WO2021054679A1 - Composition de résine thermoplastique, son procédé de préparation, et produit moulé fabriqué à partir de cette dernière - Google Patents

Composition de résine thermoplastique, son procédé de préparation, et produit moulé fabriqué à partir de cette dernière Download PDF

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Publication number
WO2021054679A1
WO2021054679A1 PCT/KR2020/012281 KR2020012281W WO2021054679A1 WO 2021054679 A1 WO2021054679 A1 WO 2021054679A1 KR 2020012281 W KR2020012281 W KR 2020012281W WO 2021054679 A1 WO2021054679 A1 WO 2021054679A1
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Prior art keywords
weight
resin composition
thermoplastic resin
aromatic vinyl
compound
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PCT/KR2020/012281
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English (en)
Korean (ko)
Inventor
장정민
김태훈
박춘호
성다은
안용희
조왕래
김호훈
Original Assignee
(주) 엘지화학
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Priority claimed from KR1020200114753A external-priority patent/KR102457383B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to CN202080006542.3A priority Critical patent/CN113166510B/zh
Priority to EP20865196.8A priority patent/EP3872133A4/fr
Priority to JP2021536691A priority patent/JP7220792B2/ja
Priority to US17/299,256 priority patent/US20220033633A1/en
Publication of WO2021054679A1 publication Critical patent/WO2021054679A1/fr

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    • 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
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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, a method for producing the same, and a molded article manufactured therefrom, and more particularly, to satisfy economical and chemical resistance at the same time, including a predetermined additive at an inexpensive cost compared to a conventional additive for chemical resistance, and It relates to a thermoplastic resin composition excellent in heat resistance and impact strength, a method for manufacturing the same, and a molded article manufactured therefrom.
  • the acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as'ASA resin') has excellent weather resistance, light resistance, colorability, chemical resistance, and impact resistance, and is thus used in various fields such as automobiles, miscellaneous goods, and construction materials.
  • ASA resin' acrylate compound-styrene-acrylonitrile copolymer
  • ASA resin is an eco-friendly material that has superior processing stability and does not contain heavy metal components compared to PVC or PP resins that have been used in the past, and is attracting attention in the field of exterior materials such as decorative sheets.
  • the ASA resin has a problem of generating press marks during the storage process or a problem in which the dimensions of the sheet are deformed during processing, and in particular, a problem of melting in the solvent component of the adhesive used in the bonding process with the substrate occurs.
  • thermoplastic resin composition that not only has excellent appearance quality, but also improves chemical resistance and satisfies the needs of consumers.
  • Patent Document 1 Korean Patent Publication No. 2006-0065980
  • the present invention is a thermoplastic resin composition that satisfies both economy and chemical resistance, and has excellent heat resistance and impact strength by including a predetermined additive at a lower cost compared to the conventional chemical resistance additive. It is intended to provide a method for manufacturing the same, and a molded article manufactured therefrom.
  • the present invention is A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.05 to 0.15 ⁇ m as a core, A-2) an average particle diameter 100 weight of base resin consisting of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer having an acrylate rubber of 0.3 to 0.6 ⁇ m as a core part; And C) 0.5 to 10 parts by weight of a polyolefin elastomer, and a heat distortion temperature (HDT) of 89° C. or higher is provided.
  • A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.05 to 0.15 ⁇ m as a core A-2) an average particle diameter 100 weight of base resin consisting of an acrylate-aromatic vinyl compound-vinyl
  • the present invention A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m as a core, A-2) an acrylic having an average particle diameter of 0.3 to 0.6 ⁇ m 100 parts by weight of a base resin composed of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having a rate rubber as a core, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; And C) 0.5 to 10 parts by weight of a polyolefin elastomer; kneading and extruding under conditions of 200 to 330° C. and 100 to 500 rpm to prepare a thermoplastic resin composition, wherein the thermoplastic resin composition has a heat deflection temperature (HDT) It provides a method for producing a thermoplastic resin composition, characterized in that more than 89 °C.
  • HDT heat
  • the present invention provides a molded article comprising the thermoplastic resin composition.
