WO2019083147A1 - Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci - Google Patents

Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci

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Publication number
WO2019083147A1
WO2019083147A1 PCT/KR2018/010016 KR2018010016W WO2019083147A1 WO 2019083147 A1 WO2019083147 A1 WO 2019083147A1 KR 2018010016 W KR2018010016 W KR 2018010016W WO 2019083147 A1 WO2019083147 A1 WO 2019083147A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
resin composition
aromatic vinyl
zinc oxide
weight
Prior art date
Application number
PCT/KR2018/010016
Other languages
English (en)
Korean (ko)
Inventor
양천석
김연경
배승용
김주성
박강열
Original Assignee
롯데첨단소재(주)
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 KR1020180064627A external-priority patent/KR102150754B1/ko
Application filed by 롯데첨단소재(주) filed Critical 롯데첨단소재(주)
Priority to US16/645,543 priority Critical patent/US20200277487A1/en
Priority to JP2020515941A priority patent/JP2021500421A/ja
Priority to CN201880068344.2A priority patent/CN111247203A/zh
Publication of WO2019083147A1 publication Critical patent/WO2019083147A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

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 weatherability, antibacterial properties, mechanical properties, and the like and a molded article produced therefrom.
  • thermoplastic resin products containing antibacterial and hygienic functions As the interest in personal health and hygiene and income levels have improved.
  • thermoplastic resin products that have been subjected to antimicrobial treatment that can remove or inhibit bacteria on the surfaces of household products and electronic products are increasing, and development of functional antibacterial material (antibacterial thermoplastic resin composition) having stable and reliable is very important It is an assignment.
  • an antibacterial thermoplastic resin composition In order to prepare such an antibacterial thermoplastic resin composition, it is necessary to add an antibacterial agent, and the antibacterial agent can be divided into an organic antibacterial agent and an inorganic antibacterial agent.
  • Organic antimicrobial agents are relatively inexpensive and have good antimicrobial activity in a small amount. However, they sometimes have human toxicity and may be effective only for certain bacteria. have. In addition, there is a disadvantage in that discoloration after processing may cause discoloration and that the antibacterial persistence is short due to the elution problem, and thus the range of the organic antibacterial agent applicable to the antibacterial thermoplastic resin composition is extremely limited.
  • the inorganic antimicrobial agent is an antimicrobial agent containing a metal component such as silver (Ag) and copper (Cu) and is excellent in thermal stability and is widely used for producing an antimicrobial thermoplastic resin composition (antibacterial resin).
  • a metal component such as silver (Ag) and copper (Cu)
  • antimicrobial resin composition antibacterial resin
  • thermoplastic resin composition which is excellent in weather resistance (discoloration resistance), antimicrobial property and antimicrobial persistence, and which is capable of realizing antifungal property and the like.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance, antibacterial properties, mechanical 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 comprises about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; About 0.1 to about 1 part by weight of zinc pyrithione; And about 0.1 to about 10 parts by weight of zinc oxide, wherein the zinc oxide has an average particle size (D50) measured by a particle size analyzer of about 0.5 to about 3 mu m, and a photoluminescence measurement of 370 to 390 nm (B / A) of the peak A of the region and the peak B of the region of 450 to 600 nm is about 0.01 to about 1.0.
  • D50 average particle size measured by a particle size analyzer of about 0.5 to about 3 mu m
  • photoluminescence measurement 370 to 390 nm (B / A) of the peak A of the region and the peak B of the region of 450 to 600 nm is about 0.01 to about 1.0.
  • the weight ratio of zinc pityrichon and zinc oxide may be from about 1: about 2 to about 1: about 10.
  • the rubber-modified aromatic vinyl-based copolymer resin may include a rubber-modified vinyl-based graft copolymer and an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer in a rubber-like polymer.
  • 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 zinc oxide has a peak position 2? Value in the range of about 35 to about 37 degrees and a size of the crystallite according to the following formula (1) when X-ray diffraction (XRD) crystallite size) value can be from about 1,000 to about 2,000 A:
  • K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).
  • 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 of from about 0.1 to about 1.0 have.
  • the zinc oxide may have an average particle size (D50) as measured by a particle size analyzer of from about 0.5 to about 2 micrometers.
  • the zinc oxide may have a specific surface area BET of less than or equal to about 15 m 2 / g, as measured by a BET analysis instrument, using a nitrogen gas adsorption method.
