WO2019164167A1 - Thermoplastic resin composition and molded article formed therefrom - Google Patents

Thermoplastic resin composition and molded article formed therefrom Download PDF

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Publication number
WO2019164167A1
WO2019164167A1 PCT/KR2019/001698 KR2019001698W WO2019164167A1 WO 2019164167 A1 WO2019164167 A1 WO 2019164167A1 KR 2019001698 W KR2019001698 W KR 2019001698W WO 2019164167 A1 WO2019164167 A1 WO 2019164167A1
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Prior art keywords
resin composition
thermoplastic resin
weight
aromatic vinyl
modified
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PCT/KR2019/001698
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French (fr)
Korean (ko)
Inventor
추동휘
권영철
김은진
정봉재
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롯데첨단소재(주)
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Publication of WO2019164167A1 publication Critical patent/WO2019164167A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/28Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in impact resistance, flowability, light weight, and the like, and a molded article formed therefrom.
  • thermoplastic resin rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) are excellent in mechanical properties, processability, appearance characteristics, etc. It is widely used as interior / exterior materials for automobiles and exterior materials for construction. In particular, with the recent trend of lightening electrical / electronic products, plastic products using thermoplastic resins are rapidly replacing the areas of glass and metal.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • a filler of low specific gravity may be applied, or a low specific gravity material such as polypropylene may be applied.
  • a low specific gravity material such as polypropylene
  • impact resistance, mechanical properties, processability (fluidity), compatibility, etc. There is a problem that property degradation occurs or the weight reduction is not sufficient.
  • thermoplastic resin composition having excellent impact resistance, flowability, light weight, balance of physical properties, and the like.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, flowability, light weight and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition may include about 100 parts by weight of a rubber modified aromatic vinyl copolymer resin including about 20 wt% to about 50 wt% of the rubber modified vinyl graft copolymer and about 50 wt% to about 80 wt% of the aromatic vinyl copolymer copolymer resin; About 1 to about 5 parts by weight of a modified polyolefin comprising a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 below; And about 5 to about 20 parts by weight of the hollow inorganic filler;
  • R 1 is a hydrogen atom or a methyl group
  • Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl modified ester group, an arylate group, or a nitrile group (-CN) .
  • the rubber-modified vinyl graft copolymer may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.
  • the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
  • the modified olefin may include about 50 to about 95 weight% of the repeating unit represented by Formula 1 and about 5 to about 50 weight% of the repeating unit represented by Formula 2 .
  • the hollow inorganic filler may be spherical hollow glass particles.
  • the weight ratio of the modified polyolefin and the hollow inorganic filler may be about 0.1: 1 to about 0.5: 1.
  • thermoplastic resin composition may have a notched Izod impact strength of 1/8 "thick specimen measured in accordance with ASTM D256 of about 12 kgf ⁇ cm / cm or more.
  • thermoplastic resin composition may be about 1.5 to about 3.5 g / 10 minutes melt flow index measured at 200 °C, 5 kgf conditions in accordance with ASTM D1238.
  • thermoplastic resin composition may have a specific gravity of about 1 or less, based on ASTM D792.
  • Another aspect of the present invention relates to a molded article.
  • the molded article is formed from the thermoplastic resin composition according to any one of the above 1 to 9.
  • the present invention has the effect of the invention of providing a thermoplastic resin composition excellent in impact resistance, flowability, light weight and the like and a molded article formed therefrom.
  • thermoplastic resin composition according to the present invention is (A) rubber-modified aromatic vinyl copolymer resin; (B) modified polyolefins; And (C) a hollow inorganic filler.
  • the rubber modified aromatic vinyl copolymer resin of the present invention may include (A1) rubber modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin.
  • Rubber-modified vinyl graft copolymer according to an embodiment of the present invention may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer.
  • the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer, and, if necessary, processability and The monomer which gives heat resistance can be further included and graft-polymerized.
  • the polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization.
  • the rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.
  • the rubbery polymer may be a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or a saturated rubber hydrogenated to the diene rubber, isoprene rubber, C 2 to C 10 alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymers (EPDM), and the like. These can be applied individually or in mixture of 2 or more types.
  • a diene rubber, (meth) acrylate rubber, etc. can be used, Specifically, butadiene rubber, butyl acrylate rubber, etc. can be used.
  • the rubbery polymer (rubber particles) has an average particle size (D50) measured by particle size analyzer of about 0.05 to about 6 ⁇ m, for example about 0.15 to about 4 ⁇ m, specifically about 0.25 to about 3.5 ⁇ m Can be.
  • the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state.
  • the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured by a light scattering particle size analyzer (nano-zs, Malvern).
  • the content of the rubbery polymer may be about 20 to about 70% by weight, for example about 25 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, the monomer mixture (aromatic The vinyl monomer and the vinyl cyanide monomer) may be about 30 to about 80 wt%, for example about 40 to about 75 wt%, of 100 wt% of the total rubber-modified vinyl graft copolymer.
  • the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.
  • the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof.
  • the aromatic vinyl monomer may be included in an amount of about 10 wt% to about 90 wt%, for example, about 40 wt% to about 90 wt% in 100 wt% of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.
  • the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide monomer may be about 10 wt% to about 90 wt%, for example about 10 wt% to about 60 wt%, in 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.
  • monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like.
  • the content may be 15% by weight or less, for example 0.1 to 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.
  • the rubber-modified vinyl graft copolymer is a copolymer in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted to a butadiene rubber polymer, and butyl acryl.
  • An acrylate-styrene-acrylonitrile graft copolymer (g-ASA) which is a copolymer in which the styrene monomer which is an aromatic vinyl type compound, and the acrylonitrile monomer which is a vinyl cyanide compound is grafted to a latex rubbery polymer can be illustrated. have.
  • the rubber-modified vinyl graft copolymer is about 20 to about 50 weight in 100% by weight of the total rubber-modified aromatic vinyl copolymer resin (rubber modified vinyl graft copolymer and aromatic vinyl copolymer resin) %, For example from about 25 to about 45% by weight.
  • the rubber-modified vinyl graft copolymer is less than about 20% by weight in 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin, impact resistance, light weight, etc. of the thermoplastic resin composition may be lowered, and about 50% by weight.
  • exceeding% there exists a possibility that fluidity
  • the aromatic vinyl copolymer resin according to one embodiment of the present invention may be an aromatic vinyl copolymer resin used in a conventional rubber-modified vinyl copolymer resin.
  • the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
  • the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.
  • the aromatic vinyl monomers include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types.
  • the content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
  • the monomer copolymerizable with the aromatic vinyl monomer for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like.
  • Vinyl cyanide monomers; (Meth) acrylic acid, maleic anhydride, N-substituted maleimide, etc. can be used, and can be used individually or in mixture of 2 or more types.
  • the content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 wt% to about 80 wt%, for example, about 20 wt% to about 70 wt% of the total 100 wt% of the aromatic vinyl copolymer copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
  • the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) of about 50,000 to about 300,000 g / mol, for example, about 90,000 to about 150,000 g / mol, measured by gel permeation chromatography (GPC). Can be.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the aromatic vinyl copolymer resin may be included in about 50 to about 80% by weight, for example about 55 to about 75% by weight of 100% by weight of the total rubber-modified aromatic vinyl copolymer resin.
  • the aromatic vinyl copolymer resin is less than about 50% by weight in 100% by weight of the total rubber-modified aromatic vinyl copolymer resin, there is a fear that the fluidity, appearance characteristics, etc. of the thermoplastic resin composition may be lowered, and exceed about 80% by weight. If it does, there exists a possibility that impact resistance, light weight, etc. may fall.
  • the modified polyolefin of the present invention can be applied together with the hollow inorganic filler to improve impact resistance, light weight, flowability, and the like of the thermoplastic resin composition.
  • Cylyl modified ester group, arylate group, nitrile group, etc. For example, a modified polyolefin including a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2 may be used.
  • R 1 is a hydrogen atom or a methyl group
  • Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl modified ester group, an arylate group, or a nitrile group (-CN) .
  • the modified polyolefin may be prepared by polymerizing olefin and at least one compound of alkyl (meth) acrylate, ethylenically unsaturated group-containing modified ester, ethylenically unsaturated group-containing arylate and acrylonitrile.
  • polymerizing an olefin and alkyl (meth) acrylate can be applied.
  • the modified olefin is about 50 to about 95% by weight of the repeating unit represented by Formula 1, for example about 70 to about 93% by weight and about 5 to about 50% by weight of the repeating unit represented by Formula 2 For example, about 7 to about 30% by weight.
