WO2018124639A2 - Composition de résine thermoplastique et article produit à partir de celle-ci - Google Patents

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

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WO2018124639A2
WO2018124639A2 PCT/KR2017/015255 KR2017015255W WO2018124639A2 WO 2018124639 A2 WO2018124639 A2 WO 2018124639A2 KR 2017015255 W KR2017015255 W KR 2017015255W WO 2018124639 A2 WO2018124639 A2 WO 2018124639A2
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Prior art keywords
thermoplastic resin
resin composition
aromatic vinyl
weight
monomer
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PCT/KR2017/015255
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English (en)
Korean (ko)
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WO2018124639A3 (fr
Inventor
함민경
박동현
이은주
권영철
양윤정
오현지
Original Assignee
롯데첨단소재(주)
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Priority to EP17887388.1A priority Critical patent/EP3564303B1/fr
Priority to US16/342,018 priority patent/US11091624B2/en
Priority to CN201780068385.7A priority patent/CN109906247B/zh
Priority claimed from KR1020170176909A external-priority patent/KR101968026B1/ko
Publication of WO2018124639A2 publication Critical patent/WO2018124639A2/fr
Publication of WO2018124639A3 publication Critical patent/WO2018124639A3/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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

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 excellent in low light resistance, weather resistance, antibacterial properties, and the like, and a molded article prepared therefrom.
  • acrylate rubber modified aromatic vinyl copolymer resins such as acrylate-styrene-acrylonitrile copolymer resin (ASA resin) are diene rubber modified aromatics such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin).
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • ASA resin acrylate-styrene-acrylonitrile copolymer resin
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • weathering stabilizers may cause problems such as deterioration in appearance characteristics and mechanical properties due to gas generation when used in excess, and are not easy to increase, and property balance may be reduced when using an acrylate rubbery polymer in excess. There is this.
  • thermoplastic resin composition having excellent low light properties, weather resistance, antibacterial properties, and the like, without deteriorating inherent physical properties of the thermoplastic resin.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in low light resistance, weather resistance, antibacterial properties and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition may be a thermoplastic resin comprising an acrylate rubber-modified vinyl graft copolymer and an aromatic vinyl copolymer resin; Crosslinked aromatic vinyl copolymer resins; And zinc oxide having an average particle size of about 0.3 to about 3 ⁇ m and a specific surface area BET of about 1 to about 10 m 2 / g.
  • the thermoplastic resin composition includes about 20 to about 80 wt% of the acrylate-based rubber-modified vinyl graft copolymer and about 20 to about 80 wt% of the aromatic vinyl copolymer resin. Parts by weight; About 0.5 to about 15 parts by weight of the crosslinked aromatic vinyl-based copolymer resin; And about 0.3 to about 10 parts by weight of zinc oxide.
  • the acrylate rubber-modified vinyl graft copolymer is a graft monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in an acrylate rubber polymer having an average particle diameter of about 350 to about 600 nm. It may be polymerized.
  • the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
  • the crosslinked aromatic vinyl copolymer resin comprises about 40 to about 80 weight percent of an aromatic vinyl monomer; About 5 to about 20 weight percent of a vinyl cyanide monomer; And about 10 to about 40 weight percent of a crosslinking agent.
  • the zinc oxide may have a size ratio (B / A) of peak A in the 370 to 390 nm region and peak B in the 450 to 600 nm region when measured by photo luminescence. have.
  • the zinc oxide has a peak position 2 ⁇ of 35 to 37 ° when analyzed by X-ray diffraction (XRD), and crystallite size according to Equation 1 below. ) Value can be from about 1,000 to about 2,000 mm 3:
  • K is a shape factor
  • ⁇ is an X-ray wavelength
  • ⁇ is an FWHM value of an X-ray diffraction peak
  • ⁇ is a peak position value. (peak position degree).
  • the weight ratio of the crosslinked aromatic vinyl copolymer resin and the zinc oxide may be about 1: 0.03 to about 1:20.
  • thermoplastic resin composition may have a glossiness of about 1 to about 55% measured at an angle of 60 ° according to ASTM D523.
  • the thermoplastic resin composition measures an initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter on a 50 mm ⁇ 90 mm ⁇ 3 mm sized injection specimen, and measures the injection specimen.
