WO2021201444A1 - Composition de résine thermoplastique et article moulé formé à partir de celle-ci - Google Patents

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

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WO2021201444A1
WO2021201444A1 PCT/KR2021/002578 KR2021002578W WO2021201444A1 WO 2021201444 A1 WO2021201444 A1 WO 2021201444A1 KR 2021002578 W KR2021002578 W KR 2021002578W WO 2021201444 A1 WO2021201444 A1 WO 2021201444A1
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thermoplastic resin
resin composition
weight
parts
aromatic vinyl
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PCT/KR2021/002578
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English (en)
Korean (ko)
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양천석
이승환
김주성
박강열
이윤규
정현문
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롯데케미칼 주식회사
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Publication of WO2021201444A1 publication Critical patent/WO2021201444A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • 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

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent flame retardancy, impact resistance, appearance characteristics, processability, and the like, and a molded article formed therefrom.
  • Thermoplastic resins such as polyolefin resins and aromatic vinyl resins have excellent mechanical, thermal, and electrical properties, and excellent chemical resistance and moldability, and are widely used in various fields.
  • the polyolefin resin belongs to one of the highly flammable resins, and it is a difficult task to make the polyolefin resin have excellent flame retardancy, etc., and the aromatic vinyl resin has no resistance to flame, When the flame is ignited, there is a problem in that the resin itself decomposes and provides raw materials to expand and sustain combustion.
  • metal hydroxides As an eco-friendly flame retardant system applicable to polyolefin resins, metal hydroxides, phosphorus-based flame retardants, etc. can be considered.
  • metal hydroxides a large amount of flame retardant is required to be input, so there is a problem in that moldability, water resistance, mechanical properties, etc. are deteriorated.
  • phosphorus-based flame retardants even if a relatively small amount is added compared to metal hydroxide, it is advantageous to implement flame retardancy without including halogens and heavy metals. It has limitations in terms of flame retardancy and appearance characteristics.
  • thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, processability, and the like, without these problems.
  • thermoplastic resin composition having excellent flame retardancy, impact resistance, appearance characteristics, processability, and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a thermoplastic resin; about 4 to about 10 parts by weight of melamine polyphosphate; about 2 to about 7 parts by weight of melamine phosphate; and about 10 to about 20 parts by weight of piperazine pyrophosphate; wherein, the mixture of melamine polyphosphate, melamine phosphate and piperazine pyrophosphate has an average particle diameter D50 of about 6 ⁇ m or less by particle size analysis, and a cumulative content of 90 It is characterized in that the particle diameter D90 of % is about 11 ⁇ m or less.
  • the thermoplastic resin may include at least one of a polyolefin resin and an aromatic vinyl-based resin.
  • the polyolefin resin may include at least one of polypropylene, polyethylene, and a propylene-ethylene copolymer.
  • the aromatic vinyl-based resin may include at least one of an aromatic vinyl-based polymer resin, an aromatic vinyl-based copolymer resin, a rubber-modified polystyrene resin, and a rubber-modified aromatic vinyl-based copolymer resin.
  • the weight ratio of the melamine polyphosphate and the melamine phosphate may be about 1:1 to about 4:1.
  • the weight ratio of the melamine polyphosphate and the piperazine pyrophosphate may be about 0.2:1 to about 0.8:1.
  • thermoplastic resin composition may have a flame retardancy of V-0 or more of a 1.5 mm thick specimen measured according to UL-94 standards.
  • thermoplastic resin composition may have a notch Izod impact strength of about 3 to about 10 kgf ⁇ cm/cm of a 1/8′′ thick specimen measured according to ASTM D256.
  • thermoplastic resin composition may have a surface roughness (Ra) of about 2 to about 15 ⁇ m of the specimen measured using a surface roughness meter.
  • 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 9.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in flame retardancy, impact resistance, appearance characteristics, workability, and the like, and a molded article formed therefrom.
  • thermoplastic resin composition according to the present invention comprises (A) a thermoplastic resin; (B) melamine polyphosphate; (C) melamine phosphate; and (D) piperazine pyrophosphate.
  • thermoplastic resin according to an embodiment of the present invention may include at least one of (A1) a polyolefin resin and (A2) an aromatic vinyl-based resin.
  • the polyolefin resin according to an embodiment of the present invention can improve mechanical properties, processability, 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), linear low density polyethylene (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer , polyethylene-based resins such as mixtures thereof; polypropylene resins such as polypropylene, propylene-ethylene copolymer, propylene-1-butene copolymer, and mixtures thereof; polymers obtained by crosslinking them; blends comprising polyisobutene; A combination of these and the like can be used.
  • polypropylene, polyethylene, propylene-ethylene copolymer, combinations thereof, and the like can be used.
  • the polyolefin resin has a melt-flow index of about 1 to about 50 g/10 min, for example, about 5 to about 30 g/10 min.
  • the thermoplastic resin composition may have excellent mechanical strength, molding processability, and the like.
  • the aromatic vinyl-based resin according to an embodiment of the present invention can improve mechanical properties, processability, and appearance characteristics of the thermoplastic resin composition, and a conventional aromatic vinyl-based resin can be used.