  • Impact resistance, fluidity (molding processability), compatibility of the thermoplastic resin composition in the above range may be excellent.
  • the modified polyolefin may be in the form of a copolymer of random, block, multiblock, or a combination thereof.
  • the modified polyolefin has a melt flow index of about 0.01 to about 40 g / 10 minutes, for example about 0.1 to about 10 g / 10 minutes, measured at 190 ° C., 2.16 kgf, according to ASTM D1238. Can be.
  • the modified polyolefin may be included in an amount of about 1 to about 5 parts by weight, for example about 2 to about 4 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin.
  • the content of the modified polyolefin is less than about 1 part by weight, the impact resistance and the like of the thermoplastic resin composition may be lowered.
  • the content of the modified polyolefin is greater than about 5 parts by weight, the lightweight, mechanical properties, etc. of the thermoplastic resin composition may be lowered. have.
  • the hollow inorganic filler according to one embodiment of the present invention is a hollow inorganic filler that is commonly used, and may be applied together with a modified polyolefin to improve impact resistance, light weight, flowability, and the like of the thermoplastic resin composition.
  • the hollow inorganic filler may be spherical hollow glass particles (glass bubble).
  • the glass constituting the hollow glass particles includes soda-lime borosilicate glass containing silicon dioxide (SiO 2 ), boron oxide (B 2 O 3 ), sodium oxide (Na 2 O), calcium oxide (CaO), and the like.
  • borosilicate glass may be used, and one or two or more glasses may be used.
  • the hollow inorganic filler may have a specific gravity of about 0.46 to about 0.6, a breaking strength of about 15,500 to about 30,000 psi, and a particle diameter of about 10 to about 60 ⁇ m.
  • the hollow inorganic filler may be a surface treated with a coupling agent or the like, but is not limited thereto.
  • the hollow inorganic filler may be included in an amount of about 5 to about 20 parts by weight, for example about 8 to about 15 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin.
  • the content of the hollow inorganic filler is less than about 5 parts by weight, there is a fear that the light weight and the like of the thermoplastic resin composition may be lowered.
  • the content of the hollow inorganic filler is greater than about 20 parts by weight, impact resistance, fluidity, and the like may be lowered.
  • the weight ratio (B) :( C) of the modified polyolefin (B) and the hollow inorganic filler (C) is about 0.1: 1 to about 0.5: 1, for example about 0.2: 1 to about 0.4 May be one.
  • the impact resistance, light weight, flowability, balance of physical properties of the thermoplastic resin composition, etc. may be more excellent.
  • the thermoplastic resin composition according to one embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition.
  • the additives include, but are not limited to, flame retardants, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like.
  • the content may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin.
  • thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets mixed with the components and melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 250 ° C, using a conventional twin screw extruder. Can be.
  • the thermoplastic resin composition has a notched Izod impact strength of at least about 12 kgf ⁇ cm / cm, for example about 13 to about 25 kgf ⁇ cm / cm, of a 1/8 ”thick specimen measured according to ASTM D256. Can be.
  • the thermoplastic resin composition has a melt flow index of about 1.5 to about 3.5 g / 10 minutes, for example about 1.8 to about 3.0 g / 10 minutes, measured at 200 ° C. and 5 kgf, based on ASTM D1238. Can be.
  • thermoplastic resin composition may have a specific gravity of about 1 or less, for example, about 0.92 to about 0.99, based on ASTM D792.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in impact resistance, fluidity, light weight, balance of physical properties, and the like, it is useful as an interior / exterior material of a lightweight electric / electronic product that can be mounted by a consumer.
  • 58-wt% butadiene rubber (average particle size: 310 nm) was used g-ABS graft copolymerized with 42 wt% styrene and acrylonitrile (weight ratio 75/25).
  • SAN resin (weight average molecular weight: 100,000 g / mol) polymerized with 71.5% by weight of styrene and 28.5% by weight of acrylonitrile was used.
  • hollow inorganic filler (C1) glass bubbles (manufacturer: 3M, product name: IM16K) were used.
  • thermoplastic resin composition of the present invention is all excellent in impact resistance, fluidity, light weight, and the like.
  • Comparative Example 1 in which a small amount of rubber-modified vinyl graft copolymer is applied, impact resistance, light weight, etc. are deteriorated
  • Comparative Example 2 in which an excessive amount of rubber-modified vinyl graft copolymer is applied, fluidity is increased. It can be seen that the deterioration and the like, in the case of Comparative Example 3 to which a small amount of the hollow inorganic filler is applied, the lightness and the like is deteriorated. It can be seen that, in the case of Comparative Examples 5 and 6 to which the impact modifiers (D1) and (D2) were applied instead of the modified polyolefin of the present invention, it can be seen that the impact resistance is lowered.

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  • Health & Medical Sciences (AREA)
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Abstract

A thermoplastic resin composition of the present invention is characterized by comprising: about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin including about 20 to about 50 wt% of a rubber-modified vinyl-based graft copolymer and about 50 to about 80 wt% of an aromatic vinyl-based copolymer resin; about 1 to about 5 parts by weight of a modified polyolefin including a repeating unit represented by chemical formula 1 and a repeating unit represented by chemical formula 2; and about 5 to about 20 parts by weight of a hollow inorganic filler. The thermoplastic resin composition is excellent in impact resistance, flowability, lightweightness, and the like.

Description

열가소성 수지 조성물 및 이로부터 형성된 성형품Thermoplastic resin composition and molded article formed therefrom
본 발명은 열가소성 수지 조성물 및 이로부터 형성된 성형품에 관한 것이다. 보다 구체적으로 본 발명은 내충격성, 유동성, 경량성 등이 우수한 열가소성 수지 조성물 및 이로부터 형성된 성형품에 관한 것이다.The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in impact resistance, flowability, light weight, and the like, and a molded article formed therefrom.
열가소성 수지로서, 아크릴로니트릴-부타디엔-스티렌 공중합체 수지(ABS 수지) 등의 고무변성 방향족 비닐계 공중합체 수지는 기계적 물성, 가공성, 외관 특성 등이 우수하여, 전기/전자 제품의 내/외장재, 자동차 내/외장재, 건축용 외장재 등으로 널리 사용되고 있다. 특히, 최근 전기/전자 제품의 경량화 추세에 따라, 열가소성 수지를 이용한 플라스틱 제품이 기존의 유리 및 금속의 영역을 빠르게 대체하고 있다.As the thermoplastic resin, rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) are excellent in mechanical properties, processability, appearance characteristics, etc. It is widely used as interior / exterior materials for automobiles and exterior materials for construction. In particular, with the recent trend of lightening electrical / electronic products, plastic products using thermoplastic resins are rapidly replacing the areas of glass and metal.
열가소성 수지 조성물의 추가적인 경량화를 위해서는 저비중의 필러(filler)를 적용하거나, 폴리프로필렌 등의 저비중 소재를 적용할 수 있으나, 이 경우, 내충격성, 기계적 물성, 가공성(유동성), 상용성 등의 물성 저하가 발생하거나 경량화가 충분하지 않다는 문제가 있다.In order to further reduce the weight of the thermoplastic resin composition, a filler of low specific gravity may be applied, or a low specific gravity material such as polypropylene may be applied. In this case, impact resistance, mechanical properties, processability (fluidity), compatibility, etc. There is a problem that property degradation occurs or the weight reduction is not sufficient.
따라서, 내충격성, 유동성, 경량성, 이들의 물성 발란스 등이 우수한 열가소성 수지 조성물의 개발이 필요한 실정이다.Therefore, there is a need for development of a thermoplastic resin composition having excellent impact resistance, flowability, light weight, balance of physical properties, and the like.
본 발명의 배경기술은 대한민국 공개특허 10-2016-0083518호 등에 개시되어 있다.Background art of the present invention is disclosed in the Republic of Korea Patent Publication No. 10-2016-0083518.
본 발명의 목적은 내충격성, 유동성, 경량성 등이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, flowability, light weight and the like.
