[go: up one dir, main page]

WO2013077492A1 - Composition de résine thermoplastique, et produit moulé l'utilisant - Google Patents

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

Info

Publication number
WO2013077492A1
WO2013077492A1 PCT/KR2011/010010 KR2011010010W WO2013077492A1 WO 2013077492 A1 WO2013077492 A1 WO 2013077492A1 KR 2011010010 W KR2011010010 W KR 2011010010W WO 2013077492 A1 WO2013077492 A1 WO 2013077492A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
meth
acrylate
thermoplastic resin
resin composition
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/KR2011/010010
Other languages
English (en)
Korean (ko)
Inventor
김인철
홍창민
박지은
정택웅
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.)
Cheil Industries Inc
Original Assignee
Cheil Industries Inc
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=48469910&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2013077492(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Priority to CN201180075074.6A priority Critical patent/CN103958599B/zh
Priority to DE112011105875.6T priority patent/DE112011105875B4/de
Priority to JP2014543398A priority patent/JP2014533763A/ja
Publication of WO2013077492A1 publication Critical patent/WO2013077492A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

  • thermoplastic resin composition and a molded article using the same.
  • ABS resins are widely used in electrical and electronic parts and office equipment because of their excellent impact resistance and workability, and good mechanical strength, heat deformation temperature, and glossiness.
  • ABS resins are widely used in electrical and electronic parts and office equipment because of their excellent impact resistance and workability, and good mechanical strength, heat deformation temperature, and glossiness.
  • high-end consumer housings such as LCD, PDP TV, audio, etc.
  • the product value is low due to the easy generation of scratches during injection molding or use and difficult to express the color of the high-quality texture.
  • ASA resin with excellent weather resistance is a general-purpose resin used for various materials such as building materials and automotive exteriors, and does not have excellent scratch resistance, and has a limit of colorability due to the characteristics of an opaque resin.
  • ABS / PMMA resin on the other hand, has excellent transparency, high color, high gloss color, and high scratch resistance according to PMMA prescription.
  • One embodiment of the present invention is to provide a transparent thermoplastic resin composition excellent in excellent weather resistance and scratch resistance.
  • Another embodiment of the present invention is to provide a molded article using the thermoplastic resin composition.
  • One embodiment of the invention graft acrylic copolymer (A); Aromatic vinyl-vinyl cyanide copolymer (B); And a polyalkyl (meth) acrylate resin (C), wherein the aromatic vinyl-vinyl cyanide copolymer (B) provides a thermoplastic resin composition comprising units derived from 5 to 25 wt% of a vinyl cyanide compound. .
  • the thermoplastic resin composition may include 50 to 200 parts by weight of the aromatic vinyl-vinyl cyanide copolymer (B) based on 100 parts by weight of the graft acrylic copolymer (A).
  • the thermoplastic resin composition may include 50 to 300 parts by weight of the polyalkyl (meth) acrylate (C) based on 100 parts by weight of the graft acrylic copolymer (A).
  • the content ratio of the aromatic vinyl-vinyl cyanide copolymer (B) and the polyalkyl (meth) acrylate (C) may be in the range of 6: 4 to 3: 7.
  • the graft acrylic copolymer (A) is a copolymer in which an acrylic rubber-like polymer is copolymerized with the aromatic vinyl monomer, the monomer copolymerizable with the aromatic vinyl monomer, or a combination thereof, graft or two or more thereof. May be a combination.
  • the monomer copolymerizable with the aromatic vinyl monomer may include a vinyl cyanide compound, and may include a content of 20 to 30 wt% of the total amount of the monomer graft-polymerized to the acrylic rubber polymer.
  • the aromatic vinyl cyanide copolymer (B) may be a copolymer of styrene and acrylonitrile, a copolymer of ⁇ -methylstyrene and acrylonitrile, or a copolymer of styrene, ⁇ -methylstyrene and acrylonitrile. have.
  • the polyalkyl (meth) acrylate resin (C) is an alkyl (meth) acrylate having an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, It may be a polymer of glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate or a combination thereof.