  • the present invention A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 1 to 30% by weight, A-2) an average particle diameter of 0.3 Acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 5 to 50% by weight, B-1) 40 to 85% by weight of aromatic vinyl polymer, and B-2) heat resistance with an acrylate rubber of to 0.6 ⁇ m as a core 100 parts by weight of a base resin consisting of 5 to 50% by weight of an aromatic vinyl polymer; And C) 0.5 to 10 parts by weight of a polyolefin elastomer.
  • thermoplastic resin composition that satisfies economy and chemical resistance at the same time, and has excellent heat resistance and impact strength, including predetermined additives at a lower cost compared to conventional additives for chemical resistance, a method of manufacturing the same, and a molded article manufactured therefrom Has the effect of providing.
  • thermoplastic resin composition of the present disclosure a method for manufacturing the same, and a molded article manufactured therefrom will be described in detail.
  • the inventors of the present invention consider that in the case of including a predetermined polymer elastomer at a low cost within a certain range instead of a chemical resistance additive such as polymethyl methacrylate, while increasing economic efficiency, chemical resistance, heat resistance, and impact All of the improved strength confirmed that it can be applied in high quality to fields requiring both high chemical resistance, heat resistance, and impact strength, such as exterior materials, especially Deco Sheet. The invention was completed.
  • thermoplastic resin composition of the present invention is A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.05 to 0.15 ⁇ m as a core, A-2) an average particle diameter of 0.3 to 0.6 ⁇ m 100 parts by weight of a base resin composed of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an acrylate rubber of the core, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer; And C) 0.5 to 10 parts by weight of a polyolefin elastomer, wherein the heat deflection temperature (HDT) is 89°C or higher.
  • the thermoplastic resin composition has excellent economy and chemical resistance at the same time, including a predetermined additive at an inexpensive cost compared to the conventional additive for chemical resistance, and has excellent effects in heat resistance and impact strength.
  • thermoplastic resin composition of the present invention is A-1) 1 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.05 to 0.15 ⁇ m as a core, A-2 ) 5 to 50% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.3 to 0.6 ⁇ m as a core, B-1) 40 to 85% by weight of an aromatic vinyl polymer, and B -2) 100 parts by weight of a base resin composed of 5 to 50% by weight of a heat-resistant aromatic vinyl polymer; And C) 0.5 to 10 parts by weight of a polyolefin elastomer.
  • economical efficiency, impact strength, chemical resistance, and heat resistance are all excellent.
  • thermoplastic resin composition of the present disclosure will be described in detail.
  • the acrylate rubber of the A-1) graft copolymer may have, for example, an average particle diameter of 0.05 to 0.15 ⁇ m, preferably 0.1 to 0.15 ⁇ m, more preferably 0.12 to 0.15 ⁇ m, and even more preferably 0.12 to It is 0.14 ⁇ m, and excellent weather resistance and impact strength can be imparted to the final thermoplastic resin composition within this range.
  • the average particle diameter can be measured using dynamic light scattering, and in detail, it can be measured using Nicomp 380 equipment (manufacturer: PSS).
  • the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of a scattering intensity.
  • the A-1) graft copolymer is, for example, 1 to 30% by weight, preferably 1 to 20% by weight, more preferably 5 to 15% by weight, even more preferably 5 to 10% by weight, based on the base resin, Weather resistance, fluidity, tensile strength and impact strength are excellent within this range.
  • the A-1) graft copolymer may be included in an amount less than that of the A-2) graft copolymer, and preferably, the A-1) graft copolymer and the A-2) graft copolymer
  • the A-1) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, and weather resistance within this range , Fluidity and impact strength are excellent.
  • the A-1) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 50% by weight of an aromatic vinyl compound, and 5 to 20% by weight of a vinyl cyan compound, within this range. It has excellent effects in weather resistance, fluidity and impact strength.
  • the A-1) graft copolymer may comprise 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, within this range. It has excellent effects in weather resistance, fluidity and impact strength.
  • a polymer comprising a compound refers to a polymer polymerized including the compound, and the unit in the polymerized polymer is derived from the compound.