본 발명의 다른 목적은 상기 열가소성 수지 조성물로부터 형성된 성형품을 제공하기 위한 것이다.Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
1. 본 발명의 하나의 관점은 열가소성 수지 조성물에 관한 것이다. 상기 열가소성 수지 조성물은 고무변성 비닐계 그라프트 공중합체 약 20 내지 약 50 중량% 및 방향족 비닐계 공중합체 수지 약 50 내지 약 80 중량%를 포함하는 고무변성 방향족 비닐계 공중합체 수지 약 100 중량부; 하기 화학식 1로 표시되는 반복단위 및 하기 화학식 2로 표시되는 반복단위를 포함하는 변성 폴리올레핀 약 1 내지 약 5 중량부; 및 중공 무기 필러 약 5 내지 약 20 중량부;를 포함한다:1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition may include about 100 parts by weight of a rubber modified aromatic vinyl copolymer resin including about 20 wt% to about 50 wt% of the rubber modified vinyl graft copolymer and about 50 wt% to about 80 wt% of the aromatic vinyl copolymer copolymer resin; About 1 to about 5 parts by weight of a modified polyolefin comprising a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 below; And about 5 to about 20 parts by weight of the hollow inorganic filler;
[화학식 1][Formula 1]
Figure PCTKR2019001698-appb-I000001
Figure PCTKR2019001698-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2019001698-appb-I000002
Figure PCTKR2019001698-appb-I000002
상기 화학식 2에서, R1은 수소 원자 또는 메틸기이고, Y는 -COOR2 (R2는 탄소수 1 내지 12의 알킬기), 글리시딜 변성 에스테르기, 아릴레이트기, 또는 니트릴기(-CN)이다.In Formula 2, R 1 is a hydrogen atom or a methyl group, Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl modified ester group, an arylate group, or a nitrile group (-CN) .
2. 상기 1 구체예에서, 상기 고무변성 비닐계 그라프트 공중합체는 고무질 중합체에 방향족 비닐계 단량체 및 시안화 비닐계 단량체를 포함하는 단량체 혼합물이 그라프트 중합된 것일 수 있다.2. In one embodiment, the rubber-modified vinyl graft copolymer may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.
3. 상기 1 또는 2 구체예에서, 상기 방향족 비닐계 공중합체 수지는 방향족 비닐계 단량체 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체의 중합체일 수 있다.3. In the above 1 or 2 embodiment, the aromatic vinyl copolymer resin may be a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
4. 상기 1 내지 3 구체예에서, 상기 변성 올레핀은 상기 화학식 1로 표시되는 반복단위 약 50 내지 약 95 중량% 및 상기 화학식 2로 표시되는 반복단위 약 5 내지 약 50 중량%를 포함할 수 있다.4. In the embodiments 1 to 3, the modified olefin may include about 50 to about 95 weight% of the repeating unit represented by Formula 1 and about 5 to about 50 weight% of the repeating unit represented by Formula 2 .
5. 상기 1 내지 4 구체예에서, 상기 중공 무기 필러는 구형의 중공 유리 입자일 수 있다.5. In the embodiments 1 to 4, the hollow inorganic filler may be spherical hollow glass particles.
6. 상기 1 내지 5 구체예에서, 상기 변성 폴리올레핀 및 상기 중공 무기 필러의 중량비는 약 0.1 : 1 내지 약 0.5 : 1일 수 있다.6. In the above 1 to 5 embodiments, the weight ratio of the modified polyolefin and the hollow inorganic filler may be about 0.1: 1 to about 0.5: 1.
7. 상기 1 내지 6 구체예에서, 상기 열가소성 수지 조성물은 ASTM D256에 의거하여 측정한 1/8" 두께 시편의 노치 아이조드 충격강도가 약 12 kgf·cm/cm 이상일 수 있다.7. In the above 1 to 6 embodiments, the thermoplastic resin composition may have a notched Izod impact strength of 1/8 "thick specimen measured in accordance with ASTM D256 of about 12 kgf · cm / cm or more.
8. 상기 1 내지 7 구체예에서, 상기 열가소성 수지 조성물은 ASTM D1238에 의거하여, 200℃, 5 kgf 조건에서 측정한 용융흐름지수가 약 1.5 내지 약 3.5 g/10분일 수 있다.8. In the above 1 to 7 embodiments, the thermoplastic resin composition may be about 1.5 to about 3.5 g / 10 minutes melt flow index measured at 200 ℃, 5 kgf conditions in accordance with ASTM D1238.
9. 상기 1 내지 8 구체예에서, 상기 열가소성 수지 조성물은 ASTM D792에 의거하여, 측정한 비중이 약 1 이하일 수 있다.9. In the above embodiments 1 to 8, the thermoplastic resin composition may have a specific gravity of about 1 or less, based on ASTM D792.
10. 본 발명의 다른 관점은 성형품에 관한 것이다. 상기 성형품은 상기 1 내지 9 중 어느 하나에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 한다.10. Another aspect of the present invention relates to a molded article. The molded article is formed from the thermoplastic resin composition according to any one of the above 1 to 9.
본 발명은 내충격성, 유동성, 경량성 등이 우수한 열가소성 수지 조성물 및 이로부터 형성된 성형품을 제공하는 발명의 효과를 갖는다.The present invention has the effect of the invention of providing a thermoplastic resin composition excellent in impact resistance, flowability, light weight and the like and a molded article formed therefrom.
이하, 본 발명을 상세히 설명하면, 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 열가소성 수지 조성물은 (A) 고무변성 방향족 비닐계 공중합체 수지; (B) 변성 폴리올레핀; 및 (C) 중공 무기 필러;를 포함한다.The thermoplastic resin composition according to the present invention is (A) rubber-modified aromatic vinyl copolymer resin; (B) modified polyolefins; And (C) a hollow inorganic filler.
본 명세서에서, 수치범위를 나타내는 "a 내지 b"는 "≥a 이고 ≤b"으로 정의한다.In the present specification, "a to b" indicating a numerical range is defined as "≥a and <b".
(A) 고무변성 방향족 비닐계 공중합체 수지(A) Rubber Modified Aromatic Vinyl Copolymer Resin
본 발명의 고무변성 방향족 비닐계 공중합체 수지는 (A1) 고무변성 비닐계 그라프트 공중합체 및 (A2) 방향족 비닐계 공중합체 수지를 포함할 수 있다.The rubber modified aromatic vinyl copolymer resin of the present invention may include (A1) rubber modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin.
(A1) 고무변성 비닐계 그라프트 공중합체(A1) rubber-modified vinyl-based graft copolymer
본 발명의 일 구체예에 따른 고무변성 비닐계 그라프트 공중합체는 고무질 중합체에 방향족 비닐계 단량체 및 시안화 비닐계 단량체를 포함하는 단량체 혼합물이 그라프트 중합된 것일 수 있다. 예를 들면, 상기 고무변성 비닐계 그라프트 공중합체는 고무질 중합체에 방향족 비닐계 단량체 및 시안화 비닐계 단량체를 포함하는 단량체 혼합물을 그라프트 중합하여 얻을 수 있으며, 필요에 따라, 상기 단량체 혼합물에 가공성 및 내열성을 부여하는 단량체를 더욱 포함시켜 그라프트 중합할 수 있다. 상기 중합은 유화중합, 현탁중합 등의 공지의 중합방법에 의하여 수행될 수 있다. 또한, 상기 고무변성 비닐계 그라프트 공중합체는 코어(고무질 중합체)-쉘(단량체 혼합물의 공중합체) 구조를 형성할 수 있으나, 이에 제한되지 않는다.Rubber-modified vinyl graft copolymer according to an embodiment of the present invention may be a graft polymerized monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in the rubber polymer. For example, the rubber-modified vinyl graft copolymer may be obtained by graft polymerization of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer, and, if necessary, processability and The monomer which gives heat resistance can be further included and graft-polymerized. The polymerization may be carried out by known polymerization methods such as emulsion polymerization and suspension polymerization. In addition, the rubber-modified vinyl graft copolymer may form a core (rubber polymer) -shell (copolymer of monomer mixture) structure, but is not limited thereto.
구체예에서, 상기 고무질 중합체로는 폴리부타디엔, 폴리(스티렌-부타디엔), 폴리(아크릴로니트릴-부타디엔) 등의 디엔계 고무 및 상기 디엔계 고무에 수소 첨가한 포화고무, 이소프렌고무, 탄소수 2 내지 10의 알킬 (메타)아크릴레이트 고무, 탄소수 2 내지 10의 알킬 (메타)아크릴레이트 및 스티렌의 공중합체, 에틸렌-프로필렌-디엔단량체 삼원공중합체(EPDM) 등을 예시할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 적용될 수 있다. 예를 들면, 디엔계 고무, (메타)아크릴레이트 고무 등을 사용할 수 있고, 구체적으로, 부타디엔계 고무, 부틸아크릴레이트 고무 등을 사용할 수 있다.In an embodiment, the rubbery polymer may be a diene rubber such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), or a saturated rubber hydrogenated to the diene rubber, isoprene rubber, C 2 to C 10 alkyl (meth) acrylate rubbers, copolymers of alkyl (meth) acrylates having 2 to 10 carbon atoms and styrene, ethylene-propylene-diene monomer terpolymers (EPDM), and the like. These can be applied individually or in mixture of 2 or more types. For example, a diene rubber, (meth) acrylate rubber, etc. can be used, Specifically, butadiene rubber, butyl acrylate rubber, etc. can be used.
