KR20050013457A - Foamable composition for non-crosslinked polyester thermoplastic elastomer and foam using the same - Google Patents

Foamable composition for non-crosslinked polyester thermoplastic elastomer and foam using the same

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Publication number
KR20050013457A
KR20050013457A KR1020030052114A KR20030052114A KR20050013457A KR 20050013457 A KR20050013457 A KR 20050013457A KR 1020030052114 A KR1020030052114 A KR 1020030052114A KR 20030052114 A KR20030052114 A KR 20030052114A KR 20050013457 A KR20050013457 A KR 20050013457A
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thermoplastic elastomer
polyester
based thermoplastic
parts
weight
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KR1020030052114A
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Korean (ko)
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김효린
이중표
석진석
안재원
이시우
이현배
김백진
김정열
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한국생산기술연구원
영보화학 주식회사
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Priority to KR1020030052114A priority Critical patent/KR20050013457A/en
Publication of KR20050013457A publication Critical patent/KR20050013457A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: Provided are an uncrosslinked foaming polyester-based thermoplastic elastomer composition and an uncrosslinked foaming polyester-based thermoplastic elastomer foam obtained from the composition which has a cell of fine average size and uniform distribution, is excellent in impact resistance, sealing property and vibration isolation and can be recycled. CONSTITUTION: The uncrosslinked foaming polyester-based thermoplastic elastomer composition comprises 60-100 parts by weight of an uncrosslinked foaming polyester-based thermoplastic elastomer; 1-10 parts by weight of a foaming agent; and 1-10 parts by weight of a viscosity controller. Preferably the composition comprises further at least one thermoplastic resin selected from the group consisting of ethylene-vinyl acetate, low density polyethylene, linear low density polyethylene, polypropylene, metallocene polyethylene, poly(vinyl alcohol), polystyrene, acrylonitrile-butadiene-styrene copolymer, poly(ethylene terephthalate) and poly(butylene terephthalate), in an amount of 5-40 parts by weight.

Description

무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물 및 이를 이용한 발포체{Foamable composition for non-crosslinked polyester thermoplastic elastomer and foam using the same}Non-crosslinked polyester-based thermoplastic elastomer composition and foam using the same {Foamable composition for non-crosslinked polyester thermoplastic elastomer and foam using the same}

본 발명은 레일 패드, 자동차 부품, 전기전자 부품, 기계 부품, 잡화 등의 재료로 유용하게 사용될 수 있는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물 및 이를 이용한 발포체에 관한 것이다.The present invention relates to a crosslinked foamable polyester-based thermoplastic elastomer composition which can be usefully used as a material for rail pads, automobile parts, electrical and electronic parts, mechanical parts, sundries, and the like, and foams using the same.

일반적으로, 고무는 물리적 자극에 대해 가역성을 나타내기 때문에 실링재, 완충재 등으로 여러 가지 산업 분야에 사용되고 있다. 그러나, 고무를 실용적인 재료로서 사용하기 위해서는 가황처리를 해야 하는데, 가황처리 공정은 거대한 설비가 필요할 뿐만 아니라 복잡한 배합기술이 필요하다. 또한, 가황처리된 고무는 가교결합이 형성되어 쉽게 리사이클이 되지 않는다는 문제점이 있다.In general, rubber has been used in various industrial fields as a sealing material, a cushioning material, and the like because it exhibits reversibility to physical stimuli. However, in order to use rubber as a practical material, the vulcanization process has to be vulcanized, and the vulcanization process requires not only huge equipment but also complicated compounding technology. In addition, the vulcanized rubber has a problem that crosslinks are formed and not easily recycled.

이와 같은 문제점을 해결하기 위하여, 에틸렌/비닐 아세테이트 공중합체, 올레핀계 부분 가교 열가소성 엘라스토머 수지 등을 이용하는 방법이 제안되었다. 이러한 엘라스토머 수지는 전술한 가황처리 공정을 생략할 수 있고, 열가소성 수지의 성형에 사용되는 설비를 이용하여 성형이 가능하기 때문에 경제성이 우수하다.In order to solve this problem, a method using an ethylene / vinyl acetate copolymer, an olefin-based partially crosslinked thermoplastic elastomer resin, or the like has been proposed. Such an elastomer resin can omit the above-mentioned vulcanization treatment process, and can be molded using equipment used for molding a thermoplastic resin, which is excellent in economy.

