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KR920009686B1 - Foamed impect absorption agent - Google Patents

Foamed impect absorption agent Download PDF

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Publication number
KR920009686B1
KR920009686B1 KR1019890014040A KR890014040A KR920009686B1 KR 920009686 B1 KR920009686 B1 KR 920009686B1 KR 1019890014040 A KR1019890014040 A KR 1019890014040A KR 890014040 A KR890014040 A KR 890014040A KR 920009686 B1 KR920009686 B1 KR 920009686B1
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South Korea
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propylene oxide
poly
foamed
polyol
hydroxyl value
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KR1019890014040A
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Korean (ko)
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KR910006354A (en
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최진석
이재명
김형수
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동성화학공업 주식회사
백정호
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Priority to KR1019890014040A priority Critical patent/KR920009686B1/en
Priority to EP90118572A priority patent/EP0420242B1/en
Priority to DE69024155T priority patent/DE69024155T2/en
Priority to JP2262944A priority patent/JPH03124720A/en
Priority to US07/592,486 priority patent/US5098936A/en
Publication of KR910006354A publication Critical patent/KR910006354A/en
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Publication of KR920009686B1 publication Critical patent/KR920009686B1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A foamed shock-absorbing material having repelling elasticity of less than 15 % and permanent coppressed deformation of less than 10 % is prepd. by mixing and high-speed agitating the prepolymer or diisocyanate monomer component having 5-25 wt.% of left isocyanate prepd. from aromatic diisocyanate and poly (propylene oxide) polyol of 20-560 mg KOH/g; and the resin component having 0.8-3.0 wt.% of water and comprising poly (propylene oxide) polyol of 17-225 mg KOH/g contg. two of terminated hydroxy functional gp. (A), poly (glycerin/ propylene oxide) polyol of 30- 1680 mg KOH/g and 3 of (A), poly (ethylene diamine/propylene oxide) polyol of 45-2245 mg KOH/g and 4 of (A), and reaction accelerater and polyalky- or polyalkoxy- siloxane.

Description

발포형 충격흡수재Foam Shock Absorber

본발명은 폴리에테르계 폴리우레탄으로 구성된 마이크로셀상의 발포형 충격흡수재에 관한 것으로서, 더욱 상세하게는 잔존 이소시아네이트를 함유하는 프리폴리머 또는 이소시아네이트모노머성분과, 아민계 지방족 폴리올을 비롯한 에테르계폴리올, 유기실록산등으로 이루어진 수지성분을 혼합주형시켜 발포성형체를 제조함으로서, 탁월한 충격흡수 효과와 복원력 및 우수한 내미끄럼성 그리고 제조시 성형비중을 자유로이 변형시킬 수 있는 새로운 물성의 발포형 충격흡수재에 관한 것이다.The present invention relates to a microcell foamed shock absorber composed of a polyether polyurethane, more specifically, a prepolymer or an isocyanate monomer component containing residual isocyanates, ether polyols including amine-based aliphatic polyols, organosiloxanes, and the like. The present invention relates to a foam-type shock absorber having a new physical property that can freely modify the molding weight during manufacture by producing a molded foam by molding a resin component made of a mixture.

지금까지 사용되고 있는 기존 충격흡수재중, 첫째, 폴리우레탄 우레아 탄성체는 산업적인 용도에서 여러 성형품의 형태로 널리 사용되고 있으면서도, 물성, 충격흡수효과, 변형회복 등의 조화가 기대에 못미칠 뿐만아니라, 비중이 높고 가격이 비싸 실질적용에 문제점이 많았다.Among the existing shock absorbers that have been used so far, first, polyurethane urea elastomers are widely used in the form of various molded articles for industrial use, but the balance between physical properties, shock absorbing effects, and deformation recovery does not meet expectations. High and expensive, there were many problems in practical use.

둘째, 마이크로셀상의 발포형 충격흡수재의 경우, 외기온도 변화에 따른 충격흡수효과 변화를 줄이기 위해, 특별히 복잡하게 변성 제조된 고가의 아민계 방향족 변성폴리올 및 방향족비닐계모노머 등을 사용해야 하였으며, 충격흡수효과를 보완하기 위해서는 아스팔트나 점착부여제 등을 비롯한 여러 충진제를 별도로 다량 첨가해야만 했다.Second, in the case of the foamed shock absorber on the microcell, in order to reduce the change of the shock absorbing effect due to the change in the ambient temperature, an expensive amine-based aromatic modified polyol and an aromatic vinyl monomer, which were specially modified and modified, had to be used. To supplement the effect, many fillers, including asphalt and tackifiers, had to be added separately.

따라서, 종래의 발포형 충격흡수재는 비중과 가격상승을 초래하여 실용성이 감소되었으며, 그 사용분야에 따라서는 적용범위가 상당히 제한적인 실정이었다.Therefore, the conventional foamed shock absorber has caused the increase in specific gravity and price, thereby reducing the practicality, the application range is quite limited depending on the field of use.

이에 본발명에서는 기존의 발포형 충격흡수재에서 폴리올성분으로 사용되었던 특수하게 제조된 아민계 방향족 변성폴리올 및 다종의 방향족비닐계모노머 등을 복합병용 하였던 점과는 달리, 단순한 아민계 지방족 폴리올과 프로필렌옥사이드 및 2~4가의 수산관능기를 가지는 폴리올만을 병용하여도 반응촉진제 및 유화제 선택에 의해 그 발포구조가 달라지게될 뿐아니라 그 물성, 특히 반발탄성이나 영구압축변형이 현저하게 개선되어 충격흡수효과 및 복원력이 우수하게 된다는 점에 착안하여 본발명을 완성하게 되었다.Therefore, in the present invention, unlike the conventional combination of a specially prepared amine-based aromatic modified polyol and a variety of aromatic vinyl monomers used as polyol components in the foam-type shock absorber, a simple amine-based aliphatic polyol and propylene oxide And the use of only polyols having 2 to tetravalent hydroxyl functional groups, the foam structure is changed by reaction promoter and emulsifier selection, and the physical properties, particularly repulsive elasticity or permanent compression deformation, are remarkably improved. With this in mind, the present invention has been completed.