구체예에서, 상기 고무질 중합체(고무 입자)는 입도분석기로 측정한 평균 입자 크기(D50)가 약 0.05 내지 약 6 ㎛, 예를 들면 약 0.15 내지 약 4 ㎛, 구체적으로 약 0.25 내지 약 3.5 ㎛일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 외관 특성 등이 우수할 수 있다. 여기서, 상기 고무질 중합체(고무 입자)의 평균 입자 크기(z-평균)는 라텍스(latex) 상태에서 광 산란(light scattering) 방법을 이용하여 측정할 수 있다. 구체적으로, 고무질 중합체 라텍스를 메쉬(mesh)에 걸러서, 고무질 중합체 중합 중발생하는 응고물 제거하고, 라텍스 0.5 g 및 증류수 30 ml를 혼합한 용액을 1,000 ml 플라스크에 따르고 증류수를 채워 시료를 제조한 다음, 시료 10 ml를 석영 셀(cell)로 옮기고, 이에 대하여, 광 산란 입도 측정기(malvern社, nano-zs)로 고무질 중합체의 평균 입자 크기를 측정할 수 있다.In embodiments, the rubbery polymer (rubber particles) has an average particle size (D50) measured by particle size analyzer of about 0.05 to about 6 μm, for example about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm Can be. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like. Here, the average particle size (z-average) of the rubbery polymer (rubber particles) may be measured using a light scattering method in a latex state. Specifically, the rubber polymer latex is filtered through a mesh to remove coagulum generated during the polymerization of the rubber polymer, and 0.5 g of latex and 30 ml of distilled water are poured into a 1,000 ml flask and filled with distilled water to prepare a sample. 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured by a light scattering particle size analyzer (nano-zs, Malvern).
구체예에서, 상기 고무질 중합체의 함량은 고무변성 비닐계 그라프트 공중합체 전체 100 중량% 중 약 20 내지 약 70 중량%, 예를 들면 약 25 내지 약 60 중량%일 수 있고, 상기 단량체 혼합물(방향족 비닐계 단량체 및 시안화 비닐계 단량체 포함)의 함량은 고무변성 비닐계 그라프트 공중합체 전체 100 중량% 중 약 30 내지 약 80 중량%, 예를 들면 약 40 내지 약 75 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 외관 특성 등이 우수할 수 있다.In embodiments, the content of the rubbery polymer may be about 20 to about 70% by weight, for example about 25 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, the monomer mixture (aromatic The vinyl monomer and the vinyl cyanide monomer) may be about 30 to about 80 wt%, for example about 40 to about 75 wt%, of 100 wt% of the total rubber-modified vinyl graft copolymer. In the above range, the thermoplastic resin composition may be excellent in impact resistance, appearance characteristics, and the like.
구체예에서, 상기 방향족 비닐계 단량체는 상기 고무질 중합체에 그라프트 공중합될 수 있는 것으로서, 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, p-t-부틸스티렌, 에틸스티렌, 비닐크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐나프탈렌 등을 예시할 수 있다. 이들은 단독으로 사용하거나, 2종 이상 혼합하여 사용할 수 있다. 상기 방향족 비닐계 단량체의 함량은 상기 단량체 혼합물 100 중량% 중 약 10 내지 약 90 중량%, 예를 들면 약 40 내지 약 90 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 가공성, 내충격성 등이 우수할 수 있다.In an embodiment, the aromatic vinyl monomer may be graft copolymerized to the rubbery polymer, styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, etc. can be illustrated. These may be used alone or in combination of two or more thereof. The aromatic vinyl monomer may be included in an amount of about 10 wt% to about 90 wt%, for example, about 40 wt% to about 90 wt% in 100 wt% of the monomer mixture. In the above range, the processability, impact resistance, and the like of the thermoplastic resin composition may be excellent.
구체예에서, 상기 시안화 비닐계 단량체는 상기 방향족 비닐계와 공중합 가능한 것으로서, 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴, 푸마로니트릴 등을 예시할 수 있다. 이들은 단독으로 사용하거나, 2종 이상 혼합하여 사용할 수 있다. 예를 들면, 아크릴로니트릴, 메타크릴로니트릴 등을 사용할 수 있다. 상기 시안화 비닐계 단량체의 함량은 상기 단량체 혼합물 100 중량% 중 약 10 내지 약 90 중량%, 예를 들면 약 10 내지 약 60 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내화학성, 기계적 특성 등이 우수할 수 있다.In one embodiment, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. It can be illustrated. These may be used alone or in combination of two or more thereof. For example, acrylonitrile, methacrylonitrile, etc. can be used. The content of the vinyl cyanide monomer may be about 10 wt% to about 90 wt%, for example about 10 wt% to about 60 wt%, in 100 wt% of the monomer mixture. In the above range, the thermoplastic resin composition may have excellent chemical resistance, mechanical properties, and the like.
구체예에서, 상기 가공성 및 내열성을 부여하기 위한 단량체로는 (메타)아크릴산, 무수말레인산, N-치환말레이미드 등을 예시할 수 있으나, 이에 한정되지 않는다. 상기 가공성 및 내열성을 부여하기 위한 단량체 사용 시, 그 함량은 상기 단량체 혼합물 100 중량% 중 15 중량% 이하, 예를 들면 0.1 내지 10 중량%일 수 있다. 상기 범위에서 다른 물성의 저하 없이, 열가소성 수지 조성물에 가공성 및 내열성을 부여할 수 있다.In a specific example, monomers for imparting processability and heat resistance may include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide, and the like. When using the monomer for imparting the processability and heat resistance, the content may be 15% by weight or less, for example 0.1 to 10% by weight of 100% by weight of the monomer mixture. In the above range, processability and heat resistance can be imparted to the thermoplastic resin composition without deteriorating other physical properties.
구체예에서, 상기 고무변성 비닐계 그라프트 공중합체로는 부타디엔계 고무질 중합체에 방향족 비닐계 화합물인 스티렌 단량체와 시안화 비닐계 화합물인 아크릴로니트릴 단량체가 그라프트된 공중합체(g-ABS), 부틸 아크릴레이트계 고무질 중합체에 방향족 비닐계 화합물인 스티렌 단량체와 시안화 비닐계 화합물인 아크릴로니트릴 단량체가 그라프트된 공중합체인 아크릴레이트-스티렌-아크릴로니트릴 그라프트 공중합체(g-ASA) 등을 예시할 수 있다.In one embodiment, the rubber-modified vinyl graft copolymer is a copolymer in which a styrene monomer, which is an aromatic vinyl compound, and an acrylonitrile monomer, which is a vinyl cyanide compound, are grafted to a butadiene rubber polymer, and butyl acryl. An acrylate-styrene-acrylonitrile graft copolymer (g-ASA) which is a copolymer in which the styrene monomer which is an aromatic vinyl type compound, and the acrylonitrile monomer which is a vinyl cyanide compound is grafted to a latex rubbery polymer can be illustrated. have.
구체예에서, 상기 고무변성 비닐계 그라프트 공중합체는 전체 고무변성 방향족 비닐계 공중합체 수지(고무변성 비닐계 그라프트 공중합체 및 방향족 비닐계 공중합체 수지) 100 중량% 중 약 20 내지 약 50 중량%, 예를 들면 약 25 내지 약 45 중량%로 포함될 수 있다. 상기 고무변성 비닐계 그라프트 공중합체가 전체 고무변성 방향족 비닐계 공중합체 수지 100 중량% 중 약 20 중량% 미만일 경우, 열가소성 수지 조성물의 내충격성, 경량성 등이 저하될 우려가 있고, 약 50 중량%를 초과할 경우, 유동성, 외관 특성 등이 저하될 우려가 있다.In embodiments, the rubber-modified vinyl graft copolymer is about 20 to about 50 weight in 100% by weight of the total rubber-modified aromatic vinyl copolymer resin (rubber modified vinyl graft copolymer and aromatic vinyl copolymer resin) %, For example from about 25 to about 45% by weight. When the rubber-modified vinyl graft copolymer is less than about 20% by weight in 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin, impact resistance, light weight, etc. of the thermoplastic resin composition may be lowered, and about 50% by weight. When exceeding%, there exists a possibility that fluidity | liquidity, an external appearance characteristic, etc. may fall.
