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WO2019132572A1 - Composition de résine thermoplastique et article moulé fabriqué avec celle-ci - Google Patents

Composition de résine thermoplastique et article moulé fabriqué avec celle-ci Download PDF

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Publication number
WO2019132572A1
WO2019132572A1 PCT/KR2018/016835 KR2018016835W WO2019132572A1 WO 2019132572 A1 WO2019132572 A1 WO 2019132572A1 KR 2018016835 W KR2018016835 W KR 2018016835W WO 2019132572 A1 WO2019132572 A1 WO 2019132572A1
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WIPO (PCT)
Prior art keywords
resin composition
thermoplastic resin
weight
rubber
aromatic vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2018/016835
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English (en)
Korean (ko)
Inventor
하동인
신승식
강태곤
이승갑
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lotte Advanced Materials Co Ltd
Original Assignee
Lotte Advanced Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180164256A external-priority patent/KR102059754B1/ko
Application filed by Lotte Advanced Materials Co Ltd filed Critical Lotte Advanced Materials Co Ltd
Priority to US16/770,672 priority Critical patent/US11702540B2/en
Priority to EP18896169.2A priority patent/EP3733772B1/fr
Publication of WO2019132572A1 publication Critical patent/WO2019132572A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • 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—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent adhesion to metal, rigidity, flame retardancy, fluidity, appearance and the like, and a molded article produced therefrom.
  • thermoplastic resin composition has a lower specific gravity than glass and metal and is excellent in properties such as moldability and impact resistance and is useful for a housing for an electric / electronic product, an automobile interior / exterior material, and a building exterior material.
  • plastic products using thermoplastic resins are rapidly replacing existing glass and metal areas.
  • thermoplastic resin compositions a PC / ABS-based thermoplastic resin composition obtained by mixing a rubber-modified aromatic vinyl copolymer resin such as an acrylonitrile-butadiene-styrene (ABS) copolymer resin with a polycarbonate (PC)
  • ABS acrylonitrile-butadiene-styrene
  • PC polycarbonate
  • thermoplastic resin composition when such a thermoplastic resin composition is excellent in adhesion to metals, it can be applied to various applications including exterior materials for portable devices. Therefore, research for improving adhesion with metals is required, and improvements in rigidity and flame retardancy Inorganic fillers such as glass fibers, talc and wollastonite, flame retardants and the like.
  • thermoplastic resin composition to which the inorganic filler such as glass fiber is applied has a disadvantage in that the fluidity and the elongation rate may be lowered, and there is a fear that the glass fiber or the like may protrude and it is difficult to realize high appearance characteristics.
  • thermoplastic resin composition having excellent adhesion to metals, rigidity, flame retardancy, fluidity, appearance, and the like.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in adhesion to metals, rigidity, flame retardance, flowability, appearance and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition is a polycarbonate resin; Rubber-modified vinyl-based graft copolymer; An average particle size of from about 400 to about 1,500 nm; An aromatic vinyl-based copolymer resin; Phosphorus flame retardant; Talc; Wollastonite; Gum polymers in which maleic anhydride is graft polymerized; And black pigments.
  • the thermoplastic resin composition comprises about 100 parts by weight of the polycarbonate resin; About 1 to about 10 parts by weight of the rubber-modified vinyl-based graft copolymer; About 0.5 to about 5 parts by weight of the above-mentioned light -bonding rubbery polymer; About 3 to about 20 parts by weight of the aromatic vinyl-based copolymer resin; About 10 to 30 parts by weight of the phosphorus flame retardant; About 3 to about 25 parts by weight of the talc; About 5 to about 20 parts by weight of the wollastonite; From about 0.01 to about 5 parts by weight of a gum polymer graft-polymerized with maleic anhydride; And from about 0.05 to about 3 parts by weight of the black pigment.
  • the large-diameter gum polymer and the aromatic vinyl-based copolymer resin comprise a rubber polymer having a viscosity of about 150 cps or more in a 5 wt% styrene solution, an aromatic vinyl monomer,
  • a rubber-modified aromatic vinyl copolymer resin a mixture of an aromatic vinyl polymer having a large average particle size of about 400 to about 1,500 nm and a continuous-phase aromatic vinyl copolymer resin
  • a copolymerizable monomer May be included in the thermoplastic resin composition.
  • the aromatic vinyl-based copolymer resin may be an aromatic vinyl-based monomer and a polymer of a monomer copolymerizable with the aromatic vinyl-based monomer.