따라서, 본발명은 종래의 발포형 충격흡수재를 일부 개선시켜서, 그 흡수재 구성성분으로서 잔존 이소시아네이트를 함유하는 프리폴리머 또는 이소시아네이트모노머성분과, 아민계 지방족폴리올을 비롯한 에테르계폴리올 유기실록산 등으로부터 제조된 수지성분을 혼합성형시켜 발포성형체를 제조함으로서 현저하게 물성이 개선된 새로운 발포형 충격흡수재를 제공하는데 그 목적이 있다.Accordingly, the present invention partially improves the conventional foamed shock absorber, and is a resin component prepared from a prepolymer or isocyanate monomer component containing residual isocyanate as its absorbent component, and an ether polyol organosiloxane including an amine aliphatic polyol. It is an object of the present invention to provide a new foam-type shock absorber with improved physical properties by producing a molded foam by mixing the molding.

이하, 본발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본발명은 폴리우레탄 마이크로셀상의 발포형 충격흡수재에 있어서, 방향족 디이소시아네이트와 수산기값이 20~560mgKOH/g인 폴리(프로필렌옥사이드)폴리올로부터 제조된 잔존 이소시아네이트 함량이 5~25중량%인 프리폴리머 성분 혹은 디이소시아네이트모노머 성분과, 쇄말단 수산관능기가 2개이고 수산기값이 17~225mgKOH/g인 폴리(프로필렌옥사이드)폴리올, 쇄말단 수산관능기가 3개이고 수산기값이 30~1680mgKOH/g인 폴리(글리세린/프로필렌옥사이드)폴리올, 쇄말단 수산관능기가 4개이고 수산기값이 45~2245mgKOH/g인 폴리(에틸렌디아민/프로필렌옥사이드)폴리올, 3급아민계 및 유기금속계 반응촉진제, 폴리알킬 혹은 폴리알콕시 실록산으로 구성되고, 수분함량이 0.8~3.0중량%인 수지성분의 혼합.고속교반으로 형성되고, 그 반발탄성이 15% 이하이고, 영구압축변형이 10% 이하인 것을 특징으로 한다.The present invention is a foam-type shock absorber on a polyurethane microcell, a prepolymer component having a residual isocyanate content of 5 to 25% by weight prepared from an aromatic diisocyanate and a poly (propylene oxide) polyol having a hydroxyl value of 20 to 560 mgKOH / g or Poly (glycerol / propylene) with diisocyanate monomer component, poly (propylene oxide) polyol having 2 chain terminal hydroxyl functional groups and 17-225 mgKOH / g hydroxyl value, and 3 chain terminal hydroxyl functional groups with 30-1680 mgKOH / g hydroxyl group value Oxide) polyol, poly (ethylenediamine / propylene oxide) polyol having 4 chain-end hydroxyl functional groups and hydroxyl value of 45-2245 mgKOH / g, tertiary amine-based and organometallic reaction accelerators, polyalkyl or polyalkoxy siloxanes, A resin component with a water content of 0.8 to 3.0% by weight, formed by high-speed stirring, having a repulsive elasticity of 15% or less, and a permanent compression deformation It is characterized by being 10% or less.

이러한, 본발명에 따른 발포형 충격흡수재는 불규칙한 인터페니트레이팅 네트워크(Interpenetrating Network)형 망상구조를 가지고 있다. 이와같은 본발명을 그 제조방법을 중심으로하여 상세하게 설명하기로 한다.Such a foam shock absorber according to the present invention has an irregular interpenetrating network type network structure. This invention will be described in detail with reference to the manufacturing method thereof.

우선, 본발명에 따른 발포형 충격흡수재를 제조하는 방법을 요약해보면 크게 2가지로 대별되는데, 이를 설명해 보면 다음과 같다.First, a summary of a method of manufacturing a foam type shock absorber according to the present invention is roughly divided into two, which will be described as follows.

[제1방법(이하 “프리폴리머법”이라함)][First Method (hereinafter referred to as "Prepolymer Method")]

폴리우레탄 마이크로셀상의 발포형 충격흡수재를 제조함에 있어서, (가) 디이소시아네이트모노머와, 프로필렌옥사이드로부터 제조된 폴리프로필렌(수산기값 20~560mgKOH/g)을 2차 부가 중합반응시켜서 프리폴리머를 제조하고, (나) 쇄말단 수산관능기가 2개이고 수산기값이 17~225mgKOH/g인 폴리(프로필렌옥사이드), 쇄말단 수산관능기가 3개이고 수산기값이 30~1680mgKOH/g인 폴리(글리세린/프로필렌옥사이드), 쇄말단 수산관능기가 4개이고 수산기값이 45~2245mgKOH/g인 폴리(에칠렌디아민/프로필렌옥사이드), 유기실록산, 그리고 반으옥진제등 첨가제를 혼합교반시켜서 수지성분을 제조한 후, (다) 상기 (가)의 프리폴리머 성분과 상기 (나)의 수지성분을 약 70℃로 예열시켜서 금형에서 주형하여 발포성형체로 제조한다.In preparing a foamed shock absorber on a polyurethane microcell, (a) a prepolymer is prepared by subjecting a diisocyanate monomer and a polypropylene (hydroxyl value 20 to 560 mgKOH / g) prepared from propylene oxide to secondary polymerization. (B) Poly (propylene oxide) having 2 chain-end hydroxyl functional groups and 17-225 mgKOH / g hydroxyl value, poly (glycerine / propylene oxide) having 3 chain-end hydroxyl functional groups and 30-1680 mgKOH / g hydroxyl value, chain The resin component is prepared by mixing and stirring additives such as poly (ethylenediamine / propylene oxide), organosiloxane, and semi-oxoxine having 4 terminal hydroxyl functional groups and a hydroxyl value of 45 to 2245 mg KOH / g. The prepolymer component of) and the resin component of (b) above are preheated to about 70 ° C. and cast in a mold to prepare a foamed molded product.

