KR100831083B1 - Polyester Thermoplastic Resin Compositions Having High Melt Strength - Google Patents
Polyester Thermoplastic Resin Compositions Having High Melt Strength Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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- C08L25/08—Copolymers of styrene
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- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/22—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 a halogen; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/70—Organic dyes or pigments; Optical brightening agents
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
Abstract
본 발명은 (A) 폴리에스테르 수지 30∼70 중량부; (B) 폴리카보네이트 수지 30∼60 중량부; (C) 스티렌계 공중합체 10∼40 중량부; 및 (D) 상기 (A)＋(B)＋(C)의 기초수지 100 중량부에 대하여 아크릴변성 폴리테트라플루오르에틸렌 0.5∼2 중량부로 이루어지며, 기계적 강도와 내충격성이 뛰어나고 용융장력이 우수하여 대형 블로우 성형품의 적용이 가능한 폴리에스테르계 열가소성 수지 조성물에 관한 것이다.The present invention (A) 30 to 70 parts by weight of polyester resin; (B) 30 to 60 parts by weight of a polycarbonate resin; (C) 10 to 40 parts by weight of the styrene copolymer; And (D) 0.5 to 2 parts by weight of acryl-modified polytetrafluoroethylene based on 100 parts by weight of the base resin of (A) + (B) + (C), and has excellent mechanical strength and impact resistance and excellent melt tension. The present invention relates to a polyester-based thermoplastic resin composition which can be applied to a large blow molded article.
폴리에스테르 수지, 폴리카보네이트 수지, 스티렌계 공중합체, 아크릴변성 폴리테트라플루오르에틸렌, 고용융장력 Polyester resin, polycarbonate resin, styrene copolymer, acrylic modified polytetrafluoroethylene, high melt strength
Description
발명의 분야Field of invention
본 발명은 폴리에스테르계 열가소성 수지 조성물에 관한 것이다. 보다 구체적으로 본 발명은 기계적 강도와 내충격성이 우수하면서도 용융장력이 높아 중공 성형성이 개선된 폴리에스테르계 열가소성 수지 조성물에 관한 것이다.The present invention relates to a polyester-based thermoplastic resin composition. More specifically, the present invention relates to a polyester-based thermoplastic resin composition having excellent mechanical strength and impact resistance but high melt tension and improved hollow moldability.
발명의 배경Background of the Invention
폴리에스테르 수지는 기계적 강도, 전기적 특성 및 내약품성을 가지고 있어 자동차, 전기전자부품 등에 널리 사용되고 있다. 그러나 폴리에스테르 수지는 Tg(유리전이온도)가 40∼60℃로 상온 및 저온에서의 내충격성이 낮은 문제점이 있어, 내충격성을 요하는 분야에 대한 적용을 위해 고무와의 합금(alloy)이 많이 연구되었다.Polyester resins are widely used in automobiles, electrical and electronic parts because they have mechanical strength, electrical properties, and chemical resistance. However, polyester resin has a Tg (glass transition temperature) of 40 ~ 60 ℃ has a low impact resistance at room temperature and low temperature, many alloys (rubber) with rubber for applications in areas requiring impact resistance Researched.
미국특허 제4,393,153호, 제4,180,494호 및 제4,034,013호에서는 에틸렌-프로필렌 공중합체(EPR), 에틸렌-프로필렌-디엔 공중합체(EPDM), 메타크릴레이트-부타디엔-스티렌 공중합체(MBS) 등을 부가하여 내충격성을 향상시키는 방법을 제시하고 있다. 그러나 이러한 방법들은 폴리에스테르 수지의 내충격성을 향상시킬 수 있으나, 중공 성형성이 저하되는 단점이 있다.US Patent Nos. 4,393,153, 4,180,494 and 4,034,013 add ethylene-propylene copolymers (EPR), ethylene-propylene-diene copolymers (EPDM), methacrylate-butadiene-styrene copolymers (MBS), and the like. It suggests how to improve impact resistance. However, these methods can improve the impact resistance of the polyester resin, but there is a disadvantage in that the hollow moldability is lowered.
