Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
  • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/24—Derivatives of hydrazine
  • C08K5/25—Carboxylic acid hydrazides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • 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
  • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3055—Cars

Definitions

• the resin composition has a weld elongation of 20% or more when the resin composition is molded into a 1.6 mm thick test piece having a weld part in the center and pulled at 10 mm/min according to ASTM D638. things are listed.
• a molded article obtained from a resin composition containing a polyacetal resin and an elastomer described in Patent Document 1 has excellent flexibility.
• resin compositions that can yield molded products that are flexible and have excellent sliding properties.
• silicone in order to improve sliding properties, it is conceivable to blend silicone into the polyacetal resin.
• the weld elongation of the resulting molded product tends to be poor.
• weld elongation deteriorates, the strength of the molded product decreases.
• the present invention aims to solve the above-mentioned problems, and provides a resin composition from which a molded article having moderate flexibility, excellent sliding properties, and excellent weld elongation can be obtained, and It is an object of the present invention to provide a molded article formed from the resin composition.
• the present inventor conducted a study and found that a predetermined amount of a core-shell elastomer having a predetermined average secondary particle diameter in the polyacetal resin and a silicone having a predetermined kinematic viscosity are blended into the polyacetal resin.
• a predetermined amount of a core-shell elastomer having a predetermined average secondary particle diameter in the polyacetal resin and a silicone having a predetermined kinematic viscosity are blended into the polyacetal resin.
• the core-shell elastomer (B) has an average secondary particle diameter of 10 to 250 nm in the polyacetal resin (A),
• the content of the core-shell elastomer (B) is 5 to 25% by mass in the resin composition
• a resin composition, wherein the silicone (C) has a kinematic viscosity at 25° C. of 4 million to 30 million cSt, and the content thereof is 0.3 to 1% by mass in the resin composition.
• ⁇ 2> The resin composition according to ⁇ 1>, wherein the core-shell elastomer (B) has a crosslinking index in the range of 0.11 to 0.30.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein in the core-shell elastomer (B), the core contains a butadiene-containing rubber and the shell contains an acrylic resin.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, further comprising a hydrazide compound and/or a urea compound.
• ⁇ 5> The resin according to any one of ⁇ 1> to ⁇ 4>, wherein the mass ratio (B)/(C) of the core-shell elastomer (B) and silicone (C) is 8 to 40.
• Composition. ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, which is used for trim clip molding.
• the core-shell elastomer (B) has a crosslinking index in the range of 0.11 to 0.30, and in the core-shell elastomer (B), the core contains a butadiene-containing rubber, the shell contains an acrylic resin, and , contains a hydrazide compound and/or a urea compound, the mass ratio (B)/(C) of the core-shell elastomer (B) and silicone (C) is 8 to 40, and is for trim clip molding, ⁇ 1 >The resin composition described in >. ⁇ 8> Pellets of the resin composition according to any one of ⁇ 1> to ⁇ 7>.
• ⁇ 9> A molded article formed from the resin composition according to any one of ⁇ 1> to ⁇ 7>.
• ⁇ 10> A molded article formed from the pellets described in ⁇ 8>.
• ⁇ 11> The molded product according to ⁇ 9>, which is a trim clip.
• ADVANTAGE OF THE INVENTION it has become possible to provide a resin composition from which a molded article with moderate flexibility, excellent sliding properties, and excellent weld elongation can be obtained, and a molded article formed from the resin composition. Ta.
• this embodiment a mode for carrying out the present invention (hereinafter simply referred to as “this embodiment”) will be described in detail.
• the present embodiment below is an illustration for explaining the present invention, and the present invention is not limited only to this embodiment.
• " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
• various physical property values and characteristic values are assumed to be at 23° C. unless otherwise stated. If the measurement methods, etc. explained in the standards shown in this specification differ from year to year, unless otherwise stated, they shall be based on the standards as of January 1, 2022.