이때, 필요에 따라서는 70℃에서 예열되고 이형제 처리가 되어있는 금형에 고속교반, 주형시키는바, 여기서 성형지수는 그 용도에 따라 1.0~2.0까지 다양하게 할 수가 있으며, 주형후에는 금형내에 약 5~10분동안 몰딩시켰다가 탈형시키고, 대기중에서 약 하루정도 포스트 큐어링(Post Curing) 시키게 되면 양호한 상태의 발포형 충격흡수재를 제조할 수가 있다.At this time, if necessary, the mold is pre-heated at 70 ° C. and the mold is subjected to high speed stirring and molding, wherein the molding index can be varied from 1.0 to 2.0 depending on the intended use. Molding for 10 minutes, demolding, and post curing in the air for about a day can produce a foamed shock absorber in good condition.

이와같은 프로폴리머법으로 제조함에 있어서, 상기 2차 부가 중합반응은 약 100℃의 온도에서 건조불활성 기체 존재하에 진행시키며, 이때 프리폴리머성분과 수지성분의 배합비를 조절하면서 소프트세그먼트와 하드세그먼트의 존재비율 및 점도등을 고려하여 이소시아네이트모노머의 량과 폴리올의 반응 배합량을 결정하여 중합감압, 탈기시켜서, 잔존 이소시아네이트의 함량이 5~25중량%가 되도록 프리폴리머를 제조하여 사용한다.In the production of such a polymer method, the secondary addition polymerization is carried out in the presence of a dry inert gas at a temperature of about 100 ℃, wherein the presence ratio of the soft segment and the hard segment while adjusting the mixing ratio of the prepolymer component and the resin component In consideration of the viscosity and the like, the amount of isocyanate monomer and the reaction compounding amount of the polyol are determined to depressurize and degas the polymerization to prepare a prepolymer so that the content of remaining isocyanate is 5 to 25% by weight.

또한, 상기 (나)의 수지성분을 제조할 경우에는 단량체상의 디올, 디아민계 반응촉진제 및 유기금속계 반응촉진제 등과 같은 첨가제를 혼합하여 사용하며, 최종 수분함량이 0.8~3.0중량%가 되도록 수지성분을 제조한다. 여기서, 상기 폴리올과 디아민계 및 유기금속계 반응촉진제는 인터페니트레이팅 네트워크(Interpenetrating-Network) 생성반응의 속도조절 및 분산효과를 위해 예컨대, 테트라메칠에칠렌디아민, 테트라메칠헥산디아민, 테트라에칠메칠렌디아민, 디에칠피페라진, 트리에칠렌디아민 등과 같은 디아민, 스테너스옥토에이트, 디부칠틴디아세테이트, 소듐바이카보네이트, 리드옥토에이트, 포타슘아세테이트등과 같은 유기금속을 수산기가 45~1120mgKOH/g인 디올모노머 혹은 폴리디올에 고속교반.분산시켜서 사용한다.In addition, in the case of preparing the resin component (b), additives such as diol, diamine-based reaction accelerator, organometallic reaction accelerator, and the like in a monomer are mixed and used, and the resin component is used so that the final moisture content is 0.8 to 3.0% by weight. Manufacture. Herein, the polyol, diamine-based and organometallic reaction accelerators may be, for example, tetramethylethylenediamine, tetramethylhexanediamine, tetraethylmethylenediamine, for the purpose of controlling the rate of dispersion and dispersing effect of the interpenetrating-network generation reaction. , Diol monomers such as diepiperazine, triethylenediamine, etc., diol monomers having a hydroxyl group of 45 to 1120 mgKOH / g, such as stenacetotoate, dibutytin diacetate, sodium bicarbonate, lead octoate, potassium acetate, and the like High speed stirring and dispersing in polydiol.

한편, 이때 사용되는 디이소시아네이트모노머로서는 톨루엔 디이소시아네이트, 자이렌디이소시아네이트, 3,3′-디메칠디페닐, 4,4′-디이소시아네이트, 파라-페닐렌디이소시아네이트, 4,4′-메칠렌비스(페닐이소시아네이트)등 방향족 디이소시아네이트를 사용할 수 있고, 아민계 지방족 폴리올로서는 헥사메칠렌디아민계, 트라이메칠 헥사메칠렌디아민계, 트라이에칠렌디아민계, 에칠렌디아민계 폴리올 등을 사용할 수 있으며, 유기실록산으로서는 폴리메칠실록산, 폴리옥시에칠렌실록산 유도체 등을 사용할 수가 있다.Meanwhile, as the diisocyanate monomer used at this time, toluene diisocyanate, xylene diisocyanate, 3,3'-dimethyldiphenyl, 4,4'-diisocyanate, para-phenylene diisocyanate, 4,4'-methylene bis ( Aromatic diisocyanate, such as phenyl isocyanate), and amine methylene diamine type | system | group, a trimethyl hexamethylene diamine type | mold, a triethylene diamine type | mold, an ethylene diamine type polyol etc. can be used as an amine type aliphatic polyol, As an organic siloxane, Methylsiloxane, polyoxyethylene siloxane derivative, etc. can be used.

[제2방법(이하 “원쇼트법”이라함)][Second method (hereinafter referred to as "one short method")]

폴리우레탄 마이크로셀상의 발포형 충격흡수재를 제조함에 있어서, (가) 디이소시아네이트모노머를 약 20℃~60℃에서 예열시키고, (나) 쇄말단 수산관능기가 2~4개이거나 홀성화 수소원자를 가지고 있는 아민계 지방족폴리올과 상기의 첨가제를 혼합교반시켜서 수지성분을 제조한후, (다) 상기 (가)의 이소시아네이트 성분과 약 70℃로 예열시킨 (나)의 수지성분을 고속교반시켜서 금형에서 주형하여 발포성형체로 제조한다.In preparing a foamed shock absorber on a polyurethane microcell, (a) pre-heat the diisocyanate monomer at about 20 ° C to 60 ° C, and (b) have 2 to 4 chain-end hydroxyl functionalities or have hydrogenated hydrogen atoms. After mixing and stirring the amine-based aliphatic polyol and the above additives to prepare a resin component, (C) the mold is molded in a mold by rapidly stirring the (I) resin component preheated to about 70 ° C with the isocyanate component (A). To prepare a foamed molded article.

