WO2021045429A1 - Composition de résine thermoplastique et produit moulé associé - Google Patents

Composition de résine thermoplastique et produit moulé associé Download PDF

Info

Publication number
WO2021045429A1
WO2021045429A1 PCT/KR2020/011328 KR2020011328W WO2021045429A1 WO 2021045429 A1 WO2021045429 A1 WO 2021045429A1 KR 2020011328 W KR2020011328 W KR 2020011328W WO 2021045429 A1 WO2021045429 A1 WO 2021045429A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
resin composition
thermoplastic resin
aromatic vinyl
graft copolymer
Prior art date
Application number
PCT/KR2020/011328
Other languages
English (en)
Korean (ko)
Inventor
성다은
김태훈
박춘호
안용희
조왕래
김호훈
장정민
Original Assignee
(주) 엘지화학
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 KR1020200106135A external-priority patent/KR102465681B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to JP2021535152A priority Critical patent/JP2022514577A/ja
Priority to US17/298,523 priority patent/US11884810B2/en
Priority to EP20861457.8A priority patent/EP3872132A4/fr
Priority to CN202080006748.6A priority patent/CN113166520B/zh
Publication of WO2021045429A1 publication Critical patent/WO2021045429A1/fr

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, while maintaining equal or higher mechanical properties and processability compared to the conventional ASA-based resin, excellent weather resistance, low surface roughness value, and emotionally soft feeling. It relates to a low-gloss thermoplastic resin composition and a molded article thereof having an even surface gloss.
  • Acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as'ASA resin') has weather resistance, aging resistance, chemical resistance, stiffness, impact resistance and processability. It is widely used in fields, etc.
  • the low gloss ASA resin a crystalline resin such as nylon was used to achieve low gloss, but there was a limit to improving weatherability and texture of the surface, which are important physical properties for exterior materials as well as low gloss.
  • Patent Literature 1 KR 2009-0095764 A
  • the present invention maintains the mechanical properties and processability equal or higher than that of the conventional ASA-based resin, has excellent weather resistance, has a low surface roughness value, and gives an emotionally soft feel, and the surface It is an object of the present invention to provide a low-gloss thermoplastic resin composition with even gloss and a molded article thereof.
  • the present invention is A-1) 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, A- 2) 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 ⁇ m, B) 0 to 35% by weight of an aromatic vinyl polymer and C) polymetha 100 parts by weight of the base resin consisting of 10 to 60% by weight of acrylate; And D) 0.5 to 10 parts by weight of polyamide.
  • thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
  • the present inventors want to achieve a matte effect by adding polyamide to the ASA resin, the present inventors control the morphology of the ASA resin and use methyl methacrylate-styrene-acrylonitrile copolymer or polymethyl methacrylate as an essential component.
  • the composition ratio of it is possible to obtain a low-gloss thermoplastic resin composition with an even surface gloss and emotionally soft due to improved weather resistance while maintaining equal or higher mechanical properties and processability compared to conventional ASA-based resins, and lowering the surface roughness value. It was confirmed that the present invention was completed by further focusing on research based on this.
  • thermoplastic resin composition of the present invention is A-1) 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, A-2) an average particle diameter An acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing 0.3 to 0.5 ⁇ m of acrylate rubber 20 to 40% by weight, B) 0 to 35% by weight of an aromatic vinyl polymer and C) 10 to polymethacrylate 100 parts by weight of the base resin consisting of 60% by weight; And D) 0.5 to 10 parts by weight of polyamide, and in this case, while maintaining the mechanical properties and processability equal to or higher than that of the conventional ASA-based resin, it has excellent weather resistance, low gloss, and even surface gloss.
  • thermoplastic resin composition that has a low surface roughness value and gives an emotionally soft feel.
  • 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, or 0.13 to 0.15 ⁇ m, and excellent weather resistance, colorability, impact strength, chemical resistance, and surface gloss properties can be imparted to the final thermoplastic resin composition within this range.