  • the phosphorus flame retardant may include at least one of a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound and a phosphazene compound.
  • the weight ratio of the talc and wollastonite may be about 1: about 0.3 to about 1: about 2.
  • the average particle size of the black pigment may be about 10 to about 24 nm.
  • thermoplastic resin composition according to any one of the above 1 to 9, wherein the thermoplastic resin composition is a thermoplastic resin composition, wherein the injection specimen having a size of 100 mm x 25 mm x 2 mm is adhered to an identical size metal specimen so as to overlap a 25 mm x 25 mm area with an adhesive according to ASTM D1002 a one after heating the sealing region for 120 seconds at 80 °C then, may be after aging for 5 minutes at room temperature, the measured adhesion strength (shear strength) of about 140 to about 300 kgf / cm 2.
  • thermoplastic resin composition may have a flame retardancy of V-1 or more of 1.0 mm thick specimen measured by UL-94 vertical test method.
  • thermoplastic resin composition according to any one of the above 1-11, wherein the thermoplastic resin composition has a melt flow index (MI) of about 30 to about 60 g / 10 measured at 220 DEG C and 5 kgf according to ASTM D1238 Lt; / RTI >
  • MI melt flow index
  • Another aspect of the invention relates to a molded article.
  • the molded article is formed from the thermoplastic resin composition according to any one of 1 to 12 above.
  • molded article according to any one of the above 13, wherein the molded article is a plastic member of an electronic device housing including a metal frame and a plastic member abutting at least one surface of the metal frame.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in adhesion to metals, rigidity, flame retardancy, fluidity, appearance and the like, and a molded article formed therefrom.
  • FIG. 1 schematically shows a cross-section of an electronic device housing according to an embodiment of the present invention.
  • thermoplastic resin composition comprises (A) a polycarbonate resin; (B) a rubber-modified vinyl-based graft copolymer; (C) an adducted rubbery polymer; (D) an aromatic vinyl-based copolymer resin; (E) phosphorus flame retardant; (F) talc; (G) wollastonite; (H) a rubbery polymer graft-polymerized with maleic anhydride; And (I) a black pigment.
  • a polycarbonate resin used for a conventional thermoplastic resin composition may be used.
  • an aromatic polycarbonate resin prepared by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, or carbonic acid diester can be used.
  • diphenols include 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) Propane, and the like, but the present invention is not limited thereto.
  • (4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 1,1- ) Cyclohexane can be used.
  • 2,2-bis (4-hydroxyphenyl) propane called bisphenol-A can be used.
  • the polycarbonate resin may be branched and may contain, for example, from about 0.05 to about 2 mol% trifunctional or more polyfunctional compounds per total of diphenols used in the polymerization, , Or a compound having a trivalent or higher phenol group may be added to the polycarbonate resin.
  • the polycarbonate resin may be used in the form of a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof.
  • the polycarbonate resin may be partially or wholly substituted with an aromatic polyester-carbonate resin obtained by polymerization reaction in the presence of an ester precursor such as a bifunctional carboxylic acid.
  • the polycarbonate resin may have a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 50,000 g / mol, such as from about 15,000 to about 40,000 g / mol.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the polycarbonate resin may have a melt flow index (MI) of about 10 to about 110 g / 10 min, measured at 300 ° C under a load of 1.2 kg, according to ISO 1133.
  • MI melt flow index
  • the polycarbonate resin may be a mixture of two or more polycarbonate resins having different melt flow indexes.
  • the rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention can improve the impact resistance, chemical resistance, and the like of the thermoplastic resin composition.
  • the rubber-modified vinyl-based graft copolymer can be obtained by copolymerizing an aromatic vinyl monomer and a monomer containing a vinyl cyanide monomer The mixture may be graft polymerized.
  • the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer to the rubber-like polymer, and if necessary, And a monomer capable of imparting heat resistance can be further graft-polymerized.
  • the polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. Further, the rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer)-shell (copolymer of a monomer mixture).
  • the rubbery polymer may be a diene rubber (rubbery polymer) such as polybutadiene, poly (styrene-butadiene) or poly (acrylonitrile-butadiene), saturated rubber hydrogenated to the diene rubber, isoprene rubber ,
  • An acrylic rubber (rubbery polymer) such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM), but the present invention is not limited thereto.
  • a diene rubber, an acrylic rubber, or the like can be used.
  • polybutadiene, polybutyl acrylate and the like can be used.