  • the weather resistance test for 3,000 hours, and after the test using a colorimeter to measure the color (L 1 * , a 1 * , b 1 * ) and then the color change calculated according to the following equation (2) ⁇ E) may be from about 0 to about 5:
  • Equation 2 ⁇ L * is the difference between the L * values before and after the test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * values before and after the test (a 1 * -a 0 * ), ⁇ b * Is the difference between the values of b * before and after the test (b 1 * -b 0 * ).
  • thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm ⁇ 5 cm size specimen, based on JIS Z 2801 antimicrobial evaluation method, and measured after incubation at 35 ° C. and RH 90% for 24 hours.
  • the antimicrobial activity may be about 2 to about 7 and about 2 to about 7.
  • Another aspect of the invention relates to a molded article.
  • the molded article is formed from the thermoplastic resin composition.
  • the present invention has the effect of the invention of providing a thermoplastic resin composition excellent in low light resistance, weather resistance, antibacterial and the like and a molded article formed therefrom.
  • thermoplastic resin composition includes (A) a thermoplastic resin comprising (A1) a rubber-modified vinyl graft copolymer and (A2) an aromatic vinyl copolymer resin; (B) crosslinked aromatic vinyl copolymer resin; And (C) zinc oxide.
  • thermoplastic resin (A) thermoplastic resin
  • thermoplastic resin of the present invention may be an acrylate rubber modified vinyl copolymer resin comprising (A1) acrylate rubber modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin.
  • the acrylate-based rubber-modified vinyl graft copolymer according to an embodiment of the present invention can improve weather resistance, low light resistance, impact resistance, etc. of the thermoplastic resin composition.
  • the monomer mixture including the vinyl cyanide monomer may be graft polymerized.
  • the acrylate rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in an acrylate rubber polymer.
  • the monomer mixture may further include a monomer that imparts processability and heat resistance, thereby graft polymerization.
  • the polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization.
  • the acrylate rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.
  • examples of the acrylate-based rubbery polymers include alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates and aromatic vinyl monomers. These may be used alone or in combination of two or more thereof.
  • alkyl acrylate rubbers of 2 to 10 carbon atoms copolymers of alkyl acrylates and styrene of 2 to 10 carbon atoms, combinations thereof, and the like may be used.
  • butyl acrylate rubber, butyl acrylate and styrene may be used. Copolymers of these, combinations thereof and the like can be used.
  • the copolymer of the alkyl (meth) acrylate and the aromatic vinyl monomer may be polymerized from about 70 to about 90 wt% of the alkyl (meth) acrylate and about 10 to about 30 wt% of the aromatic vinyl monomer. This is not restrictive.
  • the acrylate rubber polymer may have an average particle diameter of about 350 to about 600 nm, for example, about 390 to about 500 nm as measured by a particle size analyzer (Malvern DLS instrument (Nano ZS)) have. In the above range, it may be excellent in low light resistance, weather resistance, impact resistance and the like of the thermoplastic resin composition.
  • the content of the acrylate-based rubbery polymer may be about 20 to about 70% by weight, for example about 30 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl graft copolymer, the monomer
  • the content of the mixture is about 30 to about 80 wt%, for example about 40 to about 70 wt%, of 100 wt% of the total acrylate rubber-modified vinyl graft copolymer.
  • the thermoplastic resin composition may have excellent low light properties, appearance characteristics, weather resistance, impact resistance, and the like.
  • the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof.
  • the aromatic vinyl monomer may be included in an amount of about 10 wt% to about 90 wt%, for example, about 40 wt% to about 90 wt% in 100 wt% of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.
  • the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide monomer may be about 10 wt% to about 90 wt%, for example about 10 wt% to about 60 wt%, in 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.
  • monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like.
  • the content may be about 15% by weight or less, for example about 0.1 to about 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.
  • the acrylate rubber-modified vinyl graft copolymer may include an acrylate-styrene-acrylonitrile graft copolymer (g-ASA) and the like.
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • the acrylate rubber-modified vinyl graft copolymer is about 20 to about 80 weight in 100% by weight of the total thermoplastic resin (acrylate-based rubber-modified vinyl graft copolymer and aromatic vinyl-based copolymer resin) %, For example about 30 to about 70 weight percent, specifically about 50 to about 70 weight percent.