이러한, 원쇼트법의 경우 상기의 프리폴리머법과 일반적인 제조공정은 동일하나, 상기 (나)수지성분 제조공정에 있어서 프리폴리머법에서 사용된 폴리올보다 분자량이 2배~3배 정도 높은 폴리올을 당량비로 사용하여 배합 제조하는 것이 바람직하다. 그 이유는 하드세그먼트의 편재화를 방지하기 위함이다.In the case of the one-shot method, the prepolymer method and the general manufacturing process are the same, but in the (b) resin component manufacturing process, a polyol having a molecular weight of 2 to 3 times higher than the polyol used in the prepolymer method is used in an equivalent ratio. It is preferable to carry out compounding. The reason is to prevent localization of hard segments.

또한, 원쇼트법에서 성형시에는 이소시아뉴레이트결합을 유도 생성시켜서 외기온도에 따른 경도변화를 줄이도록 하기 위하여, 상기 프리폴리머법보다 약 1.5~3배 정도 많은 양의 수분함량, 즉 1~10중량%의 수분함량을 갖도록 수지성분을 제조하고, 성형지수는 1.0~3.0까지 용도에 따라 다양하게 할 수가 있다.In addition, in the one-shot method, in order to reduce the hardness change according to the ambient temperature by inducing and generating isocyanurate bonds, the water content of about 1.5 to 3 times larger than the prepolymer method, that is, 1 to 10 The resin component is prepared to have a moisture content of weight%, and the molding index can be varied depending on the use up to 1.0 to 3.0.

위에서 설명한 바와같은 방법들에 의해 제조된 본발명에 따른 발포형 충격흡수재는 1급수산기.수분 및 이소시아네이트기의 반응과 그 반응열에 의해 우레아.우레탄.뷰렛.알로파네이트 결합이 유도생성되며, 이에의해 불규칙적인 인터페니트레이팅 네트워크형 망상구조의 생성이 촉진되게 된다. 이러한 분자결합구조는 가해진 충격에너지를 망상구조가 갖는 쇄내의 세그먼트 및 불규칙한 자유부피내에 저장.전이.확산시켜줌으로써 적용된 피보호 물체에 대한 충격을 격감시키게 하는 국소가 된다. 이때, 본발명에 따르면 뷰렛결합 및 우레아결합이 과다하게 생성되면 성형품의 표면상태가 부량해지므로 주의를 필요로 한다. 또한, 이와함께 사용된 2관능성 폴리올은 탄성을 부여하여 복원력을 향상시켜 주는 역할을 한다.The foamed shock absorber according to the present invention prepared by the method as described above is induced by urea, urethane, burette, allophanate bonds by reaction of primary hydroxyl group, moisture and isocyanate group and the heat of reaction. This facilitates the generation of irregular interphenating network networks. The molecular bond structure becomes a local to reduce the impact on the applied to-be-protected object by storing, transferring, and spreading the applied impact energy in segments and irregular free volumes in the chain of the network structure. At this time, according to the present invention, when the burette bond and the urea bond are excessively generated, the surface state of the molded article is quantitatively, so care is required. In addition, the bifunctional polyol used with it serves to improve elasticity by imparting elasticity.

한편, 본발명에 따른 충격흡수재를 신발류의 안창용충격흡수 소재로 사용할 경우, 본발명에 따라 제작한 제품 시편(두께 0.3㎝~0.5㎝)을 적용부위의 형상에 따라 절단하여 안창용 금형내부의 위치에 삽입시키고 난 뒤 안창용 발포원액을 주입성형하면 본발명에 따른 시편은 안창에 접착되어 충격흡수용 안창이 제작된다.On the other hand, when the shock absorber according to the present invention is used as the shock absorbing material for footwear, the product specimen (thickness 0.3cm ~ 0.5cm) produced according to the present invention is cut in accordance with the shape of the application area to the position inside the insole mold After injection molding and injection molding the insole foam stock solution, the specimen according to the present invention is bonded to the insole to produce a shock-absorbing insole.

이때, 시편과 안창과의 접착을 위해 별도의 접착제를 사용하지 않아도 접착상태가 상당히 양호한데, 그 이유는 시편의 마이크로셀이 독립기포이기 때문에 안창 적용부위의 형상에 맞추어 절단된 조간단면의 독립 기포 사이사이로 안창용 발포원액이 침투하게 되어 시편과 물리적 혹은 때에 따라 화학적으로 결합이 형성되기 때문이다.At this time, the adhesive state is quite good even if no adhesive is used for the adhesion between the specimen and the insole, because the microcell of the specimen is an independent bubble. This is because the infiltrating foam solution for insoles penetrates between and physically or chemically bonds with the specimen.

따라서, 이와같은 본발명에 따른 발포형 충격흡수재는 종래의 것과는 달리 다음과 같은 장점을 갖게 된다.Therefore, unlike the conventional foamed shock absorber according to the present invention has the following advantages.

(1) 기존 충격흡수재에서와 같이 고가의 특수 아민계 방향족 변성폴리올 및 방향족 단량체등을 사용하지 않고서도 외기온도 변화에 따른 충격흡수 효과의 저하가 작다.(1) As in the conventional shock absorbers, the impact absorption effect is small due to the change in the outside air temperature without the use of expensive special amine-based aromatic modified polyols and aromatic monomers.

(2) 충격흡수재의 가격이 기존 제품보다 저렴하다.(2) The price of shock absorber is cheaper than existing products.