한편 폴리카보네이트 수지는 우수한 내충격성 및 내열성을 가지고 있으나 성형성이 나쁜 단점을 가지고 있으므로, 종래에는 아크릴로니트릴-부타디엔-스티렌(ABS)과의 블렌드를 통해 이를 극복하였다. 폴리카보네이트/아크릴로니트릴-부타디엔-스티렌(PC/ABS) 블렌드 수지는 폴리카보네이트의 내충격성과 내열성이 아크릴로니트릴-부타디엔-스티렌의 가공성과 조화를 이루어 사출용 전기/전자 및 자동차 용도로 널리 사용되고 있으나 중공 성형법이 사용되는 자동차 범퍼 빔, 인판넬, 각종 파이프류의 생산을 위해서는 고용융장력을 지니는 분지형 폴리카보네이트를 별도로 사용해야 하는 단점이 있다. 일반적으로 분지형 폴리카보네이트는 반응기에서 제조되나 분지구조의 제어가 어렵고, 용도에 맞는 다양한 구조의 생산이 현실적으로 어렵다.On the other hand, polycarbonate resin has excellent impact resistance and heat resistance, but has a disadvantage of poor moldability, conventionally overcomes this through a blend with acrylonitrile-butadiene-styrene (ABS). Polycarbonate / acrylonitrile-butadiene-styrene (PC / ABS) blend resins are widely used in electric / electronic and automotive applications for injection molding because the impact resistance and heat resistance of polycarbonate are in harmony with the processability of acrylonitrile-butadiene-styrene. For the production of automobile bumper beam, inpanel, and various pipes in which the blow molding method is used, there is a disadvantage in that a branched polycarbonate having high melt strength is used separately. In general, branched polycarbonate is produced in a reactor, but it is difficult to control the branching structure, and the production of various structures suitable for the use is practically difficult.
이에, 본 발명자들은 폴리에스테르 수지에 폴리카보네이트 수지, 스티렌계 공중합체 및아크릴변성 폴리테트라플루오르에틸렌을 배합함으로써 우수한 기계적 강도, 내충격성 및 고용융장력(중공 성형성)을 가지는 폴리에스테르계 열가소성 수지 조성물을 개발하기에 이른 것이다.Accordingly, the present inventors have blended a polycarbonate resin, a styrene copolymer and an acrylic modified polytetrafluoroethylene to a polyester resin to have a polyester thermoplastic resin composition having excellent mechanical strength, impact resistance and high melt strength (hollow moldability). It is early to develop.
본 발명의 목적은 기계적 강도 및 내충격성이 우수한 폴리에스테르계 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a polyester-based thermoplastic resin composition excellent in mechanical strength and impact resistance.
본 발명의 다른 목적은 용융장력이 높아 대형 중공성형 제품의 안정적인 성형이 가능한 폴리에스테르계 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a polyester-based resin composition capable of stable molding of large blow molded products due to high melt tension.
본 발명은 또 다른 목적은 폴리카보네이트계 수지에 적정량의 스티렌계 공중합체를 블렌드하여 물성을 유지하면서도 소재의 경제성을 향상시킨 수지 조성물에 관한 것이다.Another object of the present invention is to blend a styrene-based copolymer in an appropriate amount with a polycarbonate resin to maintain a physical property while improving the resin composition of the material economy.
본 발명의 상기 및 기타의 목적들은 모두 하기에 설명되는 본 발명에 의해서 달성될 수 있다.Both the above and other objects of the present invention can be achieved by the present invention described below.
발명의 요약Summary of the Invention
본 발명은 (A) 폴리에스테르 수지 30∼70 중량부; (B) 폴리카보네이트 수지 30∼60 중량부; (C) 스티렌계 공중합체 10∼40 중량부; 및 (D) 상기 (A)＋(B)＋(C)의 기초수지 100 중량부에 대하여 아크릴 변성폴리테트라플루오르에틸렌 0.5∼2 중량부로 이루어지며, 내충격성이 뛰어나고 용융장력이 우수하여 내한성이 요구되는 대형 블로우 성형품의 적용이 가능한 폴리에스테르계 열가소성 수지 조성물에 관한 것이다.The present invention (A) 30 to 70 parts by weight of polyester resin; (B) 30 to 60 parts by weight of a polycarbonate resin; (C) 10 to 40 parts by weight of the styrene copolymer; And (D) 0.5 to 2 parts by weight of acryl-modified polytetrafluoroethylene based on 100 parts by weight of the base resin of (A) + (B) + (C), and has excellent impact resistance and excellent melt tension. The present invention relates to a polyester-based thermoplastic resin composition which can be applied to a large blow molded article.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명의 폴리에스테르계 열가소성 수지 조성물은 (A) 폴리에스테르 수지 30∼70 중량부; (B) 폴리카보네이트 수지 30∼60 중량부; (C) 스티렌계 공중합체 10∼40 중량부; 및 (D) 상기 (A)＋(B)＋(C)의 기초수지 100 중량부에 대하여 아크릴 변성폴리테트라플루오르에틸렌 0.5∼2 중량부로 이루어진다.Polyester-based thermoplastic resin composition of the present invention (A) 30 to 70 parts by weight of polyester resin; (B) 30 to 60 parts by weight of a polycarbonate resin; (C) 10 to 40 parts by weight of the styrene copolymer; And (D) 0.5 to 2 parts by weight of acrylic modified polytetrafluoroethylene based on 100 parts by weight of the base resin of (A) + (B) + (C).