  • a conventional aromatic vinyl-based resin can be used.
  • at least one of an aromatic vinyl-based polymer resin, an aromatic vinyl-based copolymer resin, a rubber-modified polystyrene resin, and a rubber-modified aromatic vinyl-based copolymer resin may be used.
  • a rubber-modified polystyrene resin, a rubber-modified aromatic vinyl-based copolymer resin, a combination thereof, and the like can be used.
  • the rubber-modified polystyrene resin of the present invention is prepared by polymerizing a rubbery polymer and an aromatic vinyl monomer, and a general impact-resistant polystyrene (HIPS) resin may be used.
  • HIPS general impact-resistant polystyrene
  • the rubbery polymer includes a diene-based rubber such as polybutadiene and poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene-based rubber, isoprene rubber, and alkyl (meth)acryl having 2 to 10 carbon atoms.
  • Late rubber a copolymer of an alkyl (meth)acrylate having 2 to 10 carbon atoms and styrene, an ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in mixture of two or more.
  • a diene-based rubber, a (meth)acrylate rubber, etc. may be used, and specifically, a butadiene-based rubber, a butyl acrylate rubber, or the like may be used.
  • the rubbery polymer (rubber particles) may have an average particle size of about 0.05 to about 6 ⁇ m, for example, about 0.15 to about 4 ⁇ m, specifically about 0.25 to about 3.5 ⁇ m.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state.
  • the rubbery polymer latex is filtered through a mesh to remove coagulation generated during polymerization of the rubbery polymer, and a solution of 0.5 g of latex and 30 ml of distilled water is poured into a 1,000 ml flask and distilled water is filled to prepare a sample. , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size analyzer (malvern, nano-zs).
  • a light scattering particle size analyzer malvern, nano-zs
  • the content of the rubbery polymer may be from about 3 to about 30% by weight, for example from about 5 to about 15% by weight, based on 100% by weight of the total rubber-modified polystyrene resin.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the aromatic vinyl-based monomer includes styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene.
  • vinyl naphthalene, and the like can be exemplified. These can be used individually or in mixture of 2 or more types.
  • the content of the aromatic vinyl-based monomer may be about 70 to about 97% by weight, for example, about 85 to about 95% by weight of the total 100% by weight of the rubber-modified polystyrene resin. In the above range, molding processability, impact resistance, and appearance characteristics of the thermoplastic resin composition may be excellent.
  • the rubber-modified polystyrene resin is acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, N- during polymerization of the rubber-modified polystyrene resin in order to impart properties such as chemical resistance, processability, and heat resistance to the thermoplastic resin composition. It can polymerize by adding monomers, such as a substituted maleimide. In this case, the amount of the monomer added may be about 40% by weight or less based on 100% by weight of the total rubber-modified polystyrene resin. Chemical resistance, processability, heat resistance, etc. can be imparted to the thermoplastic resin composition without lowering other physical properties within the above range.
  • the rubber-modified polystyrene resin may be polymerized by thermal polymerization without the presence of an initiator, or may be polymerized in the presence of an initiator.
  • an initiator at least one of a peroxide-based initiator such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and an azo-based initiator such as azobis isobutyronitrile may be exemplified.
  • the rubber-modified polystyrene resin may be prepared by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.
  • the rubber-modified aromatic vinyl-based copolymer resin of the present invention may include (a1) a rubber-modified vinyl-based graft copolymer and (a2) an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer according to an embodiment of the present invention may be graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer.
  • the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture containing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer to a rubbery polymer. Graft polymerization may be performed by further including a monomer that imparts heat resistance. The polymerization may be performed by a known polymerization method such as emulsion polymerization or suspension polymerization.
  • the rubber-modified vinyl-based graft copolymer may form a core (rubber polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.
  • the rubbery polymer includes a diene rubber such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene rubber, isoprene rubber, carbon number 2 to alkyl (meth)acrylate rubber of 10, a copolymer of alkyl (meth)acrylate and styrene having 2 to 10 carbon atoms, 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.
  • a diene rubber such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-buta
  • 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 about 20 to about 70% by weight, for example, about 25 to about 60% by weight, of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic The content of the vinyl-based monomer and the cyanide-based monomer) may be about 30 to about 80% by weight, for example, about 40 to about 75% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the aromatic vinyl-based monomer may be graft copolymerized to the rubber polymer, and may include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. can be illustrated. These can be used individually or in mixture of 2 or more types.
  • the content of the aromatic vinyl-based monomer may be about 10 to about 90% by weight, for example, about 40 to about 90% by weight of 100% by weight of the monomer mixture. In the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.