그러나 올레핀계 엘라스토머 수지는 내열성이 떨어질 뿐만 아니라, 용융단계에서의 장력이 낮아 발포성형공정에서 쉽게 탈포되므로서 발포 배율이 작으며 표면이 두드러지게 거칠어지게 된다. 또한 부분 가교된 열가소성 엘라스토머 수지를 사용하므로 재활용시 가공이 용이치 않다.However, the olefin elastomer resin is not only poor in heat resistance, but also has low tension in the melting step, so that it is easily degassed in the foam molding process, so that the foaming ratio is small and the surface becomes remarkably rough. In addition, since partially crosslinked thermoplastic elastomer resin is used, processing is not easy when recycling.

따라서, 발포 배율이 높으며 탈포에 의해 표면이 거칠어지지 않고, 물성이 우수하며, 재활용이 가능한 발포성 열가소성 엘라스토머 조성물로 된 발포체의 개발도 요망된다.Therefore, it is also desirable to develop a foam made of a foamable thermoplastic elastomer composition having a high expansion ratio, which does not have a rough surface due to defoaming, excellent physical properties, and recyclability.

따라서, 본 발명이 이루고자 하는 기술적 과제는 상기와 같은 문제점들을 해결하여 셀의 평균 크기가 미세하면서 그 분포가 균일하여 표면이 거칠지 않고 발포 배율이 높으며, 내충격성, 밀폐성, 방진성 등의 물성이 우수하여 레일 패드, 자동차 부품, 전기전자 부품, 기계 부품, 잡화 등의 재료로 유용하게 사용될 수 있을 뿐만 아니라, 재활용이 가능하여 환경친화적인 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물 및 이를 이용한 발포체를 제공하는데 있다.Therefore, the technical problem to be achieved by the present invention is to solve the above problems, the average size of the cell is fine and its distribution is uniform, the surface is not rough and the foaming ratio is high, and the physical properties such as impact resistance, sealing, dustproof, etc. Not only can be usefully used as a material for rail pads, automobile parts, electrical and electronic parts, mechanical parts, miscellaneous goods, etc., but also to provide an environment-friendly non-crosslinked foamable polyester-based thermoplastic elastomer composition and a foam using the same. .

상기 기술적 과제를 달성하기 위하여 본 발명은 무가교 폴리에스테르계 열가소성 엘라스토머 60 내지 100 중량부; 발포제 1 내지 10 중량부; 및 점도 조절제 1 내지 10 중량부;를 포함하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 제공한다.The present invention to achieve the above technical problem 60 to 100 parts by weight of an uncrosslinked polyester-based thermoplastic elastomer; 1 to 10 parts by weight of blowing agent; And a viscosity modifier 1 to 10 parts by weight; provides a non-crosslinked foamable polyester-based thermoplastic elastomer composition comprising.

본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에는경제성을 높이고 발포체의 표면 질감을 높이기 위하여 에틸렌비닐아세테이트(EVA), 저밀도 폴리에틸렌(LDPE), 선형 저밀도 폴리에틸렌(LLDPE), 폴리프로필렌(PP), 메탈로센 폴리에틸렌(Metallocene PE), 폴리비닐알콜(PVA), 폴리스티렌(PS), 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS), 폴리에틸렌텔레프탈레이트(PET), 폴리부틸렌텔레프탈레이트(PBT) 등의 열가소성 수지를 더 첨가할 수 있다.In the non-crosslinked expandable polyester-based thermoplastic elastomer composition of the present invention, ethylene vinyl acetate (EVA), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metal in order to increase the economical efficiency and increase the surface texture of the foam Rosen polyethylene (Metallocene PE), polyvinyl alcohol (PVA), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) Thermoplastic resin can be further added.

본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에 있어서, 발포제로는 탄산수소 나트륨, 탄산 나트륨, 탄산수소 암모늄, 탄산암모늄, 아질산 나트륨 등의 무기 열분해형 발포제를 사용하는 것이 바람직하며, 점도 조절제로는 테프론계 수지를 사용하는 것이 바람직하다.In the non-crosslinked foamable polyester-based thermoplastic elastomer composition of the present invention, it is preferable to use inorganic pyrolytic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, sodium nitrite, and the like as the viscosity modifier. It is preferable to use teflon-based resin.

또한, 본 발명은 전술한 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 가열하여 얻어진 무가교 폴리에스테르계 열가소성 엘라스토머 발포체를 제공한다.The present invention also provides an uncrosslinked polyester-based thermoplastic elastomer foam obtained by heating the aforementioned uncrosslinked expandable polyester-based thermoplastic elastomer composition.

이하, 본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물 및 이를 이용한 발포체에 대하여 상세히 설명한다.Hereinafter, the non-crosslinked expandable polyester-based thermoplastic elastomer composition and the foam using the same will be described in detail.