이하, 본 발명의 폴리에스테르계 열가소성 수지 조성물의 각 성분에 대한 상세한 설명은 다음과 같다.Hereinafter, the detailed description of each component of the polyester-based thermoplastic resin composition of the present invention is as follows.
(A) 폴리에스테르 수지(PEs)(A) Polyester resins (PEs)
본 발명에 따른 폴리에스테르 수지는 디카르본산(dicarbonic acid)과 디올(diol)을 중합시켜 제조된다.The polyester resin according to the present invention is prepared by polymerizing dicarbonic acid and diol.
상기 디카르본산으로는 테레프탈산, 이소프탈산, 나프탈렌 디카르본산, 디페닐에테르 디카르복실산, 디페닐 디카르복실산 및 디페닐설폰 디카르복실산으로 이루어지는 군으로부터 선택된 것을 사용하는 것이 바람직하다.As the dicarboxylic acid, it is preferable to use one selected from the group consisting of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl dicarboxylic acid and diphenylsulfone dicarboxylic acid.
상기 디올 성분으로는 α, ω-디올, 예를 들면 에틸렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 네오펜틸 글리콜, 사이클로헥산 디메탄올, 2,2-비스(4-β-하이드록시페닐-페닐)-프로판, 4,4-비스(β-하이드록시에폭시)-디페닐 설폰 및 디에틸렌 글리콜로 이루어지는 군으로부터 선택된 것을 사용하는 것이 바람직하다.As the diol component, α, ω-diol, for example, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexane dimethanol, 2,2-bis (4-β-hydroxy Preference is given to using those selected from the group consisting of phenyl-phenyl) -propane, 4,4-bis (β-hydroxyepoxy) -diphenyl sulfone and diethylene glycol.
본 발명에 따른 폴리에스테르 수지의 함량은 30∼70 중량부인 것이 바람직하 며, 30∼50 중량부인 것이 더욱 바람직하다. 폴리에스테르 수지의 함량이 30 중량부 이하인 경우에는 기계적 강도가 저하되고, 70 중량부 이상인 경우에는 중공 성형성이 저하될 수 있다.The content of the polyester resin according to the present invention is preferably 30 to 70 parts by weight, more preferably 30 to 50 parts by weight. When the content of the polyester resin is 30 parts by weight or less, the mechanical strength is lowered, and when the content of the polyester resin is 70 parts by weight or more, the hollow moldability may be lowered.
(B) 폴리카보네이트 수지(PC)(B) polycarbonate resin (PC)
본 발명에 따른 폴리카보네이트 수지는 하기 화학식 1로 표시되는 디페놀류를 포스겐, 할로겐 포메이트 및 탄산 디에스테르로 이루어지는 군으로부터 선택되는 어느 하나와 반응시킴으로서 제조될 수 있다.The polycarbonate resin according to the present invention can be prepared by reacting the diphenols represented by the following formula (1) with any one selected from the group consisting of phosgene, halogen formate and diester carbonate.
[화학식 1][Formula 1]
상기 식에서, A는 단일 결합으로서 C1-C5의 알킬렌, C2-C5의 알킬리덴, C5-C6의 시클로알킬리덴, -S-또는 -SO2-를 나타낸다.Wherein A represents C 1 -C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO 2 -as a single bond.
상기 화학식 1로 나타낸 디페놀의 구체예로는 히드로퀴논, 레조시놀, 4,4'-디히드록시디페닐, 2,2-비스-(4-히드록시페닐)-프로판, 2,4-비스-(4-히드록시페닐)-2-메틸부탄, 1,1-비스-(4-히드록시페닐)-시클로헥산, 2,2-비스-(3-클로로-4-히드 록시페닐)-프로판 및 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판 등이 있다.Specific examples of the diphenol represented by Formula 1 include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis -(4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane And 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and the like.