  • the rubbery polymer (rubber particles) may have an average particle size (z-average) as measured by a particle size analyzer of from about 100 to about 600 nm, such as from about 300 to about 500 nm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state.
  • a rubbery polymer latex was smeared on a mesh to remove coagulum formed during the polymerization of the rubbery polymer, and a solution prepared by mixing 0.5 g of latex and 30 ml of distilled water was poured into a 1,000 ml flask and filled with distilled water 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 20 to about 70 weight percent, such as from about 30 to about 65 weight percent, of the total 100 weight percent of the rubber modified vinyl based graft copolymer, and the monomer mixture Vinyl monomers and vinyl cyanide monomers) may be from about 30 to about 80% by weight, for example from about 35 to about 70% by weight, based on 100% by weight of the total 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 with the rubbery polymer, and may be selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more.
  • the content of the aromatic vinyl monomer may be about 10 to about 90 wt%, for example about 40 to about 90 wt%, based on 100 wt% of the monomer mixture. Within the above range, the processability and impact resistance of the thermoplastic resin composition can be excellent.
  • the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, For example. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used.
  • the content of the vinyl cyanide monomer may be about 10 to about 90% by weight, for example about 10 to about 60% by weight, based on 100% by weight of the monomer mixture.
  • the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.
  • examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like.
  • 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.
  • the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.
  • Examples of the rubber-modified vinyl-based graft copolymer include acrylonitrile-butadiene-styrene graft copolymer (g-ABS), acrylate-styrene-acrylonitrile graft copolymer (g-ASA) For example.
  • g-ABS acrylonitrile-butadiene-styrene graft copolymer
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • the rubber-modified vinyl-based graft copolymer may be included in an amount of about 1 to about 10 parts by weight, for example, about 3 to about 7 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. In the above range, the appearance characteristics, impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent.
  • the bulky rubbery polymer according to one embodiment of the present invention has an average particle size (z-average), as measured by a particle size analyzer, of from about 400 to about 1,500 nm, such as from about 500 to about 1,000 nm, 650 nm, it is possible to improve the adhesive strength, rigidity, appearance, and the like of the thermoplastic resin composition to a metal.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state.
  • a rubbery polymer latex was smeared on a mesh to remove coagulum formed during the polymerization of the rubbery polymer, and a solution prepared by mixing 0.5 g of latex and 30 ml of distilled water was poured into a 1,000 ml flask and filled with distilled water 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 average particle size of the above-mentioned highly-gelled rubbery polymer is less than about 400 nm, adhesion of the thermoplastic resin composition to the metal, appearance (low light-curing property) and the like may be lowered.
  • the average particle size is more than about 1,500 nm, The flame retardancy and appearance characteristics of the composition may be deteriorated.
  • the above-mentioned charged rubbery polymer (C) and the aromatic vinyl-based copolymer resin (D) are a mixture of a rubbery polymer having a viscosity of about 150 cps or more in a 5 wt% styrene solution, an aromatic vinyl- A rubber-modified aromatic vinyl copolymer resin (a dispersed phase having an average particle size of about 400 to about 1,500 nm and having an average particle size of about 400 to about 1,500 nm and a continuous-phase aromatic vinyl copolymer resin (D) prepared by continuous solution polymerization of a copolymerizable monomer )) May be contained in the thermoplastic resin composition.
  • a polymerization initiator and a molecular weight regulator are mixed in a mixed solution in which the rubbery polymer, the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer and the solvent are mixed, ; Introducing the reaction solution into a first reactor to polymerize at a conversion of about 30 to about 40%; And polymerizing the polymerized polymer in the first reactor into a second reactor to obtain a polymer having a conversion of about 70 to about 80%.
  • the mixed solution comprises about 3 to about 15 weight percent of the rubbery polymer, about 50 to about 85 weight percent of the aromatic vinyl-based monomer, and about 5 to about 30 weight percent of a monomer copolymerizable with the aromatic vinyl- . ≪ / RTI >
  • the rubbery polymer contained in the mixed solution may be a diene rubber (rubbery polymer) such as polybutadiene, poly (styrene-butadiene) or poly (acrylonitrile-butadiene) But are not limited to, acrylate rubber (rubber polymer) such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more.
  • a diene rubber can be used, and specifically, a polybutadiene rubber can be used.
  • the rubbery polymer may have a viscosity in a 5 wt% styrene solution of about 150 cps or more, such as about 150 to about 300 cps, specifically about 160 to about 200 cps. In the styrene solution viscosity range, a large amount of the gum polymer can be prepared.