  • the thermoplastic resin composition may further include an additive including a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a release agent, or a combination thereof.
  • an additive including a dye, a pigment, a flame retardant, a filler, a stabilizer, a lubricant, an antibacterial agent, a release agent, or a combination thereof.
  • Another embodiment of the present invention provides a molded article manufactured using the thermoplastic resin composition.
  • the molded article may have a haze value of 5 to 20 according to ASTM D1003 standard.
  • thermoplastic resin composition may implement high transparent properties while having excellent weather resistance and scratch resistance.
  • thermoplastic resin composition may implement high transparent properties while having excellent weather resistance and scratch resistance.
  • substituted means that the hydrogen atom in the compound is a halogen atom (F, Cl, Br, I), hydroxy group, nitro group, cyano group, amino group, azido group, amidino group, hydrazino group, Hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid group or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkoxy Substituted with a substituent of a C1 to C20 alkoxy group, C6 to C30 aryl group, C6 to C30 aryloxy group, C3 to C30 cycloalkyl group, C3 to C30 cycloalkenyl group, C3 to C30 cycloalkynyl group, or a combination thereof Means that.
  • halogen atom F, Cl, Br, I
  • (meth) acrylate means that both “acrylate” and “methacrylate” are possible.
  • (meth) acrylic acid alkyl ester means that both “acrylic acid alkyl ester” and “methacrylic acid alkyl ester” are possible, and “(meth) acrylic acid ester” means both “acrylic acid ester” and “methacrylic acid ester”. It means everything is possible.
  • thermoplastic resin composition includes (A) graft acrylic copolymer, (B) aromatic vinyl-vinyl cyanide copolymer, and (C) polyalkyl (meth) acrylate resin.
  • the thermoplastic resin composition is a general-purpose resin composition including a graft acrylic copolymer, and is easily applied to various applications such as building materials, automotive exterior applications, etc., while securing transparency and improving scratch resistance.
  • each component included in the thermoplastic resin composition will be described in detail.
  • the graft acrylic copolymer (A) is a copolymer obtained by graft polymerization of an acrylic vinyl polymer with an aromatic vinyl monomer and / or a monomer copolymerizable with the aromatic vinyl monomer.
  • the acrylic rubber-like polymer forms a core
  • the monomer copolymerizable with the aromatic vinyl monomer and / or the aromatic vinyl monomer may form a shell while graft polymerization on the core, thereby forming the graft.
  • the acrylic copolymer (A) may form a core-shell structure.
  • the acrylic rubber polymer may be polymerized, including a (meth) acrylic acid alkyl ester, a (meth) acrylic acid ester, or a combination thereof.
  • the alkyl may be C1 to C10 alkyl.
  • Examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like.
  • Examples of the (meth) acrylic acid esters include (meth) acrylate. Acrylic monomers, such as these, are mentioned, It is not limited to this.
  • the acrylic rubber polymer may have a core structure including a single layer, a double layer, or a combination thereof depending on the physical properties to be implemented.
  • the acrylic rubber polymer may include a single layer rubber core including the acrylic monomer.
  • the acrylic rubber polymer may include a double layer rubber core including an inner layer including the acrylic monomer and an aromatic vinyl compound, and an outer layer including the acrylic monomer.
  • an inner layer containing an acrylic monomer and a vinyl compound may be used.
  • An acrylic rubber-like polymer including a double layer rubber core may be used.
  • the rubber core of the bilayer may be composed of an inner layer and an outer layer, for example, the inner layer includes an acrylic acid alkyl ester compound and an aromatic vinyl compound, and the outer layer is an acrylic acid alkyl ester compound. It includes.
  • the acrylic acid alkyl ester compound may be C1 to C10 alkyl acrylate, for example, methyl acrylate, butyl acrylate or the like or a combination thereof may be used.
  • alkyl substituted styrene examples include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like, but are not limited thereto.