상기 디페놀의 구체예 중에서도 2,2-비스-(4-히드록시페닐)-프로판, 2,2-비스-(3,5-디클로로-4-히드록시페닐)-프로판 및 1,1-비스-(4-히드록시페닐)-시클로헥산을 사용하는 것이 바람직하며, 특히 비스페놀-A라고 불리는 2,2-비스-(4-히드록시페닐)-프로판을 사용하는 것이 더욱 바람직하다.Among the specific examples of the diphenol, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 1,1-bis Preference is given to using-(4-hydroxyphenyl) -cyclohexane, more preferably 2,2-bis- (4-hydroxyphenyl) -propane called bisphenol-A.
본 발명에 따른 폴리카보네이트 수지는 중량평균분자량이 10,000∼200,000인 것이 바람직하며, 15,000∼80,000인 것이 더욱 바람직하다. 10,000 미만 그리고 200,000 초과인 경우에는 충격보강효과나 성형성이 저하될 수 있다.The polycarbonate resin according to the present invention preferably has a weight average molecular weight of 10,000 to 200,000, more preferably 15,000 to 80,000. If less than 10,000 and more than 200,000, the impact reinforcing effect or formability may be degraded.
본 발명에 따른 폴리카보네이트 수지로는 선형 폴리카보네이트나 분지형 폴리카보네이트가 자유로이 사용될 수 있다. 분지쇄를 갖는 폴리카보네이트의 경우, 중합에 사용되는 디페놀 전량에 대하여 0.05∼2몰%의 트리- 또는 그 이상의 다관능 화합물, 예를 들면 3가 또는 그 이상의 페놀기를 가진 화합물을 첨가하여 제조할 수 있다.As the polycarbonate resin according to the present invention, linear polycarbonate or branched polycarbonate may be freely used. In the case of polycarbonate having a branched chain, it is prepared by adding 0.05 to 2 mol% of a tri- or more polyfunctional compound, for example, a compound having a trivalent or more phenol group, based on the total amount of diphenols used for polymerization. Can be.
본 발명에 따른 폴리카보네이트 수지로는 호모폴리카보네이트와 코폴리카보네이트가 사용될 수 있으며, 또한 상기 코폴리카보네이트와 상기 폴리카보네이트의 블렌드 형태로도 사용될 수 있다.As the polycarbonate resin according to the present invention, homopolycarbonate and copolycarbonate may be used, and may also be used as a blend form of the copolycarbonate and the polycarbonate.
또한, 본 발명에 따른 폴리카보네이트 수지는 에스테르 전구체(precursor), 예를 들면 2관능 카르복실산 존재 하에 중합 반응시켜 얻어진 방향족 폴리에스테르-카보네이트 수지로 일부 또는 전량 대체될 수 있다.In addition, the polycarbonate resin according to the present invention may be partially or wholly replaced with an aromatic polyester-carbonate resin obtained by polymerizing in the presence of an ester precursor, for example a bifunctional carboxylic acid.
본 발명에 따른 바람직한 폴리카보네이트 수지의 함량은 30∼60 중량부이며, 좀 더 바람직하게는 30∼50 중량부이다. 폴리카보네이트 수지의 함량이 상기 범위를 벗어나는 경우 충격보강 효과가 미미하다.The content of the preferred polycarbonate resin according to the present invention is 30 to 60 parts by weight, more preferably 30 to 50 parts by weight. When the content of the polycarbonate resin is out of the above range, the impact reinforcing effect is insignificant.
(C) 스티렌계 공중합체(ABS)(C) Styrene Copolymer (ABS)
본 발명에 따른 스티렌계 공중합체는 스티렌 단량체 단위를 함유한 것으로, 스티렌-부타디엔 블록 공중합체, 스티렌-부타디엔-에틸렌-스티렌 블록 공중합체, 아크릴산 메틸 부타디엔 스티렌 공중합체, 아크릴로니트릴-부타디엔-스티렌 공중합체 및 아크릴로니트릴-부틸아크릴레이트-스티렌 공중합체로 이루어지는 군으로부터 선택되는 것이 바람직하며, 특히 고무함량이 30∼60%인 아크릴로니트릴-부타디엔-스티렌 공중합체, 아크릴로니트릴-부틸아크릴레이트-스티렌 공중합체가 더욱 바람직하다.Styrene-based copolymers according to the present invention contain styrene monomer units, styrene-butadiene block copolymers, styrene-butadiene-ethylene-styrene block copolymers, methyl acrylate butadiene styrene copolymers, acrylonitrile-butadiene-styrene airborne It is preferably selected from the group consisting of a copolymer and an acrylonitrile-butyl acrylate-styrene copolymer, especially an acrylonitrile-butadiene-styrene copolymer having a rubber content of 30 to 60%, acrylonitrile-butyl acrylate- More preferred are styrene copolymers.
