WO2022025409A1 - Thermoplastic resin composition and molded article formed therefrom - Google Patents

Thermoplastic resin composition and molded article formed therefrom Download PDF

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Publication number
WO2022025409A1
WO2022025409A1 PCT/KR2021/007056 KR2021007056W WO2022025409A1 WO 2022025409 A1 WO2022025409 A1 WO 2022025409A1 KR 2021007056 W KR2021007056 W KR 2021007056W WO 2022025409 A1 WO2022025409 A1 WO 2022025409A1
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weight
parts
resin composition
thermoplastic resin
composition according
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PCT/KR2021/007056
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French (fr)
Korean (ko)
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김연경
박지권
이선애
김주성
오현지
이진성
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롯데케미칼 주식회사
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Publication of WO2022025409A1 publication Critical patent/WO2022025409A1/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
    • 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
    • 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
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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 excellent in flame retardancy, impact resistance, appearance characteristics, 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 electric and electronic products because of 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 raw materials 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.
  • 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.
  • thermoplastic resin composition having excellent flame retardancy, impact resistance, and appearance characteristics.
  • 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 5 to about 20 parts by weight of a polyphenylene ether resin; about 20 to about 50 parts by weight of a polyolefin resin; about 10 to about 30 parts by weight of piperazine pyrophosphate; about 5 to about 25 parts by weight of melamine pyrophosphate; about 0.3 to about 7 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; about 1.5 to about 25 parts by weight of an ethylenemethyl acrylate copolymer; and about 1 to about 12 parts by weight of an ethylene vinyl acetate copolymer.
  • 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 polyphenylene ether resin may include a repeating unit represented by the following formula (1):
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the polyolefin resin may include at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.
  • the weight ratio of the piperazine pyrophosphate and the melamine pyrophosphate may be about 1: 0.2 to about 1: 1.5.
  • the weight ratio of the piperazine pyrophosphate and the zinc oxide may be from about 4:1 to about 60:1.
  • the weight ratio of the piperazine pyrophosphate and the sum of the ethylene methyl acrylate and ethylene vinyl acetate may be about 1: 0.1 to about 1: 1.5.
  • the weight ratio of the ethylene methyl acrylate copolymer and the ethylene vinyl acetate copolymer may be from about 0.5:1 to about 10:1.
  • thermoplastic resin composition may have a flame retardancy of V-1 or more of a 1.5 mm thick specimen measured by the UL94 vertical test method.
  • thermoplastic resin composition is a 2 mm thick specimen measured using a 1 kg weight dart based on the DuPont drop measurement method. Crack occurrence drop height may be about 55 to about 100 cm.
  • 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 10.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, and the like, and a molded article formed therefrom.
  • thermoplastic resin composition comprises (A) a rubber-modified polystyrene resin; (B) polyphenylene ether resin; (C) polyolefin resin; (D) piperazine pyrophosphate; (E) melamine pyrophosphate; (F) zinc oxide; (G) ethylene methyl acrylate copolymer; and (H) an ethylene vinyl acetate copolymer.
  • the rubber-modified polystyrene resin of the present invention is prepared by polymerizing a rubbery polymer and an aromatic vinyl monomer, and a conventional impact-resistant polystyrene (HIPS) resin may be used.
  • HIPS impact-resistant polystyrene
  • the rubbery polymer includes a diene rubber such as polybutadiene and poly(acrylonitrile-butadiene), a saturated rubber hydrogenated to the diene rubber, an isoprene rubber, an 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 may 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.
  • the polymerization can be carried out by adding a monomer such as substituted maleimide.
  • 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.
  • the initiator may be exemplified by at least one of peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and azo-based initiators such as azobis isobutyronitrile.
  • the rubber-modified polystyrene resin may be prepared by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.
  • the polyphenylene ether resin according to one embodiment of the present invention can improve heat resistance, flame retardancy, etc. of the thermoplastic resin composition, and polyphenylene ether resin used in a conventional thermoplastic resin composition may be used.
  • a polyphenylene ether resin including a repeating unit represented by the following Chemical Formula 1 may be used.
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the polyphenylene ether resin includes poly(1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1). ,4-phenylene)ether, poly(2,6-dipropyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2-methyl -6-propyl-1,4-phenylene)ether, poly(2-ethyl-6-propyl-1,4-phenylene)ether, poly(2,6-diphenyl-1,4-phenylene)ether , a copolymer of poly(2,6-dimethyl-1,4-phenylene)ether and poly(2,3,6-trimethyl-1,4-phenylene)ether, poly(2,6-dimethyl-1, A copolymer of 4-phenylene) ether and poly(2,3,5-triethyl-1,4-phenylene) ether
  • the polyphenylene ether resin may have a weight average molecular weight measured by gel permeation chromatography (GPC) of about 10,000 to about 50,000 g/mol, for example, about 20,000 to about 40,000 g/mol. Within the above range, heat resistance, flame retardancy, and the like of the thermoplastic resin composition may be excellent.
  • GPC gel permeation chromatography
  • the polyphenylene ether resin may be included in an amount of about 5 to about 20 parts by weight, for example, about 6 to about 19 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the polyphenylene ether resin 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 heat resistance of the thermoplastic resin composition may decrease, and when it exceeds about 20 parts by weight , there is a fear that the impact resistance, appearance characteristics, workability, etc. of the thermoplastic resin composition may be deteriorated.
  • the polyolefin resin according to an embodiment of the present invention can improve flame retardancy and appearance characteristics 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), and linear low-density polyethylene (LLDPE), polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer , polypropylene resins such as 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 0.5 to about 50 g/10 min, for example, about 1 to about 1 about 30 g/10 min. In the above range, the thermoplastic resin composition may have excellent flame retardancy and appearance characteristics.
  • the polyolefin resin may be included in an amount of about 20 to about 50 parts by weight, for example, about 25 to about 45 parts by weight based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the polyolefin resin is less than about 20 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 50 parts by weight, the thermoplastic resin composition There is a possibility that appearance characteristics, mechanical properties, etc. may be deteriorated.
  • Piperazine pyrophosphate of the present invention is applied together with melamine pyrophosphate, zinc oxide, ethylene methyl acrylate and ethylene vinyl acetate, and it is easy to form char even with a small content, and flame retardancy of the thermoplastic resin composition , impact resistance, appearance characteristics, etc. can be improved, and piperazine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions can be used.
  • the piperazine pyrophosphate may be included in an amount of about 10 to about 30 parts by weight, for example, about 11 to about 29 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 10 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and when it exceeds about 30 parts by weight, the thermoplastic resin There is a fear that the impact resistance, appearance characteristics, thermal stability, etc. of the composition may be deteriorated.
  • Melamine pyrophosphate of the present invention is applied together with piperazine pyrophosphate, zinc oxide, ethylene methyl acrylate and ethylene vinyl acetate to improve flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition even with a small content
  • melamine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions can be used.
  • the melamine pyrophosphate may be included in an amount of about 5 to about 25 parts by weight, for example, about 6 to about 24 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 5 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 25 parts by weight, the thermoplastic resin composition impact resistance, appearance characteristics, thermal stability, etc. may be deteriorated.
  • the weight ratio (D:E) of the piperazine pyrophosphate (D) and the melamine pyrophosphate (E) is from about 1:0.2 to about 1:1.5, for example from about 1:0.2 to about 1:1.4 can be within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
  • Zinc oxide according to an embodiment of the present invention is applied together with the piperazine pyrophosphate, melamine phosphate, melamine pyrophosphate, ethylene methyl acrylate and ethylene vinyl acetate to improve the flame retardancy and impact resistance of the thermoplastic resin composition.
  • the average particle size (D50) of a single particle (particles do not aggregate to form secondary particles) measured using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) is about 0.2 to about 3 ⁇ m, for example about 0.5 to about 3 ⁇ m.
  • 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 from Micromeritics) using a nitrogen gas adsorption method. 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, appearance characteristics of the thermoplastic resin composition may be deteriorated.
  • BET analysis equipment Surface Area and Porosity Analyzer ASAP 2020 equipment from Micromeritics
  • 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, for example, when measuring photoluminescence
  • 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, for example, when measuring photoluminescence
  • 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 appearance characteristics.
  • 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 20 to 30°C. After cooling, it can be prepared by 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 0.3 to about 7 parts by weight, for example, about 0.5 to about 5 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of zinc oxide is less than about 0.3 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and when it exceeds about 7 parts by weight, the thermoplastic resin composition There exists a possibility that impact resistance, an external appearance characteristic, etc. may fall.
  • the weight ratio (D:F) of the piperazine pyrophosphate (D) and the zinc oxide (F) is about 4 : 1 to about 60 : 1, for example, about 5 : 1 to about 50 : 1 day.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
  • the ethylene methyl acrylate copolymer of the present invention is applied to the rubber-modified polystyrene resin together with piperazine pyrophosphate, melamine pyrophosphate, zinc oxide and ethylene vinyl acetate copolymer to improve compatibility of the components of the thermoplastic resin composition, It is possible to improve the impact resistance and the like of the thermoplastic resin composition.
  • the ethylene methyl acrylate copolymer may be prepared by polymerizing ethylene and methyl acrylate.
  • the ethylene methyl acrylate copolymer comprises about 50 to about 95 wt% of ethylene repeating units, such as about 70 to about 93 wt% of methyl acrylate repeating units, and about 5 to about 50 wt% of methyl acrylate repeating units, such as from about 7 to about 30% by weight.
  • the thermoplastic resin composition may have excellent impact resistance.
  • the ethylene methyl acrylate copolymer may be in the form of a random, block, or multi-block copolymer, or a combination thereof.
  • the ethylene methyl acrylate copolymer has a melt flow index of about 0.01 to about 40 g/10 min, for example, about 0.1 to about 10, measured at 190° C. and 2.16 kgf according to ASTM D1238. g/10 min.
  • the ethylene methyl acrylate copolymer may be included in an amount of about 1.5 to about 25 parts by weight, for example, about 2 to about 20 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the ethylene methyl acrylate copolymer is less than about 1.5 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the impact resistance of the thermoplastic resin composition may decrease, and when it exceeds about 25 parts by weight , there is a possibility that the flame retardancy, appearance characteristics, workability, etc. of the thermoplastic resin composition may be deteriorated.
  • the ethylene vinyl acetate copolymer of the present invention is applied to the rubber-modified polystyrene resin together with piperazine pyrophosphate, melamine pyrophosphate, zinc oxide and ethylene methyl acrylate copolymer to improve the compatibility of the components of the thermoplastic resin composition, It is possible to improve the impact resistance and appearance characteristics of the thermoplastic resin composition.
  • the ethylene vinyl acetate copolymer may be prepared by polymerizing ethylene and vinyl acetate.
  • the ethylenevinylacetate copolymer may contain from about 50 to about 95% by weight of ethylene repeating units, for example from about 70 to about 93% by weight, and from about 5 to about 50% by weight of vinyl acetate repeating units, such as about 7 to about 30% by weight.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the ethylene vinyl acetate copolymer may be in the form of a random, block, or multi-block copolymer, and may also be used in a combination form thereof.