  • the inner layer may be a copolymer of the acrylic acid alkyl ester compound and the aromatic vinyl compound.
  • the weight ratio of the acrylic acid alkyl ester compound and the aromatic vinyl compound of the inner layer may be from 5: 5 to 90:20, and included in the weight ratio of this range, weather resistance, impact resistance, gloss and colorability suitable for use as a predetermined use A combination of aspects can be obtained.
  • the weight ratio of the inner layer and outer layer may be 20:80 Pa to 70: 300.
  • the weight ratio of the above range it is possible to obtain a physical property balance suitable for use as a predetermined use.
  • the acrylic rubber polymer may be used by mixing an acrylic copolymer including the rubber core of the single layer and an acrylic copolymer including the rubber core of the double layer.
  • the acrylic copolymer including the rubber core of the single layer and the acrylic copolymer including the rubber core of the double layer may be mixed in a weight ratio of 20:80 to 90:20, specifically, 25:75 To 75:25 by weight. When mixed in the ratio range, the coloring properties of the acrylic thermoplastic resin composition are excellent.
  • the monomer graft-polymerized to the acrylic rubber polymer includes an aromatic vinyl monomer and / or a monomer copolymerizable with the aromatic vinyl monomer.
  • the monomer copolymerizable with the aromatic vinyl monomer and / or the aromatic vinyl monomer may be graft polymerized to the acrylic rubber polymer to form a shell.
  • styrene As the aromatic vinyl monomer, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or the like, or a combination thereof may be used.
  • alkyl substituted styrenes include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
  • a vinyl cyanide compound As the monomer copolymerizable with the aromatic vinyl monomer, a vinyl cyanide compound, a heterocyclic compound, or the like can be used.
  • vinyl cyanide compound acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like or a combination thereof may be used.
  • heterocyclic compound maleic anhydride, alkyl or phenyl N-substituted maleimide, or the like, or a combination thereof may be used.
  • an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or the like or a combination thereof may be used, and among these, preferably an aromatic vinyl compound And mixtures or copolymers of vinyl cyanide compounds.
  • the aromatic vinyl compound and the vinyl cyanide compound may be composed of 6 to 90 wt% and 10 to 40 wt%.
  • the content of the vinyl cyanide compound in the total amount of the monomer graft polymerized to the acrylic rubber-like polymer may be 20 to 30% by weight.
  • the graft acrylic copolymer (A) may include 70 to 300 wt% of an acrylic rubbery polymer capable of forming a core structure and 30 to 70 wt% of a graft polymerizable polymer capable of forming a shell structure. Specifically, it may be a graft acrylic copolymer (A) comprising a rubber core of 60 to 40 wt% and a shell of 40 to 60 wt%. When the graft acrylic copolymer (A) is made within the content range, the colorability of the thermoplastic resin composition may be excellent.
  • the average particle diameter of the rubber may be from 0.07 to um.
  • the acrylic rubber polymer may be used in a bi-modal form in which an acrylic rubber polymer having a different average particle diameter of rubber is mixed.
  • an acrylic rubber polymer having a large particle size of 0.4 to 0.7 ⁇ m of rubber and an acrylic rubber polymer having a small particle size of 0.1 to 0.3 ⁇ m of rubber may be used in combination.
  • the large particle rubber particles directly absorb the impact, and the small particle rubber particles are substituted.
  • the role of dispersing the impact between the hard rubber can improve the practical impact compared to the uni-modal (-) type that uses only one type of rubber particle diameter.
  • the graft acrylic copolymer (A) may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization.
  • the aromatic vinyl cyanide copolymer (B) is a copolymer of an aromatic vinyl compound and a vinyl cyanide compound.
  • styrene As the aromatic vinyl compound, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, vinyl toluene, vinyl naphthalene or a combination thereof may be used.
  • alkyl substituted styrene include ⁇ -methyl styrene, p-methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, p-t-butyl styrene, 2,4-dimethyl styrene, and the like.
