WO2019132304A2 - Composition de résine thermoplastique et produit moulé l'utilisant - Google Patents

Composition de résine thermoplastique et produit moulé l'utilisant Download PDF

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Publication number
WO2019132304A2
WO2019132304A2 PCT/KR2018/015497 KR2018015497W WO2019132304A2 WO 2019132304 A2 WO2019132304 A2 WO 2019132304A2 KR 2018015497 W KR2018015497 W KR 2018015497W WO 2019132304 A2 WO2019132304 A2 WO 2019132304A2
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WO
WIPO (PCT)
Prior art keywords
weight
copolymer
meth
resin composition
acrylic
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/KR2018/015497
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English (en)
Korean (ko)
Other versions
WO2019132304A3 (fr
Inventor
신형섭
권기혜
김영효
김인철
박지은
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lotte Advanced Materials Co Ltd
Original Assignee
Lotte Advanced Materials Co Ltd
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 KR1020180154655A external-priority patent/KR102232505B1/ko
Application filed by Lotte Advanced Materials Co Ltd filed Critical Lotte Advanced Materials Co Ltd
Priority to EP18897181.6A priority Critical patent/EP3733767B1/fr
Priority to US16/958,798 priority patent/US11492481B2/en
Publication of WO2019132304A2 publication Critical patent/WO2019132304A2/fr
Publication of WO2019132304A3 publication Critical patent/WO2019132304A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article using the same.
  • ASA acrylonitrile-styrene-acrylate copolymer
  • PMMA polymethyl methacrylate alloy material excellent in coloring property and heat resistance Has been developed.
  • the impact strength and heat resistance of the acrylonitrile-styrene-acrylate copolymer are low compared to the acrylonitrile-styrene-acrylate copolymer used as a conventional exterior material due to the properties of the polymethylmethacrylate material.
  • a heat- There is a disadvantage in that transparency is reduced while causing a difference in refractive index between polymethyl methacrylate (PMMA) and styrene-acrylonitrile-styrene-acrylate copolymer (ASA) and polymethylmethacrylate (PMMA), which leads to reduction in colorability and a large amount of colorant.
  • thermoplastic resin composition having excellent heat resistance and coloring property is required.
  • thermoplastic resin composition capable of realizing excellent impact resistance, coloring property and heat resistance, and a molded article using the same.
  • thermoplastic resin composition (A) 60 to 85% by weight of a (meth) acrylic resin, (B) 10 to 30% by weight of an acrylic graft copolymer, and (C) 5 to 10% by weight of a maleimide- And a thermoplastic resin composition.
  • Another embodiment provides a molded article using the above-mentioned thermoplastic resin composition.
  • thermoplastic resin composition makes it possible to produce a molded article having excellent impact resistance, coloring property and heat resistance.
  • thermoplastic resin composition according to one embodiment of the present invention comprises 60 to 85% by weight of (A) a (meth) acrylic resin, 10 to 30% by weight of an acrylic graft copolymer (B), and (C) a maleimide- 5 to 10% by weight.
  • the (A) (meth) acrylic resin is excellent in coloring property so that the thermoplastic resin composition according to one embodiment can be applied to unpainted materials.
  • the (A) (meth) acrylic resin has a glass transition temperature (Tg) of 110 ° C or more, which can improve the heat resistance characteristics of the thermoplastic resin composition.
  • Tg glass transition temperature
  • the glass transition temperature of the (A) (meth) acrylic resin may be, for example, from 110 to 130 ° C, for example, from 110 to 125 ° C, for example, have.
  • the flowability of the thermoplastic resin composition can be enhanced, compatibility with other components and stress applied during processing can be reduced, and the heat resistance and colorability of the thermoplastic resin composition can be improved.
  • the (A) (meth) acrylic resin may have a weight average molecular weight of 50,000 to 300,000 g / mol.
  • the (A) (meth) acrylic resin may have a weight average molecular weight of 70,000 to 250,000 g / mol, for example, 100,000 to 200,000 g / mol. Within this range, compatibility with other components is excellent, and the fluidity and moldability of the thermoplastic resin composition can be improved.
  • the (A) (meth) acrylic resin may be a polymer of a (meth) acrylate-based monomer containing a C1 to C10 alkyl group.
  • the (A) (meth) acrylic resin is a polymer of a (meth) acrylate monomer, the compatibility with other constituents, the flowability of the thermoplastic resin composition and the molding processability can be further improved.
  • the (A) (meth) acrylic resin may be, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl (meth) acrylate, hexyl acrylate, Acrylate, n-pentyl acrylate, vinyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate And lauryl methacrylate.