  • the A-1) graft copolymer may be prepared by emulsion polymerization as an example, and in this case, it has excellent effects in chemical resistance, weather resistance, fluidity, tensile strength and impact strength.
  • the emulsion polymerization is not particularly limited in the case of using the emulsion graft polymerization method commonly carried out in the technical field to which the present invention belongs.
  • the acrylate may be, for example, one or more selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl group, and more preferably butyl acrylic Rate or ethylhexyl acrylate.
  • the aromatic vinyl compound may be, for example, one or more selected from the group consisting of styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, and p-tert-butylstyrene, preferably styrene.
  • the vinyl cyan compound may be one or more selected from the group consisting of acrylonitrile, metanitroonitrile, ethyl acrylonitrile, and isopropyl acrylonitrile, for example, and is preferably acrylonitrile.
  • the acrylate rubber of the A-2) graft copolymer may have, for example, an average particle diameter of 0.3 to 0.6 ⁇ m, preferably 0.35 to 0.5 ⁇ m, more preferably 0.4 to 0.5 ⁇ m, and even more preferably 0.45 to It is 0.50 ⁇ m, and within this range, it has good weather resistance and excellent mechanical strength such as fluidity and impact strength.
  • the A-2) graft copolymer is, for example, 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and even more preferably 11 to 25% by weight, based on the base resin, Weather resistance, fluidity and impact strength are excellent within this range.
  • the A-2) graft copolymer may include, for example, 40 to 60% by weight of an acrylate rubber, 25 to 45% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, and weather resistance within this range , Fluidity and impact strength are excellent.
  • the A-2) graft copolymer may comprise 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyan compound, within this range It has excellent effects in weather resistance, fluidity and impact strength.
  • the A-2) graft copolymer may be prepared by emulsion polymerization as an example, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
  • the emulsion polymerization is not particularly limited in the case of using the emulsion graft polymerization method commonly carried out in the technical field to which the present invention belongs.
  • the B-1) aromatic vinyl polymer may be, for example, 40 to 85% by weight, preferably 50 to 80% by weight, more preferably 60 to 85% by weight or 55 to 75% by weight, further It is preferably 60 to 70% by weight, and within this range, there are advantages of excellent flow and weather resistance, less yellowing, and easy coloring.
  • the B-1) aromatic vinyl polymer may be, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, and in this case, there is an effect of excellent chemical resistance and fluidity.
  • the B-1) aromatic vinyl polymer is preferably composed of 65 to 80% by weight of an aromatic vinyl compound and 20 to 35% by weight of a vinyl cyanide compound, and has excellent effects in chemical resistance, processability and impact strength within this range. .
  • the B-1) aromatic vinyl polymer for example, has a weight average molecular weight of 100,000 to 210,000 g/mol, preferably 120,000 to 200,000 g/mol, more preferably 150,000 to 200,000 g/mol, within this range. There are excellent effects such as fluidity and chemical resistance.
  • the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze) unless otherwise defined, and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent. ) Can be measured relative to the standard PS (standard polystyrene) sample.
  • GPC Gel Permeation Chromatography, waters breeze
  • THF tetrahydrofuran
  • the aromatic vinyl compound-vinyl cyan compound copolymer may be a styrene-acrylonitrile copolymer (SAN resin) as a preferred example, and in this case, there is an effect of excellent fluidity and the like.
  • SAN resin styrene-acrylonitrile copolymer
  • the B-1) aromatic vinyl polymer may be prepared by solution polymerization or bulk polymerization, for example, and in this case, heat resistance and fluidity are excellent.
  • the solution polymerization and block polymerization are not particularly limited when each of the solution polymerization and block polymerization methods commonly performed in the technical field to which the present invention pertains is used.
  • the B-2) heat-resistant aromatic vinyl polymer may be, for example, 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and even more preferably 10 to It is 20% by weight, and there is an effect excellent in heat resistance and chemical resistance within this range.
  • the heat-resistant aromatic vinyl polymer is not particularly limited if it is a polymer commonly referred to as a heat-resistant aromatic vinyl polymer in the technical field to which the present invention belongs, but specifically, a monomer having a high glass transition temperature (based on the polymer) compared to the styrene monomer, that is, heat resistance. It may mean an aromatic vinyl polymer comprising a monomer.
