KR20010076929A - Thermoplastic elastomer compounds for footwear - Google Patents

Thermoplastic elastomer compounds for footwear Download PDF

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KR20010076929A
KR20010076929A KR1020000004365A KR20000004365A KR20010076929A KR 20010076929 A KR20010076929 A KR 20010076929A KR 1020000004365 A KR1020000004365 A KR 1020000004365A KR 20000004365 A KR20000004365 A KR 20000004365A KR 20010076929 A KR20010076929 A KR 20010076929A
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thermoplastic elastomer
weight
parts
resin
elastomer composition
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KR100340093B1 (en
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유종선
윤정식
최경만
임성욱
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박정수
한국신발피혁연구소
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    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B13/00Burglar, theft or intruder alarms
    • G08B13/02Mechanical actuation
    • G08B13/08Mechanical actuation by opening, e.g. of door, of window, of drawer, of shutter, of curtain, of blind
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B25/00Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems
    • G08B25/01Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium
    • G08B25/012Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium using recorded signals, e.g. speech
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B25/00Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems
    • G08B25/01Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium
    • G08B25/04Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium using a single signalling line, e.g. in a closed loop
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B25/00Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems
    • G08B25/01Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium
    • G08B25/08Alarm systems in which the location of the alarm condition is signalled to a central station, e.g. fire or police telegraphic systems characterised by the transmission medium using communication transmission lines
    • GPHYSICS
    • G08SIGNALLING
    • G08BSIGNALLING OR CALLING SYSTEMS; ORDER TELEGRAPHS; ALARM SYSTEMS
    • G08B3/00Audible signalling systems; Audible personal calling systems
    • G08B3/10Audible signalling systems; Audible personal calling systems using electric transmission; using electromagnetic transmission
    • G08B3/1008Personal calling arrangements or devices, i.e. paging systems
    • G08B3/1016Personal calling arrangements or devices, i.e. paging systems using wireless transmission
    • G08B3/1025Paging receivers with audible signalling details
    • G08B3/1033Paging receivers with audible signalling details with voice message alert

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Health & Medical Sciences (AREA)
  • Audiology, Speech & Language Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Networks & Wireless Communication (AREA)
  • Electromagnetism (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A thermoplastic elastomer composition for footwear is provided, to improve flowability, abrasion resistance and durability, so that it is suitable for molding polymers. CONSTITUTION: The thermoplastic elastomer composition comprises 100 parts by weight of a base which is a styrene-based thermoplastic elastomer, or a mixture of 70-95 wt.% of a styrene-based thermoplastic elastomer and 5-30 wt.% of a polystyrene-based resin selected from general purpose polystyrene(GPPS) and high impact polystyrene(HIPS); 5-50 parts by weight of a flowability-improving agent selected from a polyolefin resin and a plasticizer; 3-50 parts by weight of silica as a filler; 0.5-20 parts by weight of an anti-abrasion improving agent; 0.2-20 parts by weight of a silane coupling agent; and other common additives. Preferably the polyolefin resin is selected from polyethylene resin, polypropylene resin, ethylene-vinyl acetate resin and ethylene-alpha olefin resin.

Description

신발용 열가소성 탄성체 조성물{Thermoplastic elastomer compounds for footwear}Thermoplastic elastomer compounds for footwear

본 발명은 신발용 열가소성 탄성체 조성물에 관한 것으로서, 더욱 상세하게는 스티렌계 열가소성 탄성체 복합체를 기재로 하고 여기에 열안정제, 산화방지제, 자외선안정제 및 통상의 첨가제가 함유되어 있는 열가소성 탄성체 조성물에 있어서, 상기 조성물 중 기재로서 스티렌계 열가소성 탄성체 단독, 또는 스티렌계 열가소성 탄성체와 폴리스티렌계 수지와의 블렌드물을 사용하고, 여기에 흐름성 개선제, 충전제 및 내마모성 향상제를 함유시켜 내마모성, 내구성 및 제반물성이 뛰어나고 흐름성이 높아 고분자 물질의 성형에 적합한 신발용 열가소성 탄성체 조성물에 관한 것이다.The present invention relates to a thermoplastic elastomer composition for shoes, and more particularly, to a thermoplastic elastomer composition based on a styrene-based thermoplastic elastomer composite and containing a heat stabilizer, an antioxidant, an ultraviolet stabilizer, and a conventional additive. Styrene-based thermoplastic elastomer alone or a blend of styrene-based thermoplastic elastomer and polystyrene-based resin is used as a base material in the composition, and it contains a flow improver, a filler, and an anti-wear enhancer, thereby providing excellent wear resistance, durability, and overall properties and flowability. The present invention relates to a thermoplastic elastomer composition for footwear suitable for molding a high molecular material.