  • the (A) (meth) acrylic resin may be polymethyl methacrylate (PMMA).
  • the (A) (meth) acrylic resin can be prepared by conventional bulk, emulsion or suspension polymerization methods using the above-described monomers using a solvent and a polymerization initiator, and is not limited to these methods.
  • the solvent include methanol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propyleneglycol monomethyl ether acetate, methylcellosolve acetate, ethylcellosolve acetate, diethylene glycol monomethyl ether, di Ethers such as ethylene glycol monoethyl ether, and combinations thereof.
  • polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy 2, 4-dimethylvaleronitrile) and the like can be used.
  • the (A) (meth) acrylic resin may be contained in an amount of 60 to 85% by weight based on the total weight of the components (A) to (C).
  • the thermoplastic resin composition according to one embodiment has an advantage that the balance of physical properties of fluidity, impact resistance and heat resistance is excellent, and heat resistance and coloring property are improved.
  • the (B) acrylic graft copolymer can be prepared by graft-polymerizing an acrylic rubber-like polymer with a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound.
  • the acrylic rubber-like polymer may be an alkyl acrylate rubber, preferably a C2 to C10 alkyl acrylate rubber.
  • alkyl acrylate rubber preferably a C2 to C10 alkyl acrylate rubber.
  • butyl acrylate rubber, ethylhexyl acrylate rubber and mixtures thereof can be used, but are not necessarily limited thereto.
  • the acrylic rubber-like polymer may be contained in an amount of 40 to 65% by weight (based on the solid content) based on the total weight of the acrylic graft copolymer (B).
  • the average particle diameter of the acrylic rubber-like polymer may be 150 to 400 nm.
  • the average particle size of the acrylic rubber-like polymer may be from 150 to 400 nm, for example, from 200 to 400 nm, for example, from 300 to 400 nm.
  • the average particle diameter is a volume average diameter, which means a Z-average particle diameter measured using a dynamic light scattering analyzer.
  • the copolymer of the aromatic vinyl compound and the vinyl cyanide compound graft-polymerized to the rubbery polymer may be an aromatic vinyl compound and a vinyl cyanide compound copolymerized in a weight ratio of 6: 4 to 8: 2.
  • aromatic vinyl compound examples include styrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene and vinylnaphthalene. These aromatic vinyl compounds may be used alone or in combination . In one embodiment of these, styrene is preferably used.
  • vinyl cyanide compound examples include acrylonitrile, methacrylonitrile, and fumaronitrile, which may be used alone or in combination.
  • Acrylonitrile may preferably be used in one of these embodiments.
  • the (B) acrylic graft copolymer may be, for example, an acrylonitrile-styrene-acrylate graft copolymer (g-ASA).
  • the acrylonitrile-styrene-acrylate graft copolymer may be prepared by graft copolymerization of an alkyl acrylate rubber with acrylonitrile and styrene to an alkyl acrylate rubber.
  • the acrylic graft copolymer (B) may be contained in an amount of 10 to 30% by weight based on the total weight of the components (A) to (C). Within the above range, the impact resistance, heat resistance and coloring property of the thermoplastic resin composition according to one embodiment can be improved.
  • the thermoplastic resin composition may include (C) a maleimide-based heat-resistant copolymer.
  • the (C) maleimide-based heat-resistant copolymer may be, for example, a N-phenyl maleimide (PMI) based copolymer.
  • the (C) maleimide-based heat-resistant copolymer may be added to further improve the heat resistance of the thermoplastic resin composition.
  • the (C) maleimide-based heat-resistant copolymer may be a terpolymer of N-phenylmaleimide, styrene and maleic anhydride.
  • the component derived from N-phenylmaleimide is included, the heat resistance of the thermoplastic resin composition can be further improved, and if it contains a component derived from styrene and maleic anhydride, the colorability of the thermoplastic resin composition can be improved .
  • the terpolymer of N-phenylmaleimide, maleic anhydride and styrene can be prepared through imidization of styrene and maleic anhydride copolymer, and the (C) maleimide-based heat resistant air Based on the total weight of the maleimide-based heat-resistant copolymer, 15 to 25% by weight of the component derived from the N-phenylmaleimide, 65 to 75% by weight of the component derived from the styrene, Component may be a copolymer of 5 to 10% by weight. Within the above range, the heat resistance of the thermoplastic resin composition can be uniformly improved, and the decrease in coloring property can be minimized.
  • the glass transition temperature (Tg) of the (C) maleimide-based heat-resistant copolymer may be 150 ° C to 220 ° C.
  • the glass transition temperature (Tg) of the (C) maleimide-based heat-resistant copolymer may be 160 ° C to 200 ° C, for example, 180 ° C to 200 ° C.