본 발명에 따른 스티렌계 공중합체의 함량은 10∼40 중량부인 것이 바람직하며, 15∼30 중량부인 것이 더욱 바람직하다. 10 중량부 미만, 40 중량부 이상인 경우 내충격성 향상 효과가 미미하고 중공 성형성도 감소할 수 있다. The content of the styrenic copolymer according to the present invention is preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight. If less than 10 parts by weight, 40 parts by weight or more, the impact resistance improvement effect is insignificant and the hollow formability may be reduced.
(D) 아크릴변성 폴리테트라플루오르에틸렌(A-PTFE)(D) acrylic modified polytetrafluoroethylene (A-PTFE)
본 발명에 사용되는 A-PTFE는 미쓰비시레이온사에 의해 이미 상업화된 제품으로, 분자량이 수백만 이상인 폴리테트라플루오르에텔렌에 아크릴기를 도입하여 블렌드되는 수지와의 상용성을 향상시켜 섬유상의 PTFE 사슬이 폴리에스테르 수지 및 폴리카보네이트 수지에 효과적으로 분산, 수지의 용융장력을 향상시킨다. 수지 내 처방은 상기 (A)＋(B)＋(C)의 기초수지 100 중량부에 대하여 0.5∼2 중량부가 바람직하며 보다 바람직하게는 1 중량부 이내이다. 2 중량부 초과에서는 더 이상의 용융장력 상승, 즉 압출 가공성의 향상이 없으며 과량 사용으로 인해 외관이 거칠어지고, 심할 경우 상분리가 일어나 수지의 충격특성 등의 저하를 가져올 수 있다. 0.5 중량부 미만인 경우에는 용융장력 향상의 효과가 미미하다.A-PTFE used in the present invention is a product already commercialized by Mitsubishi Rayon Co., Ltd., which introduces acrylic groups into polytetrafluoroethylene having a molecular weight of millions or more to improve compatibility with resins blended to form a poly PTFE chain. Effectively disperse in ester resin and polycarbonate resin, improve the melt tension of the resin. In the resin formulation, 0.5 to 2 parts by weight is preferable with respect to 100 parts by weight of the base resin of (A) + (B) + (C), more preferably within 1 part by weight. If it is more than 2 parts by weight, there is no further increase in melt tension, that is, the improvement of extrusion processability, and the appearance becomes rough due to excessive use, and in severe cases, phase separation may occur, resulting in deterioration of impact properties of the resin. If less than 0.5 parts by weight, the effect of improving the melt tension is insignificant.
본 발명의 열가소성 수지 조성물에는 상기 (A), (B), (C) 및 (D) 외에도 안정제, 산화방지제, 활제, 항균제, 이형제, 드립방지제(Anti-dripping agent), 염료, 안료 및 무기첨가제 등을 첨가할 수 있다. 이 때 각각의 함량은 (A), (B), (C) 및 (D) 전체에 대하여 0.1∼5.0% 인 것이 바람직하다.In the thermoplastic resin composition of the present invention, in addition to the above (A), (B), (C) and (D), stabilizers, antioxidants, lubricants, antibacterial agents, mold release agents, anti-dripping agents, dyes, pigments and inorganic additives Etc. can be added. In this case, the content is preferably 0.1 to 5.0% based on the total amount of (A), (B), (C) and (D).
본 발명의 수지 조성물은 수지 조성물을 제조하는 공지의 방법으로 제조할 수 있다. 예를 들면, 본 발명의 구성성분과 기타 첨가제들을 동시에 혼합한 후에, 압출기 내에서 용융 압출하고 펠렛 형태로 제조할 수 있다.The resin composition of this invention can be manufactured by the well-known method of manufacturing a resin composition. For example, the components of the present invention and other additives may be mixed simultaneously, then melt extruded in an extruder and made into pellets.
