  • Impact-resistant polystyrene (HIPS) resin is widely used in various fields such as interior and exterior materials of electrical and electronic products due to its excellent mechanical strength and molding processability.
  • HIPS Impact-resistant polystyrene
  • the impact-resistant polystyrene resin has no resistance to the flame, and when the flame is ignited by an external ignition factor, the resin itself decomposes and provides a raw material to expand and sustain combustion.
  • flame retardant used to impart flame retardancy to impact-resistant polystyrene resins are mainly prepared by mixing halogen-containing organic compounds and antimony-containing inorganic compounds to produce flame-retardant resins.
  • halogen-containing organic compound examples include decabromodiphenyl ether, decabromodiphenyl oxide, decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy oligomer, hexabromocyclododecane, 2,4,6-tris( 2,4,6-tribromophenoxy)-1,3,5 triazine and the like are mainly used.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in flame retardancy, low flammability, impact resistance, and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a rubber-modified polystyrene resin; about 3 to about 23 parts by weight of melamine pyrophosphate; about 5 to about 40 parts by weight of melamine phosphate; about 1 to about 27 parts by weight of piperazine pyrophosphate; and about 0.05 to about 10 parts by weight of zinc oxide having an average particle size of about 0.2 to about 3 ⁇ m and a specific surface area BET of about 1 to about 10 m 2 /g, wherein the melamine pyrophosphate and the piperazine fatigue It is characterized in that the weight ratio of phosphate is from about 1:0.2 to about 1:4.5.
  • the rubber-modified polystyrene resin may be a polymer of about 3 to about 30% by weight of a rubbery polymer and about 70 to about 97% by weight of an aromatic vinylic monomer.
  • the zinc oxide has a size ratio (B/A) between the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region when measuring photo luminescence. 0.01 to about 1.
  • the zinc oxide in the case of X-ray diffraction (XRD) analysis, has a peak position 2 ⁇ value in the range of 35 to 37°,
  • the crystallite size value may be from about 1,000 to about 2,000 ⁇ :
  • K is a shape factor
  • ⁇ is an X-ray wavelength
  • ⁇ is a FWHM value (degree) of an X-ray diffraction peak
  • ⁇ is a peak position value (peak position degree).
  • the weight ratio of the melamine pyrophosphate and the melamine phosphate may be about 1: 0.5 to about 1: 7.
  • the weight ratio of the melamine pyrophosphate and the zinc oxide may be about 1: 0.008 to about 1: 0.8.
  • thermoplastic resin composition may further include about 7 to about 38 parts by weight of piperazine diphosphate based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • thermoplastic resin composition may further include about 10 to about 50 parts by weight of a polyolefin resin based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the thermoplastic resin composition may have a flame retardancy of V-0 or more in a specimen having a thickness of 2.0 mm or more measured according to UL-94 standards.
  • the thermoplastic resin composition may have a Glow Wire Flammability Index (GWFI) of about 825 to about 960° C. of a 100 mm ⁇ 100 mm ⁇ 2 mm size specimen measured in accordance with UL746A,
  • GWFI Glow Wire Flammability Index
  • the HWI (Hot Wire Ignition) rating of a 125 mm ⁇ 13 mm ⁇ 1.5 mm specimen measured in accordance with UL746A may be 0 or 1.
  • thermoplastic resin composition may have a smoke density of about 190 to about 300 of a 100 mm ⁇ 100 mm ⁇ 3 mm specimen measured according to ASTM E662.
  • thermoplastic resin composition may have a notch Izod impact strength of about 4 to about 17 kgf ⁇ cm/cm of a 1/4′′ thick specimen measured according to ASTM D256.
  • Another aspect of the present invention relates to a molded article.
  • the molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of 1 to 12.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, low flammability, impact resistance, and the like, and a molded article formed therefrom.
  • thermoplastic resin composition according to the present invention comprises (A) a rubber-modified polystyrene resin; (B) melamine pyrophosphate; (C) melamine phosphate; (D) piperazine pyrophosphate; and (E) zinc oxide.
  • the rubber-modified polystyrene resin of the present invention is prepared by polymerizing a rubbery polymer and an aromatic vinyl monomer, and a general impact-resistant polystyrene (HIPS) resin may be used.
  • HIPS general impact-resistant polystyrene
  • the rubbery polymer includes a diene-based rubber such as polybutadiene and poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene-based rubber, isoprene rubber, and alkyl (meth)acryl having 2 to 10 carbon atoms.
  • Late rubber a copolymer of an alkyl (meth)acrylate having 2 to 10 carbon atoms and styrene, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in mixture of two or more.