  • the weight average molecular weight of the (C) maleimide-based heat-resistant copolymer may be 80,000 to 200,000 g / mol.
  • the weight average molecular weight of the (C) maleimide-based heat-resistant copolymer may be 100,000 to 180,000 g / mol, for example, 130,000 to 160,000 g / mol.
  • the (C) maleimide-based heat-resistant copolymer has an advantage of exhibiting excellent heat resistance and coloring property in the range of the glass transition temperature and the weight average molecular weight, and has excellent extrusion processability and fluidity.
  • the (C) maleimide-based heat-resistant copolymer may be contained in an amount of 5 to 10% by weight based on the total weight of the components (A) to (C).
  • the heat resistance and coloring property of the thermoplastic resin composition can be improved evenly.
  • the thermoplastic resin composition may further comprise one or more other additives in order to balance physical properties or, depending on the needs of the end use.
  • additives include flame retardants, surfactants, nucleating agents, coupling agents, fillers, plasticizers, impact modifiers, lubricants, antibacterial agents, mold release agents, antioxidants, inorganic additives, colorants, lubricants, antistatic agents, pigments,
  • a heat stabilizer, a UV stabilizer, an ultraviolet screening agent, a nucleating agent, an adhesive, and the like may be used alone or in combination of two or more.
  • the other additives may be appropriately contained within a range that does not impair the physical properties of the thermoplastic resin composition and specifically may be included in an amount of 50 parts by weight or less based on 100 parts by weight of the components (A) to (C) 0.1 part by weight to 30 parts by weight.
  • thermoplastic resin composition can be produced by a known production method.
  • the components and other additives according to one embodiment may be simultaneously mixed and then melted / kneaded in an extruder to form a pellet.
  • thermoplastic resin compositions of Examples 1 to 5 and Comparative Examples 1 to 8 were produced in accordance with the ingredient content ratios described in Table 1 below.
  • thermoplastic resin composition the components (A), (B) and (C) of the thermoplastic resin composition are expressed as% by weight based on the total weight of the components (A) to (C).
  • the prepared pellets were dried at 80 ° C for 4 hours, and then a specimen for measurement of physical properties and a specimen of 100 mm ⁇ 100 mm ⁇ 3.2 mm size were prepared. At this time, a 6 oz injection molding machine was used, and the cylinder temperature was set at 220 ° C and the mold temperature was set at 60 ° C.
  • Example Comparative Example One 2 3 4 5 One 2 3 4 5 6 7 8 (A) a (meth) acrylic resin PMMA 65 64 63 62 61 70 68 66 64 62 68 60 58 (B) an acryl-based graft copolymer g-ASA 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 (C) a maleimide-based heat-resistant copolymer PMI-MAH-SM (C) 5 6 7 8 9 - - - - - 2 10 12 PMI-MAH-SM (C ') - - - - - - - 2 4 6 8 - - - -
  • PMMA polymethyl methacrylate
  • Styrene-acrylate graft copolymer comprising about 60% by weight of butyl acrylate rubber having an average particle size of about 300 nm, wherein the copolymer of styrene and acrylonitrile is selected from butyl acrylate And a rubber copolymerized at a weight ratio of about 7: 3.
  • N-phenylmaleimide-maleic anhydride-styrene (PMI-MAH-SM) copolymer having a weight average molecular weight of about 150,000 g / mol and a glass transition temperature of about 177 DEG C was used.
  • the copolymer comprises about 21% by weight of the component derived from N-phenylmaleimide, about 7% by weight of the component derived from maleic anhydride, and about 72% by weight of the component derived from styrene.
  • N-phenylmaleimide-maleic anhydride-styrene (PMI-MAH-SM) copolymer having a weight average molecular weight of about 125,000 g / mol and a glass transition temperature of about 206 ° C was used.
  • the copolymer comprises about 49% by weight of the component derived from N-phenylmaleimide, about 2% by weight of the component derived from maleic anhydride, and about 49% of the component derived from styrene.
  • Colorability (%) The transmittance was measured using a GNH Tech NDH-7000 instrument with a size of 100 mm ⁇ 100 mm with a thickness of 3.2 mm. It was determined that the higher the transmittance, the better the colorability because it was transparent.
  • thermoplastic resin composition according to the embodiments of the present invention exhibits an Izod impact strength of 7 kgf ⁇ cm / cm or more while simultaneously satisfying a VST of 99 ° C or higher and a transmittance of 40% have. Accordingly, by using the (A) (meth) acrylic resin, the (B) acryl-based graft copolymer and the (C) maleimide-based heat resistant copolymer in an optimum amount, an excellent transmittance can be ensured, And a thermoplastic resin composition excellent in heat resistance can be realized.