  • the vinyl cyanide-based monomer is copolymerizable with the aromatic vinyl-based monomer, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like.
  • acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like. can be exemplified. These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide monomer may be about 10 to about 90 wt%, for example, about 10 to about 60 wt%, based on 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.
  • the monomer for imparting the processability and heat resistance may include (meth)acrylic acid, maleic anhydride, N-substituted maleimide, and the like, but is not limited thereto.
  • the content thereof may be 15% by weight or less, for example, about 0.1 to about 10% by weight based on 100% by weight of the monomer mixture.
  • processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • the rubber-modified vinyl-based graft copolymer (a1) is included in an amount of about 10 to about 50% by weight, for example, about 15 to about 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin.
  • the thermoplastic resin composition may have excellent impact resistance, molding processability, and the like.
  • the aromatic vinyl-based copolymer resin according to an embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified aromatic vinyl-based copolymer resin.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, etc., and then polymerizing it, and the polymerization is a known polymerization such as emulsion polymerization, suspension polymerization, and bulk polymerization. method can be carried out.
  • the aromatic vinyl-based monomer includes styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, and dibromostyrene. , vinyl naphthalene, etc. can be used. These may be applied alone or in mixture of two or more.
  • the content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example, about 30 to about 80% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, appearance characteristics, and the like.
  • the vinyl cyanide-based monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like. These can be used individually or in mixture of 2 or more types. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide-based monomer may be about 10 to about 80 wt%, for example, about 20 to about 70 wt%, based on 100 wt% of the total aromatic vinyl-based copolymer resin. In the above range, the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, and appearance.
  • the aromatic vinyl-based copolymer resin may be polymerized by further including a monomer for imparting processability and heat resistance to the monomer mixture.
  • a monomer for imparting processability and heat resistance (meth)acrylic acid, N-substituted maleimide, and the like may be exemplified, but the present invention is not limited thereto.
  • the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight based on 100% by weight of the monomer mixture.
  • processability and heat resistance may be imparted to the thermoplastic resin composition without deterioration of other physical properties.
  • the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw) of about 10,000 to about 300,000 g/mol, for example, about 15,000 to about 150,000 g/mol, measured by gel permeation chromatography (GPC).
  • Mw weight average molecular weight
  • the thermoplastic resin composition may have excellent mechanical strength, molding processability, and the like.
  • the aromatic vinyl-based copolymer resin (a2) is from about 50 to about 90% by weight, for example, from about 55 to about 85% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin (A) may be included.
  • the thermoplastic resin composition may have excellent impact resistance, molding processability, and appearance characteristics.
  • the melamine polyphosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine phosphate and piperazine pyrophosphate, so that even with a small content, flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition are improved.
  • melamine polyphosphate used in conventional flame-retardant thermoplastic resin compositions may be used.
  • the melamine polyphosphate may have a polymerization degree of about 100 to about 600, for example, about 200 to about 500, and a weight average molecular weight of about 20,000 to about 110,000 g/mol.
  • the melamine polyphosphate may have a weight loss measured by TGA (Thermal Gravimetric Analysis, heating rate 20° C./min in air) of about 2% or less at 260° C., and at 300° C. , may be about 3% or less.
  • TGA Thermal Gravimetric Analysis, heating rate 20° C./min in air
  • the melamine polyphosphate may be included in an amount of about 4 to about 10 parts by weight, for example, about 5 to about 9 parts by weight, based on 100 parts by weight of the thermoplastic resin.
  • the content of the melamine polyphosphate is less than about 4 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a risk that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 10 parts by weight, the resistance of the thermoplastic resin composition There exists a possibility that impact property etc. may fall.
  • the melamine phosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine polyphosphate and piperazine pyrophosphate, so that even with a small content, flame retardancy, impact resistance, and appearance characteristics of the thermoplastic resin composition are improved.
  • melamine phosphate (monomer) used in conventional flame-retardant thermoplastic resin compositions can be used.
  • the melamine phosphate may be included in an amount of about 2 to about 7 parts by weight, for example, about 3 to about 6 parts by weight based on about 100 parts by weight of the thermoplastic resin.
  • the content of the melamine phosphate is less than about 2 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a fear that the flame retardancy of the thermoplastic resin composition may be lowered, and when it exceeds about 7 parts by weight, the (extrusion) of the thermoplastic resin composition ), there is a possibility that the workability may be deteriorated.