  • the zinc oxide may have a specific surface area BET of from about 1 to about 10 m < 2 > / g as measured by a BET analytical instrument, using a nitrogen gas adsorption method.
  • thermoplastic resin composition was measured for initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter for a 50 mm ⁇ 90 mm ⁇ 2.5 mm size injection specimen, and measured in accordance with ASTM D4459 (L 1 * , a 1 * , b 1 * ) can be measured in the same manner after 1,500 hours of testing, and the color change ( ⁇ E) calculated according to the following formula 2 can be about 15 or less:
  • ⁇ L * is a difference (L 1 * -L 0 *) of the test before and after the L * value of
  • ⁇ a * is the difference between (a 1 * - a 0 * ) of the test before and after the a * value is
  • ⁇ b * Is the difference (b 1 * - b 0 * ) between the values of b * before and after the test.
  • thermoplastic resin composition is prepared by inoculating Staphylococcus aureus and Escherichia coli into a specimen of 5 cm x 5 cm in size according to JIS Z 2801 antibacterial evaluation method, culturing at 35 ° C and RH 90% for 24 hours, 3 may be about 2 to about 7, respectively,
  • Antibacterial activity log (M1 / M2)
  • M1 is the number of bacteria after 24 hours of incubation for the blank specimen
  • M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.
  • Another aspect of the present invention relates to a molded article. And the molded article is formed from the thermoplastic resin composition.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in weather resistance, antibacterial properties, mechanical properties and the like and a molded article formed therefrom.
  • thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) zinc pyrithione; And (C) zinc oxide.
  • the rubber-modified aromatic vinyl-based copolymer resin of the present invention may comprise (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.
  • an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer.
  • the rubber-modified vinyl-based graft copolymer can be polymerized by adding an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer to the rubbery polymer, and the polymerization can be carried out by emulsion polymerization, Polymerization, and the like.
  • the rubbery polymer includes a diene rubber such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene), and saturated rubber in which hydrogen is added to the diene rubber, isoprene rubber, polybutylacrylic acid And an ethylene-propylene-diene monomer terpolymer (EPDM).
  • diene rubber such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene)
  • saturated rubber in which hydrogen is added to the diene rubber isoprene rubber, polybutylacrylic acid And an ethylene-propylene-diene monomer terpolymer (EPDM).
  • EPDM ethylene-propylene-diene monomer terpolymer
  • the amount of the rubbery polymer is about 5 to about 65 weight percent, such as about 10 to about 60 weight percent, specifically about 20 to about 50 weight percent, of the total weight (100 weight percent) of the rubber modified vinyl based graft copolymer, Lt; / RTI >
  • the impact resistance and mechanical properties of the thermoplastic resin composition may be excellent in the above range.
  • the average particle size (Z-average) of the rubbery polymer (rubber particles) may be from about 0.05 to about 6 microns, for example from about 0.15 to about 4 microns, specifically from about 0.25 to about 3.5 microns.
  • the thermoplastic resin composition may have excellent impact resistance, appearance, and flame retardancy.
  • the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery copolymer, and examples thereof include styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt- But are not limited to, styrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, and vinylnaphthalene. These may be used alone or in combination of two or more.
  • the content of the aromatic vinyl monomer is about 15 to about 94 wt%, for example, about 20 to about 80 wt%, specifically about 30 to about 60 wt%, based on the total weight (100 wt%) of the rubber-modified vinyl-based graft copolymer % ≪ / RTI > Within the above range, the thermoplastic resin composition may have excellent fatigue resistance, impact resistance, and mechanical properties.
  • Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile.
  • acrylonitrile, methyl (meth) acrylate, a combination of these, and the like can be used.
  • the content of the monomer copolymerizable with the aromatic vinyl monomer is about 1 to about 50% by weight, for example about 5 to about 45% by weight, specifically about 10 to about 50% by weight based on 100% by weight of the entire rubber modified vinyl-based graft copolymer 30% by weight. In the above range, the impact resistance, fluidity, appearance and the like of the thermoplastic resin composition can be excellent.
  • the rubber-modified vinyl-based graft copolymer a copolymer (g-ABS) in which an aromatic vinyl compound and an acrylonitrile monomer, which are aromatic vinyl compounds and a vinyl cyanide compound, are grafted to a butadiene rubber- (G-MBS) in which methyl methacrylate is grafted with a styrene monomer which is an aromatic vinyl compound and a monomer copolymerizable with the aromatic vinyl compound, and the like, but the present invention is not limited thereto.