  • a diene-based rubber, a (meth)acrylate rubber, etc. may be used, and specifically, a butadiene-based rubber, a butyl acrylate rubber, or the like may be used.
  • the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 ⁇ m, for example, about 0.15 to about 4 ⁇ m, specifically about 0.25 to about 3.5 ⁇ m.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state.
  • the rubbery polymer latex is filtered through a mesh to remove coagulation generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and distilled water is filled to prepare a sample. , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size analyzer (malvern, nano-zs).
  • a light scattering particle size analyzer malvern, nano-zs
  • the content of the rubbery polymer may be from about 3 to about 30% by weight, for example, from about 5 to about 20% by weight, based on 100% by weight of the total rubber-modified polystyrene resin.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the aromatic vinyl-based monomer includes styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene.
  • vinyl naphthalene, and the like can be exemplified. These can be used individually or in mixture of 2 or more types.
  • the content of the aromatic vinyl-based monomer may be about 70 to about 97 wt%, for example, about 80 to about 95 wt%, based on 100 wt% of the total rubber-modified polystyrene resin. In the above range, molding processability, impact resistance, and appearance characteristics of the thermoplastic resin composition may be excellent.
  • the rubber-modified polystyrene resin is acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N- during polymerization of the rubber-modified polystyrene resin in order to impart properties such as chemical resistance, processability, and heat resistance to the thermoplastic resin composition. It can polymerize by adding monomers, such as a substituted maleimide. In this case, the amount of the monomer added may be about 40% by weight or less based on 100% by weight of the total rubber-modified polystyrene resin. Chemical resistance, processability, heat resistance, etc. can be imparted to the thermoplastic resin composition without lowering other physical properties within the above range.
  • the rubber-modified polystyrene resin may be polymerized by thermal polymerization without the presence of an initiator, or may be polymerized in the presence of an initiator.
  • an initiator at least one of a peroxide-based initiator such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and an azo-based initiator such as azobis isobutyronitrile may be exemplified.
  • the rubber-modified polystyrene resin may be prepared by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.
  • Melamine pyrophosphate of the present invention is applied together with melamine phosphate, piperazine pyrophosphate and zinc oxide to improve the flame retardancy and low flame retardancy of the polyolefin-based resin composition.
  • the melamine pyrophosphate used may be used.
  • the melamine pyrophosphate may be included in an amount of about 3 to about 23 parts by weight, for example, about 5 to about 20 parts by weight, based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the melamine pyrophosphate is less than about 3 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy and low flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 23 parts by weight, There is a possibility that the processability, flame retardancy, impact resistance, etc. of the thermoplastic resin composition may be deteriorated.
  • the melamine phosphate of the present invention is applied together with melamine pyrophosphate, piperazine pyrophosphate and zinc oxide to improve the flame retardancy and low flame retardancy of the polyolefin-based resin composition even with a small content, and is generally flame retardant.
  • Melamine phosphate (monomer) used in the thermoplastic resin composition may be used.
  • the melamine phosphate may be included in an amount of about 5 to about 40 parts by weight, for example, about 7 to about 37 parts by weight, based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the melamine phosphate is less than about 5 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy and low flammability of the thermoplastic resin composition may decrease, and when it exceeds about 40 parts by weight, the thermoplastic resin composition There is a possibility that the impact resistance, flame retardancy, appearance characteristics, etc. of the resin composition may be deteriorated.
  • the weight ratio (B:C) of the melamine pyrophosphate (B) and the melamine phosphate (C) is from about 1:0.5 to about 1:7, for example from about 1:0.55 to about 1:5. have.
  • the thermoplastic resin composition may have excellent flame retardancy, low flammability, impact resistance, and appearance characteristics.
  • Piperazine pyrophosphate of the present invention is applied together with melamine pyrophosphate, melamine phosphate and zinc oxide, so that it is easy to form a char even with a small content, and the flame retardancy and low flame retardancy of the polyolefin-based resin composition
  • piperazine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions may be used.
  • the piperazine pyrophosphate may be included in an amount of about 1 to about 27 parts by weight, for example, about 3 to about 25 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the piperazine pyrophosphate is less than about 1 part by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, the flame retardancy and low flame retardancy of the thermoplastic resin composition may be deteriorated, and when it exceeds about 27 parts by weight , there is a possibility that the impact resistance, flame retardancy, appearance characteristics of the thermoplastic resin composition may be deteriorated.