  • the weight ratio (B:C) of the melamine polyphosphate (B) and the melamine phosphate (C) is from about 1:1 to about 4:1, for example from about 1:1 to about 3:1.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and the like.
  • Piperazine pyrophosphate of the present invention is applied in the form of a mixture having a specific particle size and particle size distribution together with melamine polyphosphate and melamine phosphate, so that char is easy to form even with a small amount, and the composition of the thermoplastic resin composition
  • piperazine pyrophosphate used in conventional flame-retardant thermoplastic resin compositions may be used.
  • the piperazine pyrophosphate may be included in an amount of about 10 to about 20 parts by weight, for example, about 12 to about 18 parts by weight, based on about 100 parts by weight of the thermoplastic resin.
  • the content of the piperazine pyrophosphate is less than about 10 parts by weight based on about 100 parts by weight of the thermoplastic resin, there is a risk that the flame retardancy of the thermoplastic resin composition may be deteriorated, and when it exceeds about 20 parts by weight, the amount of the thermoplastic resin composition There exists a possibility that impact resistance etc. may fall.
  • the weight ratio (B:D) of the melamine polyphosphate (B) and the piperazine pyrophosphate (D) is from about 0.2:1 to about 0.8:1, for example from about 0.3:1 to about 0.7:1.
  • the thermoplastic resin composition may have excellent flame retardancy, impact resistance, and appearance characteristics.
  • thermoplastic resin composition of the present invention may be applied after mixing the melamine polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate (D), pulverizing and separating to have a specific particle size and particle size distribution.
  • the mixture containing the melamine polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate (D) is a particle size analysis method (of the particle size analysis method by laser diffraction and scattering, the dry method Mastersizer 2000E series (Malvern) equipment
  • the average particle diameter D50 by the measurement using) is about 6 ⁇ m or less, for example, about 2 to about 5 ⁇ m
  • the particle diameter D90 of 90% of the cumulative frequency is about 11 ⁇ m or less, for example, about 5 to about 10 ⁇ m. have.
  • the average particle diameter D50 of the mixture exceeds about 5 ⁇ m, there is a fear that the appearance properties of the thermoplastic resin composition may be deteriorated, and when the D90 of the mixture exceeds about 11 ⁇ m, the appearance properties of the thermoplastic resin composition, etc. There is a risk of deterioration.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additives may include, but are not limited to, impact modifiers, antioxidants, anti-drip agents, lubricants, release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof.
  • its content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.
  • thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets that are melt-extruded at about 180 to about 250° C., for example, about 200 to about 230° C., by mixing the above components and using a conventional twin-screw extruder.
  • thermoplastic resin composition may have a flame retardancy (V-test) of 1.5 mm thick specimen measured according to UL-94 standards of V-0 or more.
  • the thermoplastic resin composition has a surface roughness (Ra) of about 2 to about 15 ⁇ m, for example, using a surface profiler (manufacturer: Kosaka laboratory, device name: Surfcorder SE3500) For example, it may be about 2 to about 10 ⁇ m.
  • the thermoplastic resin composition has a notch Izod impact strength of about 3 to about 10 kgf ⁇ cm/cm, for example about 4 to about 9 kgf ⁇ of a 1/8′′ thick specimen measured according to ASTM D256. cm/cm.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be prepared in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the art to which the present invention pertains.
  • the molded article is eco-friendly because it does not apply a halogen-based flame retardant, and has excellent flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and balance of these properties, so it is useful as interior and exterior materials for electrical and electronic products.
  • g-ABS in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) was graft-copolymerized on 45 wt% of butadiene rubber having a Z-average of 310 nm was used.
  • a SAN resin (weight average molecular weight: 130,000 g/mol) in which 75% by weight of styrene and 25% by weight of acrylonitrile were polymerized was used.
  • HIPS Impact-resistant polystyrene
  • Piperazine pyrophosphate (manufacturer: Henan Chemical) was used.
  • the polyphosphate (B), melamine phosphate (C) and piperazine pyrophosphate were mixed in the amounts as shown in Tables 1, 2 and 3 below, and then pulverized and separated to have the following mixtures D50 and D90 (unit: ⁇ m)
  • Pellets were prepared by treatment, addition to the thermoplastic resin (A), and extrusion at 200°C to 230°C.
  • a specimen was prepared.
  • the prepared specimens were evaluated for physical properties by the following method, and the results are shown in Tables 1, 2 and 3 below.
  • V-test In accordance with UL-94 standards, the flame retardancy of a 1.5 mm thick specimen was measured.
  • Notched Izod impact strength (unit: kgf ⁇ cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/8′′ thick specimen was measured.
  • thermoplastic resin compositions (Examples 1 to 11) of the present invention are excellent in flame retardancy, impact resistance, appearance characteristics, (extrusion) processability, and the like.
  • thermoplastic resin composition when the melamine polyphosphate 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 the melamine polyphosphate is applied in excess of the content range of the present invention (Comparative Example 2), it can be seen that the impact resistance of the thermoplastic resin composition is lowered, and when applying the oligomeric bisphenol-A diphosphate (B2) instead of the melamine polyphosphate (Comparative Example 3), the thermoplastic resin composition It can be seen that the flame retardancy is reduced.