  • g-ABS a copolymer
  • G-MBS butadiene rubber-
  • the rubber-modified vinyl-based graft copolymer is a copolymer of about 10 to about 40% by weight, for example about 15 to about 35% by weight, of the total rubber-modified aromatic vinyl copolymer resin (A) .
  • the impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.
  • the aromatic vinyl-based copolymer resin according to one 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 comprising a monomer copolymerizable with the aromatic vinyl-based monomer such as an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the aromatic vinyl-based copolymer resin may be obtained by mixing aromatic vinyl-based monomers and aromatic vinyl-based monomers with a monomer copolymerizable therewith and the like, and the polymerization may be carried out by emulsion polymerization, suspension polymerization, Of the present invention.
  • the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene, and the like can be used, but the present invention is not limited thereto. These may be used alone or in combination 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 entire aromatic vinyl-based copolymer resin.
  • the impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.
  • Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile.
  • (Meth) acrylic acid and alkyl esters thereof, maleic anhydride, N-substituted maleimide, etc. may be used alone or in admixture of two or more.
  • the content of the monomer copolymerizable with the aromatic vinyl-based monomer may be about 10 to about 80% by weight, for example about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin.
  • the impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.
  • the aromatic vinyl-based copolymer resin has 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 / .
  • Mw weight average molecular weight
  • the thermoplastic resin composition may have excellent mechanical strength and moldability.
  • the aromatic vinyl-based copolymer resin may include about 60 to about 90% by weight, for example about 65 to about 85% by weight, of 100% by weight of the whole rubber-modified aromatic vinyl-based copolymer resin (A) have.
  • the impact resistance, fluidity (molding processability) and the like of the thermoplastic resin composition can be excellent in the above range.
  • the zinc pyrithione of the present invention can improve weather resistance and the like together with zinc oxide, and it is possible to use a compound represented by the following formula (1).
  • the zinc pyrithione may be included in an amount of from about 0.1 to about 1 part by weight, for example, from about 0.2 to about 0.6 part by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin.
  • zinc pyrithione is contained in an amount of less than about 0.1 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the weather resistance, antimicrobial properties, and the like of the thermoplastic resin composition may be lowered. There is a possibility that the initial color discoloration of the thermoplastic resin composition may occur.
  • the zinc oxide of the present invention is capable of improving the weather resistance and antimicrobial properties of the thermoplastic resin composition and is characterized in that the peak A in the region of 370 to 390 nm and the ratio of the peak B in the region of 450 to 600 nm (B / A) of from about 0.01 to about 1.0, such as from about 0.1 to about 1.0, specifically from about 0.2 to about 0.7. If the size ratio (B / A) of the peak A and the peak B of the zinc oxide is less than about 0.01, antimicrobiality and the like may be deteriorated. When the ratio B / A is more than about 1.0, the problem of initial discoloration of the thermoplastic resin, There is a concern.
  • the zinc oxide may have various shapes and may include, for example, spheres, plates, rods, combinations thereof, and the like.
  • the average particle size (D50) of single particles (the particles do not form secondary particles) measured by using a particle size analyzer (Beckman Coulter's Laser Diffraction Particle Size Analyzer LS I3 320 equipment) is about From about 0.5 to about 3 microns, for example from about 0.5 to about 2 microns, and specifically from about 0.9 to about 1.5 microns.
  • the average particle size (D50) of the zinc oxide is less than about 0.5 ⁇ ⁇ or more than about 3 ⁇ ⁇ , there is a fear that the weather resistance and the like are lowered.
  • the zinc oxide has a peak position 2? Value in the range of about 35 to about 37 degrees and a measured FWHM value (diffraction peak) in X-ray diffraction (XRD)
  • the crystallite size value calculated by applying Scherrer's equation (Equation 1) based on the Full width at Half Maximum of about 1,000 to about 2,000 A, for example, about 1,200 to about 1,800 A have.
  • Equation 1 the initial color of the thermoplastic resin composition, weather resistance (discoloration resistance), antimicrobial property, mechanical property balance thereof and the like can be excellent.
  • K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).
  • the zinc oxide may have a specific surface area BET of less than or equal to about 15 m < 2 > / g, as measured by a BET analytical instrument (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 instrument) To about 10 m < 2 > / g, and the purity may be greater than about 99%.
  • the thermoplastic resin composition may have excellent mechanical properties, discoloration resistance, and the like.