  • the heat-resistant monomer may be, for example, one or more selected from the group consisting of alpha-methylstyrene and maleimide-based compounds
  • the maleimide-based compound is, for example, maleimide, N-methyl maleimide, N-ethyl maleimide, N -Propyl maleimide, N-isopropyl maleimide, N-butyl maleimide, N-isobutyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide , N-(4-chlorophenyl) maleimide, 2-methyl-N-phenyl maleimide, N-(4-bromophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-(4- Hydroxyphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-carboxyphen
  • the B-2) heat-resistant aromatic vinyl polymer is preferably at least one selected from the group consisting of an alpha-methylstyrene-vinyl cyan compound copolymer and a maleimide-based compound-aromatic vinyl compound copolymer, and more preferably alpha-methyl It is a styrene-vinyl cyan compound copolymer, more preferably an alpha-methylstyrene-acrylonitrile copolymer, and in this case, heat resistance and impact strength are excellent.
  • the alpha-methylstyrene-vinyl cyan compound copolymer preferably comprises 50 to 80% by weight of alpha-methylstyrene and 20 to 50% by weight of the vinylcyan compound, more preferably 55 to alpha-methylstyrene.
  • the furnace may comprise 60 to 70% by weight of alpha-methylstyrene, 5 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile, and as another preferred embodiment, 65 to 70% by weight of alpha-methylstyrene %, 5 to 10% by weight of styrene, and 25 to 30% by weight of acrylonitrile may be included, and within this range, heat resistance and the like are excellent.
  • the alpha-methylstyrene-vinyl cyan compound copolymer preferably has a weight average molecular weight of 80,000 to 150,000 g/mol, more preferably 80,000 to 120,000 g/mol, and has excellent effects such as heat resistance within this range. have.
  • the alpha-methylstyrene-vinyl cyan compound copolymer preferably has a glass transition temperature of 110 to 150°C, more preferably 110 to 140°C, and has excellent effects such as heat resistance within this range.
  • the glass transition temperature (Tg) may be measured using a differential scanning calorimetry (DSC), and as a specific example, it may be measured using a differential scanning calorimeter manufactured by TA Instrument.
  • DSC differential scanning calorimetry
  • the maleimide-based compound-aromatic vinyl compound copolymer may be preferably at least one selected from the group consisting of a maleimide-based compound-styrene copolymer and a maleimide-based compound-styrene-vinyl cyan compound copolymer, more preferably It is a maleimide-based compound-styrene copolymer, more preferably an N-substituted maleimide compound-styrene-maleic anhydride copolymer, and has excellent effects in heat resistance and impact strength within this range.
  • the maleimide-based compound may be included in 30 to 70% by weight, preferably 45 to 55% by weight in the heat-resistant aromatic vinyl polymer as an example, and within this range, heat resistance and impact strength are excellent.
  • the aromatic vinyl compound may be included in 25 to 65% by weight, preferably 40 to 50% by weight, in the heat-resistant aromatic vinyl polymer as an example, and within this range, heat resistance and impact strength are excellent.
  • the vinyl cyan compound and the maleic anhydride may be included in 1 to 30% by weight, preferably 1 to 10% by weight, respectively, in the heat-resistant aromatic vinyl polymer as an example, and the heat resistance and impact strength within this range It has an excellent effect.
  • the B-2) heat-resistant aromatic vinyl polymer may be prepared by solution polymerization or bulk polymerization, for example, and in this case, heat resistance and fluidity are excellent.
  • the solution polymerization and block polymerization are not particularly limited when each of the solution polymerization and block polymerization methods commonly performed in the technical field to which the present invention pertains is used.
  • the C) polyolefin elastomer may preferably be at least one selected from the group consisting of ethylene-alpha-olefin copolymer (elastomer) and linear low density polyethylene (LLDPE), more preferably linear low density polyethylene (LLDPE), ethylene-1 -At least one selected from the group consisting of butene elastomer (EBR), ethylene-1-pentene elastomer (EPR), ethylene-1-heptene elastomer (HER), and ethylene-1-octene elastomer (EOR), more preferably It is one or more selected from the group consisting of ethylene-1-octene elastomer (EOR) and ethylene-1-butene elastomer (EBR), and has an effect of improving chemical resistance, impact strength, and heat resistance within this range.