본 발명의 조성물은 여러 가지 제품의 성형에 사용될 수 있으며, 특히 내충격성 및 용융장력이 요구되는 자동차용 제품의 제조에 적합하다.The composition of the present invention can be used for molding a variety of products, and is particularly suitable for the production of automotive products requiring impact resistance and melt tension.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이고 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
하기의 표 1의 실시예 1∼3 및 비교실시예 1∼3 에서 사용된 (A) 폴리에스테 르 수지, (B) 폴리카보네이트 수지, (C) 스티렌계 공중합체 및 (D) 아크릴변성 폴리테트라플루오르에틸렌의 제조 및 사양은 다음과 같다. (A) polyester resin, (B) polycarbonate resin, (C) styrene copolymer and (D) acrylic modified polytetra used in Examples 1 to 3 and Comparative Examples 1 to 3 of Table 1 below The production and specifications of fluoroethylene are as follows.
(A) 폴리에스테르 수지(A) polyester resin
TRE-DE2(Wintech Polymer)을 사용하였다.TRE-DE2 (Wintech Polymer) was used.
(B) 폴리카보네이트 수지(B) polycarbonate resin
Panlite LW-1225(Teijin)을 사용하였다.Panlite LW-1225 (Teijin) was used.
(C) 스티렌계 공중합체(C) Styrene Copolymer
제일모직 제품(Rubber 함량 30%) grade명 SR-0300을 사용하였다.Cheil Industries (Rubber content 30%) grade name SR-0300 was used.
(D) 아크릴변성 폴리테트라플루오르에틸렌(D) acrylic modified polytetrafluoroethylene
미쓰비시레이온사(MRC)의 A-3000 제품을 사용하였다. Mitsubishi Rayon (MRC) A-3000 was used.
실시예 1∼3 및 비교실시예 1∼3Examples 1-3 and Comparative Examples 1-3
상기에서 언급된 구성성분들을 이용하여 표 1의 실시예 1∼3 및 비교실시예 1∼3에 나타낸 조성과 같은 수지 조성물을 제조하였으며, 이들의 용융장력 및 물성도 표 1에 나타내었다.Using the above-mentioned components, the same resin compositions as those shown in Examples 1 to 3 and Comparative Examples 1 to 3 of Table 1 were prepared, and their melt tension and physical properties are also shown in Table 1.
상기 (A)∼(D)를 표 1에 나타난 각 구성성분의 조성에 따라 혼합하여 이루어 진 수지 조성물을 헨셀 믹서로 3∼10분간 균일하게 혼합시킨 후, 이축 압출기에 투입하고 압출온도 250℃, 250 rpm으로 압출하여 펠렛 형태로 제조하였다. 상기 방법에 의하여 제조된 펠렛으로부터 사출성형에 의해(10 oz 사출기에서 사출온도 250℃, 금형온도 80℃) 물성시편을 제작하고 23℃, 상대습도 50%에서 40시간 동안 방치한 후 물성을 평가하였다.The resin composition obtained by mixing the above (A) to (D) according to the composition of each component shown in Table 1 was uniformly mixed for 3 to 10 minutes with a Henschel mixer, then introduced into a twin screw extruder, and the extrusion temperature 250 ℃, Extruded at 250 rpm to form a pellet. From the pellets prepared by the above method, a physical specimen was prepared by injection molding (injection temperature of 250 ° C. and mold temperature of 80 ° C. in a 10 oz injection machine), and left for 30 hours at 23 ° C. and 50% relative humidity for evaluation of physical properties. .
물성 평가 방법Property evaluation method
(1) 아이조드(IZOD) 충격강도: ASTM D256 평가방법에 의하여 1/4″ 아이조드(IZOD) 시편에 노치를 만들어 측정하였다.(1) IZOD Impact Strength: Notched and measured in 1/4 ″ IZOD specimens by ASTM D256 evaluation method.
(2) 용융장력: 각 시편을 23℃, 상대습도 50%에서 48시간 방치한 후, 두께 1.5 mm, 너비 6 mm 그리고 길이 60 mm의 시편과 Rheometric scientific사의 RME를 이용하여 온도 260℃, Extensional rate 0.5[s-1]조건에서 시편이 끊어질 때의 Strength로 측정하였다.(2) Melt tension: Each specimen was left at 23 ℃ for 48 hours at 50% RH, and then 1.5mm thick, 6mm wide and 60mm long, and Rheometric Scientific's RME. The strength at the time of breaking the specimen at 0.5 [s -1 ] was measured.