  • the ethylene vinyl acetate copolymer has a melt flow index of about 0.01 to about 40 g/10 min, for example, about 0.1 to about 10 g, measured at 190° C. and 2.16 kgf according to ASTM D1238. It can be /10 minutes.
  • the ethylene vinyl acetate copolymer may be included in an amount of about 1 to about 12 parts by weight, for example, about 2 to about 10 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin.
  • the content of the ethylene vinyl acetate copolymer is less than about 1 part by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the impact resistance of the thermoplastic resin composition may decrease, and when it exceeds about 12 parts by weight, There exists a possibility that the flame retardance of a thermoplastic resin composition, an external appearance characteristic, etc. may fall.
  • the weight ratio (D:G+H) of the piperazine pyrophosphate (D) and the sum of the ethylene methyl acrylate and ethylene vinyl acetate (G + H) is about 1: 0.1 to about 1: 1.5, eg For example, it may be about 1: 0.2 to about 1: 1.4.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
  • the weight ratio (G:H) of the ethylene methyl acrylate copolymer (G) and the ethylene vinyl acetate copolymer (H) is about 0.5: 1 to about 10: 1, for example, about 0.6: 1 to It can be about 7:1.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
  • 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 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 one embodiment of the present invention is in the form of pellets that are melt-extruded at about 180 to about 280 ° C, for example, about 200 to about 260 ° C, by mixing the above components and using a conventional twin screw extruder.
  • thermoplastic resin composition may have a flame retardancy of V-1 or more of a 1.5 mm thick specimen measured by the UL94 vertical test method.
  • the thermoplastic resin composition has a cracking drop height of about 55 to about 100 of a 2 mm thick specimen measured using a dart weighing 1 kg based on the DuPont drop measurement method. cm, for example from about 60 to about 95 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 environmentally friendly because it does not apply a halogen-based flame retardant, and has excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof, so it is useful as interior and exterior materials for electrical and electronic products.
  • HIPS Impact-resistant polystyrene resin
  • Poly (1,4-phenylene) ether (manufacturer: Bluestar New Chemical Materials, product name: LXR-050C) was used.
  • Piperazine pyrophosphate (manufacturer: Hainan Zhongxin Chemical, Cas No.: 66034-17-1) was used.
  • Ethylene methyl acrylate copolymer (manufacturer: Dupont product name: Elvaloy AC1330) was used.
  • extrusion was performed at 230° C. to prepare pellets.
  • Specimens were prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2, 3 and 4 below.
  • Example One 2 3 4 5 6 7 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 6 10 19 10 10 10 10 (C) (parts by weight) 30 30 30 25 45 30 30 (D) (parts by weight) 25 25 25 25 25 11 29 (E) (parts by weight) 15 15 15 15 15 15 15 (F) (parts by weight) 2 2 2 2 2 2 2 2 (G) (parts by weight) 10 10 10 10 10 10 10 10 10 (H) (parts by weight) 5 5 5 5 5 5 5 5 5 (I) (parts by weight) - - - - - - - - (J) (parts by weight) - - - - - - - - Flame retardancy V-1 V-0 V-0 V-1 V-0 V-1 V-0 face impact strength 85 85 75 80 65 85 70 Appearance evaluation 4 4 3 4 3 4 3
  • Example 8 9 10 11 12 13 14 15 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 10 10 10 10 10 10 10 10 10 (C) (parts by weight) 30 30 30 30 30 30 30 30 30 30 30 30 30 (D) (parts by weight) 25 25 25 25 25 25 25 25 25 25 25 (E) (parts by weight) 6 24 15 15 15 15 15 (F) (parts by weight) 2 2 0.5 5 2 2 2 2 (G) (parts by weight) 10 10 10 10 2 20 10 10 (H) (parts by weight) 3 3 3 3 3 3 3 3 3 3 3 2 10 (I) (parts by weight) - - - - - - - - (J) (parts by weight) - - - - - - - - - - Flame retardancy V-1 V-0 V-1 V-0 V-0 V-1 V-0 V-1 face impact strength 80 70 80 65 60 90 60 90 Appearance
  • thermoplastic resin composition of the present invention has excellent flame retardancy, impact resistance, appearance characteristics, extrusion processability, and the like.
  • thermoplastic resin composition when applied below the content range of the present invention (Comparative Example 1), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 1) In Example 2), it can be seen that the impact resistance and appearance characteristics of the thermoplastic resin composition are lowered, and when the polyolefin resin is applied below the content range of the present invention (Comparative Example 3), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered. It can be seen that, when applied in excess of the content range of the present invention (Comparative Example 4), the appearance characteristics of the thermoplastic resin composition are deteriorated.
  • thermoplastic resin composition When applied less than (Comparative Example 13), it can be seen that the impact resistance of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 14), flame retardancy and appearance properties of the thermoplastic resin composition It can be seen that the lower In addition, when the phosphorus-based flame retardant (I) is applied instead of the piperazine pyrophosphate, melamine phosphate and melamine pyrophosphate of the present invention (Comparative Example 15), it can be seen that the impact resistance and appearance properties of the thermoplastic resin composition are lowered, It can be seen that when the modified polyolefin EEA (J) is applied instead of the ethylene methyl acrylate and ethylene vinyl acetate of the present invention (Comparative Example 16), the impact resistance and appearance characteristics of the thermoplastic resin composition are deteriorated.
  • phosphorus-based flame retardant (I) is applied instead of the piperazine pyrophosphate, melamine phosphate and melamine

Abstract

A thermoplastic resin composition of the present invention is characterized by comprising: about 100 parts by weight of a rubber-modified polystyrene resin; about 5 to about 20 parts by weight of a polyphenylene ether resin; about 20 to about 50 parts by weight of a polyolefin resin; about 10 to about 30 parts by weight of piperazine pyrophosphate; about 5 to about 25 parts by weight of melamine pyrophosphate; about 0.3 to about 7 parts by weight of zinc oxide having an average particle size of about 0.2 μm to about 3 μm and a specific surface area BET of about 1 to about 10 m2/g; about 1.5 to about 25 parts by weight of an ethylene methyl acrylate copolymer; and about 1 to about 12 parts by weight of an ethylene vinyl acetate copolymer. The thermoplastic resin composition has excellent flame retardancy, impact resistance, appearance characteristics, and the like.

Description

열가소성 수지 조성물 및 이로부터 형성된 성형품Thermoplastic resin composition and molded article formed therefrom
본 발명은 열가소성 수지 조성물 및 이로부터 형성된 성형품에 관한 것이다. 보다 구체적으로 본 발명은 난연성, 내충격성, 외관 특성 등이 우수한 열가소성 수지 조성물 및 이로부터 형성된 성형품에 관한 것이다.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 excellent in flame retardancy, impact resistance, appearance characteristics, and the like, and a molded article formed therefrom.
내충격 폴리스티렌(HIPS) 수지는 기계적 강도 및 성형 가공성 등이 우수하여 전기 전자 제품의 내외장재 등 다양한 분야에 광범위하게 사용되고 있다. 그러나, 내충격 폴리스티렌 수지는 불꽃에 대한 저항성이 없고, 외부의 점화 요인에 의해 불꽃이 점화되면 수지 자체가 분해하면서 원료를 제공하여 연소를 확대 지속시키는 역할을 하게 되는 문제점이 있다.Impact-resistant polystyrene (HIPS) resin is widely used in various fields such as interior and exterior materials of electric and electronic products because of its excellent mechanical strength and molding processability. However, there is a problem in that 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 raw materials to expand and sustain combustion.
내충격 폴리스티렌 수지에 난연성을 부여하는 방법으로는 난연제와 난연 보조제를 첨가하는 첨가형 난연화법이 있으며, 통상 비활성 원소인 할로겐 또는 인 등을 함유한 난연제를 첨가하여 난연화를 달성한다. 내충격 폴리스티렌 수지에 난연성을 부여하기 위해 사용되는 난연제는 주로 할로겐 함유 유기화합물과 안티몬 함유 무기화합물을 혼합 사용하여 난연성 수지를 제조한다. 상기 할로겐 함유 유기화합물로는 데카브로모디페닐에테르, 데카브로모디페닐옥사이드, 데카브로모디페닐에탄, 테트라브로모비스페놀A, 브롬화에폭시올리고머, 헥사브로모사이클로도데칸, 2,4,6-트리스(2,4,6-트리브로모페녹시)-1,3,5 트리아진 등이 주로 사용되고 있다.As a method of imparting flame retardancy to the impact-resistant polystyrene resin, there is an additive-type flame retardant method in which a flame retardant and a flame retardant auxiliary are added, and flame retardancy is achieved by adding a flame retardant containing halogen or phosphorus, which is an inactive element, usually. Flame retardants used to impart flame retardancy to impact-resistant polystyrene resins are mainly prepared by mixing halogen-containing organic compounds and antimony-containing inorganic compounds. Examples of the halogen-containing organic compound 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.
그러나, 내충격 폴리스티렌 수지가 UL 94 V-1 이상의 특성을 얻기 위해서는 할로겐 화합물과 삼산화안티몬을 과량으로 투입하여야 하며, 이로 인해 기계적 물성 저하, 유동성 등이 저하되고, 연소 시 많은 할로겐계 가스가 발생하여 친환경적이지 못하다는 단점이 있다.However, in order for the impact-resistant polystyrene resin to obtain the characteristics of UL 94 V-1 or higher, an excessive amount of halogen compounds and antimony trioxide must be added. There is a downside to not being able to.
따라서, 이러한 문제 없이, 난연성, 내충격성, 외관 특성 등이 우수한 스티렌계 열가소성 수지 조성물의 개발이 필요한 실정이다.Therefore, there is a need to develop a styrenic thermoplastic resin composition having excellent flame retardancy, impact resistance, and appearance characteristics without such problems.
본 발명의 배경기술은 대한민국 공개특허 10-2010-0068954호 등에 개시되어 있다.Background art of the present invention is disclosed in Korean Patent Laid-Open No. 10-2010-0068954 and the like.
본 발명의 목적은 난연성, 내충격성, 외관 특성 등이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.It is an object of the present invention to provide a thermoplastic resin composition having excellent flame retardancy, impact resistance, and appearance characteristics.
본 발명의 다른 목적은 상기 열가소성 수지 조성물로부터 형성된 성형품을 제공하기 위한 것이다.Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can all be achieved by the present invention described below.