  • the acrylate rubber may preferably be a core.
  • the average particle diameter can be measured using dynamic light scattering, and in detail, it can be measured using Nicomp 380 equipment (product name, 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, 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 15 to 20% by weight, and within this range, weather resistance, fluidity, tensile strength and impact strength Has an excellent effect.
  • 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, tensile strength 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, tensile strength 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, tensile strength 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 0.5 ⁇ m, preferably 0.35 to 0.5 ⁇ m, more preferably 0.4 to 0.5 ⁇ m, 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, tensile strength, and impact strength.
  • the acrylate rubber may preferably be a core.
  • the A-2) graft copolymer is, for example, 20 to 40% by weight, preferably 25 to 35% by weight, more preferably 30 to 35% by weight, and within this range, weather resistance, fluidity, tensile strength and impact strength Has an excellent effect.
  • 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, tensile strength 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, tensile strength and impact strength.
  • the A-1) graft copolymer may preferably be included in a smaller amount than the A-2) graft copolymer, and more preferably the A-1) graft copolymer and the A-2) graft
  • the weight ratio of the copolymer is 1:1.1 to 1:4, more preferably 1:1.2 to 1:2, and within this range, weather resistance, fluidity, tensile strength and impact strength are excellent.
  • the sum of the weights of the A-1) graft copolymer and A-2) graft copolymer is preferably 40 to 60% by weight, more preferably 45 to 55% by weight, and even more preferably 47 with respect to the base resin. To 53% by weight, and weather resistance, fluidity, tensile strength and impact strength are excellent within this range.
  • 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) aromatic vinyl polymer may be, for example, 0 to 35% by weight, preferably 10 to 35% by weight, more preferably less than 10% by weight, even more preferably less than 5% by weight, Most preferably, it is not included, and the weather resistance is excellent within this range, and in particular, the surface roughness value is greatly lowered, so that the gloss is even and there is an advantage of having a soft feeling when touched by hand.
  • the B) 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 cyan compound, and has excellent effects in chemical resistance and impact strength within this range.
  • the B) aromatic vinyl polymer for example, has a weight average molecular weight of 80,000 to 180,000 g/mol, preferably 80,000 to 160,000 g/mol, and has excellent effects such as tensile strength and impact strength within this range.
  • the B) aromatic vinyl polymer is, for example, an aromatic vinyl compound-vinyl cyan compound copolymer, and a preferred example is a styrene-acrylonitrile copolymer (SAN resin), an alpha-methylstyrene-acrylonitrile copolymer (heat-resistant SAN resin) or It may be a mixture of these, and in this case, there is an excellent effect such as heat resistance.
  • SAN resin styrene-acrylonitrile copolymer
  • alpha-methylstyrene-acrylonitrile copolymer heat-resistant SAN resin
  • the styrene-acrylonitrile copolymer may preferably be 15 to 35% by weight, more preferably 15 to 25% by weight, and within this range, heat resistance and the like have excellent effects.
  • the styrene-acrylonitrile copolymer is preferably made of 65 to 80% by weight of styrene and 20 to 35% by weight of acrylonitrile, and within this range, the processability and impact strength are excellent.
  • the styrene-acrylonitrile copolymer has, for example, a weight average molecular weight of 100,000 to 180,000 g/mol, preferably 100,000 to 150,000 g/mol, and has excellent effects such as heat resistance within this range.
  • the alpha-methylstyrene-acrylonitrile copolymer may preferably be 10 to 20% by weight, more preferably 12 to 18% by weight, and within this range, heat resistance and the like are excellent.
  • the alpha-methylstyrene-acrylonitrile copolymer is preferably composed of 70 to 75% by weight of alpha-methylstyrene and 25 to 30% by weight of acrylonitrile, more preferably 60 to 75% by weight of alpha-methylstyrene %, consisting of 0 to 10% by weight of styrene and 20 to 30% by weight of acrylonitrile, or containing 60 to 70% by weight of alpha-methylstyrene, 0 to 10% by weight of styrene and 25 to 30% by weight of acrylonitrile And more preferably 60 to 75% by weight of alpha-methylstyrene, 5 to 10% by weight of styrene, and 20 to 30% by weight of acrylonitrile, or 60 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-acrylonitrile copolymer preferably has a weight average molecular weight of 80,000 to 120,000 g/mol, and has excellent effects such as heat resistance within this range.