(A2) 방향족 비닐계 공중합체 수지(A2) aromatic vinyl copolymer resin
본 발명의 일 구체예에 따른 방향족 비닐계 공중합체 수지는 통상적인 고무변성 비닐계 공중합체 수지에 사용되는 방향족 비닐계 공중합체 수지일 수 있다. 예를 들면, 상기 방향족 비닐계 공중합체 수지는 방향족 비닐계 단량체 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체를 포함하는 단량체 혼합물의 중합체일 수 있다.The aromatic vinyl copolymer resin according to one embodiment of the present invention may be an aromatic vinyl copolymer resin used in a conventional rubber-modified vinyl copolymer resin. For example, the aromatic vinyl copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
구체예에서, 상기 방향족 비닐계 공중합체 수지는 방향족 비닐계 단량체 및 방향족 비닐계 단량체와 공중합 가능한 단량체 등을 혼합한 후, 이를 중합하여 얻을 수 있으며, 상기 중합은 유화중합, 현탁중합, 괴상중합 등의 공지의 중합방법에 의하여 수행될 수 있다.In an embodiment, the aromatic vinyl copolymer resin may be obtained by mixing an aromatic vinyl monomer and a monomer copolymerizable with an aromatic vinyl monomer, and then polymerizing them, and the polymerization may be emulsion polymerization, suspension polymerization, bulk polymerization, or the like. It can be carried out by a known polymerization method of.
구체예에서, 상기 방향족 비닐계 단량체로는 스티렌, α-메틸스티렌, β-메틸스티렌, p-메틸스티렌, p-t-부틸스티렌, 에틸스티렌, 비닐크실렌, 모노클로로스티렌, 디클로로스티렌, 디브로모스티렌, 비닐나프탈렌 등을 사용할 수 있다. 이들은 단독 또는 2종 이상 혼합하여 적용될 수 있다. 상기 방향족 비닐계 단량체의 함량은 방향족 비닐계 공중합체 수지 전체 100 중량% 중, 약 20 내지 약 90 중량%, 예를 들면 약 30 내지 약 80 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 유동성 등이 우수할 수 있다.In embodiments, the aromatic vinyl monomers include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, pt-butylstyrene, ethyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinylnaphthalene and the like can be used. These can be applied individually or in mixture of 2 or more types. The content of the aromatic vinyl monomer may be about 20 to about 90 wt%, for example about 30 to about 80 wt%, of 100 wt% of the total aromatic vinyl copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
구체예에서, 상기 방향족 비닐계 단량체와 공중합 가능한 단량체로는 예를 들면, 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴, 페닐아크릴로니트릴, α-클로로아크릴로니트릴, 푸마로니트릴 등의 시안화 비닐계 단량체; (메타)아크릴산, 무수말레인산, N-치환말레이미드 등을 사용할 수 있으며, 단독 또는 2종 이상 혼합하여 사용할 수 있다. 상기 방향족 비닐계 단량체와 공중합 가능한 단량체의 함량은 방향족 비닐계 공중합체 수지 전체 100 중량% 중, 약 10 내지 약 80 중량%, 예를 들면 약 20 내지 약 70 중량%일 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 유동성 등이 우수할 수 있다.In a specific embodiment, as the monomer copolymerizable with the aromatic vinyl monomer, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. Vinyl cyanide monomers; (Meth) acrylic acid, maleic anhydride, N-substituted maleimide, etc. can be used, and can be used individually or in mixture of 2 or more types. The content of the monomer copolymerizable with the aromatic vinyl monomer may be about 10 wt% to about 80 wt%, for example, about 20 wt% to about 70 wt% of the total 100 wt% of the aromatic vinyl copolymer copolymer resin. In the above range, the impact resistance, fluidity, and the like of the thermoplastic resin composition may be excellent.
구체예에서, 상기 방향족 비닐계 공중합체 수지는 GPC(gel permeation chromatography)로 측정한 중량평균분자량(Mw)이 약 50,000 내지 약 300,000 g/mol, 예를 들면, 약 90,000 내지 약 150,000 g/mol일 수 있다. 상기 범위에서 열가소성 수지 조성물의 기계적 강도, 성형성 등이 우수할 수 있다.In embodiments, the aromatic vinyl copolymer resin has a weight average molecular weight (Mw) of about 50,000 to about 300,000 g / mol, for example, about 90,000 to about 150,000 g / mol, measured by gel permeation chromatography (GPC). Can be. In the above range, the mechanical strength, moldability, and the like of the thermoplastic resin composition may be excellent.
구체예에서, 상기 방향족 비닐계 공중합체 수지는 전체 고무변성 방향족 비닐계 공중합체 수지 100 중량% 중, 약 50 내지 약 80 중량%, 예를 들면 약 55 내지 약 75 중량%로 포함될 수 있다. 상기 방향족 비닐계 공중합체 수지가 전체 고무변성 방향족 비닐계 공중합체 수지 100 중량% 중 약 50 중량% 미만일 경우, 열가소성 수지 조성물의 유동성, 외관 특성 등이 저하될 우려가 있고, 약 80 중량%를 초과할 경우, 내충격성, 경량성 등이 저하될 우려가 있다.In embodiments, the aromatic vinyl copolymer resin may be included in about 50 to about 80% by weight, for example about 55 to about 75% by weight of 100% by weight of the total rubber-modified aromatic vinyl copolymer resin. When the aromatic vinyl copolymer resin is less than about 50% by weight in 100% by weight of the total rubber-modified aromatic vinyl copolymer resin, there is a fear that the fluidity, appearance characteristics, etc. of the thermoplastic resin composition may be lowered, and exceed about 80% by weight. If it does, there exists a possibility that impact resistance, light weight, etc. may fall.
(B) 변성 폴리올레핀(B) modified polyolefin
본 발명의 변성 폴리올레핀은 중공 무기 필러와 함께 적용되어 열가소성 수지 조성물의 내충격성, 경량성, 유동성 등을 향상시킬 수 있는 것으로서, 폴리올레핀을 주쇄로 하고 그라프트 형태로 작용기(알킬 카르복실레이트기, 글리시딜 변성 에스테르기, 아릴레이트기, 니트릴기 등)를 포함하는 구조를 가질 수 있다. 예를 들면, 하기 화학식 1로 표시되는 반복단위 및 하기 화학식 2로 표시되는 반복단위를 포함하는 변성 폴리올레핀을 사용할 수 있다.The modified polyolefin of the present invention can be applied together with the hollow inorganic filler to improve impact resistance, light weight, flowability, and the like of the thermoplastic resin composition. Cylyl modified ester group, arylate group, nitrile group, etc.). For example, a modified polyolefin including a repeating unit represented by the following Chemical Formula 1 and a repeating unit represented by the following Chemical Formula 2 may be used.
[화학식 1][Formula 1]
Figure PCTKR2019001698-appb-I000003
Figure PCTKR2019001698-appb-I000003
[화학식 2][Formula 2]
Figure PCTKR2019001698-appb-I000004
Figure PCTKR2019001698-appb-I000004
상기 화학식 2에서, R1은 수소 원자 또는 메틸기이고, Y는 -COOR2 (R2는 탄소수 1 내지 12의 알킬기), 글리시딜 변성 에스테르기, 아릴레이트기, 또는 니트릴기(-CN)이다.In Formula 2, R 1 is a hydrogen atom or a methyl group, Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl modified ester group, an arylate group, or a nitrile group (-CN) .
구체예에서, 상기 변성 폴리올레핀은 올레핀과 알킬(메타)아크릴레이트, 에틸렌성 불포화기 함유 변성에스테르, 에틸렌성 불포화기 함유 아릴레이트 및 아크릴로니트릴 중 1종 이상의 화합물을 중합하여 제조할 수 있다. 예를 들면, 올레핀과 알킬(메타)아크릴레이트를 중합하여 제조한 변성 폴리올레핀을 적용할 수 있다.In embodiments, the modified polyolefin may be prepared by polymerizing olefin and at least one compound of alkyl (meth) acrylate, ethylenically unsaturated group-containing modified ester, ethylenically unsaturated group-containing arylate and acrylonitrile. For example, the modified polyolefin manufactured by superposing | polymerizing an olefin and alkyl (meth) acrylate can be applied.