1. 본 발명의 하나의 관점은 열가소성 수지 조성물에 관한 것이다. 상기 열가소성 수지 조성물은 고무변성 폴리스티렌 수지 약 100 중량부; 폴리페닐렌에테르 수지 약 5 내지 약 20 중량부; 폴리올레핀 수지 약 20 내지 약 50 중량부; 피페라진 피로포스페이트 약 10 내지 약 30 중량부; 멜라민 피로포스페이트 약 5 내지 약 25 중량부; 평균 입자 크기가 약 0.2 내지 약 3 ㎛이고, 비표면적 BET가 약 1 내지 약 10 m2/g인 산화아연 약 0.3 내지 약 7 중량부; 에틸렌메틸아크릴레이트 공중합체 약 1.5 내지 약 25 중량부; 및 에틸렌비닐아세테이트 공중합체 약 1 내지 약 12 중량부;를 포함하는 것을 특징으로 한다.1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a rubber-modified polystyrene resin; about 5 to about 20 parts by weight of a polyphenylene ether resin; about 20 to about 50 parts by weight of a polyolefin resin; about 10 to about 30 parts by weight of piperazine pyrophosphate; about 5 to about 25 parts by weight of melamine pyrophosphate; about 0.3 to about 7 parts by weight of zinc oxide having an average particle size of about 0.2 to about 3 μm and a specific surface area BET of about 1 to about 10 m 2 /g; about 1.5 to about 25 parts by weight of an ethylenemethyl acrylate copolymer; and about 1 to about 12 parts by weight of an ethylene vinyl acetate copolymer.
2. 상기 1 구체예에서, 상기 고무변성 폴리스티렌 수지는 고무질 중합체 약 3 내지 약 30 중량% 및 방향족 비닐계 단량체 약 70 내지 약 97 중량%의 중합체일 수 있다.2. In the first embodiment, 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.
3. 상기 1 또는 2 구체예에서, 상기 폴리페닐렌에테르 수지는 하기 화학식 1로 표시되는 반복단위를 포함할 수 있다:3. In embodiments 1 or 2, the polyphenylene ether resin may include a repeating unit represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2021007056-appb-I000001
Figure PCTKR2021007056-appb-I000001
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 6의 알킬기 또는 탄소수 6 내지 12의 아릴기이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
4. 상기 1 내지 3 구체예에서, 상기 폴리올레핀 수지는 폴리프로필렌, 폴리에틸렌, 프로필렌-에틸렌 공중합체 중 1종 이상을 포함할 수 있다.4. In the above 1 to 3 embodiments, the polyolefin resin may include at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.
5. 상기 1 내지 4 구체예에서, 상기 피페라진 피로포스페이트 및 상기 멜라민 피로포스페이트의 중량비는 약 1 : 0.2 내지 약 1 : 1.5일 수 있다.5. In the above 1 to 4 embodiments, the weight ratio of the piperazine pyrophosphate and the melamine pyrophosphate may be about 1: 0.2 to about 1: 1.5.
6. 상기 1 내지 5 구체예에서, 상기 피페라진 피로포스페이트 및 상기 산화아연의 중량비는 약 4 : 1 내지 약 60 : 1일 수 있다.6. In the above 1 to 5 embodiments, the weight ratio of the piperazine pyrophosphate and the zinc oxide may be from about 4:1 to about 60:1.
7. 상기 1 내지 6 구체예에서, 상기 피페라진 피로포스페이트 및 상기 에틸렌메틸아크릴레이트와 에틸렌비닐아세테이트의 합의 중량비는 약 1 : 0.1 내지 약 1 : 1.5일 수 있다.7. In the above 1 to 6 embodiments, the weight ratio of the piperazine pyrophosphate and the sum of the ethylene methyl acrylate and ethylene vinyl acetate may be about 1: 0.1 to about 1: 1.5.
8. 상기 1 내지 7 구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체 및 상기 에틸렌비닐아세테이트 공중합체의 중량비는 약 0.5 : 1 내지 약 10 : 1일 수 있다.8. In the above embodiments 1 to 7, the weight ratio of the ethylene methyl acrylate copolymer and the ethylene vinyl acetate copolymer may be from about 0.5:1 to about 10:1.
9. 상기 1 내지 8 구체예에서, 상기 열가소성 수지 조성물은 UL94 vertical test 방법으로 측정한 1.5 mm 두께 시편의 난연도가 V-1 이상일 수 있다.9. In the above embodiments 1 to 8, the thermoplastic resin composition may have a flame retardancy of V-1 or more of a 1.5 mm thick specimen measured by the UL94 vertical test method.
10. 상기 1 내지 9 구체예에서, 상기 열가소성 수지 조성물은 듀폰 드롭(DuPont drop) 측정법에 의거하여 1 kg 무게의 추(dart)를 사용하여 측정한 2 mm 두께 시편의 크랙(crack) 발생 낙하 높이가 약 55 내지 약 100 cm일 수 있다.10. In the above embodiments 1 to 9, the thermoplastic resin composition is a 2 mm thick specimen measured using a 1 kg weight dart based on the DuPont drop measurement method. Crack occurrence drop height may be about 55 to about 100 cm.
11. 본 발명의 다른 관점은 성형품에 관한 것이다. 상기 성형품은 상기 1 내지 10 중 어느 하나에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 한다.11. 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 10.
본 발명은 난연성, 내충격성, 외관 특성 등이 우수한 열가소성 수지 조성물 및 이로부터 형성된 성형품을 제공하는 발명의 효과를 갖는다.The present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, and the like, and a molded article formed therefrom.
이하, 본 발명을 상세히 설명하면, 다음과 같다.Hereinafter, the present invention will be described in detail as follows.
본 발명에 따른 열가소성 수지 조성물은 (A) 고무변성 폴리스티렌 수지; (B) 폴리페닐렌에테르 수지; (C) 폴리올레핀 수지; (D) 피페라진 피로포스페이트; (E) 멜라민 피로포스페이트; (F) 산화아연; (G) 에틸렌메틸아크릴레이트 공중합체; 및 (H) 에틸렌비닐아세테이트 공중합체;를 포함한다.The thermoplastic resin composition according to the present invention comprises (A) a rubber-modified polystyrene resin; (B) polyphenylene ether resin; (C) polyolefin resin; (D) piperazine pyrophosphate; (E) melamine pyrophosphate; (F) zinc oxide; (G) ethylene methyl acrylate copolymer; and (H) an ethylene vinyl acetate copolymer.
본 명세서에서, 수치범위를 나타내는 "a 내지 b"는 "≥a 이고 ≤b"으로 정의한다.In the present specification, "a to b" representing a numerical range is defined as "≥a and ≤b".
(A) 고무변성 폴리스티렌 수지(A) Rubber-modified polystyrene resin
본 발명의 고무변성 폴리스티렌 수지는 고무질 중합체와 방향족 비닐 단량체를 중합하여 제조된 것으로서, 통상의 내충격 폴리스티렌(HIPS) 수지를 사용할 수 있다.The rubber-modified polystyrene resin of the present invention is prepared by polymerizing a rubbery polymer and an aromatic vinyl monomer, and a conventional impact-resistant polystyrene (HIPS) resin may be used.
구체예에서, 상기 고무질 중합체로는 폴리부타디엔, 폴리(아크릴로니트릴-부타디엔) 등의 디엔계 고무 및 상기 디엔계 고무에 수소 첨가한 포화고무, 이소프렌고무, 탄소수 2 내지 10의 알킬 (메타)아크릴레이트 고무, 탄소수 2 내지 10의 알킬 (메타)아크릴레이트 및 스티렌의 공중합체, 에틸렌-프로필렌-디엔단량체 삼원공중합체(EPDM) 등을 예시할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 적용될 수 있다. 예를 들면, 디엔계 고무, (메타)아크릴레이트 고무 등을 사용할 수 있고, 구체적으로, 부타디엔계 고무, 부틸아크릴레이트 고무 등을 사용할 수 있다.In a specific embodiment, the rubbery polymer includes a diene rubber such as polybutadiene and poly(acrylonitrile-butadiene), a saturated rubber hydrogenated to the diene rubber, an isoprene rubber, an 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. For example, 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.
구체예에서, 상기 고무질 중합체(고무 입자)는 평균 입자 크기가 약 0.05 내지 약 6 ㎛, 예를 들면 약 0.15 내지 약 4 ㎛, 구체적으로 약 0.25 내지 약 3.5 ㎛일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 외관 특성 등이 우수할 수 있다. 여기서, 상기 고무질 중합체(고무 입자)의 평균 입자 크기(z-평균)는 라텍스(latex) 상태에서 광 산란(light scattering) 방법을 이용하여 측정할 수 있다. 구체적으로, 고무질 중합체 라텍스를 메쉬(mesh)에 걸러서, 고무질 중합체 중합 중 발생하는 응고물 제거하고, 라텍스 0.5 g 및 증류수 30 ml를 혼합한 용액을 1,000 ml 플라스크에 따르고 증류수를 채워 시료를 제조한 다음, 시료 10 ml를 석영 셀(cell)로 옮기고, 이에 대하여,　광 산란 입도 측정기(malvern社, nano-zs)로 고무질 중합체의 평균 입자 크기를 측정할 수 있다.In an embodiment, the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 μm, for example, about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, 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).
구체예에서, 상기 고무질 중합체의 함량은 고무변성 폴리스티렌 수지 전체 100 중량% 중 약 3 내지 약 30 중량%, 예를 들면 약 5 내지 약 20 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 외관 특성 등이 우수할 수 있다.In an embodiment, 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. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
구체예에서, 상기 방향족 비닐계 단량체로는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, p-t-부틸스티렌, 에틸스티렌, 비닐크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐나프탈렌 등을 예시할 수 있다. 이들은 단독으로 사용하거나, 2종 이상 혼합하여 사용할 수 있다. 상기 방향족 비닐계 단량체의 함량은 고무변성 폴리스티렌 수지 전체 100 중량% 중 약 70 내지 약 97 중량%, 예를 들면 약 80 내지 약 95 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 성형 가공성, 내충격성, 외관 특성 등이 우수할 수 있다.In an embodiment, the aromatic vinyl-based monomer includes styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, and the like can be exemplified. These may 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.
구체예에서, 상기 고무변성 폴리스티렌 수지는 열가소성 수지 조성물에 내화학성, 가공성, 내열성과 같은 특성을 부여하기 위해, 고무변성 폴리스티렌 수지 중합 시, 아크릴로니트릴, 아크릴산, 메타크릴산, 무수말레인산, N-치환말레이미드 등의 단량체를 부가하여 중합할 수 있다. 이 경우, 상기 단량체의 첨가량은 고무변성 폴리스티렌 수지 전체 100 중량%에 대하여, 약 40 중량% 이하일 수 있다. 상기 범위에서 다른 물성의 저하 없이, 열가소성 수지 조성물에 내화학성, 가공성 및 내열성 등을 부여할 수 있다.In an embodiment, 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. The polymerization can be carried out by adding a monomer such as 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.