  • EBR butene elastomer
  • EPR ethylene-1-pentene elastomer
  • HER ethylene-1-he
  • the C) polyolefin elastomer has a melt index (190° C., 2.16 kg) of preferably 0.3 to 20 g/10 minutes, more preferably 0.5 to 10 g/10 minutes, and even more preferably 1 to 6 g/10 minutes , More preferably, it is 1 to 5 g/10 minutes, and there is an effect of improving chemical resistance, impact strength, and heat resistance within this range.
  • the C) polyolefin elastomer may have, for example, a weight average molecular weight of 60,000 to 120,000 g/mol, preferably 80,000 to 110,000 g/mol, more preferably 90,000 to 110,000 g/mol, and within this range, chemical resistance and impact strength And there is an effect of improving the heat resistance.
  • the C) polyolefin elastomer is preferably 50 to 90% by weight of ethylene; And 10 to 50% by weight of butene, pentene, heptene or octene, and more preferably 60 to 90% by weight of ethylene; And butene, pentene, heptene or octene 10 to 40% by weight; more preferably 60 to 70% by weight of ethylene; And 30 to 40% by weight of butene, pentene, heptene or octene; and within this range, chemical resistance, impact strength, and heat resistance are further There is an improved effect.
  • the C) polyolefin elastomer may preferably have a density of 0.85 to 0.89, more preferably a density of 0.856 to 0.887, more preferably a density of 0.860 to 0.867, and even more preferably 0.860. To 0.864, and within this range, there is an effect of improving chemical resistance, impact strength, and heat resistance.
  • the C) polyolefin elastomer may be, for example, an ethylene-butene elastomer having a butene content of 10 to 40% by weight, a weight average molecular weight of 60,000 to 120,000 g/mol, and a density of 0.860 to 0.887.
  • This is an ethylene-butene elastomer having a 30 to 40% by weight, a weight average molecular weight of 90,000 to 110,000 g/mol, and a density of 0.860 to 0.864. Within this range, chemical resistance, impact strength, and heat resistance are greatly improved. have.
  • the density may be measured according to a measurement method commonly used in the technical field to which the present invention belongs, and as a specific example, it may be measured according to ASTM D-792.
  • the C) polyolefin elastomer may be, for example, 0.5 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and even more preferably 2 to 4 parts by weight based on 100 parts by weight of the base resin. It is negative, and there is an effect of improving chemical resistance, impact strength, and heat resistance within this range.
  • the C) polyolefin elastomer may be prepared by, for example, a bulk polymerization method or a solution polymerization method, and is preferably prepared by a solution polymerization method. It can be carried out using a strong catalyst.
  • thermoplastic resin composition of the present disclosure is, for example, an antioxidant, a UV stabilizer, a UV stabilizer, a fluorescent whitening agent, a lubricant, a chain extender, a release agent, a pigment, a dye, an antibacterial agent, a processing aid, a metal deactivator, a smoke inhibitor, an inorganic filler, and a glass.
  • It may further include one or more additives selected from the group consisting of fibers, anti-friction agents and anti-wear agents, and the additive is, for example, 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the base resin, More preferably, it may be 0.1 to 1 part by weight, and in this case, it is excellent in improving physical properties and low manufacturing cost, so there is an effect of excellent economic efficiency.
  • the additive is, for example, 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the base resin, More preferably, it may be 0.1 to 1 part by weight, and in this case, it is excellent in improving physical properties and low manufacturing cost, so there is an effect of excellent economic efficiency.
  • thermoplastic resin composition of the present disclosure preferably has an Izod impact strength (1/4", 23° C.) measured according to ASTM D256 of 6 kgf ⁇ cm/cm 2 or more, 6 to 15 kgf ⁇ cm/cm 2 , or 9 To 12 kgf ⁇ cm/cm 2 , and within this range, the balance of chemical resistance, impact strength, and heat resistance is excellent.
  • thermoplastic resin composition of the present disclosure may preferably have a melt index (220° C., 10 kg) measured according to ASTM D1238 of 9 g/10 min or more, 9 to 16 g/10 min, or 9 to 15 g/10 min, Within this range, there is an excellent effect in the balance of chemical resistance, impact strength, and heat resistance.
  • thermoplastic resin composition of the present disclosure may preferably have a hardness (ASTM D785, R-Scale) of less than 116, or greater than or equal to 112 to less than 116, and has an excellent effect in the balance of chemical resistance, impact strength, and heat resistance within this range. .
  • thermoplastic resin composition of the present disclosure may have a heat deflection temperature (HDT) of preferably 89.6°C or more, more preferably 89.8°C or more, still more preferably 90°C or more, and even more preferably 90.1°C or more, as measured according to ASTM D648. , Within this range, there is an excellent effect in the balance of chemical resistance, impact strength, and heat resistance.
  • HDT heat deflection temperature
  • thermoplastic resin composition of the present invention a method for preparing the thermoplastic resin composition of the present invention and a molded article including the composition will be described.
  • all the contents of the above-described thermoplastic resin composition are included.
  • thermoplastic resin composition
  • the method for producing the thermoplastic resin composition of the present invention is preferably A-1) an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer having an average particle diameter of 0.05 to 0.15 ⁇ m as a core, A-2) average Base resin 100 consisting of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, B-1) an aromatic vinyl polymer, and B-2) a heat-resistant aromatic vinyl polymer having an acrylate rubber having a particle diameter of 0.3 to 0.6 ⁇ m as a core Parts by weight; And C) 0.5 to 10 parts by weight of a polyolefin elastomer; kneading and extruding under conditions of 200 to 330° C.
  • thermoplastic resin composition wherein the thermoplastic resin composition has a heat deflection temperature (HDT) It may be 89° C. or higher, and in this case, the thermoplastic resin composition prepared in this case has excellent economical properties and chemical resistance at the same time, including a predetermined additive at an inexpensive cost compared to a conventional chemical resistance additive, and has an advantage of excellent heat resistance and impact strength.
  • HDT heat deflection temperature
  • the kneading may be, for example, kneading the base resin first, and then adding the polymeric plasticizer to kneading, and as another example, kneading the base resin and the polymeric plasticizer at once.
  • the kneading and extrusion may be performed through, for example, a single screw extruder, a twin screw extruder, or a Benbury mixer, and in this case, the composition is uniformly dispersed and thus has excellent compatibility.
  • the kneading and extrusion may be carried out within a range of, for example, a barrel temperature of 150 to 330 °C, 180 to 300 °C, 180 to 280 °C, or 200 to 250 °C, and in this case, the processing amount per unit time is adequate and sufficient melt kneading This may be possible, and there is an effect that does not cause problems such as thermal decomposition of the resin component.
  • the kneading and extrusion may be performed under conditions of, for example, 50 to 400 rpm, 100 to 350 rpm, 100 to 300 rpm, 120 to 300 rpm, or 150 to 250 rpm, and in this case, the amount of processing per unit time is appropriate. Thus, while having excellent process efficiency, there is an effect of suppressing excessive cutting.
  • the molded article of the present substrate may be made of, for example, the thermoplastic resin composition of the present substrate, and in this case, it has excellent mechanical properties such as impact strength and excellent chemical resistance, processability expressed in terms of melt index, and heat resistance.