• the resin composition of the present embodiment is a resin composition containing a polyacetal resin (A), a core-shell elastomer (B), and a silicone (C), in which the core-shell elastomer (B) is contained in the polyacetal resin (A).
• the average secondary particle diameter is 10 to 250 nm
• the content of the core-shell elastomer (B) is 5 to 25% by mass in the resin composition
• the kinematic viscosity of the silicone (C) at 25°C is 4 million ⁇ 30 million cSt, and the content is 0.3 ⁇ 1% by mass in the resin composition.
• the interfacial force applied between the core-shell elastomer (B) and the polyacetal resin (A) can be reduced, and weld elongation can be increased. Guessed. Furthermore, it is presumed that by using a predetermined amount of silicone (C) having a predetermined kinematic viscosity, it was possible to effectively suppress a decrease in weld elongation while maintaining sliding properties.
• the resin composition (A) of this embodiment contains a polyacetal resin.
• the polyacetal resin is not particularly limited, and even if it is a homopolymer containing only divalent oxymethylene groups as a constituent unit, it may contain a divalent oxymethylene group and a divalent oxyalkylene having 2 to 6 carbon atoms. It may also be a copolymer containing the group as a constituent unit.
• Examples of the oxyalkylene group having 2 to 6 carbon atoms include oxyethylene group, oxypropylene group, and oxybutylene group.
• the proportion of the oxyalkylene group having 2 to 6 carbon atoms in the total number of moles of the oxymethylene group and the oxyalkylene group having 2 to 6 carbon atoms is not particularly limited, and is 0.5 to 10 mol. % is sufficient.
• trioxane is usually used as the main raw material.
• a cyclic formal or a cyclic ether can be used.
• Specific examples of cyclic formals include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, 1,3,6-trioxocane, etc.
• Specific examples of the cyclic ether include ethylene oxide, propylene oxide, and butylene oxide.
• the resin composition of this embodiment includes a core-shell elastomer (B).
• a core-shell elastomer By using an elastomer, flexibility can be imparted to the resulting molded product. Further, by using a core-shell elastomer as the elastomer, a decrease in weld elongation can be effectively suppressed. Furthermore, by adjusting the core-shell elastomer (B) to have an average secondary particle size of 10 to 250 nm in the polyacetal resin (A), it is possible to effectively reduce weld elongation while maintaining high flexibility.
• a core-shell elastomer is a polymer with a multilayer structure having a core part and a shell layer covering part or all of the core part, and Kaneka Corporation's Kane Ace series and Mitsubishi Chemical Corporation's Metablen series are known.
• the average secondary particle diameter of the core-shell elastomer (B) in the polyacetal resin (A) is 10 to 250 nm.
• the core-shell elastomer (B) is easily dispersed in the polyacetal resin (A), and weld elongation can be increased. This is because when the average secondary particle diameter of the core-shell elastomer (B) becomes large, the core-shell elastomer (B) becomes a starting point for fracture in the molded product.
• the interfacial force applied between the core-shell elastomer (B) and the polyacetal resin (A) is also reduced, and weld elongation can be increased.
• Such an average secondary particle diameter of the core-shell elastomer (B) in the polyacetal resin (A) can be achieved by adjusting the selection of the type of core-shell elastomer (B), the fluidity of the polyacetal resin, the melt-kneading conditions, etc. be done.
• the average secondary particle diameter of the core-shell elastomer (B) is preferably 240 nm or less, more preferably 210 nm or less, even more preferably 180 nm or less, even more preferably 150 nm or less, and even more preferably 120 nm or less. It is even more preferable that Moreover, it is more preferably 30 nm or more, even more preferably 50 nm or more, even more preferably 80 nm or more, and even more preferably 100 nm or more.
• the average secondary particle diameter of the core-shell elastomer (B) is measured according to the description in the examples below.
• crosslinking index of the core-shell elastomer (B) can be adjusted, for example, by the polymerization conditions during production of the core-shell elastomer.