  • the aromatic vinyl-based monomer contained in the mixed solution is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, , Dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more.
  • examples of the monomer copolymerizable with the aromatic vinyl monomer contained in the mixed solution include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile , And fumaronitrile. These monomers may be used singly or in combination of two or more.
  • the content of the aromatic vinyl-based monomer is about 20 to about 90% by weight, for example about 30 to about 80% by weight, of the aromatic vinyl-based monomer and 100%
  • the content of the monomer copolymerizable with the aromatic vinyl monomer is from about 10 to about 80% by weight, for example, from about 20 to about 80% by weight, based on 100% by weight of the total of the aromatic vinyl monomer and the monomer copolymerizable with the aromatic vinyl monomer About 70% by weight.
  • an aromatic organic solvent may be used as the solvent.
  • ethylbenzene, xylene, toluene, etc. may be used, and these may be used alone or in combination.
  • the polymerization initiator preferably has a half life of not more than 10 minutes at the polymerization temperature of the reactor, and examples thereof include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, Bis (4-di-t-butylperoxycyclohexane) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxycyclohexane, -Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy laurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) Butyl peroxybenzoate, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, A radical initiator such as 2,2-bis (t-butylperoxy)
  • the amount of the polymerization initiator to be used may be about 0.007 to about 0.07 part by weight, for example, about 0.01 to about 0.05 part by weight based on about 100 parts by weight of the mixed solution. Within the above range, deterioration of the appearance characteristics due to the residual polymerization initiator and the like can be reduced.
  • alkylmercaptan such as t-dodecylmercaptan, n-dodecylmercaptan and the like may be used as the molecular weight modifier.
  • the amount of the molecular weight regulator to be used may be about 0.02 to about 1 part by weight, for example, about 0.03 to about 0.5 part by weight, relative to about 100 parts by weight of the mixed solution.
  • the continuous solution polymerization is preferably carried out by circulating the refrigerant through a jacket, a coil, or the like, because a heat generation due to the polymerization reaction may occur in the reactor.
  • the polymerization initiator and the reaction solution to which the molecular weight regulator is added may be added to the first reactor to polymerize at a conversion rate of about 30 to about 40%, for example, about 32 to about 38%. Stable polymerization can be carried out without excessive load on the agitator within the above range.
  • the reaction temperature in the first reactor may be from about 60 to about 150 ⁇ , such as from about 70 to about 130 ⁇ .
  • the reaction temperature may be varied depending on the reactor, the stirring speed, the kind of the polymerization initiator, and the like.
  • the stirring rate in the first reactor may be from about 140 to about 160 rpm.
  • the stirring speed may be changed according to the size of the reactor, the kind of the polymerization initiator, the reaction temperature, and the like.
  • the polymerized polymer in the first reactor is introduced into a second reactor and polymerization can be carried out until the conversion is from about 70 to about 80%. In the above range, a bulky rubbery polymer can be prepared.
  • the reaction temperature in the second reactor may be from about 80 to about 170 ⁇ , such as from about 120 to about 160 ⁇ .
  • the reaction temperature may be varied depending on the reactor, the stirring speed, the kind of the polymerization initiator, and the like.
  • the stirring rate in the second reactor may be from about 75 to about 85 rpm.
  • the stirring speed may be changed according to the size of the reactor, the kind of the polymerization initiator, the reaction temperature, and the like.
  • the continuous solution polymerization may further include devolatilizing the polymerized polymer in the second reactor to remove unreacted monomers and residual solvent.
  • the devolatilization process may be performed using a defolouring process.
  • the devolatilizing process may be performed using a single devolatilization, and in another embodiment, the devolatilizing process may remove remaining unreacted material in the first vertically coupled devolatilizer and the second devolatilization.
  • the residual monomer content may be about 1,500 ppm or less, for example, about 1,000 ppm or less, specifically about 700 ppm or less.
  • a fall-stranding DEVO type is suitable for the deflection (demagnetizing device).
  • the Paul-Stranding type devolatilizer is designed so that the angle of the cone is designed to minimize residence time and can be effectively transferred to the lower gear pump.
  • first devolatilizer and the second devolatilization when used in combination, they can be vertically connected to the upper and lower sides to minimize the connection line between the DEVOs.
  • a control valve or a regulator is installed in the first dehydration (DV-1) so that the pressure can be adjusted.