본 발명의 무가교(non-crosslinked) 발포성 폴리에스테르계 열가소성 엘라스토머 조성물은 무가교 폴리에스테르계 열가소성 엘라스토머 60 내지 100 중량부; 발포제 1 내지 10 중량부; 및 점도 조절제 1 내지 10 중량부;를 포함한다.Non-crosslinked expandable polyester-based thermoplastic elastomer composition of the present invention comprises 60 to 100 parts by weight of non-crosslinked polyester-based thermoplastic elastomer; 1 to 10 parts by weight of blowing agent; And 1 to 10 parts by weight of a viscosity modifier.

무가교 폴리에스테르계 열가소성 엘라스토머는 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르계 하드 세그멘트(hard segment)와, 폴리에틸렌글리콜(PEG), 폴리프로필렌글리콜(PPG), 폴리테트라메틸렌글리콜(PTMG)등의 폴리에테르, 산과 글리콜의 탈수 축합반응에 의해 얻어지는 폴리에스테르 등의 소프트 세그멘트(soft segment)로 이루어진 블록 공중합체이다. 본 발명의 조성물에 사용된 폴리에스테르계 열가소성 엘라스토머는 가교결합되지 않은 무가교 고분자로서, 분자사슬간의 미끄러짐 억제는 하드 세그멘트 사이의 분자간 가교결합에 의해서가 아니라 하드 세그멘트 간의 분자간 인력에 의해서 이루어진다. 이와 같은 무가교 폴리에스테르계 열가소성 엘라스토머 수지는 올레핀계 부분 가교 열가소성 엘라스토머 수지와는 달리 내열성이 우수하고, 용융단계에서도 양호한 장력을 유지하여 셀의 평균 크기가 미세하면서 그 분포가 균일하여 표면이 거칠지 않고 발포 배율이 높게 된다. 또한, 내충격성, 밀폐성, 방진성 등의 물성도 양호하며 재활용이 가능하여 환경친화적이다. 이러한 무가교 폴리에스테르계 열가소성 엘라스토머는 여러 제조회사에서 판매하고 있다. 예를 들어 듀폰(Dupont)사는 폴리부틸렌테레프탈레이트의 하드 세그먼트와 폴리에테르글리콜계의 소프트 세그먼트로 된 하이트렐 그레이드(Hytrel grade)를, 도요보(Toyobo)사는 방향족 폴리에스테르계의 방향족 세그먼트와 지방족 폴리에테르계와 소프트 세그먼트로 된 펠프렌 그레이드(Pelprene grade)를 시판하고 있으며, 그 외에 SKC사의 스카이펠 그레이드(Skypel grade), LG화학의 키플렉스 그레이드(Keyflex grade) 및 코오롱사의 코펠 그레이드(Kopel grade) 등이 있다.Non-crosslinked polyester thermoplastic elastomers include polyester hard segments such as polyethylene terephthalate and polybutylene terephthalate, polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol (PTMG). It is a block copolymer which consists of soft segments, such as a polyether, such as polyester, etc. obtained by dehydration condensation reaction of an acid and glycol. The polyester-based thermoplastic elastomer used in the composition of the present invention is an uncrosslinked non-crosslinked polymer, and the slip inhibition between the molecular chains is not caused by intermolecular cross-linking between hard segments but by intermolecular attraction between hard segments. Unlike the olefin-based partially crosslinked thermoplastic elastomer resin, the non-crosslinked polyester thermoplastic elastomer resin has excellent heat resistance, maintains a good tension even in the melting stage, and has a fine average cell size and a uniform distribution, so that the surface is not rough. The expansion ratio becomes high. In addition, it has good physical properties such as impact resistance, airtightness, and dust resistance, and is environmentally friendly since it can be recycled. Such uncrosslinked polyester-based thermoplastic elastomers are sold by various manufacturers. Dupont, for example, has a Hytrel grade consisting of a hard segment of polybutylene terephthalate and a soft segment of polyether glycol, while Toyobo has an aromatic polyester and an aliphatic of an aromatic polyester. Pelprene grades are available in polyether and soft segments. In addition, SKC's Skypel grade, LG Chem's Keyflex grade, and Kolon's Kopel grade ).

