WO2013085090A1 - Composition de résine thermoplastique et produit moulé à l'aide de celle-ci - Google Patents

Composition de résine thermoplastique et produit moulé à l'aide de celle-ci Download PDF

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Publication number
WO2013085090A1
WO2013085090A1 PCT/KR2011/009731 KR2011009731W WO2013085090A1 WO 2013085090 A1 WO2013085090 A1 WO 2013085090A1 KR 2011009731 W KR2011009731 W KR 2011009731W WO 2013085090 A1 WO2013085090 A1 WO 2013085090A1
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Prior art keywords
copolymer
weight
meth
acrylate
rubber
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PCT/KR2011/009731
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English (en)
Korean (ko)
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김인철
하진욱
홍창민
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제일모직 주식회사
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Publication of WO2013085090A1 publication Critical patent/WO2013085090A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08L33/18—Homopolymers or copolymers of 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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.
  • ABS / PMMA resin which has excellent colorability and scratch resistance, has been widely used for high quality design of home appliances.
  • the scratch characteristics are excellent, but transparency above a certain level is not realized, and high coloring is impossible.
  • High heat resistance is required to withstand the conditions of home appliances or heat sinks requiring heat resistance.
  • thermoplastic resin composition excellent in high colorability, scratch resistance and heat resistance.
  • Another embodiment of the present invention is to provide a molded article using the thermoplastic resin composition.
  • thermoplastic resin composition is based on the total of 100 parts by weight of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound, wherein N- (Substituted) may contain 1 to 20 parts by weight of the maleimide copolymer (C).
  • thermoplastic resin composition is based on 100 parts by weight of the total of the rubber-modified vinyl graft copolymer (A) and the copolymer (B) of the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound. 40 to 65 parts by weight of alkyl (meth) acrylate (D) may be included.
  • the thermoplastic resin composition may include the N- (substituted) maleimide copolymer (C) and the polyalkyl (meth) acrylate (D) in a weight ratio of 1:10 to 1: 2.
  • the copolymer (B) of the C1 to C10 alkyl substituted aromatic vinyl compound and the vinyl cyanide compound may be an ⁇ -methylstyrene-acrylonitrile copolymer.
  • the ⁇ -methylstyrene-acrylonitrile copolymer may include 15 to 25% by weight of acrylonitrile and 75 to 85% by weight of styrene.
  • the N- (substituted) maleimide copolymer (C) may include 20 to 60% by weight of maleic anhydride and N- (substituted) maleimide monomer and 40 to 80% by weight of an aromatic vinyl compound and a vinyl cyan compound.
  • the rubber-modified vinyl-based graft copolymer (A) is 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer or a combination thereof; And a vinyl polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof.
  • butadiene rubber acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane It may be a copolymer grafted to 5 to 95% by weight of the rubbery polymer of the / polyalkyl (meth) acrylate rubber composite or a combination thereof.
  • the polyalkyl (meth) acrylate (D) is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (meth) acrylate And it may be a polymer comprising a monomer selected from these combinations.
  • thermoplastic resin composition may further include an additive selected from dyes, pigments, flame retardants, fillers, stabilizers, lubricants, antibacterial agents, mold release agents, and combinations thereof.
  • thermoplastic resin composition in another embodiment, there is provided a molded article manufactured using the above-mentioned thermoplastic resin composition.
  • thermoplastic resin composition is excellent in colorability, scratch resistance and heat 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 according to an embodiment of the present invention (A) rubber modified vinyl-based graft copolymer; (B) C1 to C10 alkyl substituted aromatic vinyl compound and vinyl cyanide compound copolymer; (C) N- (substituted) maleimide copolymer; And (D) polyalkyl (meth) acrylates.
  • the thermoplastic resin composition includes a rubber-modified vinyl graft copolymer (A) having excellent transparency and (B) a C1 to C10 alkyl-substituted aromatic vinyl compound and a vinyl cyanide compound copolymer that contribute to high heat resistance. (C) N- (substituted) maleimide copolymer.
  • thermoplastic resin composition is used for automotive unpainted interior materials or housings of home appliances requiring high heat resistance and scratch resistance. It is suitable to be.
  • the rubber-modified vinyl graft copolymer is a copolymer in which 5 to 95 wt% of the vinyl polymer is grafted to 5 to 95 wt% of the rubbery polymer.
  • the vinyl polymer may include 50 to 95% by weight of the first vinyl monomer of an aromatic vinyl monomer, an acrylic monomer, a heterocyclic monomer, or a combination thereof; And a polymer composed of 5 to 50% by weight of an unsaturated nitrile monomer, an acrylic monomer that is heterogeneous with the acrylic monomer, a heterocyclic monomer that is heterogeneous with the heterocyclic monomer, or a second vinyl monomer of a combination thereof.
  • the “heterologous” means different kinds.
  • styrene As the aromatic vinyl monomer, styrene, C1 to C10 alkyl substituted styrene, halogen substituted styrene, or a combination thereof may be used.
  • alkyl substituted styrene include o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
  • the thing of (meth) acrylic-acid alkylester, (meth) acrylic acid ester, or a combination thereof can be used.
  • the alkyl means C1 to C10 alkyl.
  • Specific examples of the (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Meta) acrylates may be used.
  • heterocyclic monomer maleic anhydride, alkyl or phenyl N-substituted maleimide or a combination thereof can be used.
  • an acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof can be used as the unsaturated nitrile monomer.
  • the rubbery polymers include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene terpolymer (EPDM) rubber, polyorganosiloxane / polyalkyl (Meth) acrylate rubber composites or combinations thereof may be used.
  • the rubber particle size of the rubber-modified vinyl graft copolymer may be 0.05 to 4 ⁇ m in order to improve impact resistance and surface properties of the molded product.
  • the rubber particle size is 0.05 to 4 ⁇ m, the impact strength is excellent. Can be secured.
  • the rubber modified vinyl graft copolymer may be used alone or in the form of a mixture of two or more thereof.
  • the rubber-modified vinyl-based graft copolymer include graft copolymerization of styrene, acrylonitrile and optionally methyl (meth) acrylate in the form of a mixture of butadiene rubber, acrylic rubber or styrene / butadiene rubber. have.
  • rubber-modified vinyl-based graft copolymers include those obtained by graft copolymerization of methyl (meth) acrylate on butadiene rubber, acrylic rubber or styrene / butadiene rubber.
  • rubber-modified graft copolymers include acrylonitrile-butadiene-styrene graft copolymers.
  • the rubber-modified vinyl-based graft copolymer is well known to those skilled in the art, and may be any of emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization. Examples include adding the above-mentioned aromatic vinyl monomer in the presence of a rubbery polymer and performing emulsion polymerization or bulk polymerization using a polymerization initiator.
  • the rubber-modified vinyl graft copolymer may be included in the amount of 10 to 40% by weight, specifically, 20 to 30% by weight based on the total amount of the thermoplastic resin composition.
  • the rubber-modified vinyl-based graft copolymer is included in the above range, it is possible to secure all excellent mechanical strength, impact strength and heat resistance of the thermoplastic resin molded article.
  • the vinyl cyanide compound copolymer including the C1 to C10 alkyl-substituted aromatic vinyl compound may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and has a weight average molecular weight of 15,000 kPa to 400,000 g / mol. Can be used.
  • the 1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer improve heat resistance of the thermoplastic resin.
  • Styrene, toluene, naphthalene or a combination thereof may be used as the aromatic vinyl compound of the C1 to C10 alkyl substituted aromatic vinyl compound.
  • alkyl substituted styrene of C1 to C10 may include ⁇ -methyl styrene and p. -Methyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, pt-butyl styrene, 2,4-dimethyl styrene, etc. are mentioned .
  • vinyl cyanide compound acrylonitrile, methacrylonitrile, ethacrylonitrile or a combination thereof may be used.
  • C1 to C10 alkyl-substituted aromatic vinyl compound and vinyl cyanide compound copolymer include copolymers of ⁇ -methylstyrene and acrylonitrile, or copolymers of styrene, ⁇ -methylstyrene and acrylonitrile. These are mentioned, Preferably, the copolymer of (alpha) -methylstyrene and acrylonitrile is mentioned.
  • the copolymer may be polymerized further comprising a (meth) acrylic acid alkyl ester compound together with a C1 to C10 alkyl substituted aromatic vinyl compound and a vinyl cyanide compound.
  • the said (meth) acrylic-acid alkyl ester compound is the (meth) acrylic-acid alkyl ester which has a C1-C10 alkyl group.
  • the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer are polymerized with 50 to 90% by weight of the C1 to C10 alkyl substituted aromatic vinyl compound and 10 to 50% by weight of the vinyl cyanide compound.
  • the copolymer may be formed by polymerization of 60 to 80% by weight of the C1 to C10 alkyl substituted aromatic vinyl compound and 20 to 40% by weight of the vinyl cyanide compound.
  • the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer may be included in an amount of 40 to 60 wt% based on the total amount of the thermoplastic resin composition, for example, 40 to 50 wt%.
  • the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer are included in the above range, not only the compatibility is excellent, but also the impact resistance and heat resistance may be realized while implementing high colorability.
  • the N- (substituted) maleimide copolymer of the present invention is a copolymer of maleic anhydride, an N- (substituted) maleimide monomer, and an aromatic vinyl compound.
  • the vinyl cyan compound may be further used, in which case the N- (substituted) maleimide copolymer is a copolymer of maleic anhydride, an N- (substituted) maleimide monomer, a vinyl cyan compound, and an aromatic vinyl compound.
  • the mixed content of the maleic anhydride and N- (substituted) maleimide monomer is 20 to 60 parts by weight
  • the mixed content of the aromatic vinyl compound, optionally vinyl cyan compound is preferably 40 to 80 parts by weight.
  • the content of maleic anhydride is 0.01 to 20% by weight, and the content of N- (substituted) maleimide is preferably 80 to 99.99% by weight.
  • the content of the vinyl cyan compound in the mixture of the vinyl cyan compound and the aromatic vinyl compound is 0 to 20% by weight, the content of the aromatic vinyl compound is preferably 80 to 100% by weight.
  • N- (substituted) maleimide copolymer of the present invention is compatible with rubber modified vinyl graft copolymers (A) and C1 to C10 alkyl substituted aromatic vinyl compounds and vinyl cyanide compound copolymers (B). It is preferable, and contributes to realizing the high heat resistance of the thermoplastic resin composition.
  • the N- (substituted) maleimide monomer may be selected from the group consisting of N-methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide and mixtures thereof.
  • vinyl cyan compound Acrylonitrile, methacrylonitrile, etc. are mentioned as said vinyl cyan compound, These can be used individually or in mixture.
  • aromatic vinyl type compound alkyl substituted styrene, such as styrene, halogen substituted styrene, (alpha) -methylstyrene, etc. are mentioned, These can be used individually or in mixture.
  • the N- (substituted) maleimide copolymer is based on a total of 100 parts by weight of a rubber-modified vinyl graft copolymer (A) and a C1 to C10 alkyl substituted aromatic vinyl compound and a vinyl cyanide compound copolymer (B). It may be included in the thermoplastic resin in the amount of # 1 to 20 parts by weight, and may be included, for example, in the range of 5 to 20 parts by weight.
  • the molded article using the thermoplastic resin containing the N- (substituted) maleimide copolymer (C) in the said numerical range has high coloring property and excellent heat resistance.
  • the weight ratio of the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) to be described below may be 1:10 to 1: 2, for example 1: 7 to 1: 3 Can be.
  • the N- (substituted) maleimide copolymer and the polyalkyl (meth) acrylate (D) are used in the numerical range, the fluidity of the thermoplastic resin is increased so that the resin is not easily broken, and the heat resistance and scratch resistance This is preferable and good.
  • the polyalkyl (meth) acrylate is resistant to hydrolysis and can improve scratch resistance of the thermoplastic resin composition.
  • the said polyalkyl (meth) acrylate can be obtained by superposing
  • the alkyl (meth) acrylate has an alkyl group of C1 to C10, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyethyl (Meth) acrylate etc. are mentioned.
  • the alkyl (meth) acrylate may be included in an amount of about 3% by weight or more based on the total amount of the polyalkyl (meth) acrylate, and specifically, about 3% to about 10% by weight.
  • the polyalkyl (meth) acrylate is based on a total of 100 parts by weight of the rubber-modified vinyl graft copolymer (A) and the C1 to C10 alkyl-substituted aromatic vinyl compound and the vinyl cyanide compound copolymer (B). , 40 to 65 parts by weight may be included in the thermoplastic resin composition, for example, 50 to 60 parts by weight may be included.
  • the raw material monomer constituting the polyalkyl (meth) acrylate 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 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.
  • the weight average molecular weight of the polyalkyl (meth) acrylate is within the above range, the above-described rubber-modified vinyl graft copolymer (A) and C1 to C10 alkyl substituted aromatic vinyl compound and vinyl cyanide compound copolymer (B) It is excellent in compatibility with hydrolysis resistance, scratch resistance, workability and so on.
  • the polyalkyl (meth) acrylate can adjust the balance of scratch resistance and heat resistance while maintaining the coloring properties of the molded article prepared by adjusting the content ratio with the N- (substituted) maleimide copolymer (C).
  • the weight ratio of the N- (substituted) maleimide copolymer (C) and the polyalkyl (meth) acrylate may be 1:10 to 1: 2, for example 1: 7 to 1: 3 can be have.
  • thermoplastic resin composition may further include additional additives 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 may be appropriately 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 rubber-modified vinyl-based graft 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 aforementioned 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.
  • It consists of a core made of 58% by weight of butadiene and a shell of 42% by weight, the shell consisting of 31.5 and 10.5% by weight of styrene and acrylonitrile, respectively.
  • SAN resin having an acrylonitrile content of 27% by weight, an alphamethylstyrene content of 54% by weight and a weight average molecular weight of about 120,000.
  • SAN resin having an acrylonitrile content of 20% by weight, a styrene content of 80% by weight and a weight average molecular weight of about 100,000.
  • Methyl methacrylate is copolymerized with 5% methyl acrylate and has a molecular weight of 900,000.
  • thermoplastic resin composition according to Examples 1 to 4 and Comparative Examples 1 to 4 was prepared using the above-mentioned components with the compositions shown in Table 1 below.
  • thermoplastic resin composition having the composition shown in Table 1 to extrude / process to prepare a thermoplastic resin in pellet form.
  • HDT measured according to ASTM D648 standard (unit, °C)
  • VST measured according to ISO R306 standard (unit, °C)
  • BSP width ball type scratch profile width: According to the Cheil method, using a tungsten carbide stylus, the tip of which is 0.7 mm in diameter, is given a load of 300 g, 500 g and 1000 g, respectively, and 75 mm / min. After scratching the specimen at a speed of, the surface roughness was measured using a surface profiler and the scratch width was measured. At this time, the scratch resistance increases as the measured scratch width decreases.
  • Pencil hardness The hardness value (pencil and pencil hardness determined in JIS K5401) when the scratch does not occur by pushing the pencil five times at a speed of 10mm / s by lifting the weight of 500g with a pencil according to the hardness.
  • L value For the specimen preparation, 900-mm x 500-mm x 25-mm specimens are prepared using pellets extruded / processed by carbon black 0.1 to 0.2%. The specimens were compared for L (CCM) values using a color difference meter. The higher the measured L value, the higher the brightness of the specimen. The higher the L value, the deeper the Black. In general, if the L value is 22.0 or less, the piano black color can be realized.
  • Examples 1-4 comprise acrylonitrile-butadiene-styrene copolymer (A), alphamethylstyrene-acrylonitrile copolymer (B) and said acrylonitrile-butadiene-styrene copolymer (A), alphamethyl Polyalkyl (meth) acryl containing 8.3, 18.2, 16.7 and 3.3 parts by weight of N- (substituted) maleimide copolymer (C), respectively, based on 100 parts by weight of the total of styrene-acrylonitrile copolymer (B). It relates to a thermoplastic resin composition comprising 58.3, 63.6, 50.0 and 63.3 parts by weight of the rate (D), respectively.
  • Comparative Examples 1 and 2 do not contain N- (substituted) maleimide copolymer (C), alpha methyl styrene- acrylonitrile copolymer (B), respectively, Comparative Examples 3 and 4 to alpha methyl styrene-acrylic A thermoplastic resin composition using an acrylonitrile-styrene copolymer instead of a nitrile copolymer.
  • Comparative Example 2 is a composition containing an N- (substituted) maleimide copolymer (C), but does not contain an alphamethylstyrene-acrylonitrile copolymer (B), as in Comparative Example 1 has a low deformation temperature ( HDT) and softening point (VST).

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Abstract

La présente invention concerne une composition de résine thermoplastique, et un produit moulé à l'aide de celle-ci, et, de façon plus spécifique, concerne une composition de résine thermoplastique comprenant : (A) un copolymère greffé à base vinyle modifié par caoutchouc ; (B) un copolymère d'un composé à base vinyl aromatique substitué par alkyle en C1-C10 et un composé à base cyanovinyle ; (C) un copolymère de maléimide N-(substitué) ; et (D) un polyalkyl(méth)acrylate.
PCT/KR2011/009731 2011-12-05 2011-12-16 Composition de résine thermoplastique et produit moulé à l'aide de celle-ci WO2013085090A1 (fr)

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CN106188926A (zh) * 2014-12-31 2016-12-07 奇美实业股份有限公司 橡胶改质聚苯乙烯系树脂及其制备方法
WO2019158564A1 (fr) * 2018-02-16 2019-08-22 Ineos Styrolution Group Gmbh Composition de moulage abs résistante aux températures élevées
CN112154184A (zh) * 2018-12-21 2020-12-29 株式会社Lg化学 热塑性树脂组合物

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