• the crosslinking index of the core-shell elastomer (B) is measured and calculated by the method described in the Examples below.
• the core is preferably a rubber-based polymer.
• the rubber-based polymer preferably contains at least one selected from butadiene-containing rubber, butyl acrylate-containing rubber, 2-ethylhexyl acrylate-containing rubber, and silicone-based rubber, and preferably contains butadiene-containing rubber. More preferred.
• the shell is preferably a polymer of one or more monomers such as (meth)acrylic esters and aromatic vinyl compounds, and units derived from (meth)acrylic esters account for 50% by mass or more of the whole. Polymers (acrylic resins) are more preferred.
• the core-shell elastomer (B) used in this embodiment it is preferable that the core contains a rubber-based polymer and the shell contains an acrylic resin.
• the effects of the present invention tend to be more effectively exhibited.
• the resin composition of this embodiment contains silicone (C).
• silicone (C) By including silicone (C), the slidability of the obtained molded product can be improved.
• the kinematic viscosity at 25° C. of the silicone compound (C) used in this embodiment is 4 million cSt or more, preferably 7 million cSt or more, and more preferably 10 million cSt or more. By setting it above the lower limit value, the limit PV value tends to be further improved. Further, the kinematic viscosity at 25°C of the silicone compound (C) is 30 million cSt or less, preferably 28 million cSt or less, more preferably 25 million cSt or less, and 20 million cSt or less. It is even more preferable. By setting it below the above-mentioned upper limit, the dispersibility of silicone (C) in the polyacetal resin is improved, and weld elongation tends to be further improved.
• the content of silicone (C) in the resin composition of this embodiment is preferably 0.3% by mass or more, more preferably 0.4% by mass or more. By making it equal to or more than the lower limit, sliding properties can be improved.
• the upper limit of the content of silicone (C) in the resin composition is 1% by mass or less, preferably 0.9% by mass or less, and more preferably 0.8% by mass or less. It is preferably 0.7% by mass or less, more preferably 0.6% by mass or less, and even more preferably 0.6% by mass or less. By setting it below the above-mentioned upper limit, weld elongation can be maintained at a high level.
• the resin composition of this embodiment may contain only one type of silicone (C), or may contain two or more types of silicone (C). When two or more types are included, it is preferable that the total amount falls within the above range.
• the ratio (B)/(C) is preferably 40 or less, more preferably 35 or less, even more preferably 32 or less, even more preferably 30 or less, and 25 or less. It is even more preferable that there be. By setting it below the above-mentioned upper limit value, slidability tends to be further improved.
• the resin composition of this embodiment may contain a formaldehyde scavenger.
• a formaldehyde scavenger By including a formaldehyde scavenger, the generation of formaldehyde from the resulting molded product can be effectively suppressed.
• the formaldehyde scavenger preferably contains at least one selected from the group consisting of a hydrazide compound, a hydrazone compound of a hydrazine compound, a guanamine compound, and a urea compound, and more preferably a hydrazide compound and/or a urea compound.
• the resin composition of the present embodiment preferably contains 0.05 parts by mass or more, and more preferably 0.10 parts by mass, of a formaldehyde scavenger based on 100 parts by mass of the polyacetal resin (A). Further, the formaldehyde scavenger is preferably contained in an amount of 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, based on 100 parts by mass of the polyacetal resin.
• the resin composition of this embodiment may contain only one type of formaldehyde scavenger, or may contain two or more types of formaldehyde scavengers. When two or more types are included, the total amount falls within the above range.
• the resin composition of the present embodiment may contain any conventionally known additives and fillers within a range that does not impair the object of the present invention.
• additives and fillers used in this embodiment include thermoplastic resins other than polyacetal resins, ultraviolet absorbers, antioxidants, heat stabilizers, stabilizers, antistatic agents, carbon fibers, dyes, and carbon black.