구체예에서, 상기 고무변성 폴리스티렌 수지는 개시제의 존재 없이 열중합에 의해 중합되거나, 개시제의 존재 하에 중합될 수 있다. 상기 개시제로는 벤조일 퍼옥사이드, t-부틸 하이드로 퍼옥사이드, 아세틸 퍼옥사이드, 큐멘하이드로 퍼옥사이드 등의 과산화물계 개시제와 아조비스 이소부티로니트릴 같은 아조계 개시제 중 1종 이상을 예시할 수 있다. 상기 고무변성 폴리스티렌 수지는 괴상중합, 현탁중합, 유화중합 등의 공지의 중합방법에 의하여 수행될 수 있다.In an embodiment, 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. The initiator may be exemplified by at least one of peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and azo-based initiators such as azobis isobutyronitrile. The rubber-modified polystyrene resin may be prepared by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.
(B) 폴리페닐렌에테르 수지(B) polyphenylene ether resin
본 발명에 일 구체예에 따른 폴리페닐렌에테르 수지는 열가소성 수지 조성물의 내열성, 난연성 등을 향상시킬 수 있는 것으로서, 통상의 열가소성 수지 조성물에 사용되는 폴리페닐렌에테르 수지를 사용할 수 있다. 예를 들면, 하기 화학식 1로 표시되는 반복단위를 포함하는 폴리페닐렌에테를 수지를 사용할 수 있다.The polyphenylene ether resin according to one embodiment of the present invention can improve heat resistance, flame retardancy, etc. of the thermoplastic resin composition, and polyphenylene ether resin used in a conventional thermoplastic resin composition may be used. For example, a polyphenylene ether resin including a repeating unit represented by the following Chemical Formula 1 may be used.
[화학식 1][Formula 1]
Figure PCTKR2021007056-appb-I000002
Figure PCTKR2021007056-appb-I000002
상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 6의 알킬기 또는 탄소수 6 내지 12의 아릴기이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
구체예에서, 상기 폴리페닐렌에테르 수지로는 폴리(1,4-페닐렌)에테르, 폴리(2,6-디메틸-1,4-페닐렌)에테르, 폴리(2,6-디에틸-1,4-페닐렌)에테르, 폴리(2,6-디프로필-1,4-페닐렌)에테르, 폴리(2-메틸-6-에틸-1,4-페닐렌)에테르, 폴리(2-메틸-6-프로필-1,4-페닐렌)에테르, 폴리(2-에틸-6-프로필-1,4-페닐렌)에테르, 폴리(2,6-디페닐-1,4-페닐렌)에테르, 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,6-트리메틸-1,4-페닐렌)에테르의 공중합체, 폴리(2,6-디메틸-1,4-페닐렌)에테르와 폴리(2,3,5-트리에틸-1,4-페닐렌)에테르의 공중합체 등을 예시할 수 있다.In an embodiment, the polyphenylene ether resin includes poly(1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1). ,4-phenylene)ether, poly(2,6-dipropyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4-phenylene)ether, poly(2-methyl -6-propyl-1,4-phenylene)ether, poly(2-ethyl-6-propyl-1,4-phenylene)ether, poly(2,6-diphenyl-1,4-phenylene)ether , a copolymer of poly(2,6-dimethyl-1,4-phenylene)ether and poly(2,3,6-trimethyl-1,4-phenylene)ether, poly(2,6-dimethyl-1, A copolymer of 4-phenylene) ether and poly(2,3,5-triethyl-1,4-phenylene) ether can be exemplified.
구체예에서, 상기 폴리페닐렌에테르 수지는 GPC(gel permeation chromatography)로 측정한 중량평균분자량이 약 10,000 내지 약 50,000 g/mol, 예를 들면 약 20,000 내지 약 40,000 g/mol일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 내열성, 난연성 등이 우수할 수 있다.In an embodiment, the polyphenylene ether resin may have a weight average molecular weight measured by gel permeation chromatography (GPC) of about 10,000 to about 50,000 g/mol, for example, about 20,000 to about 40,000 g/mol. Within the above range, heat resistance, flame retardancy, and the like of the thermoplastic resin composition may be excellent.
구체예에서, 상기 폴리페닐렌에테르 수지는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 5 내지 약 20 중량부, 예를 들면 약 6 내지 약 19 중량부로 포함될 수 있다. 상기 폴리페닐렌에테르 수지의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 5 중량부 미만일 경우, 열가소성 수지 조성물의 난연성, 내열성 등이 저하될 우려가 있고, 약 20 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 외관 특성, 가공성 등이 저하될 우려가 있다.In an embodiment, the polyphenylene ether resin may be included in an amount of about 5 to about 20 parts by weight, for example, about 6 to about 19 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin. When the content of the polyphenylene ether resin 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 heat resistance of the thermoplastic resin composition may decrease, and when it exceeds about 20 parts by weight , there is a fear that the impact resistance, appearance characteristics, workability, etc. of the thermoplastic resin composition may be deteriorated.
(C) 폴리올레핀 수지(C) polyolefin resin
본 발명의 일 구체예 따른 폴리올레핀 수지는 열가소성 수지 조성물의 난연성, 외관 특성 등을 향상시킬 수 있는 것으로서, 통상의 폴리올레핀 수지를 사용할 수 있다. 예를 들면, 저밀도 폴리에틸렌(LDPE), 중밀도 폴리에틸렌(MDPE), 고밀도 폴리에틸렌(HDPE), 직쇄상 저밀도 폴리에틸렌(LLDPE) 등의 폴리에틸렌, 폴리프로필렌, 프로필렌-에틸렌 공중합체, 프로필렌-1-부텐 공중합체, 이들의 혼합물 등의 폴리프로필렌계 수지; 이들을 가교시킨 중합체; 폴리이소부텐을 포함하는 블렌드; 이들의 조합 등을 사용할 수 있다. 구체적으로는 폴리프로필렌, 폴리에틸렌, 프로필렌-에틸렌 공중합체, 이들의 조합 등을 사용할 수 있다.The polyolefin resin according to an embodiment of the present invention can improve flame retardancy and appearance characteristics of the thermoplastic resin composition, and a conventional polyolefin resin can be used. For example, polyethylene such as low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and linear low-density polyethylene (LLDPE), polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer , polypropylene resins such as mixtures thereof; polymers obtained by crosslinking them; blends comprising polyisobutene; A combination of these and the like can be used. Specifically, polypropylene, polyethylene, propylene-ethylene copolymer, combinations thereof, and the like can be used.
구체예에서, 상기 폴리올레핀 수지는 ASTM D1238에 의거하여, 230℃, 2.16 kg 하중 조건에서 측정한 유동흐름지수(Melt-flow index)가 약 0.5 내지 약 50 g/10분, 예를 들면 약 1 내지 약 30 g/10분일 수 있다. 상기 범위에서 열가소성 수지 조성물의 난연성, 외관 특성 등이 우수할 수 있다.In an embodiment, the polyolefin resin has a melt-flow index of about 0.5 to about 50 g/10 min, for example, about 1 to about 1 about 30 g/10 min. In the above range, the thermoplastic resin composition may have excellent flame retardancy and appearance characteristics.
구체예에서, 상기 폴리올레핀 수지는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 20 내지 약 50 중량부, 예를 들면 약 25 내지 약 45 중량부로 포함될 수 있다. 상기 폴리올레핀 수지의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 20 중량부 미만일 경우, 열가소성 수지 조성물의 난연성 등이 저하될 우려가 있고, 약 50 중량부를 초과할 경우, 열가소성 수지 조성물의 외관 특성, 기계적 물성 등이 저하될 우려가 있다.In an embodiment, the polyolefin resin may be included in an amount of about 20 to about 50 parts by weight, for example, about 25 to about 45 parts by weight based on 100 parts by weight of the rubber-modified polystyrene resin. When the content of the polyolefin resin is less than about 20 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 50 parts by weight, the thermoplastic resin composition There is a possibility that appearance characteristics, mechanical properties, etc. may be deteriorated.
(D) 피페라진 피로포스페이트(D) piperazine pyrophosphate
본 발명의 피페라진 피로포스페이트(piperazine pyrophosphate)는 멜라민 피로포스페이트, 산화아연, 에틸렌메틸아크릴레이트 및 에틸렌비닐아세테이트와 함께 적용되어, 적은 함량으로도 차르(char) 형성이 용이하고, 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성 등을 향상시킬 수 있는 것으로서, 통상의 난연성 열가소성 수지 조성물에 사용되는 피페라진 피로포스페이트를 사용할 수 있다.Piperazine pyrophosphate of the present invention is applied together with melamine pyrophosphate, zinc oxide, ethylene methyl acrylate and ethylene vinyl acetate, and it is easy to form char even with a small content, and flame retardancy of the thermoplastic resin composition , impact resistance, appearance characteristics, etc. can be improved, and piperazine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions can be used.
구체예에서, 상기 피페라진 피로포스페이트는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 10 내지 약 30 중량부, 예를 들면 약 11 내지 약 29 중량부로 포함될 수 있다. 상기 피페라진 피로포스페이트의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 10 중량부 미만일 경우, 열가소성 수지 조성물의 난연성 등이 저하될 우려가 있고, 약 30 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 외관 특성, 열안정성 등이 저하될 우려가 있다.In an embodiment, the piperazine pyrophosphate may be included in an amount of about 10 to about 30 parts by weight, for example, about 11 to about 29 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin. When the content of the piperazine pyrophosphate is less than about 10 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and when it exceeds about 30 parts by weight, the thermoplastic resin There is a fear that the impact resistance, appearance characteristics, thermal stability, etc. of the composition may be deteriorated.
(E) 멜라민 피로포스페이트(E) melamine pyrophosphate
본 발명의 멜라민 피로포스페이트(melamine pyrophosphate)는 피페라진 피로포스페이트, 산화아연, 에틸렌메틸아크릴레이트 및 에틸렌비닐아세테이트와 함께 적용되어, 적은 함량으로도 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성 등을 향상시킬 수 있는 것으로서, 통상의 난연성 열가소성 수지 조성물에 사용되는 멜라민 피로포스페이트를 사용할 수 있다.Melamine pyrophosphate of the present invention is applied together with piperazine pyrophosphate, zinc oxide, ethylene methyl acrylate and ethylene vinyl acetate to improve flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition even with a small content As what can be done, melamine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions can be used.
구체예에서, 상기 멜라민 피로포스페이트는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 5 내지 약 25 중량부, 예를 들면 약 6 내지 약 24 중량부로 포함될 수 있다. 상기 멜라민 피로포스페이트의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 5 중량부 미만일 경우, 열가소성 수지 조성물의 난연성 등이 저하될 우려가 있고, 약 25 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 외관 특성, 열안정성 등이 저하될 우려가 있다.In an embodiment, the melamine pyrophosphate may be included in an amount of about 5 to about 25 parts by weight, for example, about 6 to about 24 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin. When the content of the melamine pyrophosphate is less than about 5 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 25 parts by weight, the thermoplastic resin composition impact resistance, appearance characteristics, thermal stability, etc. may be deteriorated.