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

Abstract

La présente invention concerne une composition de résine thermoplastique comprenant : environ 100 parties en poids d'une résine thermoplastique ; environ 4 à environ 10 parties en poids de polyphosphate de mélamine ; environ 2 à environ 7 parties en poids de phosphate de mélamine ; et environ 10 à environ 20 parties en poids de pyrophosphate de pipérazine, un mélange associant le polyphosphate de mélamine, le phosphate de mélamine et le pyrophosphate de pipérazine étant caractérisé en ce qu'il présente, comme mesuré par un procédé d'analyse des tailles de particule, un diamètre de particule moyen D50 égal ou inférieur à environ 6 µm et un diamètre de particule D90, correspondant à 90 % de la teneur totale, égal ou inférieur à environ 11 µm. Cette composition de résine thermoplastique présente un remarquable caractère ignifuge, une excellente résistance aux chocs, de très belles caractéristiques en termes d'aspect extérieur, une très bonne aptitude au traitement et similaire.
PCT/KR2021/002578 2020-03-30 2021-03-02 Composition de résine thermoplastique et article moulé formé à partir de celle-ci WO2021201444A1 (fr)

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CN115433399A (zh) * 2022-10-09 2022-12-06 廊坊北化高分子材料有限公司 一种阻燃防水热塑性弹性体材料及制备方法及防水卷材

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KR101162260B1 (ko) * 2004-02-24 2012-07-04 가부시키가이샤 아데카 유동성이 개선된 난연제 조성물, 난연성 수지 조성물 및 그성형품
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CN114316424B (zh) * 2021-11-22 2023-08-25 金发科技股份有限公司 一种透明耐候pp/ps复合材料及其制备方法
CN115433399A (zh) * 2022-10-09 2022-12-06 廊坊北化高分子材料有限公司 一种阻燃防水热塑性弹性体材料及制备方法及防水卷材
CN115433399B (zh) * 2022-10-09 2024-01-30 廊坊北化高分子材料有限公司 一种阻燃防水热塑性弹性体材料及制备方法及防水卷材

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