본 발명의 무가교(non-crosslinked) 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에 함유된 발포제로는 유기 또는 무기 열분해형 발포제, 물, 탄화수소계 및 플론(flon)계 용제, 질소, 이산화탄소, 프로판, 부탄 등의 기체를 사용할 수있다. 이 중에서 열분해성 발포제의 예로는 탄산수소 나트륨, 탄산 나트륨, 탄산수소 암모늄, 탄산암모늄 및 아질산 나트륨 등의 무기계 발포제; N,N'-디메틸-N,N'-디니트로소테레프탈아미드, N,N'-디니트로소펜타메틸렌테트라민 등의 니트로소 화합물; 아조디카르본아미드, 아조비스이소부티로니트릴, 아조시클로헥실니트릴, 아조디아미노벤젠, 바륨 아조디카르복실 레이트등의 아조 화합물; 벤젠설포닐히드라지드, 톨루엔설포닐히드라지드, p,p'-옥시비스(벤젠설포닐히드라지드), 디페닐설폰-3,3'-디설포닐히드라지드 등의 설포닐히드라지드 화합물; 및 칼슘 아지드, 4,4'-디페닐디설포닐아지드, p-톨루엔설포닐아지드 등의 아지드 화합물 등을 들 수 있다. 특히, 탄산수소 나트륨, 탄산 나트륨, 탄산수소 암모늄, 탄산 암모늄, 아질산 나트륨 등의 무기 열분해형 발포제는 고온에서 열분해되어 이산화탄소와 수분을 방출시킨 후에 나트륨 이온이나 암모늄 이온 등의 무기 잔류물을 소량 잔류시키는데, 이러한 무기 잔류물은 핵제를 첨가한 것과 같은 효과가 있다. 따라서, 셀이 미세한 크기로 형성되게 하며 셀의 분포도 균일하게 한다. 발포제의 함량이 1 중량부 미만이면 발포 배율이 낮아지며, 10중량부를 초과하면 가스의 팽창압력이 높아져 발포체의 표면이 거칠어지며 심한 경우 셀이 파괴될 수 있다.Foaming agents contained in the non-crosslinked foamable polyester-based thermoplastic elastomer composition of the present invention include organic or inorganic thermal decomposition foaming agents, water, hydrocarbon-based and flon-based solvents, nitrogen, carbon dioxide, propane, butane, and the like. Gas can be used. Examples of the thermally decomposable blowing agent include inorganic blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and sodium nitrite; Nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide and N, N'-dinitrosopentamethylenetetramine; Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene and barium azodicarboxylate; Sulfonylhydrazide compounds such as benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide) and diphenylsulfon-3,3'-disulfonylhydrazide; And azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide and p-toluenesulfonyl azide. In particular, inorganic pyrolytic blowing agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and sodium nitrite are thermally decomposed at high temperature to release carbon dioxide and water, and there is a small amount of inorganic residue such as sodium ions or ammonium ions. This inorganic residue has the same effect as the addition of a nucleating agent. Thus, the cells are formed in a fine size and the cell distribution is also uniform. When the content of the blowing agent is less than 1 part by weight, the expansion ratio is lowered. When the content of the blowing agent is more than 10 parts by weight, the expansion pressure of the gas is increased to roughen the surface of the foam, and in severe cases, the cell may be destroyed.

또한, 본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에 함유된 점도 조절제로는 적절한 멜트 텐션(melt tention)을 유지하기 위해 첨가하는데, 테프론계 수지를 사용하는 것이 바람직하다. 테프론계 수지는 난연성 수지 조성물, 전도성 수지 조성물 그리고 우수한 내화학성, 내열성을 이용한 코팅용 수지 조성물 등에 널리 이용되고 있는 수지로서, 본 발명에 있어서 테프론계 수지는조성물의 점도를 조절함으로써 최종 제품인 엘라스토머 발포체의 물성, 특히 탄성도와 표면 광택도에 큰 영향을 미친다. 이러한 테프론계 수지로는 PTFE(Polytetrafluoroethylene), ETFE(Ethylene tetrafluoroethylene copolymer) 및 FEP(Fluorinated Ethylene Propylene coplymer) 등을 들 수 있다. 특히, PTFE(Polytetrafluoroethylene) 수지는 엘라스토머 수지 본래의 물성을 손상시키지 않으면서 용융 점도를 변화시켜, 폴리에스테르계 열가소성 엘라스토머 수지의 진공성형이나 발포성형, 압출 등의 가공작업에 요구되는 용융장력을 개량시켜 주는 장점이 있다. 점도 조절제의 함량이 1 중량부 미만일 경우에는 조성물의 점도가 너무 낮아 기포셀의 크기를 미세하게 조절하는데 어려움이 따르고, 10 중량부를 초과하면 점도가 상당히 높아지므로 발포제의 분해가스의 용해도와 확산을 떨어뜨려 발포체의 형성이 어려운 경향이 있다.In addition, the viscosity modifier contained in the non-crosslinked expandable polyester-based thermoplastic elastomer composition of the present invention is added to maintain an appropriate melt tension, and it is preferable to use a teflon-based resin. Teflon-based resins are widely used in flame retardant resin compositions, conductive resin compositions, and coating resin compositions having excellent chemical and heat resistance properties. In the present invention, teflon-based resins are used in the final product of elastomer foams by controlling the viscosity of the composition. It has a great influence on physical properties, especially elasticity and surface glossiness. Examples of such Teflon-based resins include PTFE (Polytetrafluoroethylene), ETFE (Ethylene tetrafluoroethylene copolymer), and FEP (Fluorinated Ethylene Propylene coplymer). Particularly, PTFE (Polytetrafluoroethylene) resin changes melt viscosity without impairing the original physical properties of elastomer resin, and improves melt tension required for processing operations such as vacuum forming, foam molding and extrusion of polyester thermoplastic elastomer resin. There are advantages to giving. If the content of the viscosity modifier is less than 1 part by weight, the viscosity of the composition is too low, making it difficult to finely control the size of the bubble cell, and if the content exceeds 10 parts by weight, the viscosity is considerably high. It tends to be difficult to form when foamed down.