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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 contenant (A) de 60 à 85 % en poids d'une résine à base de (méth)acrylique, (B) de 10 à 30 % en poids d'un copolymère greffé à base d'acryle, et (C) de 5 à 10 % en poids d'un copolymère résistant à la chaleur à base de maléimide, et un produit moulé l'utilisant.
PCT/KR2018/015497 2017-12-29 2018-12-07 Composition de résine thermoplastique et produit moulé l'utilisant Ceased WO2019132304A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP18897181.6A EP3733767B1 (fr) 2017-12-29 2018-12-07 Composition de résine thermoplastique et produit moulé l'utilisant
US16/958,798 US11492481B2 (en) 2017-12-29 2018-12-07 Thermoplastic resin composition including maleimide-based heat-resistant copolymer and molded product using same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0184921 2017-12-29
KR20170184921 2017-12-29
KR10-2018-0154655 2018-12-04
KR1020180154655A KR102232505B1 (ko) 2017-12-29 2018-12-04 열가소성 수지 조성물 및 이를 이용한 성형품

Publications (2)

Publication Number Publication Date
WO2019132304A2 true WO2019132304A2 (fr) 2019-07-04
WO2019132304A3 WO2019132304A3 (fr) 2019-08-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11492481B2 (en) 2017-12-29 2022-11-08 Lotte Chemical Corporation Thermoplastic resin composition including maleimide-based heat-resistant copolymer and molded product using same
US12559618B2 (en) 2019-10-31 2026-02-24 Lotte Chemical Corporation Thermoplastic resin composition and molded product manufactured therefrom

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0171619B1 (ko) * 1992-11-16 1999-03-30 채오병 내열성이 우수한 폴리카보네이트계 수지조성물
KR100550937B1 (ko) * 1999-12-21 2006-02-13 제일모직주식회사 내열성이 우수한 열가소성 수지 조성물
KR100771355B1 (ko) * 2005-08-29 2007-10-29 주식회사 엘지화학 열가소성 수지 조성물
KR20150114239A (ko) * 2014-04-01 2015-10-12 제일모직주식회사 내열성 및 착색성이 향상된 열가소성 수지 조성물
KR101874160B1 (ko) * 2015-09-30 2018-07-04 롯데첨단소재(주) 투명 열가소성 수지 조성물 및 이로부터 형성된 성형품

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11492481B2 (en) 2017-12-29 2022-11-08 Lotte Chemical Corporation Thermoplastic resin composition including maleimide-based heat-resistant copolymer and molded product using same
US12559618B2 (en) 2019-10-31 2026-02-24 Lotte Chemical Corporation Thermoplastic resin composition and molded product manufactured therefrom

Also Published As

Publication number Publication date
WO2019132304A3 (fr) 2019-08-15

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