  • the low light properties, appearance characteristics, weather resistance, impact resistance, flowability (molding processability) of the thermoplastic resin composition, balance of physical properties thereof, etc. may be excellent.
  • the aromatic vinyl copolymer resin according to one embodiment of the present invention may be an aromatic vinyl copolymer resin used in a conventional rubber-modified vinyl copolymer resin.
  • the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including a monomer copolymerizable with the aromatic vinyl monomer such as an aromatic vinyl monomer and a vinyl cyanide monomer.
  • the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.
  • the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types.
  • the content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
  • the monomer copolymerizable with the aromatic vinyl monomer for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like.
  • Vinyl cyanide monomers and the like can be used, and can be used alone or in combination of two or more.
  • the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 wt% to about 80 wt%, for example, about 20 wt% to about 70 wt% of the total 100 wt% of the aromatic vinyl copolymer copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
  • the aromatic vinyl 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, as measured by gel permeation chromatography (GPC). Can be. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.
  • the aromatic vinyl copolymer resin is included in about 20 to about 80% by weight, such as about 30 to about 70% by weight, specifically about 30 to about 50% by weight of 100% by weight of the total thermoplastic resin Can be. Impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition in the above range may be excellent.
  • Crosslinked aromatic vinyl copolymer resin is to improve the low light resistance, weather resistance, antimicrobial and the like of the thermoplastic resin composition (sample) with the zinc oxide.
  • the crosslinked aromatic vinyl copolymer resin may include an aromatic vinyl monomer; Vinyl cyanide monomers; And a polymer of the reaction mixture comprising a crosslinking agent.
  • the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types.
  • the aromatic vinyl monomer may be included in an amount of about 40 wt% to about 80 wt%, for example, about 45 wt% to about 75 wt% of the total 100 wt% of the crosslinked aromatic vinyl copolymer resin. It may be excellent in the low light properties of the thermoplastic resin composition in the above range.
  • the vinyl cyanide monomer may be acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, or the like, and may be used alone or in combination. It can mix and use the above.
  • the content of the vinyl cyanide monomer may be about 5 wt% to about 20 wt%, for example about 5 wt% to about 15 wt%, in 100 wt% of the total cross-linked aromatic vinyl copolymer resin. It may be excellent in the low light properties of the thermoplastic resin composition in the above range.
  • crosslinking agent divinylbenzene, ethylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, diallyl maleate, triallyl isocyanurate, combinations thereof, and the like may be used.
  • the content of the crosslinking agent may be about 10 wt% to about 40 wt%, for example, about 15 wt% to about 35 wt% of the total 100 wt% of the crosslinked aromatic vinyl copolymer resin. It may be excellent in the low light properties of the thermoplastic resin composition in the above range.
  • the crosslinked aromatic vinyl copolymer resin may be prepared using a conventional polymerization method such as emulsion polymerization, suspension polymerization, solution polymerization, but is not limited thereto.
  • emulsion polymerization, suspension polymerization and the like can be used.
  • a polymerization initiator and a chain transfer agent may be added to the reaction mixture having the above content to prepare a reaction mixture, and the reaction mixture may be prepared by adding the polymerization solution to an aqueous solution in which a suspension stabilizer or the like is dissolved.
  • the polymerization temperature and the polymerization time can be appropriately adjusted. For example, it may be reacted for about 1 to about 8 hours at a polymerization temperature of about 65 to about 125 ° C, specifically about 70 to about 120 ° C.
  • the polymerization initiator may be a conventional radical polymerization initiator known in the polymerization art, for example, octanoyl peroxide, decanyl peroxide, lauroyl peroxide, benzoyl peroxide, monochlorobenzoyl peroxide, dichloro Benzoyl peroxide, p-methylbenzoyl peroxide, tert-butyl perbenzoate, azobisisobutyronitrile and azobis- (2,4-dimethyl) -valeronitrile and the like may be used, but is not limited thereto. .
  • the polymerization initiator may be applied alone or by mixing two or more kinds.
  • the polymerization initiator may be included in about 0.01 to about 10 parts by weight, for example, about 0.03 to about 5 parts by weight based on about 100 parts by weight of the reaction mixture, but is not limited thereto.