본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에는 경제성을 높이고 발포체의 표면 질감을 높이기 위하여 에틸렌비닐아세테이트(EVA), 저밀도 폴리에틸렌(LDPE), 선형 저밀도 폴리에틸렌(LLDPE), 폴리프로필렌(PP), 메탈로센 폴리에틸렌(Metallocene PE), 폴리비닐알콜(PVA), 폴리스티렌(PS), 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS), 폴리에틸렌텔레프탈레이트(PET), 폴리부틸렌텔레프탈레이트(PBT) 등의 열가소성 수지를 더 첨가할 수 있다. 이러한 열가소성 수지의 함량은 바람직하게는 5 내지 40 중량부, 더욱 바람직하게는 5 내지 30 중량부이다.In the non-crosslinked expandable polyester-based thermoplastic elastomer composition of the present invention, in order to increase economics and increase the surface texture of the foam, ethylene vinyl acetate (EVA), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metal Rosen polyethylene (Metallocene PE), polyvinyl alcohol (PVA), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) Thermoplastic resin can be further added. The content of such thermoplastic resin is preferably 5 to 40 parts by weight, more preferably 5 to 30 parts by weight.

이 외에도, 본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머조성물에는 필요에 따라 발포 조제를 더 첨가할 수 있다. 발포 조제의 예로는 아연, 칼슘, 납, 철, 바륨 화합물 등의 금속 화합물, 구연산, 살리실산, 프탈산, 스테아린산 등의 유기산, 요소 또는 그 유도체를 들 수 있다. 발포 조제는 발포제의 분해 온도를 저하시키고 발포제의 분해 촉진을 촉진시키며, 기포의 균일화 등의 기능을 갖는다. 또한, 본 발명의 열가소성 엘라스토머 조성물은 무기 가스를 흡착하는 무기 다공질 분말(예컨대 제올라이트) 또는 무기 가스의 흡착량이 큰 수지(예컨대 폴리카보네이트 수지)를 더 참가할 수 있다.In addition, a foaming aid can be further added to the non-crosslinked foamable polyester thermoplastic elastomer composition of the present invention as needed. Examples of the foaming aid include metal compounds such as zinc, calcium, lead, iron and barium compounds, organic acids such as citric acid, salicylic acid, phthalic acid and stearic acid, urea or derivatives thereof. The foaming aid lowers the decomposition temperature of the foaming agent, promotes the decomposition promoting of the foaming agent, and has functions such as uniformity of bubbles. In addition, the thermoplastic elastomer composition of the present invention may further participate in inorganic porous powder (such as zeolite) that adsorbs inorganic gas or resin (such as polycarbonate resin) having a large adsorption amount of inorganic gas.