  • vinyl cyanide compound acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
  • aromatic vinyl cyanide copolymer (B) examples include a copolymer of styrene and acrylonitrile; copolymers of ⁇ -methylstyrene and acrylonitrile; Or copolymers of styrene, ⁇ -methylstyrene and acrylonitrile, and preferably copolymers of styrene and acrylonitrile.
  • the aromatic vinyl cyanide copolymer (B) may be polymerized by further including (meth) acrylic acid alkyl ester together with the aromatic vinyl compound and the vinyl cyanide compound.
  • the said (meth) acrylic-acid alkylester is the (meth) acrylic-acid alkylester which has a C1-C10 alkyl group.
  • the aromatic vinyl cyanide copolymer (B) may include a unit derived from 5 to 25 wt% of vinyl cyanide compound.
  • the aromatic vinyl-vinyl cyanide copolymer may include a unit derived from 15 to 20% by weight of a vinyl cyanide compound.
  • thermoplastic resin composition including the unit derived from the vinyl cyanide compound satisfying the above range may ensure transparency characteristics by including a relatively low content of the unit derived from the vinyl cyanide compound from the total content.
  • thermoplastic resin composition comprising an aromatic vinyl-vinyl cyanide copolymer (B) including a unit derived from a vinyl cyanide compound having a content satisfying the above range may have a haze value of 5 to 20. Can be implemented.
  • the aromatic vinyl cyanide copolymer (B) may have a weight average molecular weight in the range of 60,000 to 150,000.
  • the thermoplastic resin composition may include an aromatic vinyl-vinyl cyanide copolymer (B) in an amount of 50 to 200 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).
  • the polyalkyl (meth) acrylate resin (C) is resistant to hydrolysis and can improve scratch resistance of the thermoplastic resin composition.
  • the polyalkyl (meth) acrylate resin (C) may be obtained by polymerizing a raw material monomer containing an alkyl (meth) acrylate by a known polymerization method such as suspension polymerization, bulk polymerization, emulsion polymerization, or the like. .
  • Alkyl (meth) acrylate which is a monomer of the said polyalkyl (meth) acrylate resin (C) has C1-C10 alkyl group, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acryl
  • the rate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate, etc. are mentioned.
  • the alkyl (meth) acrylate may be included in more than 50% by weight relative to the total amount of the polyalkyl (meth) acrylate resin (C), specifically, it may be included in 80 to 99% by weight.
  • the heat resistance of the obtained molded article is improved, and because the intermolecular interaction with the graft acrylic copolymer (A) and the aromatic vinyl-vinyl cyanide copolymer (B) described above is increased, the affinity is improved. , Hydrolysis resistance and scratch resistance are improved.
  • the raw material monomer may further include a vinyl monomer in addition to the alkyl (meth) acrylate.
  • a vinyl monomer such as Aromatic vinyl monomers, such as styrene, (alpha) -methylstyrene, (rho) -methylstyrene; Unsaturated nitrile monomers, such as acrylonitrile and methacrylonitrile, etc. can be used, These can be used individually or in mixture.
  • the polyalkyl (meth) acrylate resin (C) may have a weight average molecular weight in the range of 10,000 to 200,000 g / mol, specifically, may have a range of 15,000 to 150,000 g / mol.
  • weight average molecular weight of polyalkyl (meth) acrylate resin (C) is in the said range, it is excellent in compatibility with the graft acrylic copolymer (A) and aromatic vinyl-vinyl cyanide copolymer (B) mentioned above, It has excellent degradability, scratch resistance and workability.
  • the polyalkyl (meth) acrylate resin (C) may adjust the content ratio with the aromatic vinyl-vinyl cyanide copolymer (B) to adjust the balance between scratch resistance and weather resistance while maintaining transparency characteristics of the thermoplastic resin composition.
  • the weight ratio of the aromatic vinyl-vinyl cyanide copolymer (B) and the polyalkyl (meth) acrylate resin (C) may be 6: 4 to 3: 7, preferably 6: 4 to 4: 6.
  • the thermoplastic resin composition may include a polyalkyl (meth) acrylate resin in an amount of 50 to 300 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).