(3) 비중 변화가 다양하고 그 실용범위가 넓다.(3) Variation in specific gravity varies and its practical scope is wide.

(4) 기존 발포형 충격흡수재는 별도의 아스팔트나 점착부여제등의 여러 가지 충진제 혹은 첨가제를 혼합병용하여도 충격흡수 효과가 약 85% 이하인데 반해, 본 발명에 따른 흡수재는 별도의 충진제 혹은 첨가제를 사용하지 않고도 KSM-6518 시험에서 약 10% 이내의 반발탄성이 측정되므로서, 약 90% 이상의 탁월한 충격흡수 효과가 나타났다. 특히, 저온(섭씨 10℃ 이하)에서의 충격흡수 효과는 약 95% 이상으로 극히 우수하다.(4) Existing foam-type shock absorbers have a shock absorbing effect of about 85% or less even when using a combination of various fillers or additives such as asphalt or tackifiers, whereas the absorbent according to the present invention has a separate filler or additive. In the KSM-6518 test, the resilience within 10% was measured in the test, and the impact absorption effect was about 90% or more. In particular, the effect of shock absorption at low temperatures (10 ° C. or less) is extremely good at about 95% or more.

(5) KSM-6518 시험에 따르면, 기존 발포형 충격흡수재의 영구압축변형이 상온에서 약 10% 이상인데 반해, 본 발명에 따른 흡수재의 경우는 같은 에테르형이면서도 약 2%의 영구압축변형을 나타내어 우수하다.(5) According to the KSM-6518 test, while the permanent compression deformation of the existing foamed shock absorber is about 10% or more at room temperature, the absorbent according to the present invention exhibits the permanent compression deformation of about 2% despite the same ether type. great.

(6) 발포성형체 구조상 독립 기포를 가지기 때문에 충격흡수와 동시에 방음의 효과도 지닌다.(6) Since foams have independent bubbles in their structure, they have the effect of sound absorption and sound absorption.

(7) 성형작업 공정시 기존 우레탄 발포성형기를 그대로 사용할 수 있어서 별다른 시설을 필요로 하지 않고서도 예컨대, 금형성형법, 슬라브법, 스프레이법, RIM법 등으로 성형작업을 간단하게 시행할 수 있다.(7) The existing urethane foam molding machine can be used as it is in the molding work process, so that the molding work can be easily performed by, for example, mold molding method, slab method, spray method, RIM method, etc. without requiring any facility.

(8) 구조상의 잇점으로 인해 접착성이 우수하므로 적용부분에 따라 접착에 어려움이 없다.(8) There is no difficulty in adhesion depending on the applied part because of excellent adhesiveness due to structural advantages.

상술한 바와같은 여러 가지 장점을 가지고 있는 본발명에 따른 발포형 충격흡수재는 기존에 널리 사용되었던 자동차, 전차, 공장시설, 기계, 주택내장, 자동화사무기기등 충격방지나 방진.방음을 요하는 분야뿐만아니라 산업용 부분품으로 보다 바람직하게 사용될 수 있을뿐 아니라, 스포츠제품 분야에 있어서도 메트리스, 글러브, 보드, 보호대등 여러 가지 스포츠용구에 사용할 수 있는 등 그 사용분야를 더욱 다양하게 적용시킬 수가 있다.Foam-type shock absorber according to the present invention has a number of advantages as described above in the fields that require shock prevention, dustproof and soundproofing, such as automobiles, trams, factory facilities, machinery, home interiors, automated office equipment, etc. In addition, it can be used more desirably as an industrial part, and in the field of sports products, it can be used in various fields such as mattresses, gloves, boards, guards, etc.

이하, 본발명을 실시예에 의거 더욱 상세히 설명하면 다음과 같은바, 본발명이 실시예에 의거 반드시 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not necessarily limited to the examples.

[실시예 1]Example 1

수산기값이 22인 폴리(프로필렌옥사이드)와 4,4′-메칠렌비스(페닐이소시아네이트)를 건조불활성 기체를 유입하면서 100℃에서 반응시켜 잔존 이소시아네이트 함량 19중량%로 프로폴리머성분을 제조한다.A poly (propylene oxide) having a hydroxyl value of 22 and 4,4′-methylenebis (phenylisocyanate) are reacted at 100 ° C. while introducing a dry inert gas to prepare a propolymer component having a residual isocyanate content of 19% by weight.

다른 한편으로는 수산기값이 각각 56인 폴리(프로필렌옥사이드), 폴리(글리세린/프로필렌옥사이드), 폴리(에칠렌디아민/프로필렌옥사이드)를 각각 1/1/2 당량비로 배합하고, 첨가제로서 공지의 L3급아민을 1.6-헥사메칠렌글리콜에 소정량 분산시킨 반응촉진제와, 공지의 유기금속을 수산기값 75인 폴리(프로필렌옥사이드)에 고속교반.분산시켜놓은 반응촉진제 및 폴리메칠렌실록산을 폴리올 100pbw에 대해 각각 3pbw, 6pbw, 9pbw씩 첨가하고, 80℃로 승온시키면서 1시간 30분동안 교반.배합하여 수분함량 1.5±0.01중량%의 수지성분을 제조한다.On the other hand, poly (propylene oxide), poly (glycerine / propylene oxide), and poly (ethylenediamine / propylene oxide) each having a hydroxyl value of 56 are each blended in a 1/1/2 equivalent ratio, and a known L3-class as an additive A reaction accelerator in which a predetermined amount of amine is dispersed in 1.6-hexamethylene glycol, a high speed stirring / dispersion of a known organic metal in a poly (propylene oxide) having a hydroxyl value of 75, and a polymethylene siloxane with respect to 100 pbw of polyol. 3 pbw, 6 pbw, and 9 pbw, respectively, were added and stirred and mixed for 1 hour and 30 minutes while raising the temperature to 80 ° C. to prepare a resin component having a water content of 1.5 ± 0.01 wt%.