본 발명의 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물에는 본 발명의 목적을 벗어나지 않는 한도 내에서 충전제, 내열 안정제, 노화 방지제, 내후 안정제, 대전 안정제, 금속 비누, 활제(예컨대 왁스), 안료, 염료, 핵제, 난연제, 블록킹(blocking) 방지제 등의 각종 공지 첨가제를 첨가할 수 있다. 충전제로서는 통상 고무 및 열가소성 수지의 성형가공에 사용하는 충전제를 사용할 수 있다. 이러한 충전제의 예로는 탄산 칼슘, 규산 칼슘, 클레이(clay), 카오린(kaolin), 탈크(talc), 실리카, 규조토, 운모, 아스베스토스(asbestos), 황산바륨, 황산알루미늄, 황산 칼슘, 탄산마그네슘, 이황산 몰리브덴, 그래파이트, 알루미나 등을 들 수 있다. 공지된 열안정제, 노화 방지제 및 내후 안정제의 예로서는 페놀계, 설파이트계, 페닐알칸계, 포스파이트계, 아민계 화합물 등을 들 수 있다.The non-crosslinked expandable polyester-based thermoplastic elastomer composition of the present invention includes fillers, heat stabilizers, anti-aging agents, weather stabilizers, charge stabilizers, metal soaps, lubricants (such as waxes), pigments, dyes, and the like without departing from the object of the present invention. Various known additives, such as a nucleating agent, a flame retardant, and a blocking agent, can be added. As a filler, the filler normally used for shaping | molding of rubber | gum and a thermoplastic resin can be used. Examples of such fillers are calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica, asbestos, barium sulfate, aluminum sulfate, calcium sulfate, magnesium carbonate, disulphide Acid molybdenum, graphite, alumina, etc. are mentioned. Examples of known heat stabilizers, anti-aging agents and weathering stabilizers include phenolic, sulfite, phenylalkane, phosphite, and amine compounds.

전술한 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 이용하여 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 발포체를 제조하는 방법은다음과 같다.Method for producing a cross-linked foamable polyester-based thermoplastic elastomer foam using the above-mentioned non-crosslinked expandable polyester-based thermoplastic elastomer composition is as follows.

먼저, 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 수지의 수분을 제거하는데, 수분함량이 0.2% 이하로 조절한다.First, the water of the non-crosslinked expandable polyester-based thermoplastic elastomer resin is removed, but the water content is adjusted to 0.2% or less.

이어서, 발포제를 제외한 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 압출기에 메인 피딩(main feeding)하면서 용융시킨다. 이 때 조성물을 이루는 성분들이 충분히 용융, 혼합되도록 한다.Subsequently, the crosslinked expandable polyester-based thermoplastic elastomer composition except for the blowing agent is melted while main feeding to the extruder. At this time, the components constituting the composition are sufficiently melted and mixed.

그런 다음, 발포제를 압출기에 사이드 피딩(side feeding)한다. 피딩된 발포제는 분해되어 가스를 발생시키는데, 수지 용융물에 분해된 가스가 균일하게 분산되도록 온도를 조절하며 혼합한다.The blowing agent is then side fed to the extruder. The fed blowing agent decomposes to generate gas, which is mixed with temperature control so that the decomposed gas is uniformly dispersed in the resin melt.

이어서, 압출기의 다이를 통하여 토출된 발포체를 소정 형상으로 성형한다.Subsequently, the foam discharged through the die of the extruder is molded into a predetermined shape.

이하, 본 발명을 실시예를 들어 더욱 더 상세하게 설명한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어져서는 안 된다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the invention should not be construed as limited to the embodiments described below.

실시예 1 내지 4Examples 1-4

무가교 폴리에스테르계 열가소성 엘라스토머, 발포제, 점도 조절제 및 기타 첨가물질을 하기 표 1에 기재된 조성비(단위:중량부) 및 제조조건에 따라 제조하여 발포체 시트를 얻었다.An uncrosslinked polyester-based thermoplastic elastomer, a foaming agent, a viscosity modifier and other additives were prepared according to the composition ratio (unit: parts by weight) and production conditions shown in Table 1 below to obtain a foam sheet.

본 실시예에 따른 발포체의 제조는 한국 EM사 압출기(Co-rotational twin screw extruder, Screw type:Element-screw+kneading block-type)를 사용하였다.The manufacture of the foam according to this embodiment used a South Korean EM company extruder (Co-rotational twin screw extruder, Screw type: Element-screw + kneading block-type).