• organic pigments such as, inorganic pigments such as titanium oxide, glass fibers, glass flakes, potassium titanate whiskers, and the like.
• the resin composition of this embodiment has excellent weld elongation and does not break before yielding. Specifically, when the resin composition of this embodiment is molded into an ASTM tensile test piece (thickness 1.6 mm) and a tensile test is performed according to ASTM D638, the weld elongation is 14% or more. It is preferably 17% or more, more preferably 18% or more, and even more preferably 20% or more. Further, the upper limit of the weld elongation is, for example, 300% or less.
• the resin composition of this embodiment contains the above-mentioned essential components and, if necessary, the above-mentioned arbitrary components. Any manufacturing method is selected so that the average secondary particle diameter falls within the above-mentioned range. These raw materials may be mixed and kneaded using any conventionally known method for producing a resin composition.
• L/D which is the ratio of the length L (mm) of the screw to the diameter D (mm) of the same screw, is preferably 20 or more, more preferably 30 or more, and 100 or less.
• the shape of the die nozzle is also not particularly limited, but in terms of pellet shape, a circular nozzle with a diameter of 1 mm or more is preferable, a circular nozzle with a diameter of 2 mm or more is more preferable, a circular nozzle with a diameter of 10 mm or less is preferable, and a circular nozzle with a diameter of 7 mm or less is preferable. Nozzles are more preferred.
• the melting temperature of the resin composition during melt-kneading is preferably 170°C or higher, more preferably 190°C or higher, and preferably 250°C or lower, and preferably 230°C or lower. More preferred.
• the melting temperature is preferably 170° C. or higher, melting becomes sufficient and production volume tends to improve.
• the temperature is set to 250° C. or lower, discoloration of the resin composition due to thermal deterioration tends to be effectively suppressed.
• the screw configuration of the twin-screw extruder is not particularly limited, one preferred embodiment includes having at least two kneading sections.
• the kneading section has a kneading disk and mainly contributes to melting the resin and dispersing the elastomer.
• the screw rotation speed during melt-kneading is preferably 50 rpm or more, more preferably 70 rpm or more, and preferably 500 rpm or less, and more preferably 350 rpm or less.
• the screw rotation speed is preferably 50 rpm or more, more preferably 70 rpm or more, and preferably 500 rpm or less, and more preferably 350 rpm or less.
• the discharge rate is preferably 5 kg/hr or more, more preferably 7 kg/hr or more, preferably 1,000 kg/hr or less, and more preferably 800 kg/hr or less.
• the rate is preferably 5 kg/hr or more, more preferably 7 kg/hr or more, preferably 1,000 kg/hr or less, and more preferably 800 kg/hr or less.
• the ratio (Q/Ns) between the screw rotation speed (Ns) and the discharge amount (Q) during melt-kneading depends on the screw diameter and screw configuration of the extruder, but is preferably 0.5 or more, and 0.7
• the above is more preferable, 0.9 or more is particularly preferable, 1.5 or less is preferable, 1.3 or less is even more preferable, and 1.2 or less is particularly preferable.
• the above Q/Ns is particularly preferable in an embodiment in which the screw diameter is 18 to 75 mm (even 58 mm) and the screw configuration has two kneading sections.
• Examples of the kneading machine include a kneader, a Banbury mixer, and an extruder.
• the various conditions and equipment for mixing and kneading are also not particularly limited, and may be determined by appropriately selecting from any conventionally known conditions.
• the kneading is preferably carried out at a temperature higher than the melting temperature of the polyacetal resin, specifically at a temperature higher than the melting temperature of the polyacetal resin (generally 180° C. or higher).
• the molded article of this embodiment is formed from the resin composition of this embodiment. Further, the resin composition of the present embodiment is usually made into a molded product by injection molding the pellets obtained by directly or by pelletizing the resin composition. That is, a preferable example of the molded product of this embodiment is an injection molded product.
• An injection molded product is a molded product formed by injection molding, and a weak portion (weld portion) is usually formed at a portion where molten resin joins within a mold.
• the shape of the molded product is not particularly limited and can be appropriately selected depending on the use and purpose of the molded product, such as plate, plate, rod, sheet, film, cylindrical, annular, etc.
• the resin composition of the present embodiment and molded products formed from the resin composition are, for example, automotive parts such as trim clips, seatbelt members, and headrest guides, building material parts, electric/electronic parts, office equipment parts, and daily miscellaneous goods.
• automotive parts such as trim clips, seatbelt members, and headrest guides
• building material parts such as electric/electronic parts, office equipment parts, and daily miscellaneous goods.
• examples include containers for frozen foods and beverages, home appliances such as refrigerator gaskets, hose bands, gaskets, and cable ties.
• the resin composition and molded article of this embodiment are suitable for trim clips.
• the above MVR is a melt volume rate measured under the conditions of a temperature of 190° C. and a load of 2.16 kg in accordance with ISO1133.
• the kinematic viscosity of the silicone oil and silicone gum described above is a value measured by the following method.
• 1.0 g of silicone oil or silicone gum was weighed out and dissolved in 10 mL of toluene, and the viscosity of the silicone-toluene solution was measured using a cone-plate viscometer TPE100.
• TPE100 cone-plate viscometer
• a SEM image was obtained using a scanning electron microscope (SEM). From the obtained SEM image, the average value of the maximum length of the island-shaped portions derived from the elastomer was defined as the average secondary particle diameter of the elastomer.
• the injection molding machine used was EC-100S manufactured by Shibaura Kikai Co., Ltd.
• the osmium tetroxide was vapor-deposited using an "Osmium Coater" manufactured by Meiwaforsys under conditions of 8 mA and 60 seconds.
• the scanning electron microscope was a "Scanning Electron Microscope (SEM) S-4800" manufactured by Hitachi High Technologies, and the SEM was performed under the following conditions: acceleration voltage: 1 kV, signal: LA100 (U), emission current: 6 ⁇ A, probe current: Normal. The image was acquired.
• SEM Sccanning Electron Microscope
• this 4 mm thick multi-purpose test piece (ISO test piece) was subjected to a bending test using a fully automatic bending tester at a bending test speed of 2 mm/min according to the method described in ISO178. , the flexural modulus was measured. A fully automatic bending tester manufactured by Shimadzu Corporation was used. The unit is MPa.
• the evaluation criteria are as follows. A: 1500 MPa or more, less than 2400 MPa B: 1300 MPa or more, less than 1500 MPa, or 2400 MPa or more, less than 2450 MPa C: Less than 1300 MPa, or 2450 MPa or more The results are shown in Tables 2 to 6 below.
• ⁇ Formaldehyde generation amount> The pellets obtained above were heat-treated for 4 hours in a hot air circulation dryer at a temperature of 80°C. Next, the dried pellets were used in an injection molding machine, with the cylinder temperature set at 210°C and the mold temperature set at 80°C, to produce a flat test piece of 100 mm x 40 mm x 2 mm. Regarding this test piece, the amount of formaldehyde generated in 1 g of polyacetal resin was determined by the following method in accordance with the method described in the German Automobile Industry Association standard VDA275 (Automotive interior parts - Determination of formaldehyde release amount by revised flask method). It was measured.
• the unit is the amount of formaldehyde generated ( ⁇ g) per gram of polyacetal resin, ie, ⁇ g/g-POM.
• the measurement results were evaluated according to the following criteria. A: Less than 5 ⁇ g/g-POM B: 5 ⁇ g/g-POM or more and less than 10 ⁇ g/g-POM C: 10 ⁇ g/g-POM or more
• the results are shown in Tables 2 to 6 below.

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• 2023
  • 2023-06-02 KR KR1020247041765A patent/KR20250020466A/ko active Pending
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