WO2013062170A1 - Composition de résine thermoplastique et moulage l'utilisant - Google Patents

Composition de résine thermoplastique et moulage l'utilisant Download PDF

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Publication number
WO2013062170A1
WO2013062170A1 PCT/KR2011/009111 KR2011009111W WO2013062170A1 WO 2013062170 A1 WO2013062170 A1 WO 2013062170A1 KR 2011009111 W KR2011009111 W KR 2011009111W WO 2013062170 A1 WO2013062170 A1 WO 2013062170A1
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Prior art keywords
copolymer
methacrylate
thermoplastic resin
resin composition
weight
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PCT/KR2011/009111
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English (en)
Korean (ko)
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김인철
홍창민
하진욱
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제일모직 주식회사
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Publication of WO2013062170A1 publication Critical patent/WO2013062170A1/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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • 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
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

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.
  • scratch characteristics are excellent, but transparency over a certain level is not realized, and high coloration is impossible.It is limited in application to applications requiring heat resistance, such as household appliances, due to the limitation of heat resistance. There is.
  • One embodiment of the present invention is to provide a thermoplastic resin composition excellent in high coloration, high transparency, scratch resistance and heat resistance.
  • Another embodiment of the present invention is to provide a molded article using the thermoplastic resin composition.
  • X is a single bond, oxygen (O) or sulfur (S),
  • Y is selected from the group consisting of cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group,
  • n is an integer of 0-10.
  • the high refractive index acrylic copolymer (B) may include the structural unit of Chemical Formula 1 in an amount greater than 0 to 40 wt% or less of the total content of the high refractive index acrylic copolymer.
  • the refractive index of the high refractive index acrylic copolymer (B) is greater than 1.49 and less than or equal to 1.55 Can be.
  • the absolute value of the difference between the refractive index of the graft diene copolymer (A) and the refractive index of the high refractive index acrylic copolymer (B) may be 0.00 to 0.05 kV.
  • the absolute value of the difference between the refractive index of the graft diene copolymer (A) and the refractive index of the high refractive index acrylic copolymer (B) may be 0.00 to 0.01 kPa.
  • graft diene copolymer (A) a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to a rubbery polymer derived from the diene compound, and a (meth) acrylic acid alkyl ester
  • the compound may be a secondary grafted copolymer.
  • the rubbery polymer forms a core, a polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted to form a cabinet shell, and the (meth) acrylic acid alkyl ester compound is secondary.
  • the graft diene copolymer (A) may be grafted to form an outer shell such that the copolymer is a core and a double shell structure.
  • the graft diene copolymer (A) is one comprising 30 to 70 parts by weight of diene rubber, 15 to 55 parts by weight of (meth) acrylic acid alkyl ester, 1 to 5 parts by weight of vinyl cyanide and 5 to 35 parts by weight of aromatic vinyl. Can be.
  • Monomer compound of the structural unit of Formula 1 is cyclohexyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-phenylethyl methacrylate Rate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- (4-cyclohexyl Phenyl) ethyl methacrylate, 2- (2-chlorophenyl) ethyl
  • the high refractive index acrylic copolymer (B) may be a structural unit derived from one selected from the group consisting of a vinyl monomer copolymerizable with the structural unit of Formula 1, an acrylic monomer copolymerizable with the structural unit of Formula 1, and a combination thereof. It may further include.
  • the vinyl monomer copolymerizable with the structural unit of Formula 1 and the acrylic monomer copolymerizable with the structural unit of Formula 1 include methacrylic acid esters, acrylic acid esters, acid anhydrides, esters containing hydroxyl groups, acrylamide, and methacryl Amide, acrylonitrile, methacrylonitrile, allyl glycidyl ether, glycidyl methacrylate, styrenic monomers, and combinations thereof.
  • the thermoplastic resin composition may include greater than 0 to 150 parts by weight or less of the high refractive index acrylic copolymer (B) relative to 100 parts by weight of the graft diene copolymer (A).
  • thermoplastic resin composition may further include a vinyl copolymer (C).
  • the vinyl copolymer (C) may be a copolymer formed by polymerizing 10 to 30 wt% of an aromatic vinyl compound, 0 to 20 wt% of a vinyl cyanide compound, and 50 to 90 wt% of a (meth) acrylic acid alkyl ester compound.
  • the thermoplastic resin composition may include 50 to 400 parts by weight of the vinyl copolymer (C) relative to 100 parts by weight of the graft acrylic copolymer (A).
  • 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.
  • thermoplastic resin composition is excellent in colorability, transparency, scratch resistance and heat resistance characteristics.
  • 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) a graft diene copolymer and (B) a high refractive index acrylic copolymer.
  • the thermoplastic resin composition may optionally further include a vinyl copolymer (C), and may further include additional resins and / or additives depending on the properties to be implemented.
  • thermoplastic resin composition includes a graft diene-based copolymer (A) having excellent transparency and (B) a high refractive index acrylic copolymer together with high transparency to enable high coloration, and at the same time, scratch resistance and Excellent heat resistance. Therefore, the thermoplastic resin composition can be variously applied to various uses, and is suitable for use in applications such as housings such as home appliances. Hereinafter, each component included in the thermoplastic resin composition will be described in detail.
  • the graft diene copolymer is a resin having transparency by graft polymerization of a polymer or copolymer comprising a structural unit derived from a (meth) acrylic acid alkyl ester compound to a rubbery polymer or copolymer derived from a diene compound. to be.
  • the graft diene copolymer (A) may be prepared to have a refractive index of 1.50 to 1.52.
  • the graft diene copolymer is a rubbery polymer or copolymer derived from a diene compound, the polymer of at least two compounds of an aromatic vinyl compound, a vinyl cyanide compound, and an acrylic compound is first grafted, and again ( The meta) acrylic acid alkyl ester compound may be a secondary grafted copolymer.
  • the rubbery polymer forms a core
  • the polymer of at least two of the aromatic vinyl compound, the vinyl cyanide compound, and the acrylic compound forms the inner shell while primary graft polymerizing the core
  • the acrylic acid alkyl ester compound is secondary grafted to form an outer shell
  • the graft diene-based copolymer may form a core-shell structure.
  • the rubbery polymer may be derived from a diene-based compound, and specifically, polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, or the like, or a combination thereof may be used. It is not limited, Among these, polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, or a combination thereof can be used.
  • 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.
  • a (meth) acrylic-acid alkylester, (meth) acrylic acid ester, or a combination thereof can be used.
  • the alkyl means C1 to C10 alkyl.
  • the graft diene copolymer may implement transparency, and may also compensate for scratch and strength.
  • the graft diene copolymer may include a structure formed by primary grafting on the rubbery polymer and may include a structure formed by secondary grafting on the structure.
  • the rubbery polymer forms a core structure
  • the structure formed of the primary graft is an inner shell
  • the structure formed of the secondary graft is an outer shell, and may form a core and a double shell structure.
  • the inner shell of the graft diene copolymer may be a styrene-acrylonitrile resin
  • the outer shell may be a polymethyl methacrylate (PMMA) resin
  • the inner shell and the outer shell are both methylmethacrylate-acrylonitrile-styrene copolymers.
  • the graft diene copolymer may be prepared by a known method and is not limited to any particular manufacturing method.
  • the graft diene copolymer may be prepared by the following method.
  • the shell grafted on the rubber surface is a first method of forming the inner shell and the outer shell to have a different double monomer composition.
  • the first method comprises the first step of graft polymerization of an aromatic vinyl monomer and a vinyl cyanide monomer under a fat-soluble redox-based initiator system to form a cabinet shell on the surface of the rubber, followed by alkyl (meth) acrylates under a water-soluble initiator. It is prepared by a second stage polymerization which adds an ester monomer to form an outer shell to surround the inner shell.
  • the graft diene copolymer (A) having the core and the double shell structure formed by the second step polymerization may be prepared in a powder state through a post-treatment process such as coagulation, washing, and dehydration in a post-treatment process.
  • the second method is a method in which a shell layer grafted on a rubber surface is doubled but the monomer composition ratio is the same, and a mixture of (meth) acrylic acid alkyl ester monomers, aromatic vinyl monomers and vinyl cyanide monomers, which are graft monomers, is used.
  • a portion the core is subjected to the first graft reaction under a fat-soluble redox-based initiator system, and the second step of adding a residual graft monomer mixture under a water-soluble initiator to proceed the second graft reaction.
  • a graft diene copolymer having a double shell structure formed thereon.
  • the graft diene copolymer (A) having the core and the double shell structure formed by the second step polymerization may be prepared in a powder state through a post-treatment process such as coagulation, washing, and dehydration in a post-treatment process.
  • the graft diene copolymer which forms the core and the double shell structure prepared by the above two methods is a copolymer of a diene rubber which is a core layer and a (meth) acrylic acid alkyl ester-aromatic vinyl-vinyl cyanide monomer which is a shell layer (Example For example, the refractive index of methyl methacrylate-styrene-acrylonitrile (MSAN) can be the same to improve colorability, and the copolymer of the (meth) acrylic acid alkyl ester-aromatic vinyl-vinyl cyanide monomer which is the shell layer.
  • MSAN methyl methacrylate-styrene-acrylonitrile
  • the graft diene copolymer (A) in which the core-double shell structure is formed is methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin (g-MABS).
  • the graft diene-based copolymer (A) forming the core-double shell structure is, for example, 30 to 70 parts by weight of rubber, 15 to 55 parts by weight of (meth) acrylic acid alkyl ester, 1 to 5 parts by weight of vinyl cyanide and aromatic It consists of 5 to 35 parts by weight of vinyl.
  • the content of polybutadiene or butadiene-styrene rubber latex is 30 to 70% by weight (based on solids), and then the primary cabinet is prepared using acrylonitrile and styrene monomer.
  • the secondary graft polymerization is carried out to form a shell and then to form an outer shell that surrounds the inner shell formed primarily of methyl methacrylate monomer, wherein the graft monomers are combined with the same composition as each rubber refractive index to emulsify the polymerization.
  • g-MABS resin in the form of fine powder is obtained.
  • the polybutadiene or butadiene-styrene rubber latex is 30 to 70% by weight (based on solids), and then methyl methacrylate-acrylonitrile-styrene monomer is used for each rubber.
  • coagulation-dehydration-drying gives a g-MABS resin in a fine powder state.
  • the average particle size of the rubber is preferably in the range of 0.1 to 0.3 ⁇ m.
  • the rubber particle size may be excellent in terms of impact resistance, colorability and glossiness.
  • the butadiene rubber used in the preparation of the methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin uses polybutadiene rubber alone or butadiene-styrene copolymer rubber, and has a styrene content of 0 to 30 wt%. The range of% is preferable.
  • g-MABS resin is 22.2 to 50.3 parts by weight of methyl methacrylate, 1.5 to 4.2 parts by weight of acrylonitrile, 30 to 70 parts by weight of polybutadiene rubber, and styrene 6.3 To 15.5 parts by weight.
  • g-MABS resin is 15.8 to 36.4 parts by weight of methyl methacrylate, 1.5 to 3.5 parts by weight of acrylonitrile, 30 to 70 parts by weight of butadiene-styrene rubber And styrene 12.7 to 30.1 parts by weight.
  • the graft diene copolymer (A) having the core-double shell structure preferably has a graft ratio in the range of 30 to 70%.
  • the high refractive index acrylic copolymer is a copolymer including a structural unit represented by the following Chemical Formula 1.
  • X is a single bond, oxygen (O) or sulfur (S),
  • Y is selected from the group consisting of cyclohexyl group, phenyl group, methylphenyl group, methylethylphenyl group, propylphenyl group, methoxyphenyl group, cyclohexylphenyl group, chlorophenyl group, bromophenyl group, phenylphenyl group and benzylphenyl group,
  • n is an integer of 0-10.
  • the refractive index of the high refractive index acrylic copolymer may be adjusted to reduce the difference in refractive index of the graft diene copolymer (A), thereby further improving transparency of the thermoplastic resin composition.
  • the refractive index of the high refractive index acrylic copolymer is greater than 1.49 and less than or equal to 1.55, preferably greater than 1.49 to 1.53. Since the structural unit of Chemical Formula 1 has a higher refractive index than that of the heterogeneous structural units copolymerized together, it is possible to obtain a high refractive index acrylic copolymer by adjusting the content thereof.
  • the monomer of the structural unit of Formula 1 may be copolymerized with methyl methacrylate, and the refractive index of methyl methacrylate is known as 1.49. Since the structural unit of Formula 1 has a refractive index of more than 1.49 but less than 1.55, when the content thereof is increased, the acrylic copolymer (B) having a higher refractive index may be lowered, and when the content thereof is lowered, the refractive index may be relatively lowered.
  • the high refractive index acrylic copolymer may control the refractive index by adjusting the content of the structural unit of Chemical Formula 1.
  • the high refractive index acrylic copolymer may include the structural unit of Formula 1 in an amount greater than 0 to 40 wt% or less in the total content of the high refractive index acrylic copolymer.
  • the high refractive index acrylic copolymer may include 20 to 40% by weight of the structural unit of Formula 1 of the total content of the high refractive index acrylic copolymer.
  • the refractive index of the high refractive index acrylic copolymer (B) may be such that the difference in refractive index of the graft diene copolymer (A) is 0.00 to 0.05, more preferably the difference is 0.00 to 0.01 days Can be.
  • the thermoplastic resin composition including the graft diene copolymer (A) and the high refractive index acrylic copolymer (B) having a difference in refractive index within the above range may have excellent transparency and high color performance.
  • Examples of the monomer compound of the structural unit of Formula 1 include cyclohexyl methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthiophenyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2- Phenylethyl methacrylate, 3-phenylpropyl methacrylate, 4-phenylbutyl methacrylate, 2-2-methylphenylethyl methacrylate, 2-3-methylphenylethyl methacrylate, 2-4-methylphenylethyl methacrylate Late, 2- (4-propylphenyl) ethyl methacrylate, 2- (4- (1-methylethyl) phenyl) ethyl methacrylate, 2- (4-methoxyphenyl) ethyl methacrylate, 2- ( 4-cyclohexylphenyl) ethyl methacrylate, 2- (2-chlorophenyl) e
  • the high refractive index acrylic copolymer may further include a conventional copolymerizable vinyl and / or acrylic monomer in addition to the structural unit of Chemical Formula 1.
  • a conventional copolymerizable vinyl and / or acrylic monomer in addition to the structural unit of Chemical Formula 1.
  • vinyl and / or acrylic monomers copolymerizable with the monomer of the structural unit of Formula 1 include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and benzyl methacrylate.
  • Methacrylic acid esters Acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; Acid anhydrides such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid, maleic anhydride and the like; Esters containing hydroxy groups such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, monoglycerol acrylate; Acrylamide, methacrylamide, and the like.
  • Nitriles such as acrylonitrile and methacrylonitrile are also possible, including allyl glycidyl ether; Glycidyl methacrylate; Styrene-based monomers such as styrene and ⁇ -methylstyrene may be used, but is not necessarily limited thereto. These can be used individually or in mixture of 2 or more types.
  • the high refractive index acrylic copolymer is obtained by polymerizing a monomer of the structural unit represented by Chemical Formula 1 and a conventional copolymerizable vinyl-based and / or acrylic monomer mixture, and the polymerization of the high refractive index acrylic copolymer is performed in a usual bulk, solution, suspension and Emulsification polymerization may be applied, but is not necessarily limited thereto.
  • the graft diene copolymer (A) When the graft diene copolymer (A) is included in the content ratio of the above range, it may be excellent in terms of the balance of physical properties of impact resistance, scratch resistance, gloss and coloring.
  • the high refractive index acrylic copolymer (B) may be included in an amount of greater than 0 to 150 parts by weight or less relative to 100 parts by weight of the graft diene copolymer (A), preferably the graft diene copolymer (A) 100 It may be included in the range of 25 to 100 parts by weight relative to the weight part.
  • the high refractive index acrylic copolymer (B) is a graft diene copolymer (A) in an amount ratio of greater than 0 to 150 parts by weight or less relative to 100 parts by weight of the graft diene copolymer (A). )
  • the scratch resistance of the graft diene copolymer (A) can be compensated for, and the physical properties of the color and transparency properties and the scratch resistance can be maintained.
  • the weight average molecular weight of the high refractive index acrylic copolymer (B) may be 10,000 to 50,000.
  • the vinyl copolymer may be 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 examples include copolymers 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-vinyl cyanide copolymer may be polymerized by further including a (meth) acrylic acid alkyl ester compound together with the aromatic vinyl compound and the vinyl cyanide compound.
  • the said (meth) acrylic-acid alkylester compound is the (meth) acrylic-acid alkylester which has a C1-C10 alkyl group.
  • the vinyl copolymer may be prepared by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization, and a weight average molecular weight of 15,000 kPa to 400,000 g / mol may be used.
  • the vinyl copolymer may be a copolymer formed by polymerizing 10 to 30 wt% of an aromatic vinyl compound, 0 to 20 wt% of a vinyl cyanide compound, and 50 to 90 wt% of a (meth) acrylic acid alkyl ester compound.
  • the copolymer may be formed by polymerizing 15% to 25% by weight of aromatic vinyl compound, 5% to 15% by weight of vinyl cyanide compound, and 70% to 80% by weight of (meth) acrylic acid alkyl ester compound.
  • the thermoplastic resin composition may include a vinyl copolymer having a content of 50 to 400 parts by weight based on 100 parts by weight of the graft acrylic copolymer (A).
  • 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 a range 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 May be included in an amount of 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.
  • Butadiene is a resin consisting of a core of 58 parts by weight and a shell of 42 parts by weight, the shell is composed of 31 parts by weight and 11 parts by weight of styrene and acrylonitrile, respectively.
  • SAN resin containing 25% by weight of acrylonitrile and 75% by weight of styrene and having a weight average molecular weight of 100,000
  • MSAN resin containing 5% by weight of acrylonitrile, 22% by weight of styrene and 73% by weight of methacrylate and having a weight average molecular weight of 120,000
  • MSAN resin containing 5% by weight of acrylonitrile, 22% by weight of styrene and 73% by weight of methacrylate and having a weight average molecular weight of 80,000
  • thermoplastic resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were prepared in the compositions shown in Table 1 using the above-mentioned components.
  • the refractive index difference of (B-1) or polymethyl methacrylate (B-2) is shown in Table 1 below.
  • 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 pencil 5 times at the speed of 10mm / s by lifting the weight of 500g with a pencil according to hardness. (Measuring pencil and pencil hardness determined in JIS K5401)
  • VST measured based on ISO R306 standard (unit, °C)
  • Examples 1 to 3 are thermoplastic resin compositions prepared by using the high refractive index acrylic copolymer (B) at 10 parts by weight, 20 parts by weight, and 30 parts by weight of the (B-1) benzyl methacrylate-methyl methacrylate copolymer, respectively. Is an evaluation result of, and Comparative Examples 1 to 3 are evaluation results of the thermoplastic resin composition prepared to be compared to Examples 1 to 3 in the same amount of (B-2) polymethyl methacrylate instead of the high refractive index acrylic copolymer . In comparison with Comparative Examples 1 to 3, Examples 1 to 3 can be confirmed that the haze evaluation is very excellent, and all other evaluation results such as scratch resistance, heat resistance and the like.
  • Comparative Examples 4 and 5 did not use a graft diene copolymer (A) that is not grafted alkyl methacrylate ester, and does not use a high refractive index acrylic copolymer, very poor transmittance and haze evaluation .
  • Comparative Example 7 (B-2) in the case of using an excessive amount of polymethyl methacrylate improved the BSP results than Comparative Examples 4 and 5, but it was confirmed that it does not help to improve the transmittance, haze, hardness, heat resistance, etc. .

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention propose une composition de résine thermoplastique comprenant un copolymère diénique greffé (A) et un copolymère acrylique à indice de réfraction élevé (B), le copolymère acrylique à indice de réfraction élevé comprenant des unités ayant une structure de la formule 1 définie dans la description. Le copolymère diénique greffé (A) peut être un polymère comprenant des unités structurales induites à partir d'un composé ester alkylique d'acide (méth)acrylique dans un polymère de caoutchouc induit à partir d'un composé diénique, ou peut être un copolymère polymérisé par greffage.
PCT/KR2011/009111 2011-10-27 2011-11-28 Composition de résine thermoplastique et moulage l'utilisant WO2013062170A1 (fr)

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KR10-2011-0110569 2011-10-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010171A1 (fr) * 2014-07-14 2016-01-21 (주)켐옵틱스 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif
WO2016010170A1 (fr) * 2014-07-14 2016-01-21 (주)켐옵틱스 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de préparation associé à l'aide d'un dérivé de styrène époxyde réactif

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2015008945A1 (fr) * 2013-07-19 2015-01-22 (주) 엘지화학 Composition de résine à base de (méth)acrylate ayant une excellente résistance au choc et une excellente transparence
WO2016043424A1 (fr) * 2014-09-16 2016-03-24 주식회사 엘지화학 Composition de résine thermoplastique et article moulé en résine thermoplastique préparé à partir de celle-ci
KR101644752B1 (ko) 2014-09-16 2016-08-01 주식회사 엘지화학 열가소성 수지 조성물 및 이로부터 제조된 열가소성 수지 성형품
KR102080714B1 (ko) * 2016-09-09 2020-04-23 주식회사 엘지화학 열가소성 투명 수지 및 이의 제조방법
WO2018048136A1 (fr) * 2016-09-09 2018-03-15 (주) 엘지화학 Résine transparente thermoplastique et son procédé de préparation
WO2019066375A2 (fr) * 2017-09-29 2019-04-04 주식회사 엘지화학 Composition de résine thermoplastique et produit moulé de résine thermoplastique fabriqué à partir de celle-ci
CN115386025B (zh) * 2022-09-16 2023-11-03 西安交通大学 一种含硫树脂及以含硫树脂为基底的高折射率复合材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100360987B1 (ko) * 2000-07-06 2002-11-18 주식회사 엘지화학 열가소성 투명수지의 제조방법
KR20070108008A (ko) * 2006-05-04 2007-11-08 제일모직주식회사 내스크래치성이 우수한 수지 조성물
KR20090073702A (ko) * 2007-12-31 2009-07-03 제일모직주식회사 내스크래치성과 착색성이 우수한 고내후 열가소성 수지조성물
KR20110018584A (ko) * 2009-08-18 2011-02-24 제일모직주식회사 내스크래치성 및 내열성이 우수한 항균성 열가소성 수지 조성물
KR20110035041A (ko) * 2009-09-29 2011-04-06 주식회사 엘지화학 레이저 마킹용 열가소성 수지 조성물

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100360987B1 (ko) * 2000-07-06 2002-11-18 주식회사 엘지화학 열가소성 투명수지의 제조방법
KR20070108008A (ko) * 2006-05-04 2007-11-08 제일모직주식회사 내스크래치성이 우수한 수지 조성물
KR20090073702A (ko) * 2007-12-31 2009-07-03 제일모직주식회사 내스크래치성과 착색성이 우수한 고내후 열가소성 수지조성물
KR20110018584A (ko) * 2009-08-18 2011-02-24 제일모직주식회사 내스크래치성 및 내열성이 우수한 항균성 열가소성 수지 조성물
KR20110035041A (ko) * 2009-09-29 2011-04-06 주식회사 엘지화학 레이저 마킹용 열가소성 수지 조성물

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010171A1 (fr) * 2014-07-14 2016-01-21 (주)켐옵틱스 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de fabrication associé à l'aide d'un dérivé de styrène réactif
WO2016010170A1 (fr) * 2014-07-14 2016-01-21 (주)켐옵틱스 Polymère de polystyrène réactif ayant un indice de réfraction élevé et procédé de préparation associé à l'aide d'un dérivé de styrène époxyde réactif

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