  • the first devolatilizer can be operated at a pressure of from about 100 to about 600 torr, such as from about 200 to about 500 torr, at a temperature of from about 160 to about 240 ⁇ , such as from about 180 to about 220 ⁇ , Min or less. In this range, impurities such as residual monomers can be reduced and productivity can be improved. Also, the second devolatilizer can be operated at a pressure of about 1 to about 50 torr, at a temperature of about 210 to about 250 DEG C for a residence time of about 10 minutes or less, for example, about 5 minutes or less. The color of the rubber-modified aromatic vinyl-based copolymer resin produced in the above range may be excellent.
  • the aromatic vinyl-based copolymer resin (D) of the rubber-modified aromatic vinyl-based copolymer resin is a copolymer of a monomer mixture comprising a monomer copolymerizable with the aromatic vinyl-based monomer, such as an aromatic vinyl monomer and a vinyl cyanide monomer Polymer and may have a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 300,000 g / mol, such as from about 15,000 to about 150,000 g / mol.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the thermoplastic resin composition may have excellent mechanical strength and moldability.
  • the bulky rubbery polymer (C) may be included in about 0.5 to about 5 parts by weight, for example about 1 to about 3 parts by weight, relative to about 100 parts by weight of the polycarbonate resin.
  • the adhesive strength, rigidity, appearance, impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition with the metal can be excellent.
  • the aromatic vinyl-based copolymer resin (D) may be included in an amount of about 3 to about 20 parts by weight, for example about 7 to about 15 parts by weight, per 100 parts by weight of the polycarbonate resin.
  • the thermoplastic resin composition may have excellent appearance characteristics, fluidity (molding processability), and the like.
  • the phosphorus-based flame retardant according to one embodiment of the present invention may be a phosphorus-based flame retardant used in a conventional flame retardant thermoplastic resin composition.
  • a phosphorus flame retardant such as a phosphate compound, a phosphonate compound, a phosphinate compound, a phosphine oxide compound, a phosphazene compound, Can be used. These may be used alone or in combination of two or more.
  • the phosphorus flame retardant may include an aromatic phosphate ester compound represented by the following formula (1).
  • R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, a C 6 -C 20 (C 6 -C 20) aryl group, or a C 6 -C 20 aryl
  • R 3 is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group such as resorcinol, hydroquinone, bisphenol-A, and bisphenol- And n is an integer of 0 to 10, for example, 0 to 4.
  • the aromatic phosphoric acid ester compound represented by the formula (1) may be a diaryl phosphate such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, triazylenyl phosphate, tri (2,6-dimethyl (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, tri (2,4,6-trimethylphenyl) phosphate, , Bisphenol-A diphosphate, bisphenol-A bis (diphenylphosphate), resorcinol bis (diphenylphosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinolbis (2,4-ditertiary butylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone
  • the phosphorus flame retardant may be included in from about 10 to about 30 parts by weight, for example from about 15 to about 25 parts by weight, based on about 100 parts by weight of the polycarbonate resin. Within the above range, the flame retardancy, thermal stability, fluidity and the like of the thermoplastic resin composition can be excellent.
  • the talc according to one embodiment of the present invention can improve the fluidity, rigidity, (thin film) flame retardancy, appearance, balance of physical properties, etc. of the thermoplastic resin composition together with wollastonite.
  • the talc may be a conventional plate-shaped talc.
  • the average particle size of the talc may be from about 2 to about 10 microns, for example from about 3 to about 7 microns.
  • the thermoplastic resin composition can be excellent in rigidity, dimensional stability, appearance, and the like.
  • the talc may have a bulk density of from about 0.3 to about 1.0 g / cm 3 , such as from about 0.4 to about 0.8 g / cm 3 .
  • the thermoplastic resin composition can be excellent in rigidity, dimensional stability, appearance, and the like.
  • the talc may comprise from about 3 to about 25 parts by weight, for example from about 8 to about 20 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the flowability, dimensional stability, rigidity, flame retardancy, etc. of the thermoplastic resin composition can be excellent in the above range.
  • the wollastonite according to one embodiment of the present invention can improve the flowability, stiffness, (thin film) flame retardancy, appearance, and physical properties of the thermoplastic resin composition, as well as talc.
  • the wollastonite is a calcium-based mineral
  • the white acicular minerals at least a part of the surface of which is subjected to a hydrophobic surface treatment, may be used.
  • the hydrophobic surface treatment may be, for example, coating of wollastonite with an olefin-based, epoxy-based, silane-based material or the like, but is not limited thereto.