열가소성 탄성체는 일반적으로 스포츠화, 부츠, 슬리퍼, 군화 등의 신발용의 겉창재 뿐만 아니라 절연재, 칩 케이스 등의 전기·전자재, 기어 손잡이, 보조 손잡이, 운전대 커버 및 도어 트림 등의 자동차재, 기타 완구류, 스포츠용품, 호스, 튜브, 장식재 등의 다양한 용도로 사용될 수 있다.Thermoplastic elastomers are generally used for footwear, such as sports shoes, boots, slippers, and boots, as well as electrical and electronic materials such as insulation materials and chip cases, automotive materials such as gear handles, auxiliary handles, steering wheel covers, and door trims, etc. It can be used for various purposes such as toys, sporting goods, hoses, tubes, decorative materials.

이중 현재 사용되고 있는 신발용 겉창 소재로는 열경화성 고무가 가장 일반화된 소재이며, 이로 인해 생산기술 또한 프레스에 의한 압축성형으로 제한되어 작업인력 집중에 의한 가격상승과 원소재에 대한 근본적인 물성한계를 야기하므로 제품의 고부가가치와 가격 경쟁력을 얻지 못하고 있어 새로운 소재 및 생산방식의 적용이 필수적이라 하겠다.Among them, thermosetting rubber is the most common material used for shoe outsole, and production technology is also limited to compression molding by press, which raises the price due to the concentration of workforce and fundamental property limits for raw materials. The application of new materials and production methods is indispensable because the products are not gaining high value and price competitiveness.

상기 열가소성 탄성체는 자체 비중이 1이하로서 상기 열경화성 고무에 비하여 10%이상 경량화할 수 있으며, 또한 플라스틱과 같이 사출 생산이 가능하기 때문에 대량생산 체제에 적합한 재료이지만, 신발 겉창 소재로 사용되기에는 현저히 떨어지는 물성 한계로 인해 제한적으로 사용되고 있는 실정이다.The thermoplastic elastomer has a specific gravity of 1 or less and can be reduced by more than 10% compared to the thermosetting rubber, and is also suitable for mass production because it can be injected and produced like plastic, but it is considerably inferior to being used as a shoe outsole material. Due to the physical property limitations are limited use.

이에, 본 발명자들은 종래 상기와 같은 문제점을 해결하기 위하여, 종래 열가소성 탄성체 조성물 중 기재로서 스티렌계 열가소성 탄성체 단독 또는 스티렌계 열가소성 탄성체와 폴리스티렌 수지와의 블렌드물을 기재로 하고, 다양한 첨가제를 투입하여 사출, 압출 및 열프레스 성형함으로써, 내마모성, 내구성 및 제반물성이 뛰어나고 흐름성이 높아 고분자 물질의 성형에 적합한 신발용 열가소성 탄성체 조성물을 제공하는데 그 목적이 있다.In order to solve the above problems, the present inventors use a styrene-based thermoplastic elastomer alone or a blend of a styrene-based thermoplastic elastomer and a polystyrene resin as a substrate in a conventional thermoplastic elastomer composition, and inject various additives to inject the same. It is an object of the present invention to provide a thermoplastic elastomer composition for footwear suitable for molding a polymer material by extrusion, hot press molding, and excellent wear resistance, durability and various physical properties and high flowability.

본 발명은 스티렌계 열가소성 탄성체를 기재로 하고, 여기에 산화방지제, 자외선 안정제 및 통상의 첨가제가 함유되어 있는 열가소성 탄성체 조성물에 있어서,The present invention is based on a styrenic thermoplastic elastomer, in which the thermoplastic elastomer composition containing an antioxidant, a UV stabilizer and a usual additive,

상기 기재로는 스티렌계 열가소성 탄성체 단독, 또는 스티렌계 열가소성 탄성체 70 ∼ 95 중량부와 통상적인 폴리스티렌(general purpose polystyrene: GPPS) 및 고내충격성 폴리스티렌(high impact polystyrene: HIPS) 중에서 선택된 폴리스티렌계 수지 5 ∼ 30 중량부가 블렌드된 블렌드물이 사용되고, 상기 기재 100 중량부에 대하여 폴리올레핀계 수지 및 가소제 중에서 선