  • 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 eluate ) Can be measured relative to the standard PS (standard polystyrene) sample.
  • GPC Gel Permeation Chromatography, waters breeze
  • THF tetrahydrofuran
  • the B) aromatic vinyl polymer may be prepared by, for example, suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization, and in this case, heat resistance and fluidity are excellent.
  • the suspension polymerization, emulsion polymerization, solution polymerization, and bulk 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 belongs.
  • the C) polymethacrylate may be, for example, 10 to 60% by weight, preferably 25 to 55% by weight, more preferably 25 to 50% by weight, even more preferably 30 to 50% by weight, even more preferably 35 To 50% by weight, most preferably 45 to 50% by weight, and within this range, the weather resistance is greatly improved while the mechanical properties and processability are maintained equal or higher than those of the conventional ASA-based resin, and the surface roughness value is very low. There is a soft advantage.
  • the C) polymethacrylate preferably contains 55% by weight or more of a methacrylate monomer, preferably 60% by weight or more, most preferably 65% by weight or more, and the weather resistance is greatly improved within this range, The surface roughness value is very low, so there is an emotionally soft effect.
  • the methacrylate monomer may be, for example, an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and specific examples are methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2 -It may be one or more selected from the group consisting of ethylhexyl methacrylate and lauryl methacrylate, preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, more preferably methyl methacrylate It may be a acrylate.
  • the C) polymethacrylate is preferably at least one selected from the group consisting of a polymethylmethacrylate resin and a methylmethacrylate-styrene-acrylonitrile copolymer, and preferably a polymethylmethacrylate resin or It is a methyl methacrylate-styrene-acrylonitrile copolymer, more preferably a polymethyl methacrylate resin, and within this range, the weather resistance is more excellent, and the surface roughness value is low, so that there is an emotionally soft effect.
  • the polymethyl methacrylate resin may have a weight average molecular weight of 35,000 to 200,000 g/mol, preferably 50,000 to 200,000 g/mol, and within this range, it is more excellent in weather resistance, flowability, and tensile It has excellent strength and impact strength, and has a low surface roughness value, so it has an emotionally soft effect.
  • the polymethyl methacrylate resin has a weight average molecular weight of 50,000 to 200,000 g/mol (hereinafter referred to as'high molecular weight PMMA resin') and a weight average molecular weight of 35,000 to 45,000 g/mol It may be a mixture of mol polymethyl methacrylate resin (hereinafter referred to as'low molecular weight PMMA resin').
  • the high molecular weight PMMA resin and the low molecular weight PMMA resin may have a weight ratio of 1: 0.1 to 2.0 as an example, preferably 1: 1.3 to 1.7, more preferably 1: 1.4 to 1.6, and flowability within this range, It has excellent tensile strength and impact strength, is more excellent in weather resistance, and has a low surface roughness value, so it has an emotionally soft effect.
  • the weight ratio of A and B means the weight ratio of A:B.
  • the methyl methacrylate-styrene-acrylonitrile copolymer comprises, for example, 65 to 85% by weight of methyl methacrylate, 5 to 30% by weight of styrene, and 5 to 10% by weight of acrylonitrile, within this range
  • the weather resistance is more excellent and the surface roughness value is low, so there is an emotionally soft effect.
  • the methyl methacrylate-styrene-acrylonitrile copolymer may have, for example, a weight average molecular weight of 70,000 to 140,000 g/mol, and as another example, 70,000 to 90,000 g/mol, or more than 90,000 g/mol to 140,000 g/ It may be mol or less, and within this range, weatherability is better, fluidity, tensile strength, and impact strength are excellent, and a surface roughness value is low, so that there is an emotionally soft effect.