구체예에서, 상기 변성 올레핀은 상기 화학식 1로 표시되는 반복단위 약 50 내지 약 95 중량%, 예를 들면 약 70 내지 약 93 중량% 및 상기 화학식 2로 표시되는 반복단위 약 5 내지 약 50 중량%, 예를 들면 약 7 내지 약 30 중량%를 포함할 수 있다. 상기 범위에서 열가소성 수지 조성물의 내충격성, 유동성(성형 가공성), 상용성 등이 우수할 수 있다.In embodiments, the modified olefin is about 50 to about 95% by weight of the repeating unit represented by Formula 1, for example about 70 to about 93% by weight and about 5 to about 50% by weight of the repeating unit represented by Formula 2 For example, about 7 to about 30% by weight. Impact resistance, fluidity (molding processability), compatibility of the thermoplastic resin composition in the above range may be excellent.
구체예에서, 상기 변성 폴리올레핀은 랜덤, 블록, 멀티블록의 공중합체 형태일 수 있으며, 이들의 조합 형태로도 사용될 수 있다.In an embodiment, the modified polyolefin may be in the form of a copolymer of random, block, multiblock, or a combination thereof.
구체예에서, 상기 변성 폴리올레핀은 ASTM D1238에 의거하여, 190℃, 2.16 kgf 조건에서 측정한 용융흐름지수가 약 0.01 내지 약 40 g/10분, 예를 들면, 약 0.1 내지 약 10 g/10분일 수 있다.In embodiments, the modified polyolefin has a melt flow index of about 0.01 to about 40 g / 10 minutes, for example about 0.1 to about 10 g / 10 minutes, measured at 190 ° C., 2.16 kgf, according to ASTM D1238. Can be.
구체예에서, 상기 변성 폴리올레핀은 상기 고무변성 방향족 비닐계 공중합체 수지 약 100 중량부에 대하여, 약 1 내지 약 5 중량부, 예를 들면 약 2 내지 약 4 중량부로 포함될 수 있다. 상기 변성 폴리올레핀의 함량이 약 1 중량부 미만일 경우, 열가소성 수지 조성물의 내충격성 등이 저하될 우려가 있고, 약 5 중량부를 초과할 경우, 열가소성 수지 조성물의 경량성, 기계적 물성 등이 저하될 우려가 있다.In embodiments, the modified polyolefin may be included in an amount of about 1 to about 5 parts by weight, for example about 2 to about 4 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. When the content of the modified polyolefin is less than about 1 part by weight, the impact resistance and the like of the thermoplastic resin composition may be lowered. When the content of the modified polyolefin is greater than about 5 parts by weight, the lightweight, mechanical properties, etc. of the thermoplastic resin composition may be lowered. have.
(C) 중공 무기 필러(C) hollow inorganic filler
본 발명의 일 구체예 따른 중공 무기 필러는 통상적으로 사용되는 중공 무기 필러로서, 변성 폴리올레핀과 함께 적용되어 열가소성 수지 조성물의 내충격성, 경량성, 유동성 등을 향상시킬 수 있는 것이다.The hollow inorganic filler according to one embodiment of the present invention is a hollow inorganic filler that is commonly used, and may be applied together with a modified polyolefin to improve impact resistance, light weight, flowability, and the like of the thermoplastic resin composition.
구체예에서, 상기 중공 무기 필러는 구형의 중공 유리 입자(글라스 버블(glass bubble))일 수 있다. 중공 유리 입자를 구성하는 유리로는 이산화규소(SiO2), 산화붕소(B2O3), 산화 나트륨(Na2O), 산화칼슘(CaO) 등을 포함하는 소다석회 붕규산 유리(soda-lime borosilicate glass)가 사용될 수 있으며, 1종 또는 2종 이상의 유리가 사용될 수 있다.In embodiments, the hollow inorganic filler may be spherical hollow glass particles (glass bubble). The glass constituting the hollow glass particles includes soda-lime borosilicate glass containing silicon dioxide (SiO 2 ), boron oxide (B 2 O 3 ), sodium oxide (Na 2 O), calcium oxide (CaO), and the like. borosilicate glass) may be used, and one or two or more glasses may be used.
구체예에서, 상기 중공 무기 필러는 비중이 약 0.46 내지 약 0.6일 수 있고, 파쇄 강도가 약 15,500 내지 약 30,000 psi일 수 있으며, 입자 직경이 약 10 내지 약 60 ㎛일 수 있다. 또한, 상기 중공 무기 필러로는 커플링제 등으로 표면 처리된 것을 사용 할 수 있으나, 이에 한정되지는 않는다.In embodiments, the hollow inorganic filler may have a specific gravity of about 0.46 to about 0.6, a breaking strength of about 15,500 to about 30,000 psi, and a particle diameter of about 10 to about 60 μm. In addition, the hollow inorganic filler may be a surface treated with a coupling agent or the like, but is not limited thereto.
구체예에서, 상기 중공 무기 필러는 상기 고무변성 방향족 비닐계 공중합체 수지 약 100 중량부에 대하여, 약 5 내지 약 20 중량부, 예를 들면 약 8 내지 약 15 중량부로 포함될 수 있다. 상기 중공 무기 필러의 함량이 약 5 중량부 미만일 경우, 열가소성 수지 조성물의 경량성 등이 저하될 우려가 있고, 약 20 중량부를 초과할 경우, 내충격성, 유동성 등이 저하될 우려가 있다.In an embodiment, the hollow inorganic filler may be included in an amount of about 5 to about 20 parts by weight, for example about 8 to about 15 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl copolymer resin. When the content of the hollow inorganic filler is less than about 5 parts by weight, there is a fear that the light weight and the like of the thermoplastic resin composition may be lowered. When the content of the hollow inorganic filler is greater than about 20 parts by weight, impact resistance, fluidity, and the like may be lowered.
구체예에서, 상기 변성 폴리올레핀(B) 및 상기 중공 무기 필러(C)의 중량비((B):(C))는 약 0.1 : 1 내지 약 0.5 : 1, 예를 들면 약 0.2 : 1 내지 약 0.4 : 1일 수 있다. 상기 범위에서, 열가소성 수지 조성물의 내충격성, 경량성, 유동성, 이들의 물성 발란스 등이 더 우수할 수 있다.In an embodiment, the weight ratio (B) :( C) of the modified polyolefin (B) and the hollow inorganic filler (C) is about 0.1: 1 to about 0.5: 1, for example about 0.2: 1 to about 0.4 May be one. In the above range, the impact resistance, light weight, flowability, balance of physical properties of the thermoplastic resin composition, etc. may be more excellent.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 통상의 열가소성 수지 조성물에 포함되는 첨가제를 더욱 포함할 수 있다. 상기 첨가제로는 난연제, 산화 방지제, 적하 방지제, 활제, 이형제, 핵제, 안정제, 안료, 염료, 이들의 혼합물 등을 예시할 수 있으나, 이에 제한되지 않는다. 상기 첨가제 사용 시, 그 함량은 열가소성 수지 약 100 중량부에 대하여, 약 0.001 내지 약 40 중량부, 예를 들면 약 0.1 내지 약 10 중량부일 수 있다.The thermoplastic resin composition according to one embodiment of the present invention may further include an additive included in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, flame retardants, antioxidants, anti drip agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like. When using the additive, the content may be about 0.001 to about 40 parts by weight, for example about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the thermoplastic resin.
본 발명의 일 구체예에 따른 열가소성 수지 조성물은 상기 구성 성분을 혼합하고, 통상의 이축 압출기를 사용하여, 약 200 내지 약 280℃, 예를 들면 약 220 내지 약 250℃에서 용융 압출한 펠렛 형태일 수 있다.The thermoplastic resin composition according to an embodiment of the present invention may be in the form of pellets mixed with the components and melt-extruded at about 200 to about 280 ° C, for example, about 220 to about 250 ° C, using a conventional twin screw extruder. Can be.
구체예에서, 상기 열가소성 수지 조성물은 ASTM D256에 의거하여 측정한 1/8" 두께 시편의 노치 아이조드 충격강도가 약 12 kgf·cm/cm 이상, 예를 들면 약 13 내지 약 25 kgf·cm/cm일 수 있다.In embodiments, the thermoplastic resin composition has a notched Izod impact strength of at least about 12 kgf · cm / cm, for example about 13 to about 25 kgf · cm / cm, of a 1/8 ”thick specimen measured according to ASTM D256. Can be.