  • a polyalkyl (meth) acrylate resin in an amount of 50 to 300 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).
  • thermoplastic resin composition may further include additional additives (D) in order to further impart injection moldability and physical property balance.
  • thermoplastic resin composition may further include additives such as dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, and release agents, and these may be used alone or in combination of two or more thereof.
  • additives such as dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, and release agents, and these may be used alone or in combination of two or more thereof.
  • the additive (D) may be suitably included within the range of not impairing the physical properties of the thermoplastic resin composition, specifically, may be included in 40 parts by weight or less relative to 100 parts by weight of the graft acrylic copolymer (A), More specifically, it may be included in 0.1 to 30 parts by weight.
  • thermoplastic resin composition As described above, each component contained in the thermoplastic resin composition has been described, and exemplary contents of each component have been described, but inherent inherent characteristics of each component are considered in accordance with the properties of the thermoplastic resin composition to be finally implemented. By using a properly added content can be implemented a thermoplastic resin composition.
  • thermoplastic resin composition can be manufactured by a well-known method of manufacturing a resin composition.
  • the components and other additives according to one embodiment may be mixed simultaneously, then melt extruded in an extruder and prepared in pellet form.
  • a molded article manufactured by molding the above-described thermoplastic resin composition is provided.
  • the molded article may include a molded article having a large size, a complicated structure, or a thin thickness, in which mechanical properties, thermal properties, and moldability are required, and more specifically, an automobile exterior material, and the like.
  • thermoplastic resin composition of the following Example is as follows.
  • Monomer mixture consisting of 33% by weight of acrylonitrile and 67% by weight of styrene relative to 50 parts by weight of a butylacrylate rubber having a double core structure composed of an inner core copolymerized with butyl acrylate and styrene and an outer core made of butyl acrylate rubber.
  • Graft ASA resin in double core-shell form prepared by emulsion part polymerization by weight
  • SAN resin with an acrylonitrile content of 20% by weight, a styrene content of 80% by weight, and a weight average molecular weight of 100,000
  • MSAN resin with 20% by weight acrylonitrile, 65% by weight styrene, 15% by weight methacrylate and 100,000 weight average molecular weight
  • PMMA resin with a weight average molecular weight of 110,000 consisting of methyl methacrylate
  • thermoplastic resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 7 were prepared in the compositions shown in Table 1 using the above-mentioned components.
  • thermoplastic resin composition of the composition shown in Table 1 below was added to other additives by extrusion / processing to prepare a thermoplastic resin in the form of pellets.
  • BSP All type Scratch Profile
  • Pencil hardness Hardness value when scratch does not occur by pushing the pencil 5 times at the speed of 10mm / s by lifting the weight of 500g with a pencil according to the hardness. (Measuring pencil and pencil hardness determined in JIS K5401)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Un mode de réalisation de la présente invention concerne une composition de résine thermoplastique comprenant : (A) un copolymère acrylique greffé ; (B) un copolymère vinyl-cyanovinylique aromatique ; et (C) une résine polyalkyl(méth)acrylate. Le copolymère vinyl-cyanovinylique aromatique (B) peut comprendre de 5 à 25 % en poids d'un monomère dérivé d'un composé cyanovinylique.
PCT/KR2011/010010 2011-11-24 2011-12-22 Composition de résine thermoplastique, et produit moulé l'utilisant Ceased WO2013077492A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201180075074.6A CN103958599B (zh) 2011-11-24 2011-12-22 热塑性树脂组合物和使用它的模制品
DE112011105875.6T DE112011105875B4 (de) 2011-11-24 2011-12-22 Thermoplastische Harzzusammensetzung und Formprodukt unter Verwendung derselben
JP2014543398A JP2014533763A (ja) 2011-11-24 2011-12-22 熱可塑性樹脂組成物およびこれを用いた成形品