구체예에서, 상기 피페라진 피로포스페이트(D) 및 상기 멜라민 피로포스페이트(E)의 중량비(D:E)는 약 1 : 0.2 내지 약 1 : 1.5, 예를 들면 약 1 : 0.2 내지 약 1 : 1.4일 수 있다. 상기 범위에서, 열가성 수지 조성물의 난연성, 내충격성, 외관 특성, 이들의 물성 발란스 등이 우수할 수 있다.In an embodiment, the weight ratio (D:E) of the piperazine pyrophosphate (D) and the melamine pyrophosphate (E) is from about 1:0.2 to about 1:1.5, for example from about 1:0.2 to about 1:1.4 can be Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
(F) 산화아연(F) zinc oxide
본 발명의 일 구체예에 따른 산화아연은 상기 피페라진 피로포스페이트, 멜라민 포스페이트, 멜라민 피로포스페이트, 에틸렌메틸아크릴레이트 및 에틸렌비닐아세테이트와 함께 적용되어, 열가소성 수지 조성물의 난연성, 내충격성 등을 향상시킬 수 있는 것으로서, 입도분석기(Beckman Coulter社 Laser Diffraction Particle Size Analyzer LS I3 320 장비)를 사용하여 측정한 단일 입자(입자가 뭉쳐서 2차 입자를 형성하지 않음)의 평균 입자 크기(D50)가 약 0.2 내지 약 3 ㎛, 예를 들면 약 0.5 내지 약 3 ㎛일 수 있다. 또한, 상기 산화아연은 질소가스 흡착법을 사용하여, BET 분석 장비(Micromeritics社 Surface Area and Porosity Analyzer ASAP 2020 장비)로 측정한 비표면적 BET가 약 1 내지 약 10 m2/g, 예를 들면 약 1 내지 약 7 m2/g일 수 있으며, 순도가 약 99% 이상일 수 있다. 상기 범위를 벗어날 경우, 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성 등이 저하될 우려가 있다.Zinc oxide according to an embodiment of the present invention is applied together with the piperazine pyrophosphate, melamine phosphate, melamine pyrophosphate, ethylene methyl acrylate and ethylene vinyl acetate to improve the flame retardancy and impact resistance of the thermoplastic resin composition. The average particle size (D50) of a single particle (particles do not aggregate to form secondary particles) measured using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) is about 0.2 to about 3 μm, for example about 0.5 to about 3 μm. In addition, 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 from Micromeritics) using a nitrogen gas adsorption method. 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, appearance characteristics of the thermoplastic resin composition may be deteriorated.
구체예에서, 상기 산화아연은 다양한 형태를 가질 수 있으며, 예를 들면, 구형, 플레이트형, 막대(rod)형, 이들의 조합 등을 모두 포함할 수 있다.In an embodiment, 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.
구체예에서, 상기 산화아연은 광 발광(Photo Luminescence) 측정 시, 370 내지 390 nm 영역의 피크 A와 450 내지 600 nm 영역의 피크 B의 크기비(B/A)가 약 0.01 내지 약 1.0, 예를 들면 약 0.1 내지 약 1.0, 구체적으로 약 0.1 내지 약 0.5일 수 있다. 상기 범위에서 열가소성 수지 조성물의 난연성, 내충격성 등이 우수할 수 있다.In an embodiment, 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, for example, when measuring photoluminescence For example, it may be about 0.1 to about 1.0, specifically about 0.1 to about 0.5. In the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and the like.
구체예에서, 상기 산화아연은 X선 회절(X-ray diffraction, XRD) 분석 시, 피크 위치(peak position) 2θ 값이 35 내지 37° 범위이고, 측정된 FWHM 값(회절 피크(peak)의 Full width at Half Maximum)을 기준으로 Scherrer's equation(하기 식 1)에 적용하여 연산된 미소결정의 크기(crystallite size) 값이 약 1,000 내지 약 2,000 Å, 예를 들면 약 1,200 내지 약 1,800 Å일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성 등이 우수할 수 있다.In an embodiment, the zinc oxide has a peak position 2θ 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 Å, for example, about 1,200 to about 1,800 Å. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and appearance characteristics.
[식 1][Equation 1]
미소결정 크기(D) =
Figure PCTKR2021007056-appb-I000003
Crystalline size (D) =
Figure PCTKR2021007056-appb-I000003
상기 식 1에서, K는 형상 계수(shape factor)이고, λ는 X선 파장(X-ray wavelength)이고, β는 FWHM 값(degree)이며, θ는 피크 위치 값(peak position degree)이다.In Equation 1, K is a shape factor, λ is an X-ray wavelength, β is a FWHM value (degree), and θ is a peak position degree.
구체예에서, 상기 산화아연은 금속형태의 아연을 녹인 후, 약 850 내지 약 1,000℃, 예를 들면 약 900 내지 약 950℃로 가열하여 증기화시킨 후, 산소 가스를 주입하고 20 내지 30℃로 냉각한 다음, 약 400 내지 약 900℃, 예를 들면 약 500 내지 약 800℃에서 약 30 내지 약 150분, 예를 들면 약 60 내지 약 120분 동안 가열하여 제조할 수 있다.In an embodiment, 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 20 to 30°C. After cooling, it can be prepared by 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.
구체예에서, 상기 산화아연은 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 0.3 내지 약 7 중량부, 예를 들면 약 0.5 내지 약 5 중량부로 포함될 수 있다. 상기 산화아연의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 0.3 중량부 미만일 경우, 열가소성 수지 조성물의 난연성 등이 저하될 우려가 있고, 약 7 중량부를 초과할 경우, 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하될 우려가 있다.In an embodiment, the zinc oxide may be included in an amount of about 0.3 to about 7 parts by weight, for example, about 0.5 to about 5 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin. When the content of zinc oxide is less than about 0.3 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the flame retardancy of the thermoplastic resin composition may decrease, and when it exceeds about 7 parts by weight, the thermoplastic resin composition There exists a possibility that impact resistance, an external appearance characteristic, etc. may fall.
구체예에서, 상기 피페라진 피로포스페이트(D) 및 상기 산화아연(F)의 중량비(D:F)는 약 4 : 1 내지 약 60 : 1, 예를 들면 약 5 : 1 내지 약 50 : 1일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성, 이들의 물성 발란스 등이 우수할 수 있다.In an embodiment, the weight ratio (D:F) of the piperazine pyrophosphate (D) and the zinc oxide (F) is about 4 : 1 to about 60 : 1, for example, about 5 : 1 to about 50 : 1 day. can Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
(G) 에틸렌메틸아크릴레이트 공중합체(G) ethylene methyl acrylate copolymer
본 발명의 에틸렌메틸아크릴레이트 공중합체는 상기 고무변성 폴리스티렌 수지에 피페라진 피로포스페이트, 멜라민 피로포스페이트, 산화아연 및 에틸렌비닐아세테이트 공중합체 등과 함께 적용되어, 열가소성 수지 조성물 구성 성분의 상용성을 향상시키고, 열가소성 수지 조성물의 내충격성 등을 향상시킬 수 있는 것이다.The ethylene methyl acrylate copolymer of the present invention is applied to the rubber-modified polystyrene resin together with piperazine pyrophosphate, melamine pyrophosphate, zinc oxide and ethylene vinyl acetate copolymer to improve compatibility of the components of the thermoplastic resin composition, It is possible to improve the impact resistance and the like of the thermoplastic resin composition.
구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체는 에틸렌과 메틸아크릴레이트를 중합하여 제조할 수 있다. 예를 들면, 상기 에틸렌메틸아크릴레이트 공중합체는 에틸렌 반복단위 약 50 내지 약 95 중량%, 예를 들면 약 70 내지 약 93 중량% 및 메틸아크릴레이트 반복단위 약 5 내지 약 50 중량%, 예를 들면 약 7 내지 약 30 중량%를 포함할 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성 등이 우수할 수 있다.In an embodiment, the ethylene methyl acrylate copolymer may be prepared by polymerizing ethylene and methyl acrylate. For example, the ethylene methyl acrylate copolymer comprises about 50 to about 95 wt% of ethylene repeating units, such as about 70 to about 93 wt% of methyl acrylate repeating units, and about 5 to about 50 wt% of methyl acrylate repeating units, such as from about 7 to about 30% by weight. In the above range, the thermoplastic resin composition may have excellent impact resistance.
구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체는 랜덤, 블록, 멀티블록의 공중합체 형태일 수 있으며, 이들의 조합 형태로도 사용될 수 있다.In an embodiment, the ethylene methyl acrylate copolymer may be in the form of a random, block, or multi-block copolymer, or a combination thereof.
구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체는 ASTM D1238에 의거하여, 190℃, 2.16 kgf 조건에서 측정한 용융흐름지수가 약 0.01 내지 약 40 g/10분, 예를 들면, 약 0.1 내지 약 10 g/10분일 수 있다.In an embodiment, the ethylene methyl acrylate copolymer has a melt flow index of about 0.01 to about 40 g/10 min, for example, about 0.1 to about 10, measured at 190° C. and 2.16 kgf according to ASTM D1238. g/10 min.
구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 1.5 내지 약 25 중량부, 예를 들면 약 2 내지 약 20 중량부로 포함될 수 있다. 상기 에틸렌메틸아크릴레이트 공중합체의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 1.5 중량부 미만일 경우, 열가소성 수지 조성물의 내충격성 등이 저하될 우려가 있고, 약 25 중량부를 초과할 경우, 열가소성 수지 조성물의 난연성, 외관 특성, 가공성 등이 저하될 우려가 있다.In an embodiment, the ethylene methyl acrylate copolymer may be included in an amount of about 1.5 to about 25 parts by weight, for example, about 2 to about 20 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin. When the content of the ethylene methyl acrylate copolymer is less than about 1.5 parts by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the impact resistance of the thermoplastic resin composition may decrease, and when it exceeds about 25 parts by weight , there is a possibility that the flame retardancy, appearance characteristics, workability, etc. of the thermoplastic resin composition may be deteriorated.
(H) 에틸렌비닐아세테이트 공중합체(H) ethylene vinyl acetate copolymer
본 발명의 에틸렌비닐아세테이트 공중합체는 상기 고무변성 폴리스티렌 수지에 피페라진 피로포스페이트, 멜라민 피로포스페이트, 산화아연 및 에틸렌메틸아크릴레이트 공중합체 등과 함께 적용되어, 열가소성 수지 조성물 구성 성분의 상용성을 향상시키고, 열가소성 수지 조성물의 내충격성, 외관 특성 등을 향상시킬 수 있는 것이다.The ethylene vinyl acetate copolymer of the present invention is applied to the rubber-modified polystyrene resin together with piperazine pyrophosphate, melamine pyrophosphate, zinc oxide and ethylene methyl acrylate copolymer to improve the compatibility of the components of the thermoplastic resin composition, It is possible to improve the impact resistance and appearance characteristics of the thermoplastic resin composition.