  • the molded article may include, for example, a housing of a home appliance such as an air conditioner, a vacuum cleaner, a washing machine, a refrigerator, and a TV back cover; Housings of OA devices such as computers, notebooks, monitors, facsimiles, telephones, copiers and scanners; Automobile parts such as automobile interior and exterior materials; Construction interior and exterior materials; A toy member; Leisure goods; And interior decoration, etc., may be more preferably a building exterior material, more preferably a deco sheet, in this case, the chemical resistance, impact strength and heat resistance required in the market by the thermoplastic resin composition of the present invention
  • the first graft copolymer of the emulsion polymerization method (core: 50% by weight of a butyl acrylate polymer having an average particle diameter of 130 nm, shell: 35% by weight of styrene, 15% by weight of acrylonitrile)
  • the second graft copolymer of the emulsion polymerization method (core: 50% by weight of a butyl acrylate polymer having an average particle diameter of 500 nm, shell: 35% by weight of styrene, 15% by weight of acrylonitrile)
  • Polyolefin elastomer EOR (LC150, which has a melt index (190°C, 2.16kg) of 1.0 g/10min, an octene content of 30 to 40% by weight, a density of 0.856 to 0.860, and a weight average molecular weight of 120,000 to 140,000 LG Chem) was used.
  • EOR LC150, which has a melt index (190°C, 2.16kg) of 1.0 g/10min, an octene content of 30 to 40% by weight, a density of 0.856 to 0.860, and a weight average molecular weight of 120,000 to 140,000 LG Chem
  • MI Melt index
  • Example 1 9.4 9.8 115.4 90.3 ⁇
  • Example 2 9.8 9.3 114.9 90.8 ⁇
  • Example 3 10.4 8.9 114.2 91.1 ⁇
  • Example 4 11.1 7.6 113.6 91.0 ⁇
  • Example 5 12.3 6.7 112.8 90.8 ⁇
  • Example 6 10.3 9.3 115.7 89.8 ⁇
  • Example 7 11.1 8.7 114.6 90.4 ⁇
  • Example 8 10.5 8.8 114.4 92.4 ⁇
  • thermoplastic resin composition (Examples 1 to 9) according to the present invention was compared to Comparative Example 1, which did not contain all of the polyolefin elastomer according to the present invention and the conventional chemical resistance additive, While maintaining the same or higher level, it was confirmed that the heat resistance expressed by the melt index and the heat deflection temperature was excellent, and in particular, the chemical resistance was remarkably improved.
  • thermoplastic resin composition according to the present invention (Examples 1 to 9 ) Compared to Comparative Example 2 containing a conventional chemical resistance additive, it was confirmed that the melt index, impact strength, and hardness were significantly excellent in heat resistance and chemical resistance while maintaining the same or higher level.
  • Examples 1 to 5 comprising ethylene-butene elastomers having a butene content of 30 to 40% by weight, a weight average molecular weight of 90,000 to 110,000 g/mol, and a density of 0.860 to 0.864 as the polyolefin elastomer according to the present invention are Compared to Examples 6 and 7 containing ethylene-butene elastomer having a butene content of 30 to 40% by weight, a weight average molecular weight of 60,000 to 80,000 g/mol, and a density of 0.863 to 0.867, it is more excellent in terms of impact strength and heat resistance Was able to confirm.
  • Example 10 9.7 9.5 114 89.5 ⁇
  • Example 11 10.2 9.4 113.5 89.1 ⁇
  • Example 12 9.7 9.0 115.2 89.6 ⁇
  • Example 13 10.3 8.7 115 89.4 ⁇
  • thermoplastic resin composition (Examples 10 to 13) according to the present invention was compared to Comparative Example 1 as in Examples 1 to 9 above, and the hardness and heat resistance were equal to or higher than those of Comparative Example 1 While maintaining the melt index is excellent, in particular, chemical resistance is significantly improved, compared to Comparative Example 2, while maintaining the level of the melt index, impact strength and hardness equal or higher, it can be confirmed that the heat resistance and chemical resistance are greatly excellent. there was.