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2011-0123722 2011-11-24
KR1020110123722A KR101531613B1 (ko) 2011-11-24 2011-11-24 열가소성 수지 조성물 및 이를 이용한 성형품

Publications (1)

Publication Number Publication Date
WO2013077492A1 true WO2013077492A1 (fr) 2013-05-30

Family

ID=48469910

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/010010 Ceased WO2013077492A1 (fr) 2011-11-24 2011-12-22 Composition de résine thermoplastique, et produit moulé l'utilisant

Country Status (5)

Country Link
JP (2) JP2014533763A (fr)
KR (1) KR101531613B1 (fr)
CN (1) CN103958599B (fr)
DE (1) DE112011105875B4 (fr)
WO (1) WO2013077492A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016540847A (ja) * 2014-11-21 2016-12-28 エルジー・ケム・リミテッド ポリメチルメタクリレートアクリル系共重合体アロイ高光沢組成物及び成形品
EP3875534A4 (fr) * 2018-10-31 2021-11-24 Lg Chem, Ltd. Composition de résine thermoplastique

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20150114239A (ko) 2014-04-01 2015-10-12 제일모직주식회사 내열성 및 착색성이 향상된 열가소성 수지 조성물
KR101719034B1 (ko) 2014-08-29 2017-03-22 롯데첨단소재(주) 열가소성 수지 조성물
KR20160057635A (ko) 2014-11-14 2016-05-24 롯데케미칼 주식회사 폴리카보네이트계 열가소성 수지 조성물 및 이를 이용한 제품
JP6670087B2 (ja) * 2015-01-14 2020-03-18 テクノＵｍｇ株式会社 熱可塑性樹脂組成物およびその成形品
KR101874160B1 (ko) * 2015-09-30 2018-07-04 롯데첨단소재(주) 투명 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR101965480B1 (ko) * 2016-09-29 2019-04-03 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR101890476B1 (ko) * 2016-09-30 2018-08-21 롯데첨단소재(주) 내전리방사선성 열가소성 수지 조성물 및 이를 포함하는 성형품
CN110139898B (zh) * 2016-12-30 2022-06-10 乐天尖端材料株式会社 热塑性树脂组合物和使用其的模制品
KR102226064B1 (ko) 2018-01-24 2021-03-11 주식회사 엘지화학 열가소성 수지 조성물
TWI675875B (zh) * 2018-08-20 2019-11-01 奇美實業股份有限公司 丙烯酸酯系橡膠改質樹脂組成物以及利用其製得之成型品
KR102298295B1 (ko) * 2018-10-31 2021-09-07 주식회사 엘지화학 열가소성 수지 조성물
KR102386835B1 (ko) 2019-02-19 2022-04-15 주식회사 엘지화학 열가소성 수지 조성물 및 열가소성 수지 성형품
WO2020171453A1 (fr) * 2019-02-19 2020-08-27 주식회사 엘지화학 Composition de résine thermoplastique et article moulé en résine thermoplastique
KR102465681B1 (ko) * 2019-09-06 2022-11-11 주식회사 엘지화학 열가소성 수지 조성물 및 이의 성형품
KR102547327B1 (ko) * 2019-10-07 2023-06-26 주식회사 엘지화학 Asa계 수지 조성물, 이를 포함하는 성형품 및 이 성형품의 제조방법
JP7592619B2 (ja) * 2019-10-07 2024-12-02 エルジー・ケム・リミテッド Ａｓａ系樹脂組成物、それを含む成形品及びその成形品の製造方法
KR102417772B1 (ko) * 2019-10-31 2022-07-05 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조된 성형품
WO2021261703A1 (fr) * 2020-06-26 2021-12-30 (주) 엘지화학 Composition de résine thermoplastique et article moulé comprenant celle-ci
CN114269845B (zh) * 2020-06-26 2023-09-08 株式会社Lg化学 热塑性树脂组合物和包含该组合物的成型品
JP7383805B2 (ja) 2020-07-07 2023-11-20 エルジー・ケム・リミテッド 熱可塑性樹脂及びその製造方法
KR102707172B1 (ko) * 2020-10-29 2024-09-20 주식회사 엘지화학 열가소성 수지 조성물, 이의 제조방법 및 이로부터 제조된 성형품
EP4029915B1 (fr) * 2020-10-29 2024-04-17 LG Chem, Ltd. Composition de résine thermoplastique, son procédé de préparation et article moulé fabriqué à partir de celle-ci
JP7697865B2 (ja) * 2021-10-21 2025-06-24 株式会社イノアックコーポレーション 樹脂組成物、成形体及び物品
KR20240030799A (ko) * 2022-08-31 2024-03-07 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조되는 성형품
KR20240030716A (ko) * 2022-08-31 2024-03-07 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조되는 성형품