  • the methyl methacrylate-styrene-acrylonitrile copolymer is a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 90,000 g/mol (hereinafter referred to as'low molecular weight SAMMA resin'. ) And a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 140,000 g/mol (hereinafter referred to as'high molecular weight SAMMA resin') may be mixed.
  • a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 120,000 to 140,000 g/mol hereinafter referred to as'high molecular weight SAMMA resin'
  • the low molecular weight SAMMA resin and the high molecular weight SAMMA resin may have a weight ratio of 1: 0.1 to 0.45, preferably 1: 0.2 to 0.45, more preferably 1: 0.3 to 0.45, and more preferably 1: It may be 0.35 to 0.45, and there is an advantage of excellent weather resistance within this range.
  • the C) polymethacrylate may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each commonly used in the technical field to which the present invention belongs.
  • the emulsion polymerization and suspension polymerization method to be carried out it is not particularly limited.
  • the D) polyamide is, for example, 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, more preferably 4 to 8 parts by weight, and even more preferably 4 to 6 parts by weight based on 100 parts by weight of the base resin.
  • the gloss is lowered within this range so that the matte effect is large and the physical property balance is excellent.
  • the D) polyamide refers to a thermoplastic polymer containing an amide bond, and specific examples are polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612 , Polyamide 6/66, Polyamide 6/612, Polyamide MXD6, Polyamide 6/MXD6, Polyamide 66/MXD6, Polyamide 6T, Polyamide 6I, Polyamide 6/6T, Polyamide 6/6I, Poly Amide 66/6T, Polyamide 66/6I, Polyamide 6/6T/6I, Polyamide 66/6T/6I, Polyamide 9T, Polyamide 9I, Polyamide 6/9T, Polyamide 6/9I, Polyamide 66 /9T, polyamide 6/12/9T, polyamide 6/12/9I, and polyamide 66/12/6I may be one or more selected from the group consisting of, preferably polyamide 66 (PA 6.6).
  • the D) polyamide is preferably used having a melting point of 230°C or higher, preferably 240°C or higher, more preferably 250°C or higher, and still more preferably 260 to 270°C.
  • the D) polyamide is preferably used having a relative viscosity (a 96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and even more preferably 2.4 to 2.7.
  • the relative viscosity can be measured with a Ubbelohde viscometer by the ISO 307 sulfuric acid method.
  • the method for preparing D) polyamide is not particularly limited if it is a polymerization method commonly practiced in the technical field to which the present invention belongs, and may be purchased and used commercially if it meets the definition of polyamide according to the present invention.
  • thermoplastic resin composition of the present disclosure may have a surface roughness value of 4 or less, preferably 3.5 or less, more preferably 3 or less, and even more preferably 2.5 or less, measured by 5 points with an optical profiler system.
  • thermoplastic resin composition may have a weather resistance ( ⁇ E) of 4.0 or less, preferably 3.5 or less, more preferably 3.2 or less, and even more preferably 3.0 or less, as measured by the SAE J1960 method for 2000 hours.
  • ⁇ E weather resistance
  • the thermoplastic resin composition has a flow index (MI) (220° C., load 10 kg) of 3 g/10 min or more, preferably 7 g/10 min or more, and more preferably 10 g/10 min or more according to ASTM D1238, for example. And, more preferably 12 g/10min or more, and a specific example may be 12 to 15 g/10min.
  • MI flow index
  • the thermoplastic resin composition for example, has a tensile strength (1/8 inch) of 290 kg/cm2 or more, preferably 380 kg/cm2 or more, more preferably 400 kg/cm2 or more, and even more preferably according to ASTM 638. It may be 470 kg/cm 2 or more, and a specific example may be 380 to 490 kg/cm 2.
  • thermoplastic resin composition has an Izod impact strength (1/4 inch) according to ASTM 256, for example, 7 kg ⁇ cm/cm or more, preferably 9 kg ⁇ cm/cm or more, and a specific example 7 to 11 kg ⁇ cm /Cm or 8 to 11 kg ⁇ cm/cm.
  • thermoplastic resin composition has a film gloss of 14 or less, 11 or less, or 10.5 or less, preferably 9.5 or less, and more preferably 9.3 or less, as measured at 60° with a gloss meter VG7000, as an example. 4.8 to 14.0 or 4.8 to 11.0, and within this range, there is an effect of having excellent matte properties and excellent balance of physical properties. Therefore, the thermoplastic resin composition of the present disclosure may also be referred to as a matte thermoplastic resin composition.