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

Abstract

La présente invention concerne une composition de résine thermoplastique, son procédé de préparation, et un produit moulé fabriqué à partir de cette dernière et, plus spécifiquement, une composition de résine thermoplastique, son procédé de préparation, et un produit moulé fabriqué à partir de cette dernière, la composition de résine thermoplastique comprenant : 100 parties en poids d'une résine de base constituée de A-1) un copolymère greffé d'acrylate-composé de vinyle aromatique-composé cyanure de vinyle comprenant, comme cœur de celui-ci, un caoutchouc acrylate ayant un diamètre moyen de 0,05 à 0,15 µm, A-2) un copolymère greffé d'acrylate-composé de vinyle aromatique-composé cyanure de vinyle comprenant, comme cœur de celui-ci, un caoutchouc acrylate ayant un diamètre moyen de 0,3 à 0,6 µm, B-1) un polymère de vinyle aromatique, et B-2) un polymère de vinyle aromatique résistant à la chaleur ; et C) de 0,5 à 10 parties en poids d'un élastomère de polyoléfine, la température de déflection de la chaleur (HDT) étant de 89 °C ou plus. Selon la présente invention : une composition de résine thermoplastique comprenant un additif prédéterminé qui est moins coûteux qu'un additif classique pour la résistance chimique, afin de satisfaire à la fois la faisabilité économique et la résistance chimique, et présentant une excellente résistance à la chaleur et résistance aux impacts ; son procédé de préparation ; et un produit moulé fabriqué à partir de cette dernière.
PCT/KR2020/012281 2019-09-18 2020-09-11 Composition de résine thermoplastique, son procédé de préparation, et produit moulé fabriqué à partir de cette dernière WO2021054679A1 (fr)

Priority Applications (4)

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CN202080006542.3A CN113166510B (zh) 2019-09-18 2020-09-11 热塑性树脂组合物、制备它的方法和使用它制造的模制品
EP20865196.8A EP3872133A4 (fr) 2019-09-18 2020-09-11 Composition de résine thermoplastique, son procédé de préparation, et produit moulé fabriqué à partir de cette dernière
JP2021536691A JP7220792B2 (ja) 2019-09-18 2020-09-11 熱可塑性樹脂組成物、その製造方法及びそれから製造された成形品
US17/299,256 US20220033633A1 (en) 2019-09-18 2020-09-11 Thermoplastic resin composition, method of preparing the same, and molded article manufactured using the same

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KR20190114947 2019-09-18
KR10-2019-0114947 2019-09-18
KR1020200114753A KR102457383B1 (ko) 2019-09-18 2020-09-08 열가소성 수지 조성물, 이의 제조방법 및 이로부터 제조된 성형품
KR10-2020-0114753 2020-09-08

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Citations (6)

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Publication number Priority date Publication date Assignee Title
KR20060065980A (ko) 2004-12-11 2006-06-15 주식회사 엘지화학 내화학성, 유동성 및 내변색성이 우수한 투명 공중합체수지 제조 방법 및 그 공중합체 수지
WO2014007442A1 (fr) * 2012-07-04 2014-01-09 제일모직 주식회사 Composition de résine thermoplastique et mousse moulée l'utilisant
KR20150008775A (ko) * 2013-07-15 2015-01-23 현대이피 주식회사 폴리프로필렌-폴리아미드 블렌드 조성물
KR20150068313A (ko) * 2013-12-10 2015-06-19 주식회사 엘지화학 스티렌계 내화학성 내열 수지 조성물 및 이로부터 제조된 성형품
KR20160066979A (ko) * 2014-12-03 2016-06-13 현대자동차주식회사 고유동, 고충격성 폴리올레핀 수지 조성물
KR101974164B1 (ko) * 2017-12-29 2019-04-30 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060065980A (ko) 2004-12-11 2006-06-15 주식회사 엘지화학 내화학성, 유동성 및 내변색성이 우수한 투명 공중합체수지 제조 방법 및 그 공중합체 수지
WO2014007442A1 (fr) * 2012-07-04 2014-01-09 제일모직 주식회사 Composition de résine thermoplastique et mousse moulée l'utilisant
KR20150008775A (ko) * 2013-07-15 2015-01-23 현대이피 주식회사 폴리프로필렌-폴리아미드 블렌드 조성물
KR20150068313A (ko) * 2013-12-10 2015-06-19 주식회사 엘지화학 스티렌계 내화학성 내열 수지 조성물 및 이로부터 제조된 성형품
KR20160066979A (ko) * 2014-12-03 2016-06-13 현대자동차주식회사 고유동, 고충격성 폴리올레핀 수지 조성물
KR101974164B1 (ko) * 2017-12-29 2019-04-30 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품

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