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990239A (en) * 1997-04-16 1999-11-23 Bayer Corporation Weatherable ASA composition
JP2000212377A (ja) * 1999-01-21 2000-08-02 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物
KR20100045830A (ko) * 2008-10-24 2010-05-04 주식회사 엘지화학 내스크래치성과 내열성이 우수한 내후성 열가소성 수지 조성물
KR100983872B1 (ko) * 2008-02-01 2010-09-27 금호석유화학 주식회사 고광택, 고경도 투명 열가소성 수지 조성물
KR20110073243A (ko) * 2009-12-23 2011-06-29 제일모직주식회사 내스크래치성이 우수한 열가소성 수지 조성물 및 그로부터 제조된 성형품
KR20110082122A (ko) * 2009-12-29 2011-07-18 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품품

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2045742B2 (de) * 1970-09-16 1972-12-21 Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen Transparente, schlagzaehe formmassen
JP2002047396A (ja) * 2000-07-31 2002-02-12 Kuraray Co Ltd 難燃性熱可塑性ポリエステル系樹脂組成物およびその成形用途
JP2002037989A (ja) * 2000-07-31 2002-02-06 Kuraray Co Ltd 耐熱性熱可塑性ポリエステル系樹脂組成物およびその成形用途
US6720386B2 (en) * 2002-02-28 2004-04-13 General Electric Company Weatherable styrenic blends with improved translucency
US6812282B2 (en) * 2002-09-10 2004-11-02 Bayer Polymers Llc Thermoplastic compositions providing matt surface
DE10260065A1 (de) * 2002-12-19 2004-07-01 Röhm GmbH & Co. KG Kern-Schale-Teilchen zur Schlagzähmodifizierung von Poly(meth)acrylat-Formmassen
KR100509868B1 (ko) * 2003-06-09 2005-08-22 주식회사 엘지화학 내후성 및 외관특성이 우수한 열가소성 수지 조성물
US20060069208A1 (en) * 2004-09-29 2006-03-30 General Electric Company Weatherable resinous composition with improved heat resistance
KR100815995B1 (ko) * 2006-06-08 2008-03-21 제일모직주식회사 저온 및 상온 내충격성과 착색성 및 내후성이 우수한ａｓａ 그라프트 공중합체 및 이를 포함한 열가소성 수지조성물
JP4951421B2 (ja) * 2007-06-21 2012-06-13 テクノポリマー株式会社 熱可塑性樹脂組成物
JP2009144008A (ja) * 2007-12-12 2009-07-02 Asahi Kasei Chemicals Corp 耐傷性、および耐金型汚染性に優れる熱可塑性樹脂組成物
CN102089685B (zh) * 2008-07-16 2013-07-24 3M创新有限公司 包含由甲基丙烯酸甲酯聚合物和苯乙烯丙烯腈聚合物形成的共混物的多层光学膜层
JP5255407B2 (ja) * 2008-11-12 2013-08-07 旭化成ケミカルズ株式会社 難燃性熱可塑性樹脂組成物及びそれからなる成形品
IT1392399B1 (it) 2008-12-22 2012-03-02 Valeo Spa Maniglia per porta di autoveicolo
JP2010209219A (ja) * 2009-03-10 2010-09-24 Techno Polymer Co Ltd 制電性樹脂組成物及び成形品
US8344043B2 (en) * 2009-12-23 2013-01-01 Cheil Industries Inc. Thermoplastic resin composition having good scratch resistance and molded article made therefrom
JP5687920B2 (ja) * 2010-03-03 2015-03-25 日本エイアンドエル株式会社 熱可塑性樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990239A (en) * 1997-04-16 1999-11-23 Bayer Corporation Weatherable ASA composition
JP2000212377A (ja) * 1999-01-21 2000-08-02 Mitsubishi Rayon Co Ltd 熱可塑性樹脂組成物
KR100983872B1 (ko) * 2008-02-01 2010-09-27 금호석유화학 주식회사 고광택, 고경도 투명 열가소성 수지 조성물
KR20100045830A (ko) * 2008-10-24 2010-05-04 주식회사 엘지화학 내스크래치성과 내열성이 우수한 내후성 열가소성 수지 조성물
KR20110073243A (ko) * 2009-12-23 2011-06-29 제일모직주식회사 내스크래치성이 우수한 열가소성 수지 조성물 및 그로부터 제조된 성형품
KR20110082122A (ko) * 2009-12-29 2011-07-18 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품품