  • thermoplastic resin composition may optionally be used as a heat stabilizer, light stabilizer, dye, pigment, colorant, releasing agent, antistatic agent, antibacterial agent, processing aid, metal deactivator, flame retardant, inhibitor, drip inhibitor, anti-friction agent, and anti-wear agent. 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight of at least one selected from the group consisting of, and within this range, the physical properties of the thermoplastic resin composition of the present disclosure There is an effect that the required physical properties are well implemented without deteriorating the value.
  • the method for preparing the thermoplastic resin composition of the present invention is, for example, A-1) 10 to 30% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, A -2) 20 to 40% by weight of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an acrylate rubber having an average particle diameter of 0.3 to 0.5 ⁇ m, B) 0 to 35% by weight of an aromatic vinyl polymer and C) poly 100 parts by weight of the base resin consisting of 10 to 60% by weight of methacrylate; And D) 0.5 to 10 parts by weight of polyamide; and then preparing a pellet using an extrusion kneader under conditions of 220 to 280° C.
  • thermoplastic resin composition that provides an emotionally soft feeling due to excellent weather resistance, low gloss, even surface gloss, and low surface roughness value while maintaining equal or higher physical properties and processability.
  • thermoplastic resin composition shares all the technical characteristics of the above-described thermoplastic resin composition. Therefore, a description of the overlapping part will be omitted.
  • the step of preparing the pellets using the extrusion kneader may be performed under preferably 220 to 280 °C, more preferably 240 to 280 °C, wherein the temperature refers to a temperature set in the cylinder.
  • the extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
  • the molded article of the present substrate is characterized by containing the thermoplastic resin composition of the present substrate, and in this case, the mechanical properties and processability are maintained equal or higher than that of the conventional molded article, while excellent weather resistance, low gloss, and even surface gloss.
  • the low surface roughness value has the advantage of giving an emotionally soft feel.
  • the molded article may be, for example, an extrusion molded product or an injection molded product, preferably a building exterior material, and more preferably siding, sliding doors, or windows.
  • the molded article may preferably be prepared by extruding or injecting the thermoplastic resin composition of the present disclosure at a molding temperature of 190 to 250° C., and there is an advantage in that an excellent matte effect is expressed within this range.
  • thermoplastic resin composition of the present disclosure its manufacturing method, and molded article, it is stated that other conditions or equipment that are not explicitly described can be appropriately selected within the range commonly practiced in the art, and are not particularly limited. do.
  • the first graft copolymer of the emulsion polymerization method (50% by weight of a butyl acrylate polymer having an average particle diameter of 100 nm, shell: 36% by weight of styrene, 14% by weight of acrylonitrile)
  • each of the components and contents shown in Table 1 below were kneaded and extruded at 280° C. in a twin screw extruder to prepare pellets.
  • the melt index was measured with the prepared pellets.
  • a sheet of 0.15T was prepared from the prepared pellets at a molding temperature of 220° C., and the film gloss and surface roughness values were measured. Further, the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties, and the tensile strength and impact strength were measured using this.
  • MI Melt index
  • thermoplastic resin composition (refer to Examples 1 to 10) according to the present invention has mechanical properties such as flow index, tensile strength and impact strength compared to Comparative Examples 1 and 2 that do not contain a polymethacrylate resin. While maintaining the same or more physical properties, it was confirmed that the weather resistance was excellent, the surface roughness value was low, giving an emotionally soft feeling, and the surface gloss was even and low.
  • a polymethacrylate resin was prepared.
  • the surface roughness value is 3.0 or less, specifically 2.0 to 3.0, and weather resistance ( ⁇ E ) Is 3.1 or less, specifically 1.3 to 3.3, which is very excellent compared to Comparative Examples 1 and 2, confirming that a high quality sensitive resin was prepared.