  • the zinc oxide may be prepared by melting zinc in the form of a metal and then heating to about 850 to about 1000 ⁇ , such as about 900 to about 950 ⁇ , And then heating at about 400 to about 900 DEG C, for example, about 500 to about 800 DEG C for about 30 to about 150 minutes, for example, about 60 to about 120 minutes.
  • the zinc oxide may be included in an amount of from about 0.1 to about 10 parts by weight, for example, from about 1 to about 5 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the zinc oxide is contained in an amount of less than about 0.1 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin, the weather resistance and antimicrobial properties of the thermoplastic resin composition may be lowered.
  • the zinc oxide is more than about 10 parts by weight , The mechanical properties of the thermoplastic resin composition may be deteriorated.
  • the weight ratio of zinc pyrithione and zinc oxide is from about 1: about 2 to about 1: about 10, such as about 1: about 2 to about 1: 8.
  • the weatherability, antibacterial properties, mechanical properties, and the like of the thermoplastic resin composition can be further improved in the above range.
  • the thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition.
  • the additives include, but are not limited to, a flame retardant, a filler, an antioxidant, a dripping inhibitor, a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a pigment, a dye and mixtures thereof.
  • the content thereof may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, per 100 parts by weight of the thermoplastic resin (rubber-modified aromatic vinyl copolymer resin).
  • 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 220 to about 250 ⁇ , using a conventional twin-screw extruder. .
  • thermoplastic resin composition was measured for initial color (L 0 * , a 0 * , b 0 * ) using a colorimeter for a 50 mm ⁇ 90 mm ⁇ 2.5 mm size injection specimen, and measured in accordance with ASTM D4459 (L 1 * , a 1 * , b 1 * ) was measured in the same manner after the 1,500 hour test, and the color change ( ⁇ E) calculated according to the following formula 2 was about 15 or less, for example, about 5 To about 11 hours.
  • ⁇ L * is a difference (L 1 * -L 0 *) of the test before and after the L * value of
  • ⁇ a * is the difference between (a 1 * - a 0 * ) of the test before and after the a * value is
  • ⁇ b * Is the difference (b 1 * - b 0 * ) between the values of b * before and after the test.
  • the? A * may be about 1.0 to about 1.5.
  • the thermoplastic resin composition may have excellent weather resistance (discoloration resistance), hue, and the like.
  • the thermoplastic resin composition has antibacterial effect against various bacteria such as Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Salmonella, Pneumococcus and MRSA (Methicillin-Resistant Staphylococcus aureus)
  • the antimicrobial activity values calculated according to the following formula 3 were independently in the range of about 2 to about 7 , For example from about 3 to about 6.3.
  • Antibacterial activity log (M1 / M2)
  • M1 is the number of bacteria after 24 hours of incubation for the blank specimen
  • M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.
  • the " blank specimen” is a control specimen of the test specimen (thermoplastic resin composition specimen). Specifically, in order to confirm whether or not the inoculated bacteria were normally grown, bacteria were inoculated on a petri dish and incubated for 24 hours in the same manner as the test specimens. The antibacterial activity of the test specimens . In addition, the "number of bacteria” can be counted by inoculating each specimen with the bacteria, orienting it for 24 hours, collecting the inoculated bacterial solution, diluting it, and growing it into a colony again on a culture dish. Colony grows too much, and when century is difficult, divide the divisions and count them, then convert them to actual numbers.
  • the thermoplastic resin composition may have an Izod impact strength of about 19 to about 23 kgf / cm / cm, as measured according to ASTM D256, of a 1/8 "thick extruded specimen.
  • thermoplastic resin composition was prepared by measuring the initial color (L 2 * , a 2 * , b 2 * ) for a 50 mm ⁇ 90 mm ⁇ 2.5 mm size injection molded thermoplastic resin, The initial color (L 0 * , a 0 * , b 0 * ) was measured for a 50 mm ⁇ 90 mm ⁇ 2.5 mm size injection molded thermoplastic resin composition, and then the color difference with respect to the thermoplastic resin calculated according to the following formula (DELTA E2) of about 1.5 or less, such as about 0.1 to about 1.4. In this range, there is no significant discoloration compared with the thermoplastic resin, and the color of the thermoplastic resin composition can be excellent.
  • DELTA E2 the color difference with respect to the thermoplastic resin
  • ⁇ L * is a difference between the thermoplastic resin and a thermoplastic resin composition sample of the initial L * value (L * 2 -L * 0) and, ⁇ a * is the difference between the initial value of a * of the thermoplastic resin and a thermoplastic resin composition sample (a 2 * - a 0 * ), and? b * is the difference (b 2 * - b 0 * ) between the initial b * values of the thermoplastic resin composition and the thermoplastic resin composition specimen.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the antimicrobial thermoplastic resin composition may be produced in the form of a pellet.