  • the chain transfer agent may be used to control the weight average molecular weight of the crosslinked aromatic vinyl copolymer resin and to improve thermal stability.
  • chain transfer agent conventional chain transfer agents known in the polymerization art may be used.
  • the chain transfer agent may be included in an amount of about 0.01 to about 10 parts by weight, for example about 0.02 to about 5 parts by weight, based on about 100 parts by weight of the reaction mixture. In the above range, it is possible to prepare a crosslinked aromatic vinyl copolymer resin having thermal stability and appropriate molecular weight.
  • the crosslinked aromatic vinyl copolymer resin may be polymerized by introducing the reaction mixture into an aqueous solution containing at least one additive such as a suspension stabilizer and a suspension stabilizer.
  • the additive may be included in about 0.001 to about 20 parts by weight based on about 100 parts by weight of the reaction mixture, but is not limited thereto.
  • suspension stabilizer examples include organic suspension stabilizers including homopolymers or copolymers of acrylic acid or methacrylic acid, polyalkylacrylate-acrylic acid, polyolefin-maleic acid, polyvinyl alcohol, cellulose, and the like; Inorganic suspension stabilizers including tricalcium phosphate; Mixtures thereof and the like can be used, but are not limited thereto.
  • the acrylic acid or methacrylic acid may be in the form of a salt of sodium, potassium or ammonium in order to maintain proper solubility.
  • suspension stabilizing aid disodium hydrogen phosphate, sodium dihydrogen phosphate, or the like may be used, and sodium sulfate or the like may be added to control solubility characteristics of the water-soluble polymer or monomer.
  • the crosslinked aromatic vinyl-based copolymer resin is about 0.5 to about 15 parts by weight, for example about 1 to about 10 parts by weight, specifically about 3 to about 8 parts by weight, based on about 100 parts by weight of the thermoplastic resin. It can be included as a wealth. In the above range may be excellent in the low light resistance, weather resistance, antibacterial properties of the thermoplastic resin composition.
  • Zinc oxide of the present invention can improve the weather resistance, antimicrobial properties, low light properties, etc. of the thermoplastic resin composition with the ultraviolet stabilizer, the average particle size measured by the particle size analyzer is about 0.3 to about 3 ⁇ m, for example about 0.5 To about 2 ⁇ m, specific surface area BET may be about 1 to about 10 m 2 / g, for example about 1 to about 7 m 2 / g, and purity may be about 99% or more. When it is out of the said range, there exists a possibility that the weather resistance, antibacterial property, etc. of a thermoplastic resin composition may fall.
  • the zinc oxide has a size ratio (B / A) of peak A in the 370 to 390 nm region and peak B in the 450 to 600 nm region when measured by photo luminescence, eg, For example, about 0.1 to about 1.
  • Weather resistance of the thermoplastic resin composition in the above range may be more excellent antibacterial and the like.
  • the zinc oxide has a peak position 2 ⁇ of 35 to 37 ° in X-ray diffraction (XRD) analysis, and the measured FWHM value (full of diffraction peaks).
  • the crystallite size value calculated by applying the Scherrer's equation (Equation 1) based on the width at Half Maximum may be about 1,000 to about 2,000 GPa, for example, about 1,200 to about 1,800 GPa. In the above range, the initial color of the thermoplastic resin composition, weather resistance, antibacterial and the like can be excellent.
  • Equation 1 K is a shape factor, ⁇ is an X-ray wavelength, ⁇ is an FWHM value, and ⁇ is a peak position degree.
  • the zinc oxide is dissolved in zinc in the form of metal, vaporized by heating to about 850 to about 1,000 ° C., for example, about 900 to about 950 ° C., followed by injection of oxygen gas and about 20 to about 30 After cooling to °C, if necessary, the heat treatment for about 30 minutes to about 150 minutes at about 700 to about 800 °C while injecting nitrogen / hydrogen gas into the reactor, and then cooled to room temperature (20 to 30 °C) It can manufacture.
  • the zinc oxide may be included in about 0.3 to about 10 parts by weight, for example about 0.5 to about 5 parts by weight, specifically about 0.5 to about 2.5 parts by weight, based on about 100 parts by weight of the thermoplastic resin.