구분division 실시예Example 성분명Ingredient Name 1One 22 33 44 조성물Composition 무가교 폴리에스테르계 열가소성 엘라스토머Uncrosslinked Polyester Thermoplastic Elastomer 듀폰사의 HytrelDupont's Hytrel 100100 -- -- 7070 도요보사의 PelpreneToyobo's Pelprene -- 9090 -- -- SKC사의 SkypelSKC's Skypel -- -- 8080 -- 발포제blowing agent 탄산수소나트륨Sodium bicarbonate 55 77 55 77 점도 조절제Viscosity modifier 폴리테트라플루오로에틸렌Polytetrafluoroethylene 44 44 44 44 열가소성 수지Thermoplastic resin 폴리프로필렌Polypropylene -- -- 2020 -- 폴리에틸렌Polyethylene -- -- -- 3030 에틸렌비닐아세테이트Ethylene Vinyl Acetate -- 1010 -- -- 핵제Nuclear agent 탈크Talc -- -- 22 -- 성형조건Molding conditions 압출기내 수지의 압력(kg/㎠)Pressure of resin in extruder (kg / ㎠) 5151 7878 2323 8989 압출기내 수지의 온도(℃)Temperature of resin in extruder (℃) 170170 169169 199199 173173

상기 실시예에 따른 발포체의 물성을 하기와 같이 평가하여 그 결과를 표 2에 나타냈다.The physical properties of the foam according to the above example were evaluated as follows, and the results are shown in Table 2.

(1) 발포배율(1) expansion ratio

미발포체의 평균 밀도를 발포체의 겉보기 밀도로 나누고, 얻어진 값을 발포 배율로 취했다.The average density of the unfoamed body was divided by the apparent density of the foam, and the obtained value was taken as the expansion ratio.

(2) 셀의 평균크기 및 균일성(2) average size and uniformity of cells

발포체를 전자주사현미경으로 관찰하여 셀의 평균크기를 분석하여 균일성을 평가하였다. 셀의 균일성은 발포체가 매우 균일한 크기와 형태의 기포를 가질 경우 A, 예컨대 기포가 합쳐져서 형성된 커다란 기포나 탈포공정으로 인한 평평한 기포를 가질 경우 C로 평가하고, 상기 A와 C의 중간의 기포를 가질 경우 B로 평가하였다.The foam was observed with an electron scanning microscope to analyze the average size of the cells to evaluate the uniformity. The uniformity of the cell is evaluated as A when the foam has a very uniform size and shape of bubbles, for example, C when the bubble has a large bubble formed by combining bubbles or a flat bubble due to the defoaming process, and the bubble between the A and C is evaluated. B was evaluated as having.

(3) 광택도(3) glossiness

발포체를 육안으로 보아 빛이 반사되는 정도로 보아 아주 많이 반사될 경우A(우수), 중간 정도로 반사될 경우 B(보통), 반사가 거의 이루어지지 않을 경우 C(나쁨)으로 구분하였다.When the foam is visually seen, light is reflected to a degree of reflection, and a very large amount of reflection is classified as A (excellent), a medium degree of reflection is B (usually), and if the reflection is hardly made, it is divided into C (bad).

(4) 신장율(4) elongation rate

표준상태에서 시편의 양쪽을 절단될 때까지 잡아당겨 늘어난 길이를 백분률로 나타낸 것으로 다음과 같이 구한다.As a percentage of the stretched length until the two sides of the specimen are cut under normal conditions.

신장율 = [(L-L0)/L0] × 100Elongation = [(LL 0 ) / L 0 ] × 100

여기서 L : 절단될 때 눈금사이의 시편거리,Where L is the specimen distance between scales when cut,

L0: 최초 눈금사이의 시편거리 이다.L 0 : Specimen distance between initial scales.

실시예Example 1One 22 33 44 밀도(g/㎤)Density (g / cm 3) 0.60.6 0.530.53 0.620.62 0.560.56 발포배율(배)Foam magnification (times) 1.91.9 2.12.1 1.81.8 22 인장강도(Kg/㎠)Tensile Strength (Kg / ㎠) 54.154.1 4747 4242 4545 신장율(%)Elongation (%) 492492 498498 400400 427427 셀의 균일성Uniformity of cells AA AA AA AA 광택도Glossiness AA AA AA AA

이상에서 상세히 설명한 바와 같이, 본 발명에 따른 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 이용하여 제조한 발포체는 셀의 평균 크기가 미세하면서 그 분포가 균일하여 표면이 거칠지 않고 발포 배율이 높으며, 내충격성, 밀폐성, 방진성 등의 물성이 우수하다. 따라서, 레일 패드, 자동차 부품, 전기전자 부품, 기계 부품, 잡화 등 다양한 제품에 유용하게 사용될 수 있으며, 사용 후 제품 폐기시에도 재활용이 가능하여 환경오염을 방지할 수 있다.As described in detail above, the foam prepared using the non-crosslinked foamable polyester-based thermoplastic elastomer composition according to the present invention has a fine average size of cells and a uniform distribution thereof so that the surface is not rough and foaming ratio is high, and impact resistance is high. It is excellent in physical properties such as airtightness and dustproofness. Therefore, it can be usefully used for a variety of products, such as rail pads, automobile parts, electrical and electronic parts, mechanical parts, miscellaneous goods, and can be recycled even after disposal of the product to prevent environmental pollution.