(3) 중공성형: 별도로 고안된 실험실 규모의 장비를 이용하여 수지를 260℃에서 용융시킨 후 10 oz 크기의 시약병 형상을 공기 블로잉(blowing) 방식에 의해 성형하였다. 클램핑 몰드의 온도는 60℃로 제어하였고, 페리슨은 65 g(길이 100 mm, 직경 15 mm)을 기준으로 성형 실시하였다. 중고성형품의 경우, 파팅라인, 표면요철, 터짐 그리고 편심발생, 두께편차 등의 여러 수치를 각 조건에 대해 10개의 제품을 정상적으로 생산한 후 성형품의 양호/불량판정에 반영하였다.(3) Blow Molding: After the resin was melted at 260 ° C. using a separately designed laboratory scale equipment, a 10 oz size reagent bottle shape was molded by an air blowing method. The temperature of the clamping mold was controlled at 60 ° C., and Ferrison was molded based on 65 g (length 100 mm, diameter 15 mm). In the case of used moldings, various values such as parting line, surface irregularities, bursting, eccentricity and thickness deviation were reflected in good / bad judgment of molded products after 10 products were produced normally for each condition.
상기 표 1에 나타난 바와 같이, 실시예 1∼3으로 제조된 열가소성 수지는 비교실시예 1∼3으로 제조된 열가소성 수지에 비해 기계적 강도 및 내충격성이 우수하면서도 용융장력이 매우 높은 것을 관찰할 수 있다. 또한, 중공성형 작업성을 비교했을 때, 비교실시예 1∼3은 불량품이 비교적 많이 발생한 반면 실시예 1∼3에서는 불량품이 전혀 발생하지 않아 중공성형 제품의 안정적인 성형이 가능함을 확인할 수 있다.As shown in Table 1, it can be observed that the thermoplastic resins prepared in Examples 1 to 3 have excellent mechanical strength and impact resistance while having very high melt tension as compared to the thermoplastic resins prepared in Comparative Examples 1 to 3. . In addition, when comparing the blow molding workability, Comparative Examples 1 to 3 can be seen that relatively many defective products are generated, whereas Examples 1 to 3 do not generate any defective products at all, so that stable molding of the blow molded products is possible.
본 발명은 폴리에스테르 수지, 폴리카보네이트 수지, 스티렌계 공중합체 및 아크릴변성 폴리테트라 플루오르에틸렌으로 이루어지며, 우수한 기계적 강도와 내충격성을 가지며 용융장력이 높아 대형 중공성형 제품의 안정적인 성형이 가능한 폴리에스테르계 수지 조성물을 제공하는 발명의 효과를 갖는다.The present invention is made of polyester resin, polycarbonate resin, styrene-based copolymer and acrylic modified polytetrafluoroethylene, excellent mechanical strength and impact resistance, high melt tension polyester type that can be stable molding of large blow molded products It has the effect of providing the resin composition.
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 (7)
Priority Applications (1)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010073015A (en) * | 1999-07-02 | 2001-07-31 | 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹 | Polyester- polycarbonate composition with improved hot-plate weldability |
| JP2002327108A (en) * | 2001-04-27 | 2002-11-15 | Teijin Chem Ltd | Thermoplastic resin composition suitable for blow molding having weld part and the blow molding |
| US20040006200A1 (en) * | 2002-07-02 | 2004-01-08 | Hiroyuki Nakagawa | Crystalline biodegradable resin composition |
| KR20050029242A (en) * | 2002-07-29 | 2005-03-24 | 바이엘 머티리얼사이언스 아게 | Flame-resistant moulding materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010073015A (en) * | 1999-07-02 | 2001-07-31 | 제이 엘. 차스킨, 버나드 스나이더, 아더엠. 킹 | Polyester- polycarbonate composition with improved hot-plate weldability |
| JP2002327108A (en) * | 2001-04-27 | 2002-11-15 | Teijin Chem Ltd | Thermoplastic resin composition suitable for blow molding having weld part and the blow molding |
| US20040006200A1 (en) * | 2002-07-02 | 2004-01-08 | Hiroyuki Nakagawa | Crystalline biodegradable resin composition |
| KR20050029242A (en) * | 2002-07-29 | 2005-03-24 | 바이엘 머티리얼사이언스 아게 | Flame-resistant moulding materials |
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