  • the weight ratio (B:D) of the melamine pyrophosphate (B) and the piperazine pyrophosphate (D) is about 1: 0.2 to about 1: 4.5, for example about 1: 0.25 to about 1: 4 can be
  • the weight ratio of the melamine pyrophosphate and the piperazine pyrophosphate is less than about 1: 0.2, there is a risk that the flame retardancy and low flammability of the thermoplastic resin composition may decrease, and when it exceeds about 1: 4.5, the resistance of the thermoplastic resin composition There is a possibility that impact properties, flame retardancy, appearance characteristics, etc. may be deteriorated.
  • the zinc oxide of the present invention is applied together with the melamine pyrophosphate, melamine phosphate, and piperazine pyrophosphate to improve the flame retardancy and low flame retardancy of the thermoplastic resin composition, and a particle size analyzer (Beckman Coulter, Laser Diffraction Particle Size)
  • the average particle size (D50) of single particles (particles do not aggregate to form secondary particles) measured using Analyzer, LS I3 320 equipment is about 0.2 to about 3 ⁇ m, for example, about 0.5 to about 3 ⁇ m can be
  • the zinc oxide has a specific surface area BET of about 1 to about 10 m 2 /g, for example, about 1, measured with a BET analysis equipment (Surface Area and Porosity Analyzer ASAP 2020 equipment of Micromeritics) using a nitrogen gas adsorption method.
  • thermoplastic resin composition to about 7 m 2 /g, and a purity of about 99% or more. If it is out of the above range, there is a risk that the flame retardancy, impact resistance, low flammability, etc. of the thermoplastic resin composition may be deteriorated.
  • the zinc oxide may have various shapes, and may include, for example, all of a spherical shape, a plate shape, a rod shape, and combinations thereof.
  • the zinc oxide has a size ratio (B/A) of a peak A in a 370 to 390 nm region to a peak B in a 450 to 600 nm region of about 0.01 to about 1.0, e.g.
  • it may be about 0.1 to about 1.0, specifically about 0.1 to about 0.5.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and the like.
  • the zinc oxide has a peak position 2 ⁇ value in the range of 35 to 37° in X-ray diffraction (XRD) analysis, and the measured FWHM value (full of the diffraction peak) width at Half Maximum), the crystallite size calculated by applying to Scherrer's equation (Equation 1 below) may be about 1,000 to about 2,000 ⁇ , for example, about 1,200 to about 1,800 ⁇ .
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and the like.
  • Equation 1 K is a shape factor, ⁇ is an X-ray wavelength, ⁇ is a FWHM value (degree), and ⁇ is a peak position degree.
  • the zinc oxide is evaporated by heating to about 850 to about 1,000°C, for example, about 900 to about 950°C, after dissolving metallic zinc, and then injecting oxygen gas to about 20 to about 30 It can be prepared by cooling to °C and then heating at about 400 to about 900 °C, for example, about 500 to about 800 °C for about 30 to about 150 minutes, for example, about 60 to about 120 minutes.
  • the zinc oxide may be included in an amount of about 0.05 to about 10 parts by weight, for example, about 0.1 to about 9 parts by weight based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the zinc oxide is less than about 0.05 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy and low flammability of the thermoplastic resin composition may decrease, and when it exceeds about 10 parts by weight, the thermoplastic resin composition There is a possibility that the impact resistance, flame retardancy, appearance characteristics, etc. of the resin composition may be deteriorated.
  • the weight ratio (B:E) of the melamine pyrophosphate (B) and the zinc oxide (E) is from about 1: 0.008 to about 1: 0.8, for example, from about 1: 0.008 to about 1: 0.75.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, low flammability, and the like.
  • thermoplastic resin composition according to an embodiment of the present invention may further include (F) piperazine diphosphate and/or (G) polyolefin resin.
  • Piperazine diphosphate according to an embodiment of the present invention can improve the flame retardancy and low flame retardancy of the thermoplastic resin composition, and piperazine diphosphate used in a conventional flame-retardant thermoplastic resin composition may be used.
  • the piperazine diphosphate may be further included in an amount of about 7 to about 38 parts by weight, for example, about 8 to about 37 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the thermoplastic resin composition may have excellent flame retardancy, low flammability, and the like.
  • the polyolefin resin according to an embodiment of the present invention can improve flame retardancy, low flame retardancy, and the like of the thermoplastic resin composition, and a conventional polyolefin resin can be used.
  • polyethylene such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer , polyethylene-based resins such as mixtures thereof; polypropylene resins such as polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer, and mixtures thereof; polymers obtained by crosslinking them; blends comprising polyisobutene; A combination of these and the like can be used.
  • polypropylene, polyethylene, propylene-ethylene copolymer, combinations thereof, and the like can be used.