  • the pellet may be manufactured into various molded articles through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains.
  • the molded article is useful as an antimicrobial function product or an exterior material having frequent physical contact because it is excellent in weather resistance, antimicrobial property, impact resistance, flowability (molding processability) and physical properties thereof.
  • Modified aromatic vinyl copolymer resin containing 28% by weight of the rubber-modified vinyl-based graft copolymer (A1) and 72% by weight of the (A2) aromatic vinyl-based copolymer resin was used.
  • G-ABS in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were graft copolymerized with polybutadiene rubber (PBR) having a Z-average of 310 nm and 45 wt% was used.
  • PBR polybutadiene rubber
  • SAN resin (weight average molecular weight: 130,000 g / mol) in which 68 wt% of styrene and 32 wt% of acrylonitrile were polymerized was used.
  • Zinc pyrithione (manufacturer: Wako Pure Chemicals Industries Ltd) was used.
  • the ratio of the peak A in the region of 370 to 390 nm and the peak B of the region of 450 to 600 nm in the range of 370 to 390 nm in the measurement of the average particle size, the BET surface area, the purity, and the photo luminescence of the zinc oxide (C1, B / A) and the crystallite size were measured and are shown in Table 1 below.
  • Average particle size (unit: ⁇ ⁇ ): 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 with a BET analyzer (Micromeritics Surface Area and Porosity Analyzer ASAP 2020 instrument) using a nitrogen gas adsorption method.
  • Purity (unit:%): Purity was measured using TGA thermal analysis at a temperature of 800 ° C.
  • PL size ratio (B / A): According to the photoluminescence measurement method, the spectrum emitted from a He-Cd laser (KIMMON company, 30 mW) 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. (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 additional treatment.
  • the zinc oxide powder was placed in a pelletizer having a diameter of 6 mm and pressed to form a flat specimen. Respectively.
  • K is a shape factor,? Is an X-ray wavelength,? Is an FWHM value (degree) of an X-ray diffraction peak,? Is a peak position value (peak position degree).
  • the above components were added in the amounts shown in Tables 2 and 3, and then extruded at 230 ⁇ to prepare pellets.
  • the pellets were extruded at a temperature of 230 DEG C and a mold temperature of 60 DEG C for 6 hours at 80 DEG C for 4 hours or more, .
  • the properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 2 and 3 below.
  • ⁇ L * is a difference (L 1 * -L 0 *) of the test before and after the L * value of
  • ⁇ a * is the difference between (a 1 * - a 0 * ) of the test before and after the a * value is
  • ⁇ b * Is the difference (b 1 * - b 0 * ) between the values of b * before and after the test.
  • Antibacterial activity value Staphylococcus aureus and E. coli were inoculated on a 5 cm x 5 cm specimen according to JIS Z 2801 antibacterial evaluation method, and cultured at 35 ° C and RH 90% for 24 hours. Respectively.
  • Antibacterial activity log (M1 / M2)
  • M1 is the number of bacteria after 24 hours of incubation for the blank specimen
  • M2 is the number of bacteria after 24 hours of incubation for the thermoplastic resin composition specimen.
  • ⁇ L * is a thermoplastic resin (Comparative Example 1) and the thermoplastic resin composition (Examples and Comparative Examples) of the specimen initial L * value of the difference (L 2 * -L 0 *)
  • ⁇ a * is a thermoplastic resin (Comparative example 1) and the thermoplastic resin composition (examples and Comparative examples) of samples initial a * value of the difference (a 2 * - a 0 * ) and
  • ⁇ b * is a thermoplastic resin (Comparative example 1) and the thermoplastic resin composition ( EXAMPLES AND COMPARATIVE EXAMPLES The difference (b 1 * - b 0 * ) between the initial b * values of the specimen.
  • Example One 2 3 4 (A) (parts by weight) 100 100 100 100 100 (B) (parts by weight) 0.2 0.4 0.6 0.6 (C1) (parts by weight) 1.5 1.5 1.5 1.5 4.8 (C2) (parts by weight) - - - - (C3) (parts by weight) - - - - Weatherability evaluation ( ⁇ E) 9.2 9.4 8.9 8.1
  • the antibacterial activity value (E. coli) 2 3.2 6.3 6.3 Antibacterial activity value (Staphylococcus aureus) 2.1 3 4.6 4.6 Notch Izod impact strength 21 22 21.2 19.3
  • thermoplastic resin composition of the present invention is excellent in weatherability (color change (? E)), antimicrobial activity (antibacterial activity value), mechanical properties (notch Izod impact strength (impact resistance) It can be seen that it is excellent.