그다음 상기에서 제조한 프리폴리머 성분과 수지성분을 50℃로 예열하여 위에서 서술한 바와같은 방법으로 주입성형한다. 그결과 제조된 발포성형체 시편의 물성치는 다음 표 1과 같다.Then, the prepolymer component and the resin component prepared above are preheated to 50 ° C. and injection molded in the same manner as described above. As a result, the physical properties of the prepared foamed specimens are shown in Table 1 below.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

단, 금형온도는 70℃로 하고, 크림타임/리이징타임/테크프리타임/디몰딩타임= 14초/110초/70초/10분, 자유발포비중은 0.113g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, mold temperature is 70 ℃, cream time / rising time / tech free time / demolding time = 14 seconds / 110 seconds / 70 seconds / 10 minutes, free foaming ratio is 0.113g / cc, According to the Korean Industrial Standard M-6518 Test Method, the test was performed at an outdoor temperature of 20 ° C.

[실시예 2]Example 2

수산기값이 37인 폴리(프로필렌옥사이드)와 4,4′-메칠렌비스(페닐이소시아네이트)를 건조불활성 기체를 유입시키면서 100℃에서 반응시켜, 잔존 이소시아네이트 함량 15중량%로 프리폴리머 성분을 제조한다.A poly (propylene oxide) having a hydroxyl value of 37 and 4,4′-methylene bis (phenylisocyanate) are reacted at 100 ° C. while introducing a dry inert gas to prepare a prepolymer component having a residual isocyanate content of 15% by weight.

다른 한편으로는, 수산기값이 각각 37인 폴리(프로필렌옥사이드), 수산기값이 48인 폴리(글리세린/프로필렌옥사이드), 수산기값이 56인 폴리(에칠렌디아민/프로필렌옥사이드)를 각각 1/1/1 당량비로 배합하고, 첨가제로서 실시예1과 같은 반응촉진제와 유기실록산을 폴리올 100pbw에 대해 각각 3pbw, 5pbw, 9pbw씩 첨가하고, 80℃로 승온시키면서 1시간 30분동안 교반.배합하여 수분함량 1.8±0.01중량%의 수지성분을 제조한다.On the other hand, poly (propylene oxide) having a hydroxyl value of 37 each, poly (glycerine / propylene oxide) having a hydroxyl value of 48, and poly (ethylenediamine / propylene oxide) having a hydroxyl value of 56 are each 1/1/1. The mixture was added in an equivalence ratio, and 3 pbw, 5 pbw, and 9 pbw, respectively, of the reaction promoter and organosiloxane as in Example 1 were added to 100 pbw of polyol, and the mixture was stirred for 1 hour and 30 minutes while heating to 80 ° C. A resin component of 0.01% by weight is prepared.

그 이외의 공정은 실시예 1과 동일하게 실시하였다. 그결과 제조된 발포성형체 시편의 물성치는 다음 표 2와 같다.The other process was performed similarly to Example 1. As a result, the physical properties of the prepared foamed specimens are shown in Table 2 below.

[표 2]TABLE 2

Figure kpo00002
Figure kpo00002

단, 금형온도는 70℃로 하고, 크림타임/라이징타임/테크프리타임/디몰딩타임= 10초/130초/150초/7분, 자유발포비중은 0.110g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, the mold temperature is 70 ℃, cream time / rising time / tech free time / de-molding time = 10 seconds / 130 seconds / 150 seconds / 7 minutes, free foaming weight 0.110g / cc, property test conditions Korea It was performed at an outdoor temperature of 20 ° C. according to the Industrial Standard M-6518 Test Method.

[실시예 3]Example 3

수산기값이 22인 폴리(프로필렌옥사이드)와 4,4′-메칠렌비스(페닐이소시아네이트)를 건조불활성 기체를 유입하면서 100℃에서 반응시켜, 잔존 이소시아네이트 함량 18중량%로 프리폴리머 성분을 제조한다.A poly (propylene oxide) having a hydroxyl value of 22 and 4,4′-methylene bis (phenylisocyanate) are reacted at 100 ° C. while introducing a dry inert gas to prepare a prepolymer component with a residual isocyanate content of 18% by weight.

다른 한편으로는 수산기값이 각각 45인 폴리(프로필렌옥사이드), 수산기값이 51인 폴리(글리세린/프로필렌옥사이드), 수산기값이 70인 폴리(에칠렌디아민/프로필렌옥사이드)를 각각 2/1.5/1 당량비로 배합하고, 첨가제로서 실시예 1과 같은 반응촉진제와 유기실록산을 폴리올 100pbw에 대해 각각 3pbw, 6pbw, 7pbw씩 첨가하고, 80℃로 승온시키면서 1시가 30분동안 교반.배합하여 수분함량 2.00±0.01중량%의 수지성분을 제조한다.On the other hand, 2 / 1.5 / 1 equivalent ratio of poly (propylene oxide) having a hydroxyl value of 45, poly (glycerine / propylene oxide) having a hydroxyl value of 51, and poly (ethylenediamine / propylene oxide) having a hydroxyl value of 70, respectively 3 pbw, 6 pbw, and 7 pbw, respectively, were added to 100 pbw of the polyol, and the reaction promoter and organosiloxane as in Example 1 were added as additives, and the temperature was raised to 80 ° C. for 1 hour for 30 minutes. A resin component in weight% is prepared.

그 이외의 공정은 실시예 1과 동일하게 실시하였다. 그겨과 제조된 발포성형체 시편의 물성치는 다음 표 3과 같다.The other process was performed similarly to Example 1. Then, the physical properties of the prepared foamed specimens are shown in Table 3 below.

[표 3]TABLE 3

Figure kpo00003
Figure kpo00003

단, 금형온도는 70℃이고, 크림타임/라이징타임/테크프리타임/디몰딩타임=10초/90초/60초/7분, 자유발포 비중은 0.102g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, the mold temperature is 70 ℃, cream time / rising time / tech free time / de-molding time = 10 seconds / 90 seconds / 60 seconds / 7 minutes, free foaming specific gravity 0.102g / cc, property test conditions Korea It carried out at the outdoor temperature of 20 degreeC according to the standard standard M-6518 test method.