  • the wollastonite has an average height (diameter) of from about 5 to about 10 microns, such as from about 6 to about 9 microns, and an aspect ratio of from about 1: about 7 to about 1: about 9 Lt; / RTI > Within the above range, the thermoplastic resin composition may have excellent rigidity, dimensional stability, impact resistance, and the like.
  • the wollastonite may have a bulk density of from about 0.3 to about 0.6 g / cm 3 , such as from about 0.4 to about 0.5 g / cm 3 .
  • the stiffness and dimensional stability of the thermoplastic resin composition in the above range can be excellent.
  • the wollastonite may be included in about 5 to about 20 parts by weight, for example about 7 to about 15 parts by weight, relative to about 100 parts by weight of the polycarbonate resin.
  • the flowability, dimensional stability, rigidity, flame retardancy, etc. of the thermoplastic resin composition can be excellent in the above range.
  • the weight ratio of talc (F) to wollastonite (G) (F) :( G) is from about 1: about 0.1 to about 1: about 5, such as from about 1: : It can be about 2 days. Within the above range, dimensional stability and rigidity of the thermoplastic resin composition can be excellent.
  • the rubber-like polymer in which the maleic anhydride is graft-polymerized according to one embodiment of the present invention improves the compatibility, dispersibility, etc. of the constituent components of the thermoplastic resin composition to improve the fluidity, impact resistance, thermal stability, dimensional stability, (MAH, maleic anhydride) may be graft-polymerized on a rubbery polymer (such as a copolymer of an olefin and / or an aromatic vinyl monomer) and the like.
  • a rubbery polymer such as a copolymer of an olefin and / or an aromatic vinyl monomer
  • the rubbery polymer in which the maleic anhydride is graft-polymerized includes ethylene-octene rubber (MAH-g-EOR) in which maleic anhydride is graft polymerized, ethylene-butene rubber in which maleic anhydride is graft- (MAH-g-EBR), an ethylene-propylene-diene monomer terpolymer (MAH-g-EPDM) in which maleic anhydride is graft-polymerized, a styrene-ethylene-butadiene-styrene copolymer in which maleic anhydride is graft polymerized -g-SEBS), graft-polymerized maleic anhydride (MAH-g-PP), and maleic anhydride graft-polymerized polyethylene (MAH-g-PE).
  • MAH-g-EOR ethylene-octene rubber
  • MAH-g-EBR ethylene-butene rubber in which maleic
  • the gum polymers wherein the maleic anhydride is graft polymerized include olefins such as ethylene, alpha-olefins; And an aromatic vinyl-based monomer such as styrene; and graft-polymerizing maleic anhydride on the rubbery polymer as a copolymer of the monomer mixture.
  • the rubbery polymer in which the maleic anhydride is graft-polymerized is a styrene-ethylene-butadiene-styrene copolymer having a melt flow index (MI) of about 10 to about 50 g / 10 min SEBS) copolymer, or the like, by adding peroxide to the rubbery polymer to break the ethylene bond and generate free radicals to introduce maleic anhydride into the ethylene bond.
  • MI melt flow index
  • the 100 percent by weight maleic anhydride grafted rubber may have a maleic anhydride content of from about 0.1 to about 3 percent by weight and a rubbery polymer content of from about 95 to about 99.9 percent by weight, But is not limited thereto.
  • the maleic anhydride-grafted rubbery polymer may be included in from about 0.01 to about 5 parts by weight, for example from about 0.1 to about 3 parts by weight, based on about 100 parts by weight of the polycarbonate resin.
  • the thermoplastic resin composition may have excellent flow properties, thermal stability, and appearance characteristics.
  • the black pigment according to one embodiment of the present invention is capable of improving the appearance and rigidity of the thermoplastic resin composition.
  • carbon black or the like can be used as the black pigment.
  • the black pigment may have an average particle size (D50, volume average) as measured by a particle size analyzer of from about 10 to about 24 nm, such as from about 15 to about 22 nm. Within the above range, the appearance properties such as hue of the thermoplastic resin composition may be excellent.
  • the black pigment may be included in an amount of from about 0.05 to about 3 parts by weight, for example, from about 0.3 to about 2 parts by weight, relative to about 100 parts by weight of the polycarbonate resin.
  • the thermoplastic resin composition may have excellent appearance characteristics, rigidity, flame retardancy and the like.
  • thermoplastic resin composition according to an embodiment of the present invention may further contain additives such as a releasing agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant aid, an antistatic agent, an antioxidant, and a mixture thereof.
  • additives such as a releasing agent, a lubricant, a plasticizer, a heat stabilizer, a light stabilizer, a flame retardant aid, an antistatic agent, an antioxidant, and a mixture thereof.
  • the additive used in the conventional thermoplastic resin composition may be used without limitation.
  • the additive include polyethylene wax, a fluorine-containing polymer, a silicone oil, a metal salt of stearic acid, a metal salt of montanic acid, a mold release agent such as montanic ester wax; Nucleating agents such as clay; Antioxidants such as hindered phenol-based compounds; Mixtures thereof, and the like may be used, but the present invention is not limited thereto.
  • the additive may be included in an amount of about 0.1 to about 40 parts by weight based on about 100 parts by weight of the polycarbonate resin, but is not limited thereto.
  • thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above components and melt-extruding at a temperature of about 200 to about 280 ⁇ , for example, about 250 to about 260 ⁇ , using a conventional twin-screw extruder. .
  • thermoplastic resin composition was prepared by bonding an injection sample having a size of 100 mm x 25 mm x 2 mm to an identical size metal specimen with an adhesive so as to overlap an area of 25 mm x 25 mm, (Adhesive) strength of about 140 to about 300 kgf / cm 2 , such as from about 150 to about 250 kgf / cm 2 , measured after aging at room temperature for 5 minutes, after heating the adhesive site for 120 seconds have.
  • thermoplastic resin composition may have a flame retardancy of V-1 or more of a 1.0 mm thick specimen measured by the UL-94 vertical test method.
  • the thermoplastic resin composition has a melt flow index (MI) of about 30 to about 60 g / 10 minutes measured at 220 DEG C and 5 kgf according to ASTM D1238, 45 to about 55 g / 10 min.
  • MI melt flow index
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the molded article may be a plastic member of an electronic device housing including a metal frame and a plastic member in contact with at least one side of the metal frame.
  • an electronic device housing according to an embodiment of the present invention includes a metal frame 10; And at least one plastic member (20) in contact with at least one surface of the metal frame (10), wherein the plastic member is formed from the thermoplastic resin composition.
  • the shapes of the metal frame 10 and the plastic member 20 are not limited to the drawings, and may have various shapes.
  • the metal frame 10 and the plastic member 20 have a structure in which at least one side is in contact with each other.
  • the contacting structure may be implemented by gluing or inserting, and the contacting method is not limited.
  • the metal frame 10 may be a stainless steel frame, a plastic member, or the like, which is applicable to a conventional electronic device housing, and is commercially available.
  • the plastic member 20 may be formed from the polycarbonate resin composition through various molding methods such as injection molding, extrusion molding, vacuum molding, casting molding and the like.
  • the plastic member 20 may be formed by a hot water molding method, a rapid heat cycle molding (RHCM) method, or the like, and may be a 22 to 85 inch thin film type television, a thin film type monitor, a cover, a rear cover, and the like.
  • RHCM rapid heat cycle molding
  • the plastic member 20 is also applicable to external specifications such as a hairline pattern and a corrosion pattern.
  • a bisphenol-A polycarbonate resin (flow index (measured under the conditions of MI, ISO 1133, 300 ° C, and 1.2 kg): 90 ⁇ 10 g / 10 min) was used.
  • G-ABS in which 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) were graft copolymerized was used in 45% by weight of butadiene rubber (average particle size: 310 nm)
  • BR-1 ASADENE 55AE
  • the prepared mixed solution was fed into the reactor at a rate of 25 kg / hr.
  • the first reactor was controlled at a stirring speed of 150 rpm, and the conversion was adjusted to a level of 35%.
  • the stirring rate was adjusted to 80 rpm and the conversion was 75%.
  • the remaining unreacted material was removed by defoaming, and a pellet-shaped rubber-modified aromatic vinyl copolymer resin (ABS resin, A mixture (content (dispersed phase: continuous phase): 12% by weight: 88% by weight) of an extruded rubbery polymer ((C1), dispersed phase) and an aromatic vinyl copolymer resin (SAN resin Respectively.
  • ABS resin A mixture (content (dispersed phase: continuous phase): 12% by weight: 88% by weight) of an extruded rubbery polymer ((C1), dispersed phase) and an aromatic vinyl copolymer resin
  • SAN resin aromatic vinyl copolymer resin
  • (C1) and (C2) rubbery polymer and (D2) aromatic vinyl-based copolymer resin were obtained in the same manner as in (C1) and (D2) except that the stirring speed of the first reactor was changed to 170 rpm and the stirring speed of the second reactor was changed to 90 rpm.
  • the average particle size of the rubber polymer (C2) thus prepared was 305 nm, and the weight average molecular weight of the SAN resin (D2) was 130,000 g / mol.
  • (C3) rubber polymer and (D3) aromatic vinyl-based copolymer resin: (C1) and (D3) were prepared in the same manner as in the above (1) except that the stirring speed of the first reactor was changed to 130 rpm and the stirring speed of the second reactor was changed to 70 rpm.
  • the average particle size of the rubber polymer (C3) thus prepared was 5,160 nm, and the weight average molecular weight of the SAN resin (D3) was 130,000 g / mol.
  • Bisphenol-A diphosphate (trade name: Yoke Chemical, product name: YOKE BDP) was used.
  • Talc manufactured by KOCH, product name: KCM 6300, bulk density: 0.4 to 0.6 g / cm 3 ) was used.
  • the wollastonite (manufacturer: NYCO ⁇ , product name:: 4W, a bulk density of 0.4 to 0.5 g / cm 3) was used.
  • MAH-g-EBR manufactured by Mitsui, product name: TAFMER
  • Carbon black (manufacturer: OCI, product name: HIBLACK, average particle size: 18 nm) was used.
  • the above components were added in the amounts as shown in Table 1, and then extruded at 250 ⁇ to prepare pellets.
  • the extruded extrudate was a biaxial extruder having an L / D of 36 and a diameter of 45 mm.
  • the pellet was dried at 80 ° C. for 4 hours or more, and then extruded at a molding temperature of 250 to 260 ° C. and a mold temperature of 60 ° C.
  • the properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.
  • Adhesive strength (shear stress, unit: kgf / cm 2 ): An injection specimen of 100 mm ⁇ 25 mm ⁇ 2 mm size was extruded in the same size metal (aluminum) specimen and 25 mm ⁇ And the adhesive portion was heated at 80 DEG C for 120 seconds using a heat gun and then aged at room temperature for 5 minutes (manufactured by Henkel Co., Ltd. under the trade name of LOCTITE HF8150R) After aging, the adhesive strength was measured.
  • MI Melt-flow index
  • Example Comparative Example One 2 3 4 One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 5 5 5 5 15 5 5 5 5 5 (C1) (parts by weight) 1.2 1.8 2.4 1.8 - 1.8 1.8 - - (C2) (parts by weight) - - - - - - - 1.8 - (C3) (parts by weight) - - - - - - - 1.8 (D1) (parts by weight) 8.8 13.2 17.6 13.2 - 13.2 13.2 - - (D2) (parts by weight) - - - - - - 13.2 - (D3) (parts by weight) - - - - - - - 13.2 - (E) (parts by weight) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
  • thermoplastic resin composition of the present invention has excellent adhesion (adhesion strength), flame retardancy (flame retardancy) and fluidity (melt flow index) .
  • Comparative Example 4 using the rubbery polymer (C2) and the aromatic vinyl copolymer resin (D2) instead of the larger amount of the gum polymer (C1) and the aromatic vinyl copolymer resin (D1) of the present invention
  • Comparative Example 5 using the rubbery polymer (C3) and the aromatic vinyl copolymer resin (D3) instead of the largely charged rubber polymer (C1) and the aromatic vinyl copolymer resin (D1) Flame retardancy and the like are deteriorated.

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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)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine thermoplastique qui comprend : une résine de polycarbonate ; un copolymère greffé à base de vinyle modifié par du caoutchouc ; un polymère de caoutchouc à grande taille de particule présentant une taille de particule moyenne variant d'environ 400 à environ 1 500 nm ; une résine copolymère à base de vinyle aromatique ; un retardateur de flamme à base de phosphore ; du talc ; de la wollastonite ; un polymère de caoutchouc greffé à de l'anhydride maléique ; et un pigment noir. Cette composition de résine thermoplastique présente des propriétés supérieures en termes d'adhérence au métal, de résistance, d'ininflammabilité, de fluidité et d'aspect.
PCT/KR2018/016835 2017-12-29 2018-12-28 Composition de résine thermoplastique et article moulé fabriqué avec celle-ci Ceased WO2019132572A1 (fr)

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Cited By (1)

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US11702540B2 (en) 2017-12-29 2023-07-18 Lotte Chemical Corporation Thermoplastic resin composition and molded article manufactured therefrom

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US11702540B2 (en) 2017-12-29 2023-07-18 Lotte Chemical Corporation Thermoplastic resin composition and molded article manufactured therefrom

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