  • the thermoplastic resin composition may have excellent weather resistance, antibacterial property, low lightness, and the like.
  • the weight ratio (B: C) of the crosslinked aromatic vinyl copolymer resin (B) and the zinc oxide (C) is about 1: 0.03 to about 1:20, for example about 1: 0.08 to about 1 May be two. In the above range, the low light resistance, weather resistance, antimicrobial properties, etc. of the thermoplastic resin composition may be more excellent.
  • the thermoplastic resin composition according to one embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additive may include weather stabilizers, flame retardants, fillers, antioxidants, anti-drip agents, lubricants, mold release agents, nucleating agents, antistatic agents, pigments, dyes, mixtures thereof, and the like, but are not limited thereto.
  • the 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 about 100 parts by weight of the thermoplastic resin.
  • thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets which are mixed with the above components and melt-extruded at 200 to 280 ° C, for example, 220 to 250 ° C, using a conventional twin screw extruder.
  • thermoplastic resin composition may have a glossiness measured at an angle of 60 ° according to ASTM D523 from about 1% to about 55%, for example from about 10% to about 50%.
  • the thermoplastic resin composition measures an initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter on a 50 mm ⁇ 90 mm ⁇ 3 mm sized injection specimen, and measures the injection specimen.
  • the weather resistance test for 3,000 hours, and after the test using a colorimeter to measure the color (L 1 * , a 1 * , b 1 * ) and then the color change calculated according to the following equation (2) ⁇ E) may be about 0 to about 5, for example about 1 to about 3.
  • Equation 2 ⁇ L * is the difference between the L * values before and after the test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * values before and after the test (a 1 * -a 0 * ), ⁇ b * Is the difference between the values of b * before and after the test (b 1 * -b 0 * ).
  • thermoplastic resin composition is inoculated with Staphylococcus aureus and Escherichia coli on a 5 cm ⁇ 5 cm size specimen, based on JIS Z 2801 antimicrobial evaluation method, and measured after incubation at 35 ° C. and RH 90% for 24 hours.
  • the antimicrobial activity may be about 2 to about 7 and about 2 to about 7, for example about 2.5 to about 6 and about 2.5 to about 6.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in low light resistance, weather resistance, antibacterial property, impact resistance, flowability (molding processability), the balance of physical properties thereof, etc., the interior / exterior materials of electric / electronic products, automotive interior / exterior materials, building exterior materials, for example, pool bottom Useful for baths, decks, etc.
  • thermoplastic resin (A) thermoplastic resin
  • An acrylate rubber-modified vinyl copolymer resin containing 60 wt% of (A1) acrylate rubber-modified aromatic vinyl graft copolymer and 40% by weight of (A2) aromatic vinyl-based copolymer resin was used.
  • G-ASA in which butyl acrylate rubber having an average particle diameter of 45 mm by weight was 400 nm and graft copolymerized with 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) was used.
  • a SAN resin (weight average molecular weight: 130,000 g / mol) polymerized with 71% by weight of styrene and 29% by weight of acrylonitrile was used.
  • a solution (a) was prepared by mixing 60% by weight of styrene, 10% by weight of acrylonitrile, 30% by weight of divinylbenzene (crosslinking agent) and 1.0 part by weight of an initiator, and 0.2 parts by weight of polyvinyl alcohol was completely dissolved in water to give an aqueous solution (b ),
  • the prepared two solutions were homogenized at 500 rpm for 1 minute using a high speed homogenizer and then polymerized at 90 ° C. for 7 hours in a four-necked flask reactor under nitrogen atmosphere.
  • the polymer synthesized by the above reaction was filtered, washed with water, and the filtrate was put in a vacuum oven and dried for one day to use a white odorless spherical polymer powder as a crosslinked aromatic vinyl copolymer resin.
  • Average particle size (unit: ⁇ m): The average particle size (volume average) was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument).
  • BET surface area (unit: m 2 / g): The BET surface area was measured by BET analysis equipment (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 equipment) using nitrogen gas adsorption.
  • Purity (Unit:%): Purity was measured using TGA thermal analysis with weight remaining at 800 ° C.