[실시예 4]Example 4

수산기값이 28인 폴리(프로필렌옥사이드)와 4,4′-메칠렌비스(페닐이소시아네이트)를 건조불활성 기체를 유입하면서 100℃에서 반응시켜, 잔존 이소시아네이트 함량 20중량%로 프리폴리머 성분을 제조한다.A poly (propylene oxide) having a hydroxyl value of 28 and 4,4′-methylene bis (phenylisocyanate) are reacted at 100 ° C. while introducing a dry inert gas to prepare a prepolymer component having a residual isocyanate content of 20% by weight.

다른 한편으로는, 수산기값이 각각 37인 폴리(프로필렌옥사이드), 수산기값이 84인 폴리(글리세린/프로필렌옥사이드), 수산기값이 75인 폴리(에칠렌디아민/프로필렌옥사이드)를 각각 1/1/1 당량비로 배합하고, 첨가제로서 실시예1과 같은 반응촉진제와 유기실록산을 폴리올 100pbw에 대해 각각 4pbw, 6pbw, 6pbw씩 첨가하고, 80℃로 승온시키면서 1시간 30분동안 교반.배합하여 수분함량 2.0±0.01중량%의 수지성분을 제조한다.On the other hand, poly (propylene oxide) having a hydroxyl value of 37 each, poly (glycerine / propylene oxide) having a hydroxyl value of 84, and poly (ethylenediamine / propylene oxide) having a hydroxyl value of 75 are each 1/1/1. 4 equivalents, 6 pbw and 6 pbw of the same reaction promoter and organic siloxane as 100 g of polyol were added to 100 pbw of polyol, and stirred for 1 hour and 30 minutes while raising the temperature to 80 ° C. A resin component of 0.01% by weight is prepared.

그 이외의 공정은 실시예 1과 동일하게 실시하였다. 그결과 제조된 발포성형체 시편의 물성치는 다음 표 4와 같다.The other process was performed similarly to Example 1. As a result, the physical properties of the prepared foamed specimens are shown in Table 4 below.

[표 4]TABLE 4

Figure kpo00004
Figure kpo00004

단, 금형온도는 70℃로 하고, 크림타임/라이징타임/테크프리타임/디몰딩타임= 10초/90초/100초/7분, 자유 발포비중은 0.107g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, mold temperature is 70 ℃, cream time / rising time / tech free time / demolding time = 10 seconds / 90 seconds / 100 seconds / 7 minutes, free foaming specific gravity is 0.107g / cc, property test condition is Korea It was performed at an outdoor temperature of 20 ° C. according to the Industrial Standard M-6518 Test Method.

[실시예 5]Example 5

수산기값이 28인 폴리(프로필렌옥사이드)와 4,4′-메칠렌비스(페닐이소시아네이트)를 건조불활성 기체를 유입하면서 100℃에서 반응시켜, 잔존 이소시아네이트 함량 20중량%로 프리폴리머 성분을 제조한다.A poly (propylene oxide) having a hydroxyl value of 28 and 4,4′-methylene bis (phenylisocyanate) are reacted at 100 ° C. while introducing a dry inert gas to prepare a prepolymer component having a residual isocyanate content of 20% by weight.

다른 한편으로는, 수산기값이 각각 56인 폴리(프로필렌옥사이드), 수산기값이 48인 폴리(글리세린/프로필렌옥사이드), 수산기값이 64인 폴리(에칠렌디아민/프로필렌옥사이드)를 각각 3/1/1 당량비로 배합하고, 첨가제로서 실시예1과 같은 반응촉진제와 유기실록산을 폴리올 100pbw에 대해 각각 4pbw, 10pbw, 10pbw씩 첨가하고, 80℃로 승온시키면서 1시간 30분동안 교반.배합하여 수분함량 1.5±0.01중량%의 수지성분을 제조한다.On the other hand, poly (propylene oxide) having a hydroxyl value of 56 each, poly (glycerine / propylene oxide) having a hydroxyl value of 48, and poly (ethylenediamine / propylene oxide) having a hydroxyl value of 64 are each 3/1/1. 4 equivalents, 10 pbw, and 10 pbw of the same reaction promoter and organosiloxane were added to 100 pbw of polyol, respectively, and stirred for 1 hour and 30 minutes while raising the temperature to 80 ° C. A resin component of 0.01% by weight is prepared.

그 이외의 공정은 실시예 1과 동일하게 실시하였다. 그결과 제조된 발포성형체 시편의 물성치는 다음 표 5와 같다.The other process was performed similarly to Example 1. As a result, the physical properties of the prepared foamed specimens are shown in Table 5 below.

[표 5]TABLE 5

Figure kpo00005
Figure kpo00005

단, 금형온도는 60℃로 하고, 크림타임/라이징타임/테크프리타임/디몰딩타임= 11초/140초/70초/7분, 자유 발포비중은 0.125g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, mold temperature is 60 ℃, cream time / rising time / tech free time / demolding time = 11 seconds / 140 seconds / 70 seconds / 7 minutes, free foaming specific gravity is 0.125g / cc, and property test condition is Korea It was performed at an outdoor temperature of 20 ° C. according to the Industrial Standard M-6518 Test Method.

[실시예 6]Example 6

일반적인 작업방법 및 조건은 실시예 5와 동일하게 실시하였다. 그결과 제조된 발포성형체 시편의 물성치는 다음 표 6과 같다.General working methods and conditions were carried out in the same manner as in Example 5. As a result, the physical properties of the prepared foamed specimens are shown in Table 6 below.

[표 6]TABLE 6

Figure kpo00006
Figure kpo00006

단, 금형온도는 60℃로 하고, 크림타임/라이징타임/테크프리타임/디몰딩타임= 11초/140초/70초/7분, 자유 발포비중은 0.125g/cc, 물성시험조건은 한국공업표준규격 M-6518 시험법에 의거 외기온도 20℃에서 행하였다.However, mold temperature is 60 ℃, cream time / rising time / tech free time / demolding time = 11 seconds / 140 seconds / 70 seconds / 7 minutes, free foaming specific gravity is 0.125g / cc, and property test condition is Korea It was performed at an outdoor temperature of 20 ° C. according to the Industrial Standard M-6518 Test Method.

[비교예][Comparative Example]

[표 7]TABLE 7

Figure kpo00007
Figure kpo00007

Claims (4)

폴리우레탄 마이크로셀상의 발포형 충격흡수재에 있어서, 방향족 디이소시아네이트와 수산기값이 20~560mgKOH/g인 폴리(프로필렌옥사이드)폴리올로부터 제조된 잔존 이소시아네이트 함량이 5~25중량%인 프리폴리머 성분 혹은 디이소시아네이트모노머 성분과, 쇄말단 수산관능기가 2개이고 수산기값이 17~225mgKOH/g인 폴리(프로필렌옥사이드)폴리올, 쇄말단 수산관능기가 3개이고 수산기값이 30~1680mgKOH/g인 폴리(글리세린/프로필렌옥사이드)폴리올, 쇄말단 수산관능기가 4개이고 수산기값이 45~2245mgKOH/g인 폴리(에틸렌디아민/프로필렌옥사이드)폴리올, 3급아민계 및 유기금속계 반응촉진데, 폴리알킬 혹은 폴리알콕시 실록산으로 구성되고, 수분함량이 0.8~3.0중량%인 수지성분의 혼합.고속교반으로 형성되고, 그 반발탄성이 15% 이하이고, 영구압축변형이 10% 이하인 것을 특징으로 하는 발포형 충격흡수재.Foamed shock absorbers on polyurethane microcells, with prepolymer components or diisocyanate monomers having a residual isocyanate content of 5 to 25% by weight, prepared from aromatic diisocyanates and poly (propylene oxide) polyols having a hydroxyl value of 20 to 560 mgKOH / g. Components, poly (propylene oxide) polyols having two chain-end hydroxyl functional groups and 17-225 mgKOH / g hydroxyl value, and poly (glycerine / propylene oxide) polyols having three chain-end hydroxyl functional groups and 30-1680 mgKOH / g hydroxyl value , Poly (ethylenediamine / propyleneoxide) polyol having 4 chain-end hydroxyl functional groups and hydroxyl value of 45 ~ 2245mgKOH / g, tertiary amine and organometallic reactions, consisting of polyalkyl or polyalkoxy siloxane, water content 0.8 to 3.0% by weight of the resin component is mixed, formed by high-speed stirring, the resilience is less than 15%, the permanent compression deformation is less than 10% Foam-type shock absorber, characterized in that. 폴리우레탄 마이크로셀상으이 발포형 충격습수재를 제조함에 있어서, (가) 디이소시아네이트모노머와, 프로필렌옥사이드로부터 제조된 폴리디올을 2차 부가 중합반응시켜서 프리폴리머를 제조하고, (나) 쇄말단 수산관능기가 2~4개이거나 활성화 수소원자를 가지고 있는 프로필렌옥사이드계 폴리올 및 아민계 지방족폴리올과 반응촉진제, 유기실록산등을 혼합교반시켜서 수지성분을 제조한후, (다) 상기 (가)의 프리폴리머 성분과 상기 (나)의 수지성분을 약 70℃로 예열시켜서 고속교반.주형시킴으로써 발포성형체로 제조함을 특징으로 하는 발포형 충격흡수재의 제조방법.In preparing a foam type impact modulus material on a polyurethane microcell, (a) a secondary addition polymerization reaction of a diisocyanate monomer and a polydiol prepared from propylene oxide to prepare a prepolymer, and (b) a chain-end hydroxyl functional group After mixing and stirring two to four propylene oxide-based polyols and amine-based aliphatic polyols having an active hydrogen atom, reaction accelerators, organosiloxanes, and the like to prepare a resin component, (c) the prepolymer component of (a) and the A method for producing a foamed shock absorber, characterized in that the resin component of (b) is preheated to about 70 ° C. and stirred at high speed to form a foamed molded product. 제3항에 있어서, 상기 (나)의 반응촉진제 성분은 모노머상 혹은 저분자량 폴리디올에 디아민 및 유기금속을 혼합사용하여서 제조함을 특징으로 하는 발포형 충격흡수재의 제조방법.The method of claim 3, wherein the reaction promoter component of (b) is prepared by mixing diamine and organometallic in monomer phase or low molecular weight polydiol. 제3항에 있어서, 수지성분은 0.3~3.0중량%의 수분을 함유하도록 제조함을 특징으로 하는 발포형 충격흡수재의 제조방법.The method of manufacturing a foamed shock absorber according to claim 3, wherein the resin component is prepared to contain 0.3 to 3.0% by weight of water.
KR1019890014040A 1989-09-29 1989-09-29 Foamed impect absorption agent KR920009686B1 (en)

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KR1019890014040A KR920009686B1 (en) 1989-09-29 1989-09-29 Foamed impect absorption agent
EP90118572A EP0420242B1 (en) 1989-09-29 1990-09-27 An impact resistant polyurethane foam
DE69024155T DE69024155T2 (en) 1989-09-29 1990-09-27 An impact-resistant polyurethane foam
JP2262944A JPH03124720A (en) 1989-09-29 1990-09-29 Shock-absorbing material comprising polyurethane foam and its manufacture
US07/592,486 US5098936A (en) 1989-09-29 1990-10-01 Impact resistant polyurethane foam and a method for manufacturing thereof

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100836581B1 (en) * 2007-03-29 2008-06-10 (주)생활낙원 The impact relief member manufactured by the polyurethane foam and their manufacturing method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100836581B1 (en) * 2007-03-29 2008-06-10 (주)생활낙원 The impact relief member manufactured by the polyurethane foam and their manufacturing method

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