Landscapes

  • 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 et un produit moulé associé et, plus spécifiquement, une composition de résine thermoplastique et un produit moulé associé, la composition de résine thermoplastique comprenant : 100 parties en poids d'une résine de base constituée de A-1) 10 à 30 % en poids d'un copolymère greffé acrylate-composé vinylique aromatique-composé de cyanure de vinyle comprenant un caoutchouc acrylate présentant un diamètre moyen de 0,05 à 0,15 µm, A-2) 20 à 40 % en poids d'un copolymère greffé acrylate-composé vinylique aromatique-composé de cyanure de vinyle comprenant un caoutchouc acrylate présentant un diamètre moyen de 0,3 à 0,5 µm, B) 0 à 35 % en poids d'un polymère vinylique aromatique et C) 10 à 60 % en poids d'un polyméthacrylate ; et D) 0,5 à 10 parties en poids d'un polyamide. La présente invention concerne : une composition de résine thermoplastique à faible brillance dotée de propriétés mécaniques, d'une aptitude au traitement et analogues, qui sont au moins équivalentes à celles d'une résine classique à base d'ASA, et qui présente également une excellente résistance aux intempéries, une faible valeur de rugosité de surface pour une sensation de douceur, et un brillant de surface uniforme ; et un produit moulé associé.
PCT/KR2020/011328 2019-09-06 2020-08-25 Composition de résine thermoplastique et produit moulé associé WO2021045429A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2021535152A JP2022514577A (ja) 2019-09-06 2020-08-25 熱可塑性樹脂組成物及びその成形品
US17/298,523 US11884810B2 (en) 2019-09-06 2020-08-25 Thermoplastic resin composition and molded article including the same
EP20861457.8A EP3872132A4 (fr) 2019-09-06 2020-08-25 Composition de résine thermoplastique et produit moulé associé
CN202080006748.6A CN113166520B (zh) 2019-09-06 2020-08-25 热塑性树脂组合物和包含该热塑性树脂组合物的模制品

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2019-0110417 2019-09-06
KR20190110417 2019-09-06
KR1020200106135A KR102465681B1 (ko) 2019-09-06 2020-08-24 열가소성 수지 조성물 및 이의 성형품
KR10-2020-0106135 2020-08-24

Publications (1)

Publication Number Publication Date
WO2021045429A1 true WO2021045429A1 (fr) 2021-03-11

Family

ID=74852701

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/011328 WO2021045429A1 (fr) 2019-09-06 2020-08-25 Composition de résine thermoplastique et produit moulé associé

Country Status (1)

Country Link
WO (1) WO2021045429A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113136100A (zh) * 2021-05-10 2021-07-20 会通新材料股份有限公司 Pa6/asa合金材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050030643A (ko) * 2002-08-01 2005-03-30 란세스 코포레이션 저광택 외관을 갖는 열가소성 조성물
KR20060016165A (ko) * 2004-08-17 2006-02-22 주식회사 엘지화학 그라프트 공중합체 조성물 및 이를 이용한 열가소성 수지조성물
KR20090095764A (ko) 2008-03-06 2009-09-10 주식회사 엘지화학 내광 및 무광택 특성이 우수한 열가소성 수지 조성물
KR20150069888A (ko) * 2013-12-16 2015-06-24 금호석유화학 주식회사 내후성이 우수한 저광택 열가소성 수지 조성물, 이를 이용한 저광택 시트 및 복합물
KR20170062984A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조되는 성형품
KR20180023492A (ko) * 2016-08-26 2018-03-07 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR20190110417A (ko) 2018-03-20 2019-09-30 재단법인 제주테크노파크 기능성 강화 탈염 용암해수 미네랄 제제의 제조 방법
KR20200106135A (ko) 2020-07-27 2020-09-11 주식회사 바이오젠 유산균 발효여과액을 이용한 유산균의 배양방법 및 재순환 연속 배양 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20050030643A (ko) * 2002-08-01 2005-03-30 란세스 코포레이션 저광택 외관을 갖는 열가소성 조성물
KR20060016165A (ko) * 2004-08-17 2006-02-22 주식회사 엘지화학 그라프트 공중합체 조성물 및 이를 이용한 열가소성 수지조성물
KR20090095764A (ko) 2008-03-06 2009-09-10 주식회사 엘지화학 내광 및 무광택 특성이 우수한 열가소성 수지 조성물
KR20150069888A (ko) * 2013-12-16 2015-06-24 금호석유화학 주식회사 내후성이 우수한 저광택 열가소성 수지 조성물, 이를 이용한 저광택 시트 및 복합물
KR20170062984A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조되는 성형품
KR20180023492A (ko) * 2016-08-26 2018-03-07 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR20190110417A (ko) 2018-03-20 2019-09-30 재단법인 제주테크노파크 기능성 강화 탈염 용암해수 미네랄 제제의 제조 방법
KR20200106135A (ko) 2020-07-27 2020-09-11 주식회사 바이오젠 유산균 발효여과액을 이용한 유산균의 배양방법 및 재순환 연속 배양 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3872132A4