Claims (6)

무가교 폴리에스테르계 열가소성 엘라스토머 60 내지 100 중량부;60 to 100 parts by weight of non-crosslinked polyester-based thermoplastic elastomer; 발포제 1 내지 10 중량부; 및1 to 10 parts by weight of blowing agent; And 점도 조절제 1 내지 10 중량부;를 포함하는 것을 특징으로 하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물.1 to 10 parts by weight of the viscosity modifier; non-crosslinked foamable polyester-based thermoplastic elastomer composition comprising a. 제1항에 있어서, 에틸렌비닐아세테이트(EVA), 저밀도 폴리에틸렌(LDPE), 선형 저밀도 폴리에틸렌(LLDPE), 폴리프로필렌(PP), 메탈로센 폴리에틸렌(Metallocene PE), 폴리비닐알콜(PVA), 폴리스티렌(PS), 아크릴로니트릴-부타디엔-스티렌 공중합체(ABS), 폴리에틸렌텔레프탈레이트(PET) 및 폴리부틸렌텔레프탈레이트(PBT)로 이루어진 군으로부터 선택된 어느 하나 이상의 열가소성 수지를 더 포함하는 것을 특징으로 하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물.The method of claim 1, wherein ethylene vinyl acetate (EVA), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metallocene polyethylene (Metallocene PE), polyvinyl alcohol (PVA), polystyrene ( PS), acrylonitrile-butadiene-styrene copolymer (ABS), polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) is one or more thermoplastic resin selected from the group consisting of Cross-linkable polyester-based thermoplastic elastomer composition. 제2항에 있어서, 상기 열가소성 수지의 함량은 5 내지 40 중량부인 것을 특징으로 하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물.3. The crosslinked foamable polyester-based thermoplastic elastomer composition according to claim 2, wherein the thermoplastic resin is present in an amount of 5 to 40 parts by weight. 제1항에 있어서, 상기 발포제는 탄산수소 나트륨, 탄산 나트륨, 탄산수소 암모늄, 탄산암모늄 및 아질산 나트륨으로 이루어진 그룹으로부터 선택된 하나 이상의 무기 열분해형 발포제를 포함하는 것을 특징으로 하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물.The non-crosslinked foamable polyester thermoplastic according to claim 1, wherein the blowing agent comprises at least one inorganic pyrolytic blowing agent selected from the group consisting of sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and sodium nitrite. Elastomer composition. 제1항 또는 제2항에 있어서, 상기 점도 조절제는 테프론계 수지인 것을 특징으로 하는 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물.The non-crosslinked foamable polyester thermoplastic elastomer composition according to claim 1 or 2, wherein the viscosity modifier is a Teflon resin. 제1항 내지 제5항에 기재된 무가교 발포성 폴리에스테르계 열가소성 엘라스토머 조성물을 가열하여 얻어진 무가교 폴리에스테르계 열가소성 엘라스토머 발포체.A crosslinked polyester-based thermoplastic elastomer foam obtained by heating the crosslinked foamable polyester-based thermoplastic elastomer composition according to claim 1.
KR1020030052114A 2003-07-28 2003-07-28 Foamable composition for non-crosslinked polyester thermoplastic elastomer and foam using the same KR20050013457A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100967806B1 (en) * 2008-07-04 2010-07-05 (주)반도 Production Method of Polyolefine Foam Film and the Foam Film Produced by This Method
KR20180135200A (en) * 2017-06-12 2018-12-20 (주)엘지하우시스 Non crosslinked olefin resin composition and foam and method for manufacturing the same
KR20190143576A (en) * 2018-06-21 2019-12-31 한화컴파운드 주식회사 Sound insulation and sound absorption composition for automobile
CN114989570A (en) * 2022-04-27 2022-09-02 中山大学 Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100967806B1 (en) * 2008-07-04 2010-07-05 (주)반도 Production Method of Polyolefine Foam Film and the Foam Film Produced by This Method
KR20180135200A (en) * 2017-06-12 2018-12-20 (주)엘지하우시스 Non crosslinked olefin resin composition and foam and method for manufacturing the same
KR20190143576A (en) * 2018-06-21 2019-12-31 한화컴파운드 주식회사 Sound insulation and sound absorption composition for automobile
CN114989570A (en) * 2022-04-27 2022-09-02 中山大学 Crosslinked thermoplastic elastomer micro-foaming coiled material and preparation method and application thereof

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