구체예에서, 상기 에틸렌비닐아세테이트 공중합체는 에틸렌과 비닐아세테이트를 중합하여 제조할 수 있다. 예를 들면, 상기 에틸렌비닐아세테이트 공중합체는 에틸렌 반복단위 약 50 내지 약 95 중량%, 예를 들면 약 70 내지 약 93 중량% 및 비닐아세테이트 반복단위 약 5 내지 약 50 중량%, 예를 들면 약 7 내지 약 30 중량%를 포함할 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 외관 특성 등이 우수할 수 있다.In an embodiment, the ethylene vinyl acetate copolymer may be prepared by polymerizing ethylene and vinyl acetate. For example, the ethylenevinylacetate copolymer may contain from about 50 to about 95% by weight of ethylene repeating units, for example from about 70 to about 93% by weight, and from about 5 to about 50% by weight of vinyl acetate repeating units, such as about 7 to about 30% by weight. In the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
구체예에서, 상기 에틸렌비닐아세테이트 공중합체는 랜덤, 블록, 멀티블록의 공중합체 형태일 수 있으며, 이들의 조합 형태로도 사용될 수 있다.In an embodiment, the ethylene vinyl acetate copolymer may be in the form of a random, block, or multi-block copolymer, and may also be used in a combination form thereof.
구체예에서, 상기 에틸렌비닐아세테이트 공중합체는 ASTM D1238에 의거하여, 190℃, 2.16 kgf 조건에서 측정한 용융흐름지수가 약 0.01 내지 약 40 g/10분, 예를 들면, 약 0.1 내지 약 10 g/10분일 수 있다.In an embodiment, the ethylene vinyl acetate copolymer has a melt flow index of about 0.01 to about 40 g/10 min, for example, about 0.1 to about 10 g, measured at 190° C. and 2.16 kgf according to ASTM D1238. It can be /10 minutes.
구체예에서, 상기 에틸렌비닐아세테이트 공중합체는 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 1 내지 약 12 중량부, 예를 들면 약 2 내지 약 10 중량부로 포함될 수 있다. 상기 에틸렌비닐아세테이트 공중합체의 함량이 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 1 중량부 미만일 경우, 열가소성 수지 조성물의 내충격성 등이 저하될 우려가 있고, 약 12 중량부를 초과할 경우, 열가소성 수지 조성물의 난연성, 외관 특성 등이 저하될 우려가 있다.In an embodiment, the ethylene vinyl acetate copolymer may be included in an amount of about 1 to about 12 parts by weight, for example, about 2 to about 10 parts by weight, based on 100 parts by weight of the rubber-modified polystyrene resin. When the content of the ethylene vinyl acetate copolymer is less than about 1 part by weight based on about 100 parts by weight of the rubber-modified polystyrene resin, there is a risk that the impact resistance of the thermoplastic resin composition may decrease, and when it exceeds about 12 parts by weight, There exists a possibility that the flame retardance of a thermoplastic resin composition, an external appearance characteristic, etc. may fall.
구체예에서, 상기 피페라진 피로포스페이트(D) 및 상기 에틸렌메틸아크릴레이트와 에틸렌비닐아세테이트의 합(G+H)의 중량비(D:G+H)는 약 1 : 0.1 내지 약 1 : 1.5, 예를 들면 약 1 : 0.2 내지 약 1 : 1.4일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성, 이들의 물성 발란스 등이 우수할 수 있다.In an embodiment, the weight ratio (D:G+H) of the piperazine pyrophosphate (D) and the sum of the ethylene methyl acrylate and ethylene vinyl acetate (G + H) is about 1: 0.1 to about 1: 1.5, eg For example, it may be about 1: 0.2 to about 1: 1.4. Within the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
구체예에서, 상기 에틸렌메틸아크릴레이트 공중합체(G) 및 상기 에틸렌비닐아세테이트 공중합체(H)의 중량비(G:H)는 약 0.5 : 1 내지 약 10 : 1, 예를 들면 약 0.6 : 1 내지 약 7 : 1일 수 있다. 상기 범위에서 열가소성 수지 조성물의 난연성, 내충격성, 외관 특성, 이들의 물성 발란스 등이 우수할 수 있다.In an embodiment, the weight ratio (G:H) of the ethylene methyl acrylate copolymer (G) and the ethylene vinyl acetate copolymer (H) is about 0.5: 1 to about 10: 1, for example, about 0.6: 1 to It can be about 7:1. In the above range, the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 통상의 열가소성 수지 조성물에 포함되는 첨가제를 더욱 포함할 수 있다. 상기 첨가제로는 충격보강제, 산화방지제, 적하방지제, 활제, 이형제, 핵제, 대전방지제, 안정제, 안료, 염료, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다. 상기 첨가제 사용 시, 그 함량은 상기 고무변성 폴리스티렌 수지 약 100 중량부에 대하여, 약 0.001 내지 약 40 중량부, 예를 들면 약 0.1 내지 약 10 중량부일 수 있다.The thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additives 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. When the additive is used, 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.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 상기 구성 성분을 혼합하고, 통상의 이축 압출기를 사용하여, 약 180 내지 약 280℃, 예를 들면 약 200 내지 약 260℃에서 용융 압출한 펠렛 형태일 수 있다.The thermoplastic resin composition according to one embodiment of the present invention is in the form of pellets that are melt-extruded at about 180 to about 280 ° C, for example, about 200 to about 260 ° C, by mixing the above components and using a conventional twin screw extruder. can
구체예에서, 상기 열가소성 수지 조성물은 UL94 vertical test 방법으로 측정한 1.5 mm 두께 시편의 난연도가 V-1 이상일 수 있다.In an embodiment, the thermoplastic resin composition may have a flame retardancy of V-1 or more of a 1.5 mm thick specimen measured by the UL94 vertical test method.
구체예에서, 상기 열가소성 수지 조성물은 듀폰 드롭(DuPont drop) 측정법에 의거하여 1 kg 무게의 추(dart)를 사용하여 측정한 2 mm 두께 시편의 크랙(crack) 발생 낙하 높이가 약 55 내지 약 100 cm, 예를 들면 약 60 내지 약 95 cm일 수 있다.In an embodiment, the thermoplastic resin composition has a cracking drop height of about 55 to about 100 of a 2 mm thick specimen measured using a dart weighing 1 kg based on the DuPont drop measurement method. cm, for example from about 60 to about 95 cm.
본 발명에 따른 성형품은 상기 열가소성 수지 조성물로부터 형성된다. 상기 열가소성 수지 조성물은 펠렛 형태로 제조될 수 있으며, 제조된 펠렛은 사출성형, 압출성형, 진공성형, 캐스팅성형 등의 다양한 성형방법을 통해 다양한 성형품(제품)으로 제조될 수 있다. 이러한 성형방법은 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 잘 알려져 있다. 상기 성형품은 할로겐계 난연제를 적용하지 않아 친환경적이며, 난연성, 내충격성, 외관 특성, 이들의 물성 발란스 등이 우수하므로, 전기 전자 제품의 내외장재 등으로 유용하다.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 environmentally friendly because it does not apply a halogen-based flame retardant, and has excellent flame retardancy, impact resistance, appearance characteristics, and balance of physical properties thereof, so it is useful as interior and exterior materials for electrical and electronic products.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로, 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail through examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예Example
이하, 실시예 및 비교예에서 사용된 각 성분의 사양은 다음과 같다.Hereinafter, the specifications of each component used in Examples and Comparative Examples are as follows.
(A) 고무변성 폴리스티렌 수지(A) Rubber-modified polystyrene resin
내충격 폴리스티렌(HIPS) 수지(제조사: IDEMITSU, 제품명: PSI060)를 사용하였다.Impact-resistant polystyrene (HIPS) resin (manufacturer: IDEMITSU, product name: PSI060) was used.
(B) 폴리페닐렌에테르 수지(B) polyphenylene ether resin
폴리(1,4-페닐렌)에테르(제조사: Bluestar New Chemical Materials, 제품명: LXR-050C)를 사용하였다.Poly (1,4-phenylene) ether (manufacturer: Bluestar New Chemical Materials, product name: LXR-050C) was used.
(C) 폴리올레핀 수지(C) polyolefin resin
ASTM D1238에 의거하여, 230℃, 2.16 kg 하중 조건에서 측정한 유동흐름지수(MI)가 12 g/10분인 폴리프로필렌 수지(제조사: 롯데케미칼, 제품명: B-311)를 사용하였다.Based on ASTM D1238, a polypropylene resin (manufacturer: Lotte Chemical, product name: B-311) having a flow index (MI) of 12 g/10 min measured at 230°C and a load of 2.16 kg was used.
(D) 피페라진 피로포스페이트(D) piperazine pyrophosphate
피페라진 피로포스페이트(제조사: Hainan Zhongxin Chemical, Cas No.: 66034-17-1)를 사용하였다.Piperazine pyrophosphate (manufacturer: Hainan Zhongxin Chemical, Cas No.: 66034-17-1) was used.
(E) 멜라민 피로포스페이트(E) melamine pyrophosphate
멜라민 피로포스페이트(제조사: Budenheim, 제품명: Budit 311MPP)를 사용하였다.Melamine pyrophosphate (manufacturer: Budenheim, product name: Budit 311MPP) was used.
(F) 산화아연(F) zinc oxide
금속형태의 아연을 녹인 후, 900℃로 가열하여 증기화시킨 후, 산소 가스를 주입하고 상온(25℃)으로 냉각하여, 1차 중간물을 얻었다. 다음으로, 해당 1차 중간물을 700℃에서 90분 동안 열처리를 진행한 후, 상온(25℃)으로 냉각하여 제조한 산화아연(평균 입자 크기: 1.2 ㎛, 비표면적 BET: 4 m2/g)을 사용하였다.After melting zinc in metal form, it was heated to 900° C. to vaporize it, and then oxygen gas was injected and cooled to room temperature (25° C.) to obtain a primary intermediate. Next, the zinc oxide prepared by heat-treating the primary intermediate at 700° C. for 90 minutes, and then cooling to room temperature (25° C.) (average particle size: 1.2 μm, specific surface area BET: 4 m 2 /g ) was used.
(G) 에틸렌메틸아크릴레이트 공중합체(G) ethylene methyl acrylate copolymer
에틸렌메틸아크릴레이트 공중합체(제조사: Dupont 제품명: Elvaloy AC1330)를 사용하였다.Ethylene methyl acrylate copolymer (manufacturer: Dupont product name: Elvaloy AC1330) was used.
(H) 에틸렌비닐아세테이트 공중합체(H) ethylene vinyl acetate copolymer
에틸렌비닐아세테이트 공중합체(제조사: 삼성토탈, 제품명: E153F)를 사용하였다.An ethylene vinyl acetate copolymer (manufacturer: Samsung Total, product name: E153F) was used.
(I) 올리고머형 비스페놀-A 디포스페이트(bisphenol-A diphosphate, 제조사: Yoke Chemical, 제품명: YOKE BDP)를 사용하였다.(I) oligomeric bisphenol-A diphosphate (manufacturer: Yoke Chemical, product name: YOKE BDP) was used.