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113136100A (zh) * 2021-05-10 2021-07-20 会通新材料股份有限公司 Pa6/asa合金材料及其制备方法
CN113136100B (zh) * 2021-05-10 2022-03-22 会通新材料股份有限公司 Pa6/asa合金材料及其制备方法

Similar Documents

Publication Publication Date Title
WO2017095060A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué à partir de cette dernière
WO2018038573A1 (fr) Composition de résine thermoplastique et article moulé fabriqué à partir de celle-ci
WO2013077492A1 (fr) Composition de résine thermoplastique, et produit moulé l'utilisant
WO2014007442A1 (fr) Composition de résine thermoplastique et mousse moulée l'utilisant
WO2013115610A1 (fr) Composition de copolymère greffé à base d'asa
WO2015152468A1 (fr) Composition de résine thermoplastique dotée d'une résistance à la chaleur et une propriété de coloration améliorées
KR20210029670A (ko) 열가소성 수지 조성물 및 이의 성형품
WO2012086901A1 (fr) Composition de résine acrylique et articles moulés à base de celle-ci
WO2013085090A1 (fr) Composition de résine thermoplastique et produit moulé à l'aide de celle-ci
WO2013062170A1 (fr) Composition de résine thermoplastique et moulage l'utilisant
WO2020091338A1 (fr) Composition de résine thermoplastique et produit moulé l'utilisant
WO2018124517A1 (fr) Composition de résine thermoplastique, son procédé de préparation et article moulé manufacturé la comprenant
WO2013094889A1 (fr) Copolymère à base acrylique retardateur de flamme, composition de résine le comprenant et forme moulante à base de celle-ci
WO2019103519A2 (fr) Composition de résine
WO2022186484A1 (fr) Composition de résine thermoplastique et matériau extérieur formé à partir de celle-ci
WO2021045429A1 (fr) Composition de résine thermoplastique et produit moulé associé
WO2011081317A2 (fr) Composition de résine thermoplastique et pièce moulée à l'aide de celle-ci
WO2013094844A1 (fr) Composition de résine thermoplastique permettant d'améliorer le phénomène de turbidité blanche à des températures basses
WO2017095031A1 (fr) Composition de résine thermoplastique possédant d'excellentes propriétés de matité et de brillance, et article moulé produit à partir de ladite composition
WO2022146043A1 (fr) Composition de résine thermoplastique et produit moulé l'utilisant
WO2017105007A1 (fr) Copolymère greffé à base de vinyle modifié par du caoutchouc et composition de résine thermoplastique le contenant
WO2020130400A1 (fr) Composition de résine thermoplastique
WO2022211458A1 (fr) Composition de résine thermoplastique et article fabriqué à l'aide de celle-ci
WO2024117628A1 (fr) Composition de résine thermoplastique et article moulé l'utilisant
WO2022045795A1 (fr) Composition de résine thermoplastique et article moulé préparé à partir de celle-ci

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20861457

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020861457

Country of ref document: EP

Effective date: 20210525

ENP Entry into the national phase

Ref document number: 2021535152

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE