WO2023033492A1 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Thermoplastic resin composition and molded product manufactured therefrom Download PDF

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Publication number
WO2023033492A1
WO2023033492A1 PCT/KR2022/012915 KR2022012915W WO2023033492A1 WO 2023033492 A1 WO2023033492 A1 WO 2023033492A1 KR 2022012915 W KR2022012915 W KR 2022012915W WO 2023033492 A1 WO2023033492 A1 WO 2023033492A1
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weight
thermoplastic resin
resin composition
copolymer
aromatic vinyl
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PCT/KR2022/012915
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French (fr)
Korean (ko)
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김한나
홍상현
반균하
송봉준
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롯데케미칼 주식회사
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Publication of WO2023033492A1 publication Critical patent/WO2023033492A1/en

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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
    • 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
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • thermoplastic resin composition relates to a thermoplastic resin composition and a molded article manufactured therefrom.
  • ABS resins represented by acrylonitrile-butadiene-styrene copolymer (ABS) resins are widely used in various applications due to their excellent moldability, mechanical properties, appearance, secondary processability, and the like.
  • a molded article manufactured using a styrenic resin can be widely applied to various products requiring painting/non-painting, and can be applied, for example, to various interior/exterior materials of automobiles and/or electronic devices.
  • electrostatic coating is a generally widely used coating method.
  • electrostatic painting is a method of painting after imparting electrical conductivity to the surface of a molded product.
  • a pretreatment such as a conductive primer on the surface of the molded product.
  • the conductive primer increases the number of processes and manufacturing time, recently, by further including various conductive materials (eg, carbon nanotubes, etc.) and/or conductivity developing additives in the styrenic resin, the molded article itself manufactured therefrom is more than a certain level. Methods of making the electrical conductivity intrinsic have been proposed.
  • thermoplastic resin composition capable of electrostatic painting without application of a conductive primer.
  • An object of the present invention is to provide a thermoplastic resin composition having excellent electrical conductivity and excellent physical properties such as impact resistance, stiffness, fluidity, and the like, and a molded product manufactured therefrom.
  • thermoplastic resin composition comprising (C) 3 to 10 parts by weight of a polyether-ester-amide block copolymer and (D) 1 to 10 parts by weight of polyalkylene glycol is provided. .
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer includes a core made of a butadiene-based rubbery polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound on the core-shell may be a rescue.
  • An average particle diameter of the butadiene-based rubbery polymer may be 0.2 to 1.0 ⁇ m.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may include 55 to 80% by weight of an aromatic vinyl compound-derived component and 20 to 45% by weight of a vinyl cyanide compound-derived component based on 100% by weight.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 80,000 to 300,000 g/mol.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.
  • the (C) polyether-ester-amide block copolymer is an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine-dicarboxylic acid salt; polyalkylene glycol; and dicarboxylic acids having 4 to 20 carbon atoms.
  • the (D) polyalkylene glycol may have a number average molecular weight of 4,000 to 10,000 g/mol.
  • the (D) polyalkylene glycol may be polyethylene glycol.
  • the thermoplastic resin composition may further include at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, a colorant, and an impact modifier.
  • at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, a colorant, and an impact modifier.
  • thermoplastic resin composition described above is provided.
  • the molded article may have a surface resistance of 10 12.0 ⁇ /sq or less measured on a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4). .
  • the molded article may have a flexural modulus of 18,000 to 22,000 kgf/cm 2 measured for a specimen having a thickness of 6.4 mm in accordance with ASTM D790.
  • the molded article may have a flow rate of 24 g/10 min or more measured at 220° C. under a load condition of 10 kg.
  • thermoplastic resin composition according to one embodiment and a molded article using the same exhibit excellent electrical conductivity and excellent physical properties such as impact resistance, stiffness, fluidity, etc., and can be widely applied to the molding of various products used by painting and uncoating, In particular, it can be usefully applied to molded articles for painting requiring electrostatic painting.
  • the average particle diameter of the rubbery polymer is the volume average diameter, and means the Z-average particle diameter measured using a dynamic light scattering analyzer.
  • thermoplastic resin composition comprising (C) 3 to 10 parts by weight of a polyether-ester-amide block copolymer and (D) 1 to 10 parts by weight of polyalkylene glycol is provided. .
  • the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer imparts excellent impact resistance to the thermoplastic resin composition.
  • the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a core made of a butadiene-based rubbery polymer component and a shell by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound in the center. It may have a core-shell structure in which a shell is formed.
  • the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer according to an embodiment is graft-polymerized by adding an aromatic vinyl compound and a vinyl cyanide compound to a butadiene-based rubbery polymer and performing conventional polymerization methods such as emulsion polymerization and bulk polymerization. can be manufactured.
  • the butadiene-based rubbery polymer may be selected from the group consisting of butadiene rubbery polymers, butadiene-styrene rubbery polymers, butadiene-acrylonitrile rubbery polymers, butadiene-acrylate rubbery polymers, and mixtures thereof.
  • the aromatic vinyl compound may be selected from the group consisting of styrene, ⁇ -methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.
  • the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.
  • the average particle diameter of the butadiene-based rubbery polymer of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be, for example, 0.2 to 1.0 ⁇ m, for example, 0.2 to 0.8 ⁇ m, and for example, 0.25 to 0.50 ⁇ m.
  • the thermoplastic resin composition may exhibit excellent impact resistance and appearance characteristics.
  • the butadiene-based rubbery polymer is 40 to 70% by weight, for example 40 to 60% by weight, for example 50 to 60% by weight can be included Meanwhile, a weight ratio of the aromatic vinyl compound and the cyanide vinyl compound graft-polymerized to the center of the butadiene-based rubbery polymer component may be 6:4 to 8:2.
  • the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
  • the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be included in an amount of 20 to 40% by weight, for example, 25 to 40% by weight, for example, 30 to 40% by weight, based on 100% by weight of the base resin. Within the weight % range, the thermoplastic resin composition may have excellent impact resistance and balance of physical properties.
  • the aromatic vinyl-vinyl cyanide copolymer may maintain compatibility between components of the thermoplastic resin composition at a certain level.
  • the aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of greater than or equal to 80,000 g/mol, such as greater than or equal to 85,000 g/mol, such as greater than or equal to 90,000 g/mol, such as greater than or equal to 300,000 g/mol or less, for example 200,000 g/mol or less, for example 80,000 to 300,000 g/mol, for example 80,000 to 200,000 g/mol.
  • the weight average molecular weight was measured using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) after dissolving the powder sample in tetrahydrofuran (THF) (using polystyrene as a standard sample).
  • GPC Gel Permeation Chromatography
  • the aromatic vinyl-vinyl cyanide copolymer may be prepared through conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization of an aromatic vinyl compound and a vinyl cyanide compound.
  • the aromatic vinyl compound may be selected from the group consisting of styrene, ⁇ -methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.
  • the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.
  • the aromatic vinyl-vinyl cyanide copolymer may include, for example, 55% by weight or more, for example, 60% by weight or more, for example, 65% by weight or more of the aromatic vinyl compound-derived component based on 100% by weight, For example, it may contain 80% by weight or less, for example, 75% by weight or less, for example, 55 to 80% by weight, for example, 60 to 75% by weight.
  • the aromatic vinyl-vinyl cyanide copolymer may include, for example, 20% by weight or more, for example, 25% by weight or more of the component derived from the vinyl cyanide compound, based on 100% by weight, for example, 45% by weight Or less, for example, 40% by weight or less, for example, 20 to 45% by weight, for example, 25 to 40% by weight.
  • the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).
  • SAN styrene-acrylonitrile copolymer
  • the aromatic vinyl-vinyl cyanide copolymer may be included in 60 to 80% by weight, for example, 60 to 75% by weight, for example, 60 to 70% by weight, based on 100% by weight of the base resin.
  • Compatibility of components in the thermoplastic resin composition may be excellent in the above weight % range.
  • the polyether-ester-amide block copolymer can provide a predetermined electrical conductivity to the thermoplastic resin composition and molded articles manufactured therefrom.
  • polyether-ester-amide block copolymer may allow the thermoplastic resin composition and molded articles manufactured therefrom to exhibit the above-described electrical conductivity while maintaining an excellent physical property balance.
  • polyether-ester-amide block copolymer for example, an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a salt of a diamine-dicarboxylic acid; polyalkylene glycol; and a reaction product of a dicarboxylic acid having 4 to 20 carbon atoms.
  • the aminocarboxylic acids having 6 or more carbon atoms include ⁇ -aminocaproic acid, ⁇ -aminoenanthic acid, ⁇ -aminocaprylic acid, ⁇ -aminopelargonic acid, ⁇ -aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like
  • examples of the lactam include ⁇ -caprolactam, enantlactam, capryllactam, and laurolactam
  • the diamine-dicarboxylic acid examples include diamine-dicarboxylic acid salts such as hexamethylenediamine-adipic acid salts and hexamethylenediamine-isophthalic acid salts.
  • salts of aminocarboxylic acids having 6 or more carbon atoms lactams, and diamine-dicarboxylic acids
  • salts of 12-aminododecanoic acid, ⁇ -caprolactam, and hexamethylenediamine-adipic acid, respectively. can be heard
  • the polyalkylene glycol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene glycol and propylene glycol, a copolymer of ethylene glycol and tetrahydrofuran etc.
  • polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like can be used.
  • examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanedioic acid.
  • the bond between the salt of the aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond, and the aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms may form an ester bond.
  • a bond between the salt of carboxylic acid and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and a bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms may be an ester bond.
  • the polyether-ester-amide block copolymer can be prepared by a known synthesis method, for example, the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424 It can be manufactured according to.
  • the polyether-ester-amide block copolymer may include 10 to 95% by weight of the polyether-ester block.
  • the thermoplastic resin composition may have excellent electrical conductivity and heat resistance.
  • the polyether-ester-amide block copolymer may be included in an amount of 3 to 10 parts by weight, for example, 5 to 10 parts by weight, based on 100 parts by weight of the base resin.
  • thermoplastic resin composition and molded articles manufactured therefrom may exhibit excellent electrical conductivity while maintaining excellent physical property balance.
  • the polyalkylene glycol, together with the polyether-ester-amide block copolymer, can give a thermoplastic resin composition and a molded article manufactured therefrom to exhibit predetermined electrical conductivity.
  • the polyalkylene glycol may include polyalkylene glycol, polyalkylene glycol ether, and/or polyalkylene glycol ester.
  • polyalkylene glycol polyols used in conventional thermoplastic resin compositions may be used without limitation, and examples include polyethylene glycol, polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol dodecyl ether, and polyethylene glycol benzyl ether.
  • the polyalkylene glycol may have a number average molecular weight (Mn) of 4,000 to 10,000 g/mol, for example, 5,000 to 10,000 g/mol, as measured by gel permeation chromatography (GPC). there is.
  • Mn number average molecular weight
  • the polyalkylene glycol may be included in 1 to 10 parts by weight, for example, 2 to 8 parts by weight, for example, 3 to 5 parts by weight, based on 100 parts by weight of the base resin. Electrical conductivity may be excellent while maintaining the balance of various physical properties of the thermoplastic resin composition in the above weight part range.
  • thermoplastic resin composition in addition to the components (A) to (D), the thermoplastic resin composition according to an embodiment is used to balance the physical properties under the condition of maintaining excellent balance of electrical conductivity and various physical properties, or the final thermoplastic resin composition. One or more additives necessary for use may be further included.
  • nucleating agents as the additives, nucleating agents, coupling agents, fillers, plasticizers, lubricants, release agents, antibacterial agents, heat stabilizers, antioxidants, UV stabilizers, flame retardants, colorants, impact modifiers, etc. may be used, and these may be used alone or in combination of two or more can be used as the additives.
  • thermoplastic resin composition may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the base resin, but is not limited thereto.
  • thermoplastic resin composition according to the present invention can be prepared by a known method for preparing a thermoplastic resin composition.
  • thermoplastic resin composition according to the present invention may be prepared in the form of pellets by mixing the components of the present invention and other additives and then melt-kneading them in an extruder.
  • a molded article according to one embodiment of the present invention may be manufactured from the above-described thermoplastic resin composition through a known molding method.
  • the molded article may be manufactured by methods such as extrusion molding and injection molding, but is not limited thereto.
  • the molded article has a surface resistance of 10 12.0 ⁇ measured for a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4) /sq or less, such as 10 11.9 ⁇ /sq or less, such as 10 11.8 ⁇ /sq or less, such as 10 11.7 ⁇ /sq or less, such as 10 11.6 ⁇ /sq or less.
  • a surface resistance measuring device manufactured by a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4) /sq or less, such as 10 11.9 ⁇ /sq or less, such as 10 11.8 ⁇ /sq or less, such as 10 11.7 ⁇ /sq or less, such as 10 11.6 ⁇ /sq or less.
  • the molded article has a flexural modulus of 18,000 kgf/cm 2 or more, for example, 19,000 kgf/cm 2 or more, for example, 20,000 kgf/cm, measured for a specimen having a thickness of 6.4 mm, according to ASTM D790. 2 or more, for example 22,000 kgf/cm 2 or less, for example 21,000 kgf/cm 2 or less, for example 18,000 to 22,000 kgf/cm 2 , for example 18,000 to 21,000 kgf/cm 2 .
  • the molded article may have a flow rate of 24 g/10 min or more, 25 g/10 min or more, or 26 g/10 min or more, measured at 220° C. under a 10 kg load condition, according to ASTM D1238.
  • thermoplastic resin composition has excellent electrical conductivity and various physical properties, it can be widely applied to various products used for painting and uncoating, and in particular, it can be usefully applied to molded products for painting requiring electrostatic painting.
  • thermoplastic resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4 were prepared according to the component content ratios shown in Table 1 below.
  • Polyamide 6-polyethylene oxide block copolymer (PA6-b-PE0) (Sanyo, PELECTRON AS)
  • Polyethylene glycol having a number average molecular weight of about 8,000 g/mol (Lotte Chemical Co.)
  • Example comparative example One One 2 3 4 surface resistance 10 11.2 10 10.4 10 13.5 10 10.0 10 13.5 Izod impact strength 33.7 24.1 31.2 40.6 42.2 27.4 flexural modulus 18,400 19,600 21,500 19,100 17,700 20,000 Current flow index 26.0 39.2 9.6 14.8 22.0 2.7

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The present invention relates to a thermoplastic resin composition and a molded product manufactured therefrom, the thermoplastic resin composition comprising, on the basis of 100 parts by weight of a base resin including (A1) 20-40 wt% of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer and (B) 60-80 wt% of an aromatic vinyl-vinyl cyanide copolymer, (C) 3-10 parts by weight of a polyether ester amide block copolymer, and (D) 1-10 parts by weight of polyalkylene glycol.

Description

열가소성 수지 조성물 및 이로부터 제조된 성형품Thermoplastic resin composition and molded articles produced therefrom
열가소성 수지 조성물 및 이로부터 제조된 성형품에 관한 것이다.It relates to a thermoplastic resin composition and a molded article manufactured therefrom.
아크릴로니트릴-부타디엔-스티렌 공중합체(ABS) 수지로 대표되는 스티렌계 수지는 그 우수한 성형성, 기계적 특성, 외관, 2차 가공성 등으로 인해 다양한 용도에 광범위하게 사용되고 있다. Styrene-based resins represented by acrylonitrile-butadiene-styrene copolymer (ABS) resins are widely used in various applications due to their excellent moldability, mechanical properties, appearance, secondary processability, and the like.
스티렌계 수지를 이용하여 제조되는 성형품은 도장/무도장이 요구되는 여러 제품에 광범위하게 적용될 수 있으며, 예를 들어 자동차 및/또는 전자기기의 각종 내/외장재 등에 적용될 수 있다.A molded article manufactured using a styrenic resin can be widely applied to various products requiring painting/non-painting, and can be applied, for example, to various interior/exterior materials of automobiles and/or electronic devices.
이 중, 각종 내/외장재에 심미적 효과를 부여하기 위한 방안으로 스티렌계 수지를 이용하여 제조된 성형품에 도장 작업을 수행하는 경우가 있다. 도장의 방법은 특별히 제한되지 않으나, 일반적으로 널리 사용되는 도장 방식으로 정전 도장을 들 수 있다. 이러한 정전 도장은 성형품 표면에 전기 전도성을 부여한 다음 도장을 진행하는 방법으로, 대체로 표면저항이 높은 플라스틱 계열 성형품에 정전 도장을 적용하기 위해서는 성형품 표면에 전도성 프라이머(primer) 등의 전처리를 수행해야 할 필요가 있다.Among these, as a way to give aesthetic effects to various interior/exterior materials, there is a case in which a painting operation is performed on a molded product manufactured using a styrenic resin. The coating method is not particularly limited, but electrostatic coating is a generally widely used coating method. Such electrostatic painting is a method of painting after imparting electrical conductivity to the surface of a molded product. In general, in order to apply electrostatic painting to a plastic-based molded product with high surface resistance, it is necessary to perform a pretreatment such as a conductive primer on the surface of the molded product. there is
전도성 프라이머의 도포는 공정 수 및 제조시간을 증가시키므로, 최근 스티렌계 수지에 각종 전도성 물질(예컨대, 탄소나노튜브 등) 및/또는 전도성 발현 첨가제를 더 포함시킴으로써 이로부터 제조된 성형품 자체가 일정수준 이상의 전기 전도성을 내재하도록 하는 방법이 제안된 바 있다. Since the application of the conductive primer increases the number of processes and manufacturing time, recently, by further including various conductive materials (eg, carbon nanotubes, etc.) and/or conductivity developing additives in the styrenic resin, the molded article itself manufactured therefrom is more than a certain level. Methods of making the electrical conductivity intrinsic have been proposed.
하지만 스티렌계 수지에 전도성 물질 및/또는 전도성 발현 첨가제를 첨가할 경우, 스티렌계 수지의 물성 밸런스가 손상됨에 따라 예기치 않은 각종 물성 저하가 발생할 우려가 있다. However, when a conductive material and/or a conductive developing additive are added to the styrenic resin, the balance of physical properties of the styrenic resin may be damaged, resulting in various unexpected physical property degradation.
이에 따라, 전도성 프라이머의 도포 없이 정전 도장을 가능하게 하는 열가소성 수지 조성물의 개발이 필요한 실정이다.Accordingly, there is a need to develop a thermoplastic resin composition capable of electrostatic painting without application of a conductive primer.
우수한 전기 전도성을 나타내면서 내충격성, 강성, 유동성 등의 제반 물성이 우수한 열가소성 수지 조성물, 및 이를 이로부터 제조된 성형품을 제공하고자 한다.An object of the present invention is to provide a thermoplastic resin composition having excellent electrical conductivity and excellent physical properties such as impact resistance, stiffness, fluidity, and the like, and a molded product manufactured therefrom.
일 구현예에 따르면, (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체 20 내지 40 중량% 및 (B) 방향족 비닐-시안화 비닐 공중합체 60 내지 80 중량%를 포함하는 기초 수지 100 중량부에 대하여, (C) 폴리에테르-에스테르-아미드(polyether-ester-amide) 블록 공중합체 3 내지 10 중량부, 및 (D) 폴리알킬렌글리콜 1 내지 10 중량부를 포함하는 열가소성 수지 조성물이 제공된다. According to one embodiment, (A) 20 to 40% by weight of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer and (B) 100% by weight of a base resin including 60 to 80% by weight of an aromatic vinyl-vinyl cyanide copolymer A thermoplastic resin composition comprising (C) 3 to 10 parts by weight of a polyether-ester-amide block copolymer and (D) 1 to 10 parts by weight of polyalkylene glycol is provided. .
상기 (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 부타디엔계 고무질 중합체로 이루어진 코어, 및 방향족 비닐 화합물과 시안화 비닐 화합물이 상기 코어에 그라프트 중합되어 형성된 쉘을 포함하는 코어-쉘 구조일 수 있다.The (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer includes a core made of a butadiene-based rubbery polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound on the core-shell may be a rescue.
상기 부타디엔계 고무질 중합체의 평균 입경은 0.2 내지 1.0 ㎛일 수 있다.An average particle diameter of the butadiene-based rubbery polymer may be 0.2 to 1.0 μm.
상기 (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체일 수 있다.The (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
상기 (B) 방향족 비닐-시안화 비닐 공중합체는 100 중량%를 기준으로 방향족 비닐 화합물 유래 성분 55 내지 80 중량%, 및 시안화 비닐 화합물 유래 성분 20 내지 45 중량%를 포함할 수 있다.The (B) aromatic vinyl-vinyl cyanide copolymer may include 55 to 80% by weight of an aromatic vinyl compound-derived component and 20 to 45% by weight of a vinyl cyanide compound-derived component based on 100% by weight.
상기 (B) 방향족 비닐-시안화 비닐 공중합체는 중량평균분자량이 80,000 내지 300,000 g/mol일 수 있다.The (B) aromatic vinyl-vinyl cyanide copolymer may have a weight average molecular weight of 80,000 to 300,000 g/mol.
상기 (B) 방향족 비닐-시안화 비닐 공중합체는 스티렌-아크릴로니트릴 공중합체일 수 있다.The (B) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.
상기 (C) 폴리에테르-에스테르-아미드 블록 공중합체는 탄소수 6 이상의 아미노카르복실산, 락탐, 또는 디아민-디카르복실산 염; 폴리알킬렌글리콜; 및 탄소수 4 내지 20의 디카르복실산의 반응 생성물일 수 있다.The (C) polyether-ester-amide block copolymer is an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine-dicarboxylic acid salt; polyalkylene glycol; and dicarboxylic acids having 4 to 20 carbon atoms.
상기 (D) 폴리알킬렌글리콜의 수평균분자량은 4,000 내지 10,000 g/mol일 수 있다.The (D) polyalkylene glycol may have a number average molecular weight of 4,000 to 10,000 g/mol.
상기 (D) 폴리알킬렌글리콜은 폴리에틸렌글리콜일 수 있다.The (D) polyalkylene glycol may be polyethylene glycol.
상기 열가소성 수지 조성물은 핵제, 커플링제, 충전제, 가소제, 활제, 이형제, 항균제, 열 안정제, 산화 방지제, 자외선 안정제, 난연제, 착색제, 충격보강제 중에서 선택되는 적어도 하나의 첨가제를 더 포함할 수 있다.The thermoplastic resin composition may further include at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, a colorant, and an impact modifier.
한편, 다른 구현예에 따르면 전술한 열가소성 수지 조성물로부터 제조된 성형품이 제공된다.Meanwhile, according to another embodiment, a molded article manufactured from the thermoplastic resin composition described above is provided.
상기 성형품은 표면저항 측정장치(제조사: SIMCO-ION사, 장치명: Worksurface Tester ST-4)를 사용하여 100 mm x 100 mm x 3.2 mm 시편에 대해 측정한 표면저항이 1012.0 Ω/sq 이하일 수 있다.The molded article may have a surface resistance of 10 12.0 Ω/sq or less measured on a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4). .
상기 성형품은 ASTM D790에 의거하여, 두께 6.4 mm의 시편에 대해 측정한 굴곡탄성율이 18,000 내지 22,000 kgf/cm2일 수 있다.The molded article may have a flexural modulus of 18,000 to 22,000 kgf/cm 2 measured for a specimen having a thickness of 6.4 mm in accordance with ASTM D790.
상기 성형품은 ASTM D1238에 의거하여, 220℃, 10 kg 하중 조건에서 측정한 유동흐름지수가 24 g/10min 이상일 수 있다.According to ASTM D1238, the molded article may have a flow rate of 24 g/10 min or more measured at 220° C. under a load condition of 10 kg.
일 구현예에 따른 열가소성 수지 조성물과 이를 이용한 성형품은 우수한 전기 전도성을 나타내면서 내충격성, 강성, 유동성 등의 제반 물성이 우수하여, 도장, 무도장으로 사용하는 여러 가지 제품의 성형에 광범위하게 적용될 수 있으며, 특히, 정전 도장이 필요한 도장용 성형품에 유용하게 적용될 수 있다.The thermoplastic resin composition according to one embodiment and a molded article using the same exhibit excellent electrical conductivity and excellent physical properties such as impact resistance, stiffness, fluidity, etc., and can be widely applied to the molding of various products used by painting and uncoating, In particular, it can be usefully applied to molded articles for painting requiring electrostatic painting.
이하, 본 발명의 구현예를 상세히 설명하기로 한다. 다만, 이는 예시로서 제시되는 것으로, 이에 의해 본 발명이 제한되지는 않으며 본 발명은 첨부된 청구범위에 의해 정의될 뿐이다.Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the appended claims.
본 발명에 있어서는 특별히 언급하지 않는 한 고무질 중합체의 평균 입경이란 체적평균 직경이고, 동적 광산란(Dynamic light scattering) 분석기기를 이용하여 측정한 Z-평균 입경을 의미한다.In the present invention, unless otherwise specified, the average particle diameter of the rubbery polymer is the volume average diameter, and means the Z-average particle diameter measured using a dynamic light scattering analyzer.
일 구현예에 따르면, (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체 20 내지 40 중량% 및 (B) 방향족 비닐-시안화 비닐 공중합체 60 내지 80 중량%를 포함하는 기초 수지 100 중량부에 대하여, (C) 폴리에테르-에스테르-아미드(polyether-ester-amide) 블록 공중합체 3 내지 10 중량부, 및 (D) 폴리알킬렌글리콜 1 내지 10 중량부를 포함하는 열가소성 수지 조성물이 제공된다.According to one embodiment, (A) 20 to 40% by weight of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer and (B) 100% by weight of a base resin including 60 to 80% by weight of an aromatic vinyl-vinyl cyanide copolymer A thermoplastic resin composition comprising (C) 3 to 10 parts by weight of a polyether-ester-amide block copolymer and (D) 1 to 10 parts by weight of polyalkylene glycol is provided. .
이하, 상기 열가소성 수지 조성물에 포함되는 각 성분에 대하여 구체적으로 설명한다.Hereinafter, each component included in the thermoplastic resin composition will be described in detail.
(A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체(A) Butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer
일 구현예에서 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 열가소성 수지 조성물에 우수한 내충격성을 부여한다. 일 구현예에서, 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 부타디엔계 고무질 중합체 성분으로 된 중심부(코어, core)와 그 중심부에 방향족 비닐 화합물과 시안화 비닐 화합물을 그라프트 중합 반응시켜 쉘(shell)을 형성한 코어-쉘(core-shell) 구조를 가질 수 있다.In one embodiment, the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer imparts excellent impact resistance to the thermoplastic resin composition. In one embodiment, the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a core made of a butadiene-based rubbery polymer component and a shell by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound in the center. It may have a core-shell structure in which a shell is formed.
일 구현예에 따른 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 부타디엔계 고무질 중합체에 방향족 비닐 화합물과 시안화 비닐 화합물을 첨가하고 유화중합, 괴상중합 등 통상의 중합방법을 통해 그라프트 중합함으로써 제조될 수 있다.The butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer according to an embodiment is graft-polymerized by adding an aromatic vinyl compound and a vinyl cyanide compound to a butadiene-based rubbery polymer and performing conventional polymerization methods such as emulsion polymerization and bulk polymerization. can be manufactured.
상기 부타디엔계 고무질 중합체는 부타디엔 고무질 중합체, 부타디엔-스티렌 고무질 중합체, 부타디엔-아크릴로니트릴 고무질 중합체, 부타디엔-아크릴레이트 고무질 중합체 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.The butadiene-based rubbery polymer may be selected from the group consisting of butadiene rubbery polymers, butadiene-styrene rubbery polymers, butadiene-acrylonitrile rubbery polymers, butadiene-acrylate rubbery polymers, and mixtures thereof.
상기 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌, p-t-부틸스티렌, 2,4-디메틸스티렌, 클로로스티렌, 비닐톨루엔, 비닐나프탈렌 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.The aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.
상기 시안화 비닐 화합물은 아크릴로니트릴, 메타크릴로니트릴, 푸마로니트릴 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.The vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.
상기 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체의 부타디엔계 고무질 중합체의 평균 입경은 예를 들어 0.2 내지 1.0 ㎛, 예를 들어 0.2 내지 0.8 ㎛, 예를 들어 0.25 내지 0.50 ㎛일 수 있다. 상기 범위를 만족할 경우 열가소성 수지 조성물은 우수한 내충격성 및 외관 특성을 나타낼 수 있다.The average particle diameter of the butadiene-based rubbery polymer of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be, for example, 0.2 to 1.0 μm, for example, 0.2 to 0.8 μm, and for example, 0.25 to 0.50 μm. When the above range is satisfied, the thermoplastic resin composition may exhibit excellent impact resistance and appearance characteristics.
상기 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체 100 중량%에 대하여, 상기 부타디엔계 고무질 중합체는 40 내지 70 중량%, 예를 들어 40 내지 60 중량%, 예를 들어 50 내지 60 중량%로 포함될 수 있다. 한편, 상기 부타디엔계 고무질 중합체 성분으로 된 중심부에 그라프트 중합되는 상기 방향족 비닐 화합물과 상기 시안화 비닐 화합물의 중량비는 6 : 4 내지 8 : 2일 수 있다.With respect to 100% by weight of the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer, the butadiene-based rubbery polymer is 40 to 70% by weight, for example 40 to 60% by weight, for example 50 to 60% by weight can be included Meanwhile, a weight ratio of the aromatic vinyl compound and the cyanide vinyl compound graft-polymerized to the center of the butadiene-based rubbery polymer component may be 6:4 to 8:2.
일 구현예에서, 상기 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체일 수 있다.In one embodiment, the butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
상기 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 기초 수지 100 중량%에 대하여 20 내지 40 중량%, 예를 들어 25 내지 40 중량%, 예를 들어 30 내지 40 중량%로 포함될 수 있다. 상기 중량% 범위에서 열가소성 수지 조성물이 우수한 내충격성 및 제반 물성 밸런스를 가질 수 있다. The butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be included in an amount of 20 to 40% by weight, for example, 25 to 40% by weight, for example, 30 to 40% by weight, based on 100% by weight of the base resin. Within the weight % range, the thermoplastic resin composition may have excellent impact resistance and balance of physical properties.
(B) 방향족 비닐-시안화 비닐 공중합체(B) Aromatic vinyl-vinyl cyanide copolymer
일 구현예에서 방향족 비닐-시안화 비닐 공중합체는 열가소성 수지 조성물의 구성요소들 간의 상용성을 일정 수준으로 유지시켜 줄 수 있다.In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may maintain compatibility between components of the thermoplastic resin composition at a certain level.
일 구현예에서, 상기 방향족 비닐-시안화 비닐 공중합체는 중량평균 분자량이 80,000 g/mol 이상, 예를 들어 85,000 g/mol 이상, 예를 들어 90,000 g/mol 이상이고, 예를 들어 300,000 g/mol 이하, 예를 들어 200,000 g/mol 이하일 수 있으며, 예를 들어 80,000 내지 300,000 g/mol, 예를 들어 80,000 내지 200,000 g/mol일 수 있다. In one embodiment, the aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of greater than or equal to 80,000 g/mol, such as greater than or equal to 85,000 g/mol, such as greater than or equal to 90,000 g/mol, such as greater than or equal to 300,000 g/mol or less, for example 200,000 g/mol or less, for example 80,000 to 300,000 g/mol, for example 80,000 to 200,000 g/mol.
본 발명에서 중량평균 분자량은 분체 시료를 테트라하이드로퓨란(THF)에 녹인 후, Agilent Technologies社의 1200 series 겔 투과 크로마토그래피(Gel Permeation Chromatography: GPC)를 이용하여 측정(표준시료로 폴리스티렌을 사용함)한 것이다.In the present invention, the weight average molecular weight was measured using Agilent Technologies' 1200 series Gel Permeation Chromatography (GPC) after dissolving the powder sample in tetrahydrofuran (THF) (using polystyrene as a standard sample). will be.
일 구현예에서, 상기 방향족 비닐-시안화 비닐 공중합체는 방향족 비닐 화합물과 시안화 비닐 화합물을 유화중합, 현탁중합, 용액중합, 괴상중합 등 통상의 중합방법을 통해 제조될 수 있다.In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be prepared through conventional polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization of an aromatic vinyl compound and a vinyl cyanide compound.
상기 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌, p-t-부틸스티렌, 2,4-디메틸스티렌, 클로로스티렌, 비닐톨루엔, 비닐나프탈렌 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.The aromatic vinyl compound may be selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, and mixtures thereof.
상기 시안화 비닐 화합물은 아크릴로니트릴, 메타크릴로니트릴, 푸마로니트릴 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.The vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and mixtures thereof.
상기 방향족 비닐-시안화 비닐 공중합체는 100 중량%를 기준으로 상기 방향족 비닐 화합물 유래 성분을 예를 들어 55 중량% 이상, 예를 들어 60 중량% 이상, 예를 들어 65 중량% 이상 포함할 수 있고, 예를 들어 80 중량% 이하, 예를 들어 75 중량% 이하 포함할 수 있으며, 예를 들어 55 내지 80 중량%, 예를 들어 60 내지 75 중량% 포함할 수 있다. The aromatic vinyl-vinyl cyanide copolymer may include, for example, 55% by weight or more, for example, 60% by weight or more, for example, 65% by weight or more of the aromatic vinyl compound-derived component based on 100% by weight, For example, it may contain 80% by weight or less, for example, 75% by weight or less, for example, 55 to 80% by weight, for example, 60 to 75% by weight.
또한, 상기 방향족 비닐-시안화 비닐 공중합체는 100 중량%를 기준으로 상기 시안화 비닐 화합물 유래 성분을 예를 들어 20 중량% 이상, 예를 들어 25 중량% 이상 포함할 수 있고, 예를 들어 45 중량% 이하, 예를 들어 40 중량% 이하 포함할 수 있으며, 예를 들어 20 내지 45 중량%, 예를 들어 25 내지 40 중량% 포함할 수 있다.In addition, the aromatic vinyl-vinyl cyanide copolymer may include, for example, 20% by weight or more, for example, 25% by weight or more of the component derived from the vinyl cyanide compound, based on 100% by weight, for example, 45% by weight Or less, for example, 40% by weight or less, for example, 20 to 45% by weight, for example, 25 to 40% by weight.
일 구현예에서, 상기 방향족 비닐-시안화 비닐 공중합체는 스티렌-아크릴로니트릴 공중합체(SAN)일 수 있다.In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer (SAN).
일 구현예에서, 상기 방향족 비닐-시안화 비닐 공중합체는 기초 수지 100 중량%에 대하여 60 내지 80 중량%, 예를 들어 60 내지 75 중량%, 예를 들어 60 내지 70 중량%로 포함될 수 있다. 상기 중량% 범위에서 열가소성 수지 조성물 내 성분들의 상용성이 우수할 수 있다.In one embodiment, the aromatic vinyl-vinyl cyanide copolymer may be included in 60 to 80% by weight, for example, 60 to 75% by weight, for example, 60 to 70% by weight, based on 100% by weight of the base resin. Compatibility of components in the thermoplastic resin composition may be excellent in the above weight % range.
(C) 폴리에테르-에스테르-아미드 블록 공중합체(C) polyether-ester-amide block copolymer
일 구현예에서 폴리에테르-에스테르-아미드 블록 공중합체는 열가소성 수지 조성물 및 이로부터 제조된 성형품에 소정의 전기 전도성을 나타내도록 할 수 있다. In one embodiment, the polyether-ester-amide block copolymer can provide a predetermined electrical conductivity to the thermoplastic resin composition and molded articles manufactured therefrom.
또한, 상기 폴리에테르-에스테르-아미드 블록 공중합체는 열가소성 수지 조성물 및 이로부터 제조된 성형품이 우수한 물성 밸런스를 유지하면서도 전술한 전기 전도성을 나타내도록 할 수 있다. In addition, the polyether-ester-amide block copolymer may allow the thermoplastic resin composition and molded articles manufactured therefrom to exhibit the above-described electrical conductivity while maintaining an excellent physical property balance.
일 구현예에서, 폴리에테르-에스테르-아미드 블록 공중합체로서, 예를 들면, 탄소수 6 이상의 아미노카르복실산, 락탐, 또는 디아민-디카르복실산의 염; 폴리알킬렌글리콜; 및 탄소수 4 내지 20의 디카르복실산의 반응 생성물을 사용할 수 있다. In one embodiment, as the polyether-ester-amide block copolymer, for example, an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a salt of a diamine-dicarboxylic acid; polyalkylene glycol; and a reaction product of a dicarboxylic acid having 4 to 20 carbon atoms.
일 구현예에서, 상기 탄소수 6 이상의 아미노카르복실산으로는, ω-아미노카프로산, ω-아미노에난트산, ω-아미노카프릴산, ω-아미노펠아르곤산, ω-아미노카프르산, 11-아미노운데칸산, 12-아미노도데칸산 등을 들 수 있고, 상기 락탐으로는 ε-카프로락탐, 에난트락탐, 카프릴락탐, 라우로락탐 등을 들 수 있고, 상기 디아민-디카르복실산의 염으로는 헥사메틸렌디아민-아디핀산의 염, 헥사메틸렌디아민-이소프탈산의 염등과 같은 디아민-디카르복실산 염 등을 예시할 수 있다. 예를 들어, 상기 탄소수 6 이상의 아미노카르복실산, 락탐, 및 디아민-디카르복실산의 염으로는, 각각 12-아미노도데칸산, ε-카프로락탐, 및 헥사메틸렌디아민-아디핀산의 염을 들 수 있다. In one embodiment, the aminocarboxylic acids having 6 or more carbon atoms include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like, and examples of the lactam include ε-caprolactam, enantlactam, capryllactam, and laurolactam, and the diamine-dicarboxylic acid Examples of acid salts include diamine-dicarboxylic acid salts such as hexamethylenediamine-adipic acid salts and hexamethylenediamine-isophthalic acid salts. For example, as the salts of aminocarboxylic acids having 6 or more carbon atoms, lactams, and diamine-dicarboxylic acids, salts of 12-aminododecanoic acid, ε-caprolactam, and hexamethylenediamine-adipic acid, respectively. can be heard
일 구현예에서, 상기 폴리알킬렌글리콜로는 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜, 폴리헥사메틸렌글리콜, 에틸렌글리콜과 프로필렌글리콜의 블록 또는 랜덤 공중합체, 에틸렌글리콜과 테트라히드로퓨란의 공중합체 등을 예시할 수 있다. 예를 들면, 폴리에틸렌글리콜, 에틸렌글리콜과 프로필렌글리콜의 공중합체 등을 사용할 수 있다. In one embodiment, the polyalkylene glycol is polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene glycol and propylene glycol, a copolymer of ethylene glycol and tetrahydrofuran etc. can be exemplified. For example, polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, and the like can be used.
일 구현예에서, 상기 탄소수 4 내지 20의 디카르복실산으로는 테레프탈산, 1,4-시클로헥산디카르복실산, 세바신산, 아디프산, 도데칸디오익산 등을 예시할 수 있다. In one embodiment, examples of the dicarboxylic acid having 4 to 20 carbon atoms include terephthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanedioic acid.
상기 탄소수 6 이상의 아미노카르복실산, 락탐, 또는 디아민-디카르복실산의 염과 상기 폴리알킬렌글리콜의 결합은 에스테르 결합일 수 있고, 상기 탄소수 6 이상의 아미노카르복실산, 락탐, 또는 디아민-디카르복실산의 염과 상기 탄소수 4 내지 20의 디카르복실산의 결합은 아미드 결합일 수 있고, 상기 폴리알킬렌글리콜과 상기 탄소수 4 내지 20의 디카르복실산의 결합은 에스테르 결합일 수 있다. The bond between the salt of the aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms and the polyalkylene glycol may be an ester bond, and the aminocarboxylic acid, lactam, or diamine-dicarboxylic acid having 6 or more carbon atoms may form an ester bond. A bond between the salt of carboxylic acid and the dicarboxylic acid having 4 to 20 carbon atoms may be an amide bond, and a bond between the polyalkylene glycol and the dicarboxylic acid having 4 to 20 carbon atoms may be an ester bond.
일 구현예에서, 상기 폴리에테르-에스테르-아미드 블록 공중합체는 공지된 합성방법에 의해 제조될 수 있으며, 예를 들면, 일본 특허공보 소56-045419 및 일본 특허공개 소55-133424에 개시된 합성방법에 따라 제조될 수 있다. In one embodiment, the polyether-ester-amide block copolymer can be prepared by a known synthesis method, for example, the synthesis method disclosed in Japanese Patent Publication No. 56-045419 and Japanese Patent Publication No. 55-133424 It can be manufactured according to.
일 구현예에서, 상기 폴리에테르-에스테르-아미드 블록 공중합체는 폴리에테르-에스테르 블록을 10 내지 95 중량% 포함할 수 있다. 상기 범위에서 열가소성 수지 조성물의 전기 전도성 및 내열성 등이 우수할 수 있다. In one embodiment, the polyether-ester-amide block copolymer may include 10 to 95% by weight of the polyether-ester block. Within the above range, the thermoplastic resin composition may have excellent electrical conductivity and heat resistance.
일 구현예에서, 상기 폴리에테르-에스테르-아미드 블록 공중합체는 상기 기초 수지 100 중량부에 대하여, 3 내지 10 중량부, 예를 들면 5 내지 10 중량부로 포함될 수 있다. In one embodiment, the polyether-ester-amide block copolymer may be included in an amount of 3 to 10 parts by weight, for example, 5 to 10 parts by weight, based on 100 parts by weight of the base resin.
상기 폴리에테르-에스테르-아미드 블록 공중합체의 함량이 전술한 범위를 만족할 경우, 열가소성 수지 조성물 및 이로부터 제조된 성형품이 우수한 물성 밸런스를 유지하면서 동시에 우수한 전기 전도성을 나타낼 수 있다. When the content of the polyether-ester-amide block copolymer satisfies the aforementioned range, the thermoplastic resin composition and molded articles manufactured therefrom may exhibit excellent electrical conductivity while maintaining excellent physical property balance.
(D) 폴리알킬렌글리콜(D) polyalkylene glycol
일 구현예에서 폴리알킬렌글리콜은 폴리에테르-에스테르-아미드 블록 공중합체와 함께 열가소성 수지 조성물 및 이로부터 제조된 성형품에 소정의 전기 전도성을 나타내도록 할 수 있다. In one embodiment, the polyalkylene glycol, together with the polyether-ester-amide block copolymer, can give a thermoplastic resin composition and a molded article manufactured therefrom to exhibit predetermined electrical conductivity.
상기 폴리알킬렌글리콜은 폴리알킬렌글리콜, 폴리알킬렌글리콜의 에테르, 및/또는 폴리알킬렌글리콜의 에스테르를 포함할 수 있다. 상기 폴리알킬렌글리콜로는 통상의 열가소성 수지 조성물에 사용되는 폴리올이 제한 없이 사용될 수 있으며, 예를 들면, 폴리에틸렌글리콜, 폴리에틸렌글리콜 메틸에테르, 폴리에틸렌글리콜 디메틸에테르, 폴리에틸렌글리콜 도데실에테르, 폴리에틸렌글리콜 벤질에테르, 폴리에틸렌글리콜 디벤질에테르, 폴리에틸렌글리콜-4-노닐페닐에테르, 폴리프로필렌글리콜, 폴리프로필렌글리콜 메틸에테르, 폴리프로필렌글리콜 디메틸에테르, 폴리프로필렌글리콜 도데실에테르, 폴리프로필렌글리콜 벤질에테르, 폴리프로필렌글리콜 디벤질에테르, 폴리프로필렌글리콜-4-노닐페닐에테르, 폴리테트라메틸렌글리콜, 폴리에틸렌글리콜 디초산에스테르, 폴리에틸렌글리콜 초산 프로피온산 에스테르, 폴리에틸렌글리콜 디부티르산 에스테르, 폴리에틸렌글리콜 디스테아린산 에스테르, 폴리에틸렌글리콜 디벤조산 에스테르, 폴리에틸렌글리콜 디-2,6-디메틸벤조산 에스테르, 폴리에틸렌글리콜 디-p-tert-부틸벤조산 에스테르, 폴리에틸렌글리콜 디카프릴산 에스테르, 폴리프로필렌글리콜 디초산 에스테르, 폴리프로필렌글리콜 초산 프로피온산 에스테르, 폴리프로필렌글리콜 디부티르산 에스테르, 폴리프로필렌글리콜 디스테아린산 에스테르, 폴리프로필렌글리콜 디벤조산 에스테르, 폴리프로필렌글리콜 디-2,6-디메틸벤조산 에스테르, 폴리프로필렌글리콜 디-p-tert-부틸벤조산 에스테르, 폴리프로필렌글리콜 디카프릴산 에스테르 등을 예시할 수 있으나, 이에 제한되지 않는다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The polyalkylene glycol may include polyalkylene glycol, polyalkylene glycol ether, and/or polyalkylene glycol ester. As the polyalkylene glycol, polyols used in conventional thermoplastic resin compositions may be used without limitation, and examples include polyethylene glycol, polyethylene glycol methyl ether, polyethylene glycol dimethyl ether, polyethylene glycol dodecyl ether, and polyethylene glycol benzyl ether. , Polyethylene glycol dibenzyl ether, polyethylene glycol-4-nonylphenyl ether, polypropylene glycol, polypropylene glycol methyl ether, polypropylene glycol dimethyl ether, polypropylene glycol dodecyl ether, polypropylene glycol benzyl ether, polypropylene glycol dibenzyl Ether, polypropylene glycol-4-nonylphenyl ether, polytetramethylene glycol, polyethylene glycol diacetic acid ester, polyethylene glycol acetic acid propionic acid ester, polyethylene glycol dibutyric acid ester, polyethylene glycol distearic acid ester, polyethylene glycol dibenzoic acid ester, polyethylene glycol di -2,6-dimethylbenzoic acid ester, polyethylene glycol di-p-tert-butylbenzoic acid ester, polyethylene glycol dicaprylic acid ester, polypropylene glycol diacetic acid ester, polypropylene glycol acetic acid propionic acid ester, polypropylene glycol dibutyric acid ester, poly Examples include propylene glycol distearic acid ester, polypropylene glycol dibenzoic acid ester, polypropylene glycol di-2,6-dimethylbenzoic acid ester, polypropylene glycol di-p-tert-butylbenzoic acid ester, polypropylene glycol dicaprylic acid ester, and the like. It may, but is not limited thereto. These can be used individually or in mixture of 2 or more types.
일 구현예에서, 상기 폴리알킬렌글리콜은 겔 투과 크로마토그래피(Gel Permeation Chromatography: GPC)로 측정한 수평균분자량(Mn)이 4,000 내지 10,000 g/mol, 예를 들면 5,000 내지 10,000 g/mol일 수 있다.In one embodiment, the polyalkylene glycol may have a number average molecular weight (Mn) of 4,000 to 10,000 g/mol, for example, 5,000 to 10,000 g/mol, as measured by gel permeation chromatography (GPC). there is.
일 구현예에서, 상기 폴리알킬렌글리콜은 상기 기초 수지 100 중량부에 대하여, 1 내지 10 중량부, 예를 들어 2 내지 8 중량부, 예를 들어 3 내지 5 중량부로 포함될 수 있다. 상기 중량부 범위에서 열가소성 수지 조성물의 제반 물성 밸런스가 유지되면서 전기 전도성이 우수할 수 있다.In one embodiment, the polyalkylene glycol may be included in 1 to 10 parts by weight, for example, 2 to 8 parts by weight, for example, 3 to 5 parts by weight, based on 100 parts by weight of the base resin. Electrical conductivity may be excellent while maintaining the balance of various physical properties of the thermoplastic resin composition in the above weight part range.
(E) 첨가제(E) additives
일 구현예에 따른 열가소성 수지 조성물은 상기 성분 (A) 내지 (D) 외에도, 전기 전도성과 제반 물성 밸런스를 모두 우수하게 유지하는 조건 하에 각 물성들 간의 균형을 맞추기 위해, 혹은 상기 열가소성 수지 조성물의 최종 용도에 따라 필요한 1종 이상의 첨가제를 더 포함할 수 있다.In addition to the components (A) to (D), the thermoplastic resin composition according to an embodiment is used to balance the physical properties under the condition of maintaining excellent balance of electrical conductivity and various physical properties, or the final thermoplastic resin composition. One or more additives necessary for use may be further included.
구체적으로, 상기 첨가제로서는, 핵제, 커플링제, 충전제, 가소제, 활제, 이형제, 항균제, 열 안정제, 산화 방지제, 자외선 안정제, 난연제, 착색제, 충격보강제　등이 사용될 수 있고 이들은 단독으로 혹은 2종 이상의 조합으로 사용될 수 있다. Specifically, as the additives, nucleating agents, coupling agents, fillers, plasticizers, lubricants, release agents, antibacterial agents, heat stabilizers, antioxidants, UV stabilizers, flame retardants, colorants, impact modifiers, etc. may be used, and these may be used alone or in combination of two or more can be used as
이들 첨가제는 열가소성 수지 조성물의 물성을 저해하지 않는 범위 내에서 적절히 포함될 수 있고, 구체적으로는 기초 수지 100 중량부에 대하여 20 중량부 이하로 포함될 수 있으나, 이에 제한되는 것은 아니다.These additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on 100 parts by weight of the base resin, but is not limited thereto.
본 발명에 따른 열가소성 수지 조성물은 열가소성 수지 조성물을 제조하는 공지의 방법에 의해서 제조될 수 있다.The thermoplastic resin composition according to the present invention can be prepared by a known method for preparing a thermoplastic resin composition.
예를 들어, 본 발명에 따른 열가소성 수지 조성물은 본 발명의 구성 성분과 기타 첨가제들을 혼합한 후 압출기 내에서 용융 혼련하여 펠렛(pellet) 형태로 제조할 수 있다.For example, the thermoplastic resin composition according to the present invention may be prepared in the form of pellets by mixing the components of the present invention and other additives and then melt-kneading them in an extruder.
본 발명의 일 구현예에 따른 성형품은 상술한 열가소성 수지 조성물로부터 공지의 성형 방법을 통해 제조될 수 있다. 예를 들어, 상기 성형품은 압출 성형, 사출 성형 등의 방법으로 제조될 수 있고, 이들에 제한되지 않는다.A molded article according to one embodiment of the present invention may be manufactured from the above-described thermoplastic resin composition through a known molding method. For example, the molded article may be manufactured by methods such as extrusion molding and injection molding, but is not limited thereto.
일 구현예에서, 상기 성형품은 표면저항 측정장치(제조사: SIMCO-ION사, 장치명: Worksurface Tester ST-4)를 사용하여 100 mm x 100 mm x 3.2 mm 시편에 대해 측정한 표면저항이 1012.0 Ω/sq 이하, 예를 들어 1011.9 Ω/sq 이하, 예를 들어 1011.8 Ω/sq 이하, 예를 들어 1011.7 Ω/sq 이하, 예를 들어 1011.6 Ω/sq 이하일 수 있다.In one embodiment, the molded article has a surface resistance of 10 12.0 Ω measured for a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4) /sq or less, such as 10 11.9 Ω/sq or less, such as 10 11.8 Ω/sq or less, such as 10 11.7 Ω/sq or less, such as 10 11.6 Ω/sq or less.
일 구현예에서, 상기 성형품은 ASTM D790에 의거하여, 두께 6.4 mm의 시편에 대해 측정한 굴곡탄성율이 18,000 kgf/cm2 이상, 예를 들어 19,000 kgf/cm2 이상, 예를 들어 20,000 kgf/cm2 이상, 예를 들어 22,000 kgf/cm2 이하, 예를 들어 21,000 kgf/cm2 이하, 예를 들어 18,000 내지 22,000 kgf/cm2, 예를 들어 18,000 내지 21,000 kgf/cm2일수 있다.In one embodiment, the molded article has a flexural modulus of 18,000 kgf/cm 2 or more, for example, 19,000 kgf/cm 2 or more, for example, 20,000 kgf/cm, measured for a specimen having a thickness of 6.4 mm, according to ASTM D790. 2 or more, for example 22,000 kgf/cm 2 or less, for example 21,000 kgf/cm 2 or less, for example 18,000 to 22,000 kgf/cm 2 , for example 18,000 to 21,000 kgf/cm 2 .
일 구현예에서, 상기 성형품은 ASTM D1238에 의거하여, 220℃, 10 kg 하중 조건에서 측정한 유동흐름지수가 24 g/10min 이상, 25 g/10min 이상, 26 g/10min 이상일 수 있다.In one embodiment, the molded article may have a flow rate of 24 g/10 min or more, 25 g/10 min or more, or 26 g/10 min or more, measured at 220° C. under a 10 kg load condition, according to ASTM D1238.
이와 같이, 상기 열가소성 수지 조성물은 우수한 전기 전도성, 및 제반 물성을 가지므로 도장, 무도장으로 사용하는 여러 가지 제품에 광범위하게 적용될 수 있으며, 특히, 정전 도장이 필요한 도장용 성형품에도 유용하게 적용될 수 있다.As described above, since the thermoplastic resin composition has excellent electrical conductivity and various physical properties, it can be widely applied to various products used for painting and uncoating, and in particular, it can be usefully applied to molded products for painting requiring electrostatic painting.
이하에서 본 발명을 실시예 및 비교예를 통하여 보다 상세하게 설명하고자 하나, 하기의 실시예 및 비교예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것은 아니다.Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples, but the following Examples and Comparative Examples are for the purpose of explanation and are not intended to limit the present invention.
실시예 1 및 2 및 비교예 1 내지 4Examples 1 and 2 and Comparative Examples 1 to 4
실시예 1 및 2, 및 비교예 1 내지 4의 열가소성 수지 조성물은 하기 표 1 에 기재된 성분 함량비에 따라 제조되었다. The thermoplastic resin compositions of Examples 1 and 2 and Comparative Examples 1 to 4 were prepared according to the component content ratios shown in Table 1 below.
표 1에서, (A), 및 (B)는 기초 수지에 포함되는 것으로 기초 수지 총 중량을 기준으로 중량%로 나타내었고, (C), 및 (D)는 기초 수지에 첨가되는 것으로서 기초 수지 100 중량부에 대한 중량부로 나타내었다.In Table 1, (A) and (B) are included in the base resin and are expressed in weight% based on the total weight of the base resin, and (C) and (D) are added to the base resin, and the base resin 100 It is expressed in parts by weight to parts by weight.
표 1에 기재된 성분을 건식 혼합하고, 이축 압출기(L/D=44, Φ=45mm)의 공급부에 정량적으로 연속 투입하여 용융/혼련하였다. 이어서, 이축 압출기를 통해 펠렛화된 열가소성 수지 조성물을 약 80℃에서 약 4 시간 동안 건조한 후, 실린더 온도 약 240℃, 금형 온도 약 60℃의 120톤 사출 성형기를 사용하여 물성 평가용 시편을 각각 제조하였다.The components listed in Table 1 were dry mixed, and quantitatively and continuously introduced into the feed section of a twin screw extruder (L/D = 44, φ = 45 mm) to melt/knead. Subsequently, after drying the pelletized thermoplastic resin composition at about 80 ° C. for about 4 hours through a twin-screw extruder, specimens for physical property evaluation were prepared using a 120-ton injection molding machine with a cylinder temperature of about 240 ° C and a mold temperature of about 60 ° C. did
실시예Example 비교예comparative example
1One 22 1One 22 33 44
(A)(A) 3030 3030 3030 3030 3030 3030
(B)(B) 7070 7070 7070 7070 7070 7070
(C)(C) 88 88 -- 88 1414 --
(D)(D) 33 55 -- -- -- 55
상기 표 1 에 기재된 각 구성에 대한 설명은 다음과 같다. A description of each configuration described in Table 1 is as follows.
(A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체(A) Butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer
부타디엔 고무질 중합체로 이루어진 코어(평균 입경: 약 0.25 ㎛) 약 58 중량%에 아크릴로니트릴과 스티렌(아크릴로니트릴 : 스티렌 중량비 = 약 2.5 : 약 7.5)이 상기 코어에 그라프트 중합되어 형성된 쉘을 포함하는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체(롯데케미칼社)Includes a shell formed by graft polymerization of acrylonitrile and styrene (acrylonitrile: styrene weight ratio = about 2.5: about 7.5) to about 58% by weight of a core made of butadiene rubbery polymer (average particle diameter: about 0.25 μm) acrylonitrile-butadiene-styrene graft copolymer (Lotte Chemical Co.)
(B) 방향족 비닐-시안화 비닐 공중합체(B) Aromatic vinyl-vinyl cyanide copolymer
아크릴로니트릴 약 32 중량% 및 스티렌 약 68 중량%를 포함하는 단량체 혼합물로부터 공중합된 중량평균분자량이 약 120,000 g/mol인 스티렌-아크릴로니트릴 공중합체(롯데케미칼社) A weight average molecular weight of about 120,000 g / mol copolymerized from a monomer mixture containing about 32% by weight of acrylonitrile and about 68% by weight of styrene Styrene-acrylonitrile copolymer (Lotte Chemical Co.)
(C) 폴리에테르-에스테르-아미드 블록 공중합체(C) polyether-ester-amide block copolymer
폴리아미드 6-폴리에틸렌 옥사이드 블록 공중합체(PA6-b-PE0)(Sanyo社, PELECTRON AS)Polyamide 6-polyethylene oxide block copolymer (PA6-b-PE0) (Sanyo, PELECTRON AS)
(D) 폴리알킬렌글리콜(D) polyalkylene glycol
수평균분자량이 약 8,000 g/mol인 폴리에틸렌글리콜(롯데케미칼社)Polyethylene glycol having a number average molecular weight of about 8,000 g/mol (Lotte Chemical Co.)
실험예Experimental example
실험 결과를 하기 표 2에 나타내었다. The experimental results are shown in Table 2 below.
(1) 전기 전도성(단위: Ω/sq): 표면저항 측정장치(제조사: SIMCO-ION사, 장치명: Worksurface Tester ST-4)를 사용하여 100 mm x 100 mm x 3.2 mm 시편에 대한 표면저항을 측정하였다.(1) Electrical conductivity (unit: Ω/sq): The surface resistance of a 100 mm x 100 mm x 3.2 mm specimen was measured using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4). measured.
(2) 내충격성(단위: kgf·cm/cm): ASTM D256에 의거하여, 1/4" 두께 시편에 대한 노치 아이조드 충격강도를 측정하였다.(2) Impact resistance (unit: kgf cm/cm): According to ASTM D256, the notched Izod impact strength of a 1/4" thick specimen was measured.
(3) 강성(단위: kgf/cm2): ASTM D790에 의거하여, 두께 6.4 mm의 시편에 대한 굴곡탄성율(flexural modulus)을 측정하였다. (3) Stiffness (unit: kgf/cm 2 ): In accordance with ASTM D790, the flexural modulus of a specimen having a thickness of 6.4 mm was measured.
(4) 유동성(단위: g/10min): ASTM D1238에 의거하여, 펠렛 형태의 시료에 대해 220℃, 10 kg 하중 조건에서 유동흐름지수(melt flow index)를 측정하였다.(4) Flowability (unit: g/10min): In accordance with ASTM D1238, the melt flow index was measured for pellet-type samples at 220° C. under a load of 10 kg.
실시예Example 비교예comparative example
1One 22 1One 22 33 44
표면저항surface resistance 1011.2 10 11.2 1010.4 10 10.4 1013.5 10 13.5 1013.5 10 13.5 1010.0 10 10.0 1013.5 10 13.5
아이조드 충격강도Izod impact strength 33.733.7 24.124.1 31.231.2 40.640.6 42.242.2 27.427.4
굴곡탄성율flexural modulus 18,40018,400 19,60019,600 21,50021,500 19,10019,100 17,70017,700 20,00020,000
유동흐름지수Current flow index 26.026.0 39.239.2 9.69.6 14.814.8 22.022.0 2.72.7
상기 표 1 및 표 2로부터, 실시예 1과 실시예 2와 같이 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체, 방향족 비닐-시안화 비닐 공중합체, 폴리에테르-에스테르-아미드 블록 공중합체, 및 폴리알킬렌글리콜을 최적의 함량으로 사용함으로써, 우수한 전기 전도성을 유지하면서 비교예들 대비 우수한 내충격성, 강성, 및 유동성을 나타내는 열가소성 수지 조성물, 및 이를 이용한 성형품을 제공할 수 있다는 것을 확인할 수 있다.From Tables 1 and 2, butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymers, aromatic vinyl-vinyl cyanide copolymers, polyether-ester-amide block copolymers, and It can be confirmed that by using polyalkylene glycol in an optimal amount, a thermoplastic resin composition exhibiting excellent impact resistance, stiffness, and fluidity compared to comparative examples while maintaining excellent electrical conductivity, and a molded article using the same can be provided.
이상에서 본 발명을 앞서 기재한 바에 따라 바람직한 실시예를 통해 설명하였지만, 본 발명은 이에 한정되지 않으며 다음에 기재하는 특허청구범위의 개념과 범위를 벗어나지 않는 한, 다양한 수정 및 변형이 가능하다는 것을 본 발명이 속하는 기술 분야에 종사하는 자들은 쉽게 이해할 것이다.Although the present invention has been described through preferred embodiments as described above, the present invention is not limited thereto and various modifications and variations are possible without departing from the concept and scope of the claims described below. Those working in the technical field to which the invention belongs will readily understand.

Claims (15)

  1. (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체 20 내지 40 중량%; 및 (A) 20 to 40% by weight of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer; and
    (B) 방향족 비닐-시안화 비닐 공중합체 60 내지 80 중량%(B) 60 to 80% by weight of an aromatic vinyl-vinyl cyanide copolymer
    를 포함하는 기초 수지 100 중량부에 대하여 Based on 100 parts by weight of the base resin containing
    (C) 폴리에테르-에스테르-아미드(polyether-ester-amide) 블록 공중합체 3 내지 10 중량부, 및 (C) 3 to 10 parts by weight of a polyether-ester-amide block copolymer, and
    (D) 폴리알킬렌글리콜 1 내지 10 중량부를 포함하는 열가소성 수지 조성물. (D) A thermoplastic resin composition containing 1 to 10 parts by weight of polyalkylene glycol.
  2. 제1항에서,In paragraph 1,
    상기 (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 부타디엔계 고무질 중합체로 이루어진 코어, 및 방향족 비닐 화합물과 시안화 비닐 화합물이 상기 코어에 그라프트 중합되어 형성된 쉘을 포함하는 코어-쉘 구조인 열가소성 수지 조성물.The (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer includes a core made of a butadiene-based rubbery polymer, and a shell formed by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound on the core-shell Structure of the thermoplastic resin composition.
  3. 제2항에서,In paragraph 2,
    상기 부타디엔계 고무질 중합체의 평균 입경이 0.2 내지 1.0 ㎛인 열가소성 수지 조성물.The thermoplastic resin composition wherein the butadiene-based rubbery polymer has an average particle diameter of 0.2 to 1.0 μm.
  4. 제1항 내지 제3항 중 어느 한 항에서,In any one of claims 1 to 3,
    상기 (A) 부타디엔계 고무변성 방향족 비닐-시안화 비닐 그라프트 공중합체는 아크릴로니트릴-부타디엔-스티렌 그라프트 공중합체인 열가소성 수지 조성물.The (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer.
  5. 제1항 내지 제4항 중 어느 한 항에서,In any one of claims 1 to 4,
    상기 (B) 방향족 비닐-시안화 비닐 공중합체는 100 중량%를 기준으로 방향족 비닐 화합물 유래 성분 55 내지 80 중량% 및 시안화 비닐 화합물 유래 성분 20 내지 45 중량%를 포함하는 열가소성 수지 조성물.The (B) aromatic vinyl-vinyl cyanide copolymer is a thermoplastic resin composition comprising 55 to 80% by weight of an aromatic vinyl compound-derived component and 20 to 45% by weight of a vinyl cyanide compound-derived component based on 100% by weight.
  6. 제1항 내지 제5항 중 어느 한 항에서,In any one of claims 1 to 5,
    상기 (B) 방향족 비닐-시안화 비닐 공중합체는 중량평균분자량이 80,000 내지 300,000 g/mol인, 열가소성 수지 조성물.The (B) aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight of 80,000 to 300,000 g / mol, a thermoplastic resin composition.
  7. 제1항 내지 제6항 중 어느 한 항에서,In any one of claims 1 to 6,
    상기 (B) 방향족 비닐-시안화 비닐 공중합체는 스티렌-아크릴로니트릴 공중합체인 열가소성 수지 조성물.The (B) aromatic vinyl-vinyl cyanide copolymer is a styrene-acrylonitrile copolymer, the thermoplastic resin composition.
  8. 제1항 내지 제7항 중 어느 한 항에서,In any one of claims 1 to 7,
    상기 (C) 폴리에테르-에스테르-아미드 블록 공중합체는 탄소수 6 이상의 아미노카르복실산, 락탐, 또는 디아민-디카르복실산 염; 폴리알킬렌글리콜; 및 탄소수 4 내지 20의 디카르복실산의 반응 생성물인, 열가소성 수지 조성물.The (C) polyether-ester-amide block copolymer is an aminocarboxylic acid having 6 or more carbon atoms, a lactam, or a diamine-dicarboxylic acid salt; polyalkylene glycol; And a reaction product of a dicarboxylic acid having 4 to 20 carbon atoms.
  9. 제1항 내지 제8항 중 어느 한 항에서,In any one of claims 1 to 8,
    상기 (D) 폴리알킬렌글리콜의 수평균분자량은 4,000 내지 10,000 g/mol인, 열가소성 수지 조성물.The number average molecular weight of the (D) polyalkylene glycol is 4,000 to 10,000 g / mol, the thermoplastic resin composition.
  10. 제1항 내지 제9항 중 어느 한 항에서,In any one of claims 1 to 9,
    상기 (D) 폴리알킬렌글리콜은 폴리에틸렌글리콜인, 열가소성 수지 조성물. The (D) polyalkylene glycol is polyethylene glycol, a thermoplastic resin composition.
  11. 제1항 내지 제10항 중 어느 한 항에서,In any one of claims 1 to 10,
    핵제, 커플링제, 충전제, 가소제, 활제, 이형제, 항균제, 열 안정제, 산화 방지제, 자외선 안정제, 난연제, 착색제, 충격보강제 중에서 선택되는 적어도 하나의 첨가제를 더 포함하는 열가소성 수지 조성물.A thermoplastic resin composition further comprising at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, a colorant, and an impact modifier.
  12. 제1항 내지 제11항 중 어느 한 항에 따른 열가소성 수지 조성물로부터 제조된 성형품.A molded article manufactured from the thermoplastic resin composition according to any one of claims 1 to 11.
  13. 제12항에서,In paragraph 12,
    상기 성형품은 표면저항 측정장치(제조사: SIMCO-ION사, 장치명: Worksurface Tester ST-4)를 사용하여 100 mm x 100 mm x 3.2 mm 시편에 대해 측정한 표면저항이 1012.0 Ω/sq 이하인 성형품.The molded article has a surface resistance measured on a 100 mm x 100 mm x 3.2 mm specimen using a surface resistance measuring device (manufacturer: SIMCO-ION, device name: Worksurface Tester ST-4) of 10 12.0 Ω / sq or less.
  14. 제12항 또는 제13항에서,In claim 12 or 13,
    상기 성형품은 ASTM D790에 의거하여, 두께 6.4 mm의 시편에 대해 측정한 굴곡탄성율이 18,000 내지 22,000 kgf/cm2인, 성형품.The molded article has a flexural modulus of 18,000 to 22,000 kgf / cm 2 measured for a specimen having a thickness of 6.4 mm in accordance with ASTM D790.
  15. 제12항 내지 제14항 중 어느 한 항에서,In any one of claims 12 to 14,
    상기 성형품은 ASTM D1238에 의거하여, 220℃, 10 kg 하중 조건에서 측정한 유동흐름지수가 24 g/10min 이상인, 성형품.According to ASTM D1238, the molded article has a flow rate of 24 g / 10min or more measured at 220 ° C. under a load of 10 kg.
PCT/KR2022/012915 2021-08-31 2022-08-30 Thermoplastic resin composition and molded product manufactured therefrom WO2023033492A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002500237A (en) * 1997-12-24 2002-01-08 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Antistatic polymer composition and molded article thereof
KR20060107503A (en) * 2003-08-08 2006-10-13 로디아 엔지니어링 플라스틱스 에스.에이. Electrostatic composition based on a polyamide matrix
JP2009532547A (en) * 2006-04-04 2009-09-10 ロディア オペレーションズ Conductive composition based on polyamide matrix
KR20140141145A (en) * 2013-05-31 2014-12-10 제일모직주식회사 Thermoplastic Resin Composition Having Excellent Conductivity and Impact Strength
KR20180077044A (en) * 2016-12-28 2018-07-06 롯데첨단소재(주) Thermoplastic resin composition and article produced therefrom

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Publication number Priority date Publication date Assignee Title
JP2002500237A (en) * 1997-12-24 2002-01-08 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Antistatic polymer composition and molded article thereof
KR20060107503A (en) * 2003-08-08 2006-10-13 로디아 엔지니어링 플라스틱스 에스.에이. Electrostatic composition based on a polyamide matrix
JP2009532547A (en) * 2006-04-04 2009-09-10 ロディア オペレーションズ Conductive composition based on polyamide matrix
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KR20180077044A (en) * 2016-12-28 2018-07-06 롯데첨단소재(주) Thermoplastic resin composition and article produced therefrom

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