구체예에서, 상기 열가소성 수지 조성물은 ASTM D1238에 의거하여, 200℃, 5 kgf 조건에서 측정한 용융흐름지수가 약 1.5 내지 약 3.5 g/10분, 예를 들면 약 1.8 내지 약 3.0 g/10분 일 수 있다.In an embodiment, the thermoplastic resin composition has a melt flow index of about 1.5 to about 3.5 g / 10 minutes, for example about 1.8 to about 3.0 g / 10 minutes, measured at 200 ° C. and 5 kgf, based on ASTM D1238. Can be.
구체예에서, 상기 열가소성 수지 조성물은 ASTM D792에 의거하여, 측정한 비중이 약 1 이하, 예를 들면 약 0.92 내지 약 0.99일 수 있다.In an embodiment, the thermoplastic resin composition may have a specific gravity of about 1 or less, for example, about 0.92 to about 0.99, based on ASTM D792.
본 발명에 따른 성형품은 상기 열가소성 수지 조성물로부터 형성된다. 상기 열가소성 수지 조성물은 펠렛 형태로 제조될 수 있으며, 제조된 펠렛은 사출성형, 압출성형, 진공성형, 캐스팅성형 등의 다양한 성형방법을 통해 다양한 성형품(제품)으로 제조될 수 있다. 이러한 성형방법은 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 잘 알려져 있다. 상기 성형품은 내충격성, 유동성, 경량성, 이들의 물성 발란스 등이 우수하므로, 소비자가 장착 가능한 경량 전기/전자 제품의 내/외장재 등으로 유용하다.The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be prepared in a pellet form, and the prepared pellet may be manufactured into various molded products (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known by those skilled in the art. Since the molded article is excellent in impact resistance, fluidity, light weight, balance of physical properties, and the like, it is useful as an interior / exterior material of a lightweight electric / electronic product that can be mounted by a consumer.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로, 본 발명을 제한하는 것으로 해석되어서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예Example
이하, 실시예 및 비교예에서 사용된 각 성분의 사양은 다음과 같다.Hereinafter, the specification of each component used in the Example and the comparative example is as follows.
(A) 고무변성 방향족 비닐계 공중합체 수지(A) Rubber Modified Aromatic Vinyl Copolymer Resin
하기 (A1) 고무변성 비닐계 그라프트 공중합체 및 (A2) 방향족 비닐계 공중합체 수지를 혼합하여 사용하였다.The following (A1) rubber modified vinyl graft copolymer and (A2) aromatic vinyl copolymer resin were mixed and used.
(A1) 고무변성 비닐계 그라프트 공중합체(A1) rubber-modified vinyl-based graft copolymer
58 중량%의 부타디엔 고무(평균 입자 크기: 310 nm)에 42 중량%의 스티렌 및 아크릴로니트릴(중량비: 75/25)가 그라프트 공중합된 g-ABS를 사용하였다.58-wt% butadiene rubber (average particle size: 310 nm) was used g-ABS graft copolymerized with 42 wt% styrene and acrylonitrile (weight ratio 75/25).
(A2) 방향족 비닐계 공중합체 수지(A2) aromatic vinyl copolymer resin
스티렌 71.5 중량% 및 아크릴로니트릴 28.5 중량%가 중합된 SAN 수지(중량평균분자량: 100,000 g/mol)를 사용하였다.SAN resin (weight average molecular weight: 100,000 g / mol) polymerized with 71.5% by weight of styrene and 28.5% by weight of acrylonitrile was used.
(B) 변성 폴리올레핀(B) modified polyolefin
(B1) 에틸렌/메틸아크릴레이트 공중합체(제조사: Dupont, 제품명: Elvaloy AC1330)를 사용하였다.(B1) Ethylene / methylacrylate copolymer (manufacturer: Dupont, product name: Elvaloy AC1330) was used.
(B2) 무수말레산 변성 폴리올레핀(MAH-grafted Ethylene-1-butene copolymer, 제조사: Mitsui chemical, 제품명: Tafmer MH7020)을 사용하였다.(B2) maleic anhydride-modified polyolefin (MAH-grafted Ethylene-1-butene copolymer, manufactured by Mitsui chemical, product name: Tafmer MH7020) was used.
(C) 무기 필러(C) weapon filler
(C1) 중공 무기 필러로서, 글라스 버블(제조사: 3M, 제품명: IM16K)을 사용하였다.As the hollow inorganic filler (C1), glass bubbles (manufacturer: 3M, product name: IM16K) were used.
(C2) 유리 섬유(제조사: NEG, 제품명: T351/R)를 사용하였다.(C2) Glass fiber (manufacturer: NEG, product name: T351 / R) was used.
(D) 충격보강제(D) impact modifier
(D1) 실리콘 함유 공중합체 코어-쉘 구조의 공중합체(제조사: Kaneka, 제품명: M-210)를 사용하였다.(D1) Silicone-containing copolymer A copolymer having a core-shell structure (manufacturer: Kaneka, product name: M-210) was used.
(D2) 아크릴레이트계 공중합체 코어-쉘 구조의 공중합체(제조사: MRC, 제품명: Metablen S-RK-200)를 사용하였다.(D2) Acrylate copolymer A copolymer having a core-shell structure (manufacturer: MRC, product name: Metablen S-RK-200) was used.
실시예Example 1 내지 4 및  1 to 4 and 비교예Comparative example 1 내지 8 1 to 8
상기 각 구성 성분을 하기 표 1 및 2에 기재된 바와 같은 함량으로 첨가한 후, 230℃에서 압출하여 펠렛을 제조하였다. 압출은 L/D=36, 직경 45 mm인 이축 압출기를 사용하였으며, 제조된 펠렛은 80℃에서 2시간 이상 건조 후, 6 Oz 사출기(성형 온도 230℃, 금형 온도: 60℃)에서 사출하여 시편을 제조하였다. 제조된 시편에 대하여 하기의 방법으로 물성을 평가하고, 그 결과를 하기 표 1 및 2에 나타내었다.Each of the components was added in an amount as described in Tables 1 and 2, followed by extrusion at 230 ° C. to prepare pellets. Extrusion was performed using a twin screw extruder having a diameter of L / D = 36 and 45 mm, and the prepared pellets were dried at 80 ° C. for at least 2 hours, and then injected into a specimen at a 6 Oz injection machine (molding temperature 230 ° C., mold temperature: 60 ° C.). Was prepared. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1 and 2 below.
물성 측정 방법Property measurement method
(1) 내충격성 평가: ASTM D256에 의거하여, 1/8" 두께 시편의 노치 아이조드 충격 강도(단위: kgf·cm/cm)를 측정하였다.(1) Impact Resistance Evaluation: According to ASTM D256, the notched Izod impact strength (unit: kgf · cm / cm) of the 1/8 ”thick specimen was measured.
(2) 유동성 평가: ASTM D1238에 의거하여, 200℃, 5 kgf 조건에서 용융흐름지수(MI, 단위: g/10분)를 측정하였다.(2) Flowability evaluation: According to ASTM D1238, the melt flow index (MI, unit: g / 10 min) was measured at 200 ° C and 5 kgf conditions.
(3) 비중: ASTM D792에 의거하여, 비중을 측정하였다.(3) Specific gravity: Specific gravity was measured according to ASTM D792.
실시예Example
1One 22 33 44
(A)(중량%)(A) (% by weight) (A1)(A1) 4040 4040 4040 4040
(A2)(A2) 6060 6060 6060 6060
(B1) (중량부)(B1) (parts by weight) 22 44 33 33
(B2) (중량부)(B2) (parts by weight) -- -- -- --
(C1) (중량부)(C1) (parts by weight) 1010 1010 88 1515
(C2) (중량부)(C2) (parts by weight) -- -- -- --
(D1) (중량부)(D1) (parts by weight) -- -- -- --
(D2) (중량부)(D2) (parts by weight) -- -- -- --
노치 아이조드 충격강도Notch Izod Impact Strength 14.614.6 18.718.7 21.121.1 13.113.1
유동흐름지수Flow Flow Index 1.81.8 2.02.0 2.82.8 1.81.8
비중importance 0.950.95 0.940.94 0.970.97 0.920.92
* 중량부: 기초 수지 (A) 100 중량부에 대한 중량부* Parts by weight: parts by weight based on 100 parts by weight of the base resin (A)
비교예Comparative example
1One 22 33 44 55 66 77 88
(A)(중량%)(A) (% by weight) (A1)(A1) 1515 6060 4040 4040 4040 4040 4040 4040
(A2)(A2) 8585 4040 6060 6060 6060 6060 6060 6060
(B1) (중량부)(B1) (parts by weight) 33 33 33 33 -- -- -- 33
(B2) (중량부)(B2) (parts by weight) -- -- -- -- -- -- 33 --
(C1) (중량부)(C1) (parts by weight) 1010 1010 44 2121 1010 1010 1010 --
(C2) (중량부)(C2) (parts by weight) -- -- -- -- -- -- -- 1010
(D1) (중량부)(D1) (parts by weight) -- -- -- -- 33 -- --
(D2) (중량부)(D2) (parts by weight) -- -- -- -- 33 -- --
노치 아이조드 충격강도Notch Izod Impact Strength 8.28.2 26.126.1 24.724.7 10.810.8 11.811.8 11.411.4 11.311.3 6.56.5
유동흐름지수Flow Flow Index 3.23.2 0.80.8 3.33.3 0.70.7 2.02.0 1.91.9 2.32.3 1.21.2
비중importance 0.980.98 0.920.92 1.001.00 0.900.90 0.940.94 0.940.94 0.950.95 1.131.13
* 중량부: 기초 수지 (A) 100 중량부에 대한 중량부* Parts by weight: parts by weight based on 100 parts by weight of the base resin (A)
상기 결과로부터, 본 발명의 열가소성 수지 조성물은 내충격성, 유동성, 경량성 등이 모두 우수함을 알 수 있다.From the above results, it can be seen that the thermoplastic resin composition of the present invention is all excellent in impact resistance, fluidity, light weight, and the like.