  • the polyolefin resin has a melt-flow index of about 1 to about 50 g/10 min, for example about 4 to about 50 g/10 min, measured at 230° C. and 2.16 kg load condition according to ASTM D1238. about 30 g/10 min.
  • the thermoplastic resin composition may have excellent mechanical strength, molding processability, and the like.
  • the polyolefin resin may be further included in an amount of about 10 to about 50 parts by weight, for example, about 15 to about 45 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin.
  • the thermoplastic resin composition may have excellent flame retardancy, low flammability, and moldability.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additives may include, but are not limited to, impact modifiers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof.
  • its content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin.
  • thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets that are melt-extruded at about 180 to about 250° C., for example, about 200 to about 230° C., by mixing the above components and using a conventional twin-screw extruder.
  • thermoplastic resin composition may have a flame retardancy of V-0 or more of a 2.0 mm thick specimen measured according to UL-94 standards.
  • the thermoplastic resin composition has a Glow Wire Flammability Index (GWFI) of 100 mm ⁇ 100 mm ⁇ 2 mm size specimen measured in accordance with UL746A of about 825 to about 960° C., for example, about 850 to about 960° C. may be, and the HWI (Hot Wire Ignition) rating of a 125 mm ⁇ 13 mm ⁇ 1.5 mm specimen measured in accordance with UL746A may be 0 or 1.
  • GWFI Glow Wire Flammability Index
  • Grade 0 Ignite after more than 120 seconds
  • Grade 1 Ignite from more than 60 seconds to 120 seconds or less
  • Grade 2 Ignition from more than 30 seconds and less than 60 seconds
  • Grade 3 Ignition from more than 15 seconds and less than 30 seconds
  • Grade 4 7 Fires over 15 seconds or less
  • Grade 5 Fires at 7 seconds or less
  • the thermoplastic resin composition may have a smoke density of about 190 to about 300, for example, about 210 to about 295, of a 100 mm ⁇ 100 mm ⁇ 3 mm specimen measured according to ASTM E662.
  • the thermoplastic resin composition has a notch Izod impact strength of about 4 to about 17 kgf ⁇ cm/cm, for example, about 4.1 to about 15 kgf ⁇ , of a 1/4′′ thick specimen measured according to ASTM D256. cm/cm.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be prepared in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the art to which the present invention pertains.
  • the molded article is eco-friendly because it does not apply a halogen-based flame retardant, and has excellent flame retardancy, low flammability, impact resistance, and balance of physical properties thereof, so it is useful as interior and exterior materials for electrical and electronic products.
  • a rubber-modified polystyrene resin (manufacturer: IDEMITSU, product name: PSI060) was used.
  • Melamine phosphate (manufacturer: BASF, product name: Melapur®MP) was used.
  • Piperazine pyrophosphate (manufacturer: Hainan Zhongxin Chemical, Cas No.: 66034-17-1) was used.
  • Piperazine diphosphate (manufacturer: Lotte Chemical) was used.
  • Average particle size (unit: ⁇ m): Using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment), the average particle size (volume average) was measured.
  • PL size ratio (B/A) According to the photoluminescence measurement method, a He-Cd laser (KIMMON, 30mW) with a wavelength of 325 nm is incident on the specimen at room temperature and the emitted spectrum is measured using a CCD detector. was used, and the temperature of the CCD detector was maintained at -70°C. The size ratio (B/A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured.
  • the injection specimen was subjected to PL analysis by injecting a laser into the specimen without additional treatment, and zinc oxide powder was placed in a 6 mm diameter pelletizer and compressed to produce a flat specimen. did.
  • Equation 1 K is a shape factor, ⁇ is an X-ray wavelength, ⁇ is a FWHM value (degree), and ⁇ is a peak position degree.
  • extrusion was performed at 200° C. to prepare pellets.
  • the physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 2, 3, 4 and 5 below.
  • GWFI Glow Wire Flammability Index
  • HWI Hot Wire Ignition
  • Notched Izod impact strength (unit: kgf ⁇ cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/4′′ thick specimen was measured.
  • Example One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 5 12 20 12 12 12 (C) (parts by weight) 22 22 22 7 37 22 (D) (parts by weight) 12 12 12 12 12 3 (E1) (parts by weight) One One One One One One (E2) (parts by weight) - - - - - - (E3) (parts by weight) - - - - - - (F) (parts by weight) 22 22 22 22 22 22 22 (G) (parts by weight) - - - - - - - Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 GWFI 960 960 960 960 HWI 0 rating 1st grade 0 rating 1st grade 1st grade 0 rating smoke density 285 280 260 290 265 293 Notched I
  • Example 7 8 9 10 11 12 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 12 12 12 12 12 12 (C) (parts by weight) 22 22 22 22 22 22 22 (D) (parts by weight) 25 12 12 12 12 (E1) (parts by weight) One 0.1 9 One One (E2) (parts by weight) - - - - - - (E3) (parts by weight) - - - - - - (F) (parts by weight) 22 22 22 8 37 22 (G) (parts by weight) - - - - - 25 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 GWFI 960 960 960 960 HWI 1st grade 1st grade 1st grade 1st grade 1st grade 1st grade 0 rating smoke density 269 287 270 295 256 266 Notched Izo
  • comparative example 7 8 9 10 11 12 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 12 12 12 12 12 (C) (parts by weight) 22 22 22 22 22 22 (D) (parts by weight) 12 12 12 12 - - (E1) (parts by weight) 0.01 13 - - One One (E2) (parts by weight) - - One - - - (E3) (parts by weight) - - - One - - (F) (parts by weight) - - - - 5 40 (G) (parts by weight) - - - - - - - - Flame retardancy fail V-0 V-1 fail fail V-0 GWFI 775 775 750 775 775 750 HWI 2nd grade 2nd grade 2nd grade 2nd grade 2nd grade 2nd grade smoke density 340 278 325 310 350 275 Notched Izod Impact Strength 5.5 1.5 4.5 0.9
  • thermoplastic resin compositions (Examples 1 to 12) of the present invention have excellent flame retardancy, low flammability, and impact resistance.
  • thermoplastic resin composition when melamine phosphate is applied in less than the content range of the present invention (Comparative Example 3), the flame retardancy of the thermoplastic resin composition, It can be seen that the low ductility is lowered, and when the melamine phosphate is applied in excess of the content range of the present invention (Comparative Example 4), it can be seen that the impact resistance of the thermoplastic resin composition is lowered.
  • piperazine pyrophosphate is applied below the content range of the present invention (Comparative Example 5), it can be seen that the flame retardancy and low flammability of the thermoplastic resin composition are lowered, and piperazine pyrophosphate exceeds the content range of the present invention.
  • thermoplastic resin composition When applied (Comparative Example 6), it can be seen that the impact resistance and flame retardancy of the thermoplastic resin composition are lowered. In addition, when zinc oxide is applied below the content range of the present invention (Comparative Example 7), it can be seen that the flame retardancy and low flammability of the thermoplastic resin composition are lowered, and zinc oxide is applied in excess of the content range of the present invention. In the case (Comparative Example 8), it can be seen that the impact resistance, flame retardancy, etc. of the thermoplastic resin composition are lowered, and when zinc oxide (E2) is applied instead of the zinc oxide (E1) of the present invention (Comparative Example 9), the thermoplastic resin composition It can be seen that the flame retardancy, low flame retardancy, etc.
  • thermoplastic resin composition when zinc oxide (E3) is applied (Comparative Example 10), it can be seen that the flame retardancy, low flammability, impact resistance, etc. of the thermoplastic resin composition are reduced. It can be seen that when a small amount or an excessive amount of piperazine diphosphate is applied instead of piperazine pyrophosphate (Comparative Examples 11 and 12), the flame retardancy, low flammability, and/or impact resistance of the thermoplastic resin composition is reduced.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine thermoplastique qui comprend : environ 100 parties en poids d'une résine de polystyrène modifiée par du caoutchouc ; environ 3 à 23 parties en poids de pyrophosphate de mélamine ; environ 5 à 40 parties en poids de phosphate de mélamine ; environ 1 à 27 parties en poids de pyrophosphate de pipérazine ; et environ 0,05 à 10 parties en poids d'oxyde de zinc présentant une taille moyenne de particules d'environ 0,2 à 3 µm et une surface spécifique BET d'environ 1 à 10 m2/g, le rapport pondéral entre le pyrophosphate de mélamine et le pyrophosphate de pipérazine étant d'environ 1 : 0,2 à 1 : 4,5. La composition de résine thermoplastique présente un excellent caractère ignifuge, ne dégage que peu de fumée, se caractérise par une remarquable résistance aux chocs et similaire.
PCT/KR2020/018721 2019-12-30 2020-12-18 Composition de résine thermoplastique et produit moulé formé à partir de celle-ci WO2021137490A1 (fr)

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KR101656914B1 (ko) * 2010-04-14 2016-09-12 다우 글로벌 테크놀로지스 엘엘씨 개선된 난연성을 가진 스티렌 블록 공중합체-기재 조성물
JP2017008221A (ja) * 2015-06-23 2017-01-12 株式会社Adeka 難燃性合成樹脂組成物
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