  • PL size ratio (B / A) According to the photo luminescence measuring method, a spectrum of light emitted by a He-Cd laser (Kimmon, 30mW) having a wavelength of 325 nm at room temperature is measured by a CCD detector. The temperature of the CCD detector was maintained at -70 ° C. The size ratio (B / A) of the peak A in the 370 to 390 nm region and the peak B in the 450 to 600 nm region was measured.
  • the injection specimen was subjected to PL analysis by injecting a laser into the specimen without any treatment, and the zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to produce a flat specimen. It was.
  • Equation 1 K is a shape factor, ⁇ is an X-ray wavelength, ⁇ is an FWHM value, and ⁇ is a peak position degree.
  • Equation 2 ⁇ L * is the difference between the L * values before and after the test (L 1 * -L 0 * ), ⁇ a * is the difference between the a * values before and after the test (a 1 * -a 0 * ), ⁇ b * Is the difference between the values of b * before and after the test (b 1 * -b 0 * ).
  • Antibacterial activity value In accordance with JIS Z 2801 antimicrobial evaluation method, 5 cm ⁇ 5 cm size specimen was inoculated with Staphylococcus aureus and E. coli, and measured after culturing for 24 hours at 35 °C, RH 90% conditions.
  • Notched Izod Impact Strength (Unit: kgf ⁇ cm / cm): Notch was evaluated by making a notch on a 1/8 ”thick Izod specimen according to the evaluation method specified in ASTM D256.
  • MI Melt index
  • Example One 2 3 4 5 (A) (parts by weight) 100 100 100 100 100 100 (B) (parts by weight) 6 10
  • One 6 6 (C) (part by weight) (C1) 2 2 2 5 0.5 (C2) - - - - - (C3) - - - - - Glossiness (%) 30 10 50
  • Color change ( ⁇ E) 1.8 2.0 1.9 1.3 3.0 Antibacterial activity level (E. coli) 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 2.5 Antibacterial activity level (Staphococcus) 6 4.5 6 6 6 2.5 Notch Izod Impact Strength 40 22 55 35 42 Melt index 3.0 2.5 3.2 3.3 2.9
  • thermoplastic resin composition of the present invention is excellent in all of low light resistance, weather resistance, antibacterial properties and the like.
  • Comparative Example 1 which does not use a cross-linked aromatic vinyl copolymer resin, it was found that low glossiness was decreased due to high glossiness. It can be seen that this is reduced, in the case of Comparative Examples 3 and 4 using zinc oxide (C2) and (C3) instead of zinc oxide (C1) of the present invention, it can be seen that the antimicrobial, weather resistance and the like.

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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

L'invention concerne une composition de résine thermoplastique qui comprend: une résine thermoplastique comprenant un copolymère greffé de vinyle modifié par un caoutchouc d'acrylate et une résine de copolymère de vinyle aromatique; une résine de copolymère de vinyle aromatique réticulé; et de l'oxyde de zinc présentant une dimension moyenne des particules d'environ 0,3 à 3 µm et une surface spécifique BET d'environ 1 à 10 m2/g. La composition de résine thermoplastique et l'article formé à partir de celle-ci sont excellents pour leur faible brillance, leur résistance aux intempéries et leurs propriétés antimicrobiennes, etc.
PCT/KR2017/015255 2016-12-27 2017-12-21 Composition de résine thermoplastique et article produit à partir de celle-ci WO2018124639A2 (fr)

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EP17887388.1A EP3564303B1 (fr) 2016-12-27 2017-12-21 Composition de résine thermoplastique et article produit à partir de celle-ci
US16/342,018 US11091624B2 (en) 2016-12-27 2017-12-21 Thermoplastic resin composition and article produced therefrom
CN201780068385.7A CN109906247B (zh) 2016-12-27 2017-12-21 热塑性树脂组合物和由其制成的制品

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US11091624B2 (en) 2016-12-27 2021-08-17 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and article produced therefrom

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KR100988999B1 (ko) 2007-10-19 2010-10-20 주식회사 엘지화학 아크릴레이트-스티렌-아크릴로니트릴 중합체, 이의제조방법, 및 이를 포함하는 열가소성 수지 조성물

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11091624B2 (en) 2016-12-27 2021-08-17 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and article produced therefrom

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