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016540847A (ja) * 2014-11-21 2016-12-28 エルジー・ケム・リミテッド ポリメチルメタクリレートアクリル系共重合体アロイ高光沢組成物及び成形品
EP3875534A4 (fr) * 2018-10-31 2021-11-24 Lg Chem, Ltd. Composition de résine thermoplastique
US11608401B2 (en) 2018-10-31 2023-03-21 Lg Chem, Ltd. Thermoplastic resin composition

Also Published As

Publication number Publication date
CN103958599A (zh) 2014-07-30
KR101531613B1 (ko) 2015-06-25
DE112011105875T5 (de) 2014-08-21
KR20130057795A (ko) 2013-06-03
JP6263234B2 (ja) 2018-01-17
JP2014533763A (ja) 2014-12-15
CN103958599B (zh) 2018-01-05
DE112011105875B4 (de) 2019-05-23
JP2016196656A (ja) 2016-11-24

Similar Documents

Publication Publication Date Title
WO2013077492A1 (fr) Composition de résine thermoplastique, et produit moulé l'utilisant
WO2013085090A1 (fr) Composition de résine thermoplastique et produit moulé à l'aide de celle-ci
WO2018038573A1 (fr) Composition de résine thermoplastique et article moulé fabriqué à partir de celle-ci
WO2017095060A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué à partir de cette dernière
WO2014007442A1 (fr) Composition de résine thermoplastique et mousse moulée l'utilisant
WO2013062170A1 (fr) Composition de résine thermoplastique et moulage l'utilisant
WO2012053693A1 (fr) Résine thermoplastique ayant une transparence élevée et une résistance au choc élevée et empêchant un blanchiment à basse température
WO2015152468A1 (fr) Composition de résine thermoplastique dotée d'une résistance à la chaleur et une propriété de coloration améliorées
WO2020091338A1 (fr) Composition de résine thermoplastique et produit moulé l'utilisant
WO2020111552A1 (fr) Composition de résine thermoplastique et article moulé formé à partir de celle-ci
WO2012086901A1 (fr) Composition de résine acrylique et articles moulés à base de celle-ci
WO2011081317A2 (fr) Composition de résine thermoplastique et pièce moulée à l'aide de celle-ci
WO2013094889A1 (fr) Copolymère à base acrylique retardateur de flamme, composition de résine le comprenant et forme moulante à base de celle-ci
WO2017057904A1 (fr) Composition de résine thermoplastique et produit moulé la comprenant
WO2018124517A1 (fr) Composition de résine thermoplastique, son procédé de préparation et article moulé manufacturé la comprenant
WO2017095031A1 (fr) Composition de résine thermoplastique possédant d'excellentes propriétés de matité et de brillance, et article moulé produit à partir de ladite composition
WO2022182138A1 (fr) Composition de résine thermoplastique et article moulé faisant appel à celle-ci
WO2023033437A1 (fr) Composition polymère d'extinction présentant une excellente résistance aux intempéries et une excellente résistance aux chocs, et feuille mate la comprenant
WO2021045429A1 (fr) Composition de résine thermoplastique et produit moulé associé
WO2022045795A1 (fr) Composition de résine thermoplastique et article moulé préparé à partir de celle-ci
WO2017105007A1 (fr) Copolymère greffé à base de vinyle modifié par du caoutchouc et composition de résine thermoplastique le contenant
WO2022146043A1 (fr) Composition de résine thermoplastique et produit moulé l'utilisant
WO2021086001A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué à partir de celle-ci
WO2016080758A1 (fr) Composition de poly(méthacrylate de méthyle)-alliage de copolymère acrylique super brillante et produit moulé
WO2024049091A1 (fr) Composition de résine thermoplastique et produit moulé fabriqué 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: 11876257

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014543398

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1120111058756

Country of ref document: DE

Ref document number: 112011105875

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11876257

Country of ref document: EP

Kind code of ref document: A1