  • Comparative Example 1 in which zinc pyrithione and zinc oxide were not used, it was found that weatherability and antimicrobiality were largely lowered.
  • Comparative Examples 2 and 3 in which zinc oxide was not used weatherability, (Comparative Example 1) and the discoloration occurred as the content of the zinc pyrithione was increased as compared with that of the thermoplastic resin (Comparative Example 1).
  • Comparative Example 4 in which zinc pyrithione was not used, it was found that the weather resistance, antimicrobial property and mechanical properties were relatively lower than those in Examples, and zinc oxide (C2) was used instead of zinc oxide
  • Comparative Examples 5 and 6 it was found that the weather resistance was largely lowered, and in Comparative Example 7 in which the content of zinc pyrithione exceeded the range of the present invention, the initial discoloration was severe and the appearance characteristics were deteriorated
  • the content of zinc pyrithione in Comparative Example 8 was lower than the range of the present invention, the antimicrobial activity and the weather resistance were lowered.
  • Comparative Examples 8 and 9 using zinc oxide (C3) instead of zinc oxide (C1) of the present invention, it can be seen that the weather resistance is greatly 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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne une composition de résine thermoplastique comprenant : environ 100 parties en poids d'une résine à base d'un copolymère de vinyle aromatique modifiée par un caoutchouc ; environ 0,1 à 1 partie en poids de pyrithione de zinc ; et environ 0,1 à 10 parties en poids d'oxyde de zinc où la taille de particule moyenne (D50) de l'oxyde de zinc, mesurée par un analyseur de tailles de particules, est d'environ 0,5-3 µm, et le rapport des taille (B/A) du pic A de la région à 370-390 nm au pic B de la région à 450-600 nm est d'environ 0,01-1,0 pendant la mesure de la photoluminescence. La composition de résine thermoplastique présente une excellente propriété de résistance aux intempéries, propriété antibactérienne, propriété mécanique et autres.
PCT/KR2018/010016 2017-10-26 2018-08-30 Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci WO2019083147A1 (fr)

Priority Applications (3)

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US16/645,543 US20200277487A1 (en) 2017-10-26 2018-08-30 Thermoplastic Resin Composition and Molded Product Manufactured Therefrom
JP2020515941A JP2021500421A (ja) 2017-10-26 2018-08-30 熱可塑性樹脂組成物及びこれから製造された成形品
CN201880068344.2A CN111247203A (zh) 2017-10-26 2018-08-30 热塑性树脂组合物和由其制造的模制品

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KR10-2017-0140219 2017-10-26
KR20170140219 2017-10-26
KR10-2018-0064627 2018-06-05
KR1020180064627A KR102150754B1 (ko) 2017-10-26 2018-06-05 열가소성 수지 조성물 및 이로부터 제조된 성형품

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1129416A (ja) * 1997-07-04 1999-02-02 Daiwa Kagaku Kogyo Kk 熱可塑性プラスチックの抗菌防カビ組成物
JPH1135787A (ja) * 1997-07-24 1999-02-09 Techno Polymer Kk 抗菌性熱可塑性樹脂組成物
JP2005343821A (ja) * 2004-06-02 2005-12-15 Fuji Photo Film Co Ltd ピリチオン化合物及びこれを用いたマイクロカプセル
KR20150138275A (ko) * 2013-03-28 2015-12-09 팍스 플라스틱스 비브이 항균 폴리머 및 그 제조방법

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JPH1129416A (ja) * 1997-07-04 1999-02-02 Daiwa Kagaku Kogyo Kk 熱可塑性プラスチックの抗菌防カビ組成物
JPH1135787A (ja) * 1997-07-24 1999-02-09 Techno Polymer Kk 抗菌性熱可塑性樹脂組成物
JP2005343821A (ja) * 2004-06-02 2005-12-15 Fuji Photo Film Co Ltd ピリチオン化合物及びこれを用いたマイクロカプセル
KR20150138275A (ko) * 2013-03-28 2015-12-09 팍스 플라스틱스 비브이 항균 폴리머 및 그 제조방법

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