반면, 고무변성 비닐계 그라프트 공중합체를 소량 적용한 비교예 1의 경우, 내충격성, 경량성 등이 저하됨을 알 수 있고, 고무변성 비닐계 그라프트 공중합체를 과량 적용한 비교예 2의 경우, 유동성 등이 저하됨을 알 수 있으며, 중공 무기 필러를 소량 적용한 비교예 3의 경우, 경량성 등이 저하됨을 알 수 있고, 중공 무기 필러를 과량 적용한 비교예 4의 경우, 내충격성, 유동성 등이 저하됨을 알 수 있으며, 본 발명의 변성 폴리올레핀 대신에 충격 보강제 (D1) 및 (D2)를 적용한 비교예 5 및 6의 경우, 내충격성이 저하됨을 알 수 있다. 또한, 본 발명의 변성 폴리올레핀 대신에 무수말레산 변성 폴리올레핀을 적용한 비교예 7의 경우, 내충격성이 저하됨을 알 수 있고, 중공 무기 필러 대신에 유리 섬유를 적용한 비교예 8의 경우, 경량성, 내충격성, 유동성 등이 저하됨을 알 수 있다.On the other hand, in Comparative Example 1 in which a small amount of rubber-modified vinyl graft copolymer is applied, impact resistance, light weight, etc. are deteriorated, and in Comparative Example 2 in which an excessive amount of rubber-modified vinyl graft copolymer is applied, fluidity is increased. It can be seen that the deterioration and the like, in the case of Comparative Example 3 to which a small amount of the hollow inorganic filler is applied, the lightness and the like is deteriorated. It can be seen that, in the case of Comparative Examples 5 and 6 to which the impact modifiers (D1) and (D2) were applied instead of the modified polyolefin of the present invention, it can be seen that the impact resistance is lowered. In addition, in the case of Comparative Example 7 in which maleic anhydride-modified polyolefin was applied instead of the modified polyolefin of the present invention, impact resistance was lowered. In the case of Comparative Example 8 in which glass fiber was applied instead of hollow inorganic filler, It can be seen that impact, fluidity and the like are deteriorated.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (10)

  1. 고무변성 비닐계 그라프트 공중합체 약 20 내지 약 50 중량% 및 방향족 비닐계 공중합체 수지 약 50 내지 약 80 중량%를 포함하는 고무변성 방향족 비닐계 공중합체 수지 약 100 중량부;About 100 parts by weight of a rubber modified aromatic vinyl copolymer resin comprising about 20 to about 50 wt% of the rubber modified vinyl graft copolymer and about 50 to about 80 wt% of the aromatic vinyl copolymer resin;
    하기 화학식 1로 표시되는 반복단위 및 하기 화학식 2로 표시되는 반복단위를 포함하는 변성 폴리올레핀 약 1 내지 약 5 중량부; 및About 1 to about 5 parts by weight of a modified polyolefin comprising a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2 below; And
    중공 무기 필러 약 5 내지 약 20 중량부;를 포함하는 것을 특징으로 하는 열가소성 수지 조성물:About 5 to about 20 parts by weight of the hollow inorganic filler; thermoplastic resin composition comprising:
    [화학식 1][Formula 1]
    Figure PCTKR2019001698-appb-I000005
    Figure PCTKR2019001698-appb-I000005
    [화학식 2][Formula 2]
    Figure PCTKR2019001698-appb-I000006
    Figure PCTKR2019001698-appb-I000006
    상기 화학식 2에서, R1은 수소 원자 또는 메틸기이고, Y는 -COOR2 (R2는 탄소수 1 내지 12의 알킬기), 글리시딜 변성 에스테르기, 아릴레이트기, 또는 니트릴기(-CN)이다.In Formula 2, R 1 is a hydrogen atom or a methyl group, Y is -COOR 2 (R 2 is an alkyl group having 1 to 12 carbon atoms), a glycidyl modified ester group, an arylate group, or a nitrile group (-CN) .
  2. 제1항에 있어서, 상기 고무변성 비닐계 그라프트 공중합체는 고무질 중합체에 방향족 비닐계 단량체 및 시안화 비닐계 단량체를 포함하는 단량체 혼합물이 그라프트 중합된 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the rubber-modified vinyl graft copolymer is a graft polymerized monomer mixture including an aromatic vinyl monomer and a vinyl cyanide monomer in a rubbery polymer.
  3. 제1항 또는 제2항에 있어서, 상기 방향족 비닐계 공중합체 수지는 방향족 비닐계 단량체 및 상기 방향족 비닐계 단량체와 공중합 가능한 단량체의 중합체인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 1 or 2, wherein the aromatic vinyl copolymer resin is a polymer of an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, 상기 변성 올레핀은 상기 화학식 1로 표시되는 반복단위 약 50 내지 약 95 중량% 및 상기 화학식 2로 표시되는 반복단위 약 5 내지 약 50 중량%를 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The method according to any one of claims 1 to 3, wherein the modified olefin is about 50 to about 95% by weight of the repeating unit represented by Formula 1 and about 5 to about 50% by weight of the repeating unit represented by Formula 2 Thermoplastic resin composition comprising a.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 중공 무기 필러는 구형의 중공 유리 입자인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 4, wherein the hollow inorganic filler is a spherical hollow glass particle.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, 상기 변성 폴리올레핀 및 상기 중공 무기 필러의 중량비는 약 0.1 : 1 내지 약 0.5 : 1인 것을 특징으로 하는 열가소성 수지 조성물.6. The thermoplastic resin composition of claim 1, wherein the weight ratio of the modified polyolefin and the hollow inorganic filler is about 0.1: 1 to about 0.5: 1. 7.
  7. 제1항 내지 제6항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 ASTM D256에 의거하여 측정한 1/8" 두께 시편의 노치 아이조드 충격강도가 약 12 kgf·cm/cm 이상인 것을 특징으로 하는 열가소성 수지 조성물.7. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a notched Izod impact strength of at least about 12 kgf · cm / cm, measured in accordance with ASTM D256. Thermoplastic resin composition.
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 ASTM D1238에 의거하여, 200℃, 5 kgf 조건에서 측정한 용융흐름지수가 약 1.5 내지 약 3.5 g/10분인 것을 특징으로 하는 열가소성 수지 조성물.8. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition has a melt flow index of about 1.5 to about 3.5 g / 10 minutes, measured at 200 ° C. and 5 kgf, based on ASTM D1238. 9. Thermoplastic resin composition.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 상기 열가소성 수지 조성물은 ASTM D792에 의거하여, 측정한 비중이 약 1 이하인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to any one of claims 1 to 8, wherein the thermoplastic resin composition has a specific gravity measured based on ASTM D792 of about 1 or less.
  10. 제1항 내지 제9항 중 어느 한 항에 따른 열가소성 수지 조성물로부터 형성되는 것을 특징으로 하는 성형품.A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 9.
PCT/KR2019/001698 2018-02-22 2019-02-12 Thermoplastic resin composition and molded article formed therefrom WO2019164167A1 (en)

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KR20060131373A (en) * 2005-06-16 2006-12-20 제일모직주식회사 High heat abs resin composition having improved crack and chemical resistance
KR20130067516A (en) * 2011-12-14 2013-06-25 주식회사 엘지화학 Thermoplastic abs resin composition with excellent impact strength
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