(J) 변성 폴리올레핀(EEA: ethylene-ethyl acrylate copolymer, 제조사: Dupont, 제품명: EVAFLEX-EEA A714)을 사용하였다.(J) Modified polyolefin (EEA: ethylene-ethyl acrylate copolymer, manufacturer: Dupont, product name: EVAFLEX-EEA A714) was used.
실시예 1 내지 15 및 비교예 1 내지 16Examples 1 to 15 and Comparative Examples 1 to 16
상기 각 구성 성분을 하기 표 1, 2, 3 및 4에 기재된 바와 같은 함량으로 첨가한 후, 230℃에서 압출하여 펠렛을 제조하였다. 압출은 L/D=44, 직경 45 mm인 이축 압출기를 사용하였으며, 제조된 펠렛은 80℃에서 4시간 이상 건조 후, 6 oz 사출기(성형 온도 230℃, 금형 온도: 70℃)에서 사출 성형하여 시편을 제조하였다. 제조된 시편에 대하여 하기의 방법으로 물성을 평가하고, 그 결과를 하기 표 1, 2, 3 및 4에 나타내었다.After adding each of the components in the amounts as shown in Tables 1, 2, 3 and 4 below, extrusion was performed at 230° C. to prepare pellets. For extrusion, a twin-screw extruder with L/D = 44 and a diameter of 45 mm was used, and the pellets were dried at 80 ° C. for 4 hours or more, and then injection molded in a 6 oz injection machine (molding temperature 230 ° C, mold temperature: 70 ° C). Specimens were prepared. The prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2, 3 and 4 below.
물성 측정 방법How to measure physical properties
(1) 난연도: UL94 vertical test 방법으로 측정한 1.5 mm 두께 시편의 난연도를 측정하였다.(1) Flame retardancy: The flame retardancy of a 1.5 mm thick specimen measured by the UL94 vertical test method was measured.
(2) 면 충격강도(단위: cm): 듀폰 드롭 테스트(DuPont drop test) 방식의 낙추 평가장비로 1 kg 무게의 추(dart)를 사용하여 2 mm 두께 시편의 크랙(crack) 발생 낙하 높이를 측정하였다.(2) Surface impact strength (unit: cm): Using a 1 kg weight dart as an evaluation device for the DuPont drop test method, the cracking height of the 2 mm thick specimen was measured. measured.
(3) 외관 평가: 실시예 및 비교예에서 제조된 펠렛을 80℃에서 4시간 이상 건조한 후, 9 cm × 32 cm 크기(단차, BOSS, 2-Gate)로 제작된 평판 금형을 적용한 사출 성형기(성형 온도 220 내지 250℃, 금형 온도: 60 내지 100℃)에서 사출 성형하여 시편을 제조하였다. 제조된 시편의 플로우 마크(flow mark) 및 웰드 라인(weld lime) 이색을 육안으로 확인하고, 하기 기준에 따라, 점수를 부여하였으며, 1 및 2의 경우, 외관이 불량한 것으로 판단하였고, 3 및 4의 경우, 외관 특성이 우수한 것으로 판단하였다.(3) Appearance evaluation: After drying the pellets prepared in Examples and Comparative Examples at 80 ° C. for 4 hours or more, an injection molding machine using a flat mold made of 9 cm × 32 cm (step difference, BOSS, 2-Gate) ( A specimen was prepared by injection molding at a molding temperature of 220 to 250° C., a mold temperature of 60 to 100° C.). The flow mark and the weld lime of the prepared specimen were visually checked, and a score was given according to the following criteria, and in the case of 1 and 2, it was determined that the appearance was poor, 3 and 4 In the case of , it was judged that the appearance characteristics were excellent.
(1: 플로우 마크(flow mark) 및 웰드 라인(weld lime) 이색 70 내지 100% 발생, 2: 플로우 마크(flow mark) 및 웰드 라인(weld lime) 이색 50 내지 70% 미만 발생, 3: 플로우 마크(flow mark) 및 웰드 라인(weld lime) 이색 10 내지 50% 미만 발생, 4: 플로우 마크(flow mark) 및 웰드 라인(weld lime) 이색 10% 미만 발생)(1: flow mark and weld line dichroism 70 to 100% occurrence, 2: flow mark and weld line dichroism less than 50 to 70% occurrence, 3: flow mark (flow mark and weld line heterochromatic occurrence less than 10 to 50%, 4: flow mark and weld line heterochromatic occurrence less than 10%)
실시예Example
1One 22 33 44 55 66 77
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100
(B) (중량부)(B) (parts by weight) 66 1010 1919 1010 1010 1010 1010
(C) (중량부)(C) (parts by weight) 3030 3030 3030 2525 4545 3030 3030
(D) (중량부)(D) (parts by weight) 2525 2525 2525 2525 2525 1111 2929
(E) (중량부)(E) (parts by weight) 1515 1515 1515 1515 1515 1515 1515
(F) (중량부)(F) (parts by weight) 22 22 22 22 22 22 22
(G) (중량부)(G) (parts by weight) 1010 1010 1010 1010 1010 1010 1010
(H) (중량부)(H) (parts by weight) 55 55 55 55 55 55 55
(I) (중량부)(I) (parts by weight) -- -- -- -- -- -- --
(J) (중량부)(J) (parts by weight) -- -- -- -- -- -- --
난연도Flame retardancy V-1V-1 V-0V-0 V-0V-0 V-1V-1 V-0V-0 V-1V-1 V-0V-0
면 충격강도face impact strength 8585 8585 7575 8080 6565 8585 7070
외관 평가Appearance evaluation 44 44 33 44 33 44 33
실시예Example
88 99 1010 1111 1212 1313 1414 1515
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100 100100
(B) (중량부)(B) (parts by weight) 1010 1010 1010 1010 1010 1010 1010 1010
(C) (중량부)(C) (parts by weight) 3030 3030 3030 3030 3030 3030 3030 3030
(D) (중량부)(D) (parts by weight) 2525 2525 2525 2525 2525 2525 2525 2525
(E) (중량부)(E) (parts by weight) 66 2424 1515 1515 1515 1515 1515 1515
(F) (중량부)(F) (parts by weight) 22 22 0.50.5 55 22 22 22 22
(G) (중량부)(G) (parts by weight) 1010 1010 1010 1010 22 2020 1010 1010
(H) (중량부)(H) (parts by weight) 33 33 33 33 33 33 22 1010
(I) (중량부)(I) (parts by weight) -- -- -- -- -- -- -- --
(J) (중량부)(J) (parts by weight) -- -- -- -- -- -- -- --
난연도Flame retardancy V-1V-1 V-0V-0 V-1V-1 V-0V-0 V-0V-0 V-1V-1 V-0V-0 V-1V-1
면 충격강도face impact strength 8080 7070 8080 6565 6060 9090 6060 9090
외관 평가Appearance evaluation 44 33 44 44 44 33 33 44
비교예comparative example
1One 22 33 44 55 66 77 88
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100 100100
(B) (중량부)(B) (parts by weight) 33 2525 1010 1010 1010 1010 1010 1010
(C) (중량부)(C) (parts by weight) 3030 3030 1515 5050 3030 3030 3030 3030
(D) (중량부)(D) (parts by weight) 2020 2020 2020 2020 77 3535 2020 2020
(E) (중량부)(E) (parts by weight) 1515 1515 1515 1515 1515 1515 33 3030
(F) (중량부)(F) (parts by weight) 22 22 22 22 22 22 22 22
(G) (중량부)(G) (parts by weight) 1010 1010 1010 1010 1010 1010 1010 1010
(H) (중량부)(H) (parts by weight) 55 55 55 55 55 55 55 55
(I) (중량부)(I) (parts by weight) -- -- -- -- -- -- -- --
(J) (중량부)(J) (parts by weight) -- -- -- -- -- -- -- --
난연도Flame retardancy V-2V-2 V-0V-0 V-2V-2 V-0V-0 B.OB.O. V-0V-0 V-2V-2 V-0V-0
면 충격강도face impact strength 8585 5050 8585 7070 7070 3535 8080 4040
외관 평가Appearance evaluation 33 1One 33 1One 33 1One 44 1One
비교예comparative example
99 1010 1111 1212 1313 1414 1515 1616
(A) (중량부)(A) (parts by weight) 100100 100100 100100 100100 100100 100100 100100 100100
(B) (중량부)(B) (parts by weight) 1010 1010 1010 1010 1010 1010 1010 1010
(C) (중량부)(C) (parts by weight) 3030 3030 3030 3030 3030 3030 3030 3030
(D) (중량부)(D) (parts by weight) 2020 2525 2525 2525 2525 2525 -- 2525
(E) (중량부)(E) (parts by weight) 1515 1515 1515 1515 1515 1515 -- 1515
(F) (중량부)(F) (parts by weight) 0.10.1 1010 22 22 22 22 22 22
(G) (중량부)(G) (parts by weight) 1010 1010 1One 3030 1010 1010 1010 --
(H) (중량부)(H) (parts by weight) 55 55 55 55 0.50.5 1515 55 --
(I) (중량부)(I) (parts by weight) -- -- -- -- -- -- 4040 --
(J) (중량부)(J) (parts by weight) -- -- -- -- -- -- -- 1515
난연도Flame retardancy V-2V-2 V-0V-0 V-0V-0 V-2V-2 V-0V-0 V-2V-2 V-0V-0 V-0V-0
면 충격강도face impact strength 8080 2020 1515 9090 3030 9090 1010 2020
외관 평가Appearance evaluation 44 22 44 1One 33 1One 1One 1One
상기 결과로부터, 본 발명의 열가소성 수지 조성물은 난연성, 내충격성, 외관 특성, 압출 가공성 등이 모두 우수함을 알 수 있다.From the above results, it can be seen that the thermoplastic resin composition of the present invention has excellent flame retardancy, impact resistance, appearance characteristics, extrusion processability, and the like.
반면, 폴리페닐렌에테르 수지를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 1), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 2), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있으며, 폴리올레핀 수지를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 3), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 4), 열가소성 수지 조성물의 외관 특성 등이 저하됨을 알 수 있다. 피페라진 피로포스페이트를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 5), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 6), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있으며, 멜라민 피로포스페이트를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 7), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 8), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있다. 본 발명의 산화아연을 본 발명의 함량 범위 미만으로 적용할 경우(비교예 9), 열가소성 수지 조성물의 난연성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 10), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있으며, 에틸렌메틸아크릴레이트 공중합체를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 11), 열가소성 수지 조성물의 내충격성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 12), 열가소성 수지 조성물의 난연성, 외관 특성 등이 저하됨을 알 수 있으며, 에틸렌비닐아세테이트 공중합체를 본 발명의 함량 범위 미만으로 적용할 경우(비교예 13), 열가소성 수지 조성물의 내충격성 등이 저하됨을 알 수 있고, 본 발명의 함량 범위 보다 초과하여 적용할 경우(비교예 14), 열가소성 수지 조성물의 난연성, 외관 특성 등이 저하됨을 알 수 있다. 또한, 본 발명의 피페라진 피로포스페이트, 멜라민 포스페이트 및 멜라민 피로포스페이트 대신에 인계 난연제 (I)를 적용할 경우(비교예 15), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있고, 본 발명의 에틸렌메틸아크릴레이트와 에틸렌비닐아세테이트 대신에 변성 폴리올레핀 EEA (J)를 적용할 경우(비교예 16), 열가소성 수지 조성물의 내충격성, 외관 특성 등이 저하됨을 알 수 있다.On the other hand, when the polyphenylene ether resin is applied below the content range of the present invention (Comparative Example 1), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 1) In Example 2), it can be seen that the impact resistance and appearance characteristics of the thermoplastic resin composition are lowered, and when the polyolefin resin is applied below the content range of the present invention (Comparative Example 3), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered. It can be seen that, when applied in excess of the content range of the present invention (Comparative Example 4), the appearance characteristics of the thermoplastic resin composition are deteriorated. When piperazine pyrophosphate is applied below the content range of the present invention (Comparative Example 5), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 6) , it can be seen that the impact resistance and appearance characteristics of the thermoplastic resin composition are lowered, and when melamine pyrophosphate is applied in less than the content range of the present invention (Comparative Example 7), it can be seen that the flame retardancy of the thermoplastic resin composition is reduced, , it can be seen that when applied in excess of the content range of the present invention (Comparative Example 8), the impact resistance and appearance characteristics of the thermoplastic resin composition are deteriorated. When the zinc oxide of the present invention is applied below the content range of the present invention (Comparative Example 9), it can be seen that the flame retardancy of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 10) ), it can be seen that the impact resistance and appearance characteristics of the thermoplastic resin composition are lowered, and when the ethylene methyl acrylate copolymer is applied below the content range of the present invention (Comparative Example 11), the impact resistance of the thermoplastic resin composition, etc. It can be seen that the decrease, and when applied in excess of the content range of the present invention (Comparative Example 12), it can be seen that the flame retardancy and appearance characteristics of the thermoplastic resin composition are lowered, and the ethylene vinyl acetate copolymer is in the content range of the present invention. When applied less than (Comparative Example 13), it can be seen that the impact resistance of the thermoplastic resin composition is lowered, and when applied in excess of the content range of the present invention (Comparative Example 14), flame retardancy and appearance properties of the thermoplastic resin composition It can be seen that the lower In addition, when the phosphorus-based flame retardant (I) is applied instead of the piperazine pyrophosphate, melamine phosphate and melamine pyrophosphate of the present invention (Comparative Example 15), it can be seen that the impact resistance and appearance properties of the thermoplastic resin composition are lowered, It can be seen that when the modified polyolefin EEA (J) is applied instead of the ethylene methyl acrylate and ethylene vinyl acetate of the present invention (Comparative Example 16), the impact resistance and appearance characteristics of the thermoplastic resin composition are deteriorated.
이제까지 본 발명에 대하여 실시예들을 중심으로 살펴보았다. 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자는 본 발명이 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 변형된 형태로 구현될 수 있음을 이해할 수 있을 것이다. 그러므로, 개시된 실시예들은 한정적인 관점이 아니라 설명적인 관점에서 고려되어야 한다. 본 발명의 범위는 전술한 설명이 아니라 특허청구범위에 나타나 있으며, 그와 동등한 범위 내에 있는 모든 차이점은 본 발명에 포함된 것으로 해석되어야 할 것이다.Up to now, the present invention has been mainly examined in the examples. Those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in modified forms without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments are to be considered in an illustrative rather than a restrictive sense. The scope of the present invention is indicated in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

Claims (11)

  1. 고무변성 폴리스티렌 수지 약 100 중량부;About 100 parts by weight of a rubber-modified polystyrene resin;
    폴리페닐렌에테르 수지 약 5 내지 약 20 중량부;about 5 to about 20 parts by weight of polyphenylene ether resin;
    폴리올레핀 수지 약 20 내지 약 50 중량부;about 20 to about 50 parts by weight of a polyolefin resin;
    피페라진 피로포스페이트 약 10 내지 약 30 중량부;about 10 to about 30 parts by weight of piperazine pyrophosphate;
    멜라민 피로포스페이트 약 5 내지 약 25 중량부;about 5 to about 25 parts by weight of melamine pyrophosphate;
    평균 입자 크기가 약 0.2 내지 약 3 ㎛이고, 비표면적 BET가 약 1 내지 약 10 m2/g인 산화아연 약 0.3 내지 약 7 중량부;about 0.3 to about 7 parts by weight of zinc oxide having an average particle size of about 0.2 to about 3 μm and a specific surface area BET of about 1 to about 10 m 2 /g;
    에틸렌메틸아크릴레이트 공중합체 약 1.5 내지 약 25 중량부; 및about 1.5 to about 25 parts by weight of an ethylenemethyl acrylate copolymer; and
    에틸렌비닐아세테이트 공중합체 약 1 내지 약 12 중량부;를 포함하는 것을 특징으로 하는 열가소성 수지 조성물.A thermoplastic resin composition comprising; about 1 to about 12 parts by weight of an ethylene vinyl acetate copolymer.
  2. 제1항에 있어서, 상기 고무변성 폴리스티렌 수지는 고무질 중합체 약 3 내지 약 30 중량% 및 방향족 비닐계 단량체 약 70 내지 약 97 중량%의 중합체인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 1, wherein the rubber-modified polystyrene resin comprises about 3 to about 30 wt% of a rubbery polymer and about 70 to about 97 wt% of an aromatic vinylic monomer.
  3. 제1항 또는 제2항에 있어서, 상기 폴리페닐렌에테르 수지는 하기 화학식 1로 표시되는 반복단위를 포함하는 것을 특징으로 하는 열가소성 수지 조성물:The thermoplastic resin composition according to claim 1 or 2, wherein the polyphenylene ether resin comprises a repeating unit represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2021007056-appb-I000004
    Figure PCTKR2021007056-appb-I000004
    상기 화학식 1에서, R1, R2, R3 및 R4는 각각 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 6의 알킬기 또는 탄소수 6 내지 12의 아릴기이다.In Formula 1, R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, 상기 폴리올레핀 수지는 폴리프로필렌, 폴리에틸렌, 프로필렌-에틸렌 공중합체 중 1종 이상을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyolefin resin comprises at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 피페라진 피로포스페이트 및 상기 멜라민 피로포스페이트의 중량비는 약 1 : 0.2 내지 약 1 : 1.5인 것을 특징으로 하는 열가소성 수지 조성물.5. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the weight ratio of the piperazine pyrophosphate and the melamine pyrophosphate is from about 1:0.2 to about 1:1.5.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, 상기 피페라진 피로포스페이트 및 상기 산화아연의 중량비는 약 4 : 1 내지 약 60 : 1인 것을 특징으로 하는 열가소성 수지 조성물.6. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the weight ratio of the piperazine pyrophosphate and the zinc oxide is from about 4:1 to about 60:1.
  7. 제1항 내지 제6항 중 어느 한 항에 있어서, 상기 피페라진 피로포스페이트 및 상기 에틸렌메틸아크릴레이트와 에틸렌비닐아세테이트의 합의 중량비는 약 1 : 0.1 내지 약 1 : 1.5인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 6, wherein the weight ratio of the sum of the piperazine pyrophosphate and the ethylene methyl acrylate and ethylene vinyl acetate is about 1: 0.1 to about 1: 1.5. .
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, 상기 에틸렌메틸아크릴레이트 공중합체 및 상기 에틸렌비닐아세테이트 공중합체의 중량비는 약 0.5 : 1 내지 약 10 : 1인 것을 특징으로 하는 열가소성 수지 조성물.8. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the weight ratio of the ethylene methyl acrylate copolymer and the ethylene vinyl acetate copolymer is from about 0.5:1 to about 10:1.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 UL94 vertical test 방법으로 측정한 1.5 mm 두께 시편의 난연도가 V-1 이상인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition has a flame retardancy of V-1 or more of a 1.5 mm thick specimen measured by the UL94 vertical test method.
  10. 제1항 내지 제9항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 듀폰 드롭(DuPont drop) 측정법에 의거하여 1 kg 무게의 추(dart)를 사용하여 측정한 2 mm 두께 시편의 크랙(crack) 발생 낙하 높이가 약 55 내지 약 100 cm인 것을 특징으로 하는 열가소성 수지 조성물.10. The method according to any one of claims 1 to 9, wherein the thermoplastic resin composition is a 2 mm thick specimen measured using a dart weighing 1 kg based on the DuPont drop measurement method. ) The thermoplastic resin composition, characterized in that the generated drop height is about 55 to about 100 cm.
  11. 제1항 내지 제10항 중 어느 한 항에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 하는 성형품.A molded article, characterized in that it is formed from the thermoplastic resin composition according to any one of claims 1 to 10.
PCT/KR2021/007056 2020-07-30 2021-06-07 Thermoplastic resin composition and molded article formed therefrom WO2022025409A1 (en)

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WO2023219272A1 (en) * 2022-05-13 2023-11-16 롯데케미칼 주식회사 Thermoplastic resin composition and molded article formed therefrom

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JPS5598239A (en) * 1979-01-22 1980-07-26 Asahi Chem Ind Co Ltd Non-flammable resin composition
KR20110094698A (en) * 2010-02-17 2011-08-24 엘에스전선 주식회사 Modified polyphenylene oxide-polyolefin composition with improved mechanical properties and processability and electrical cable produced therewith
KR20140087912A (en) * 2012-12-31 2014-07-09 제일모직주식회사 Thermoplastic resin composition and article including same
JP2017031351A (en) * 2015-08-04 2017-02-09 株式会社Adeka Flame retardant resin composition
WO2019132575A1 (en) * 2017-12-29 2019-07-04 롯데첨단소재(주) Thermoplastic resin composition and molded article manufactured therefrom

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JPS5598239A (en) * 1979-01-22 1980-07-26 Asahi Chem Ind Co Ltd Non-flammable resin composition
KR20110094698A (en) * 2010-02-17 2011-08-24 엘에스전선 주식회사 Modified polyphenylene oxide-polyolefin composition with improved mechanical properties and processability and electrical cable produced therewith
KR20140087912A (en) * 2012-12-31 2014-07-09 제일모직주식회사 Thermoplastic resin composition and article including same
JP2017031351A (en) * 2015-08-04 2017-02-09 株式会社Adeka Flame retardant resin composition
WO2019132575A1 (en) * 2017-12-29 2019-07-04 롯데첨단소재(주) Thermoplastic resin composition and molded article manufactured therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023219272A1 (en) * 2022-05-13 2023-11-16 롯데케미칼 주식회사 Thermoplastic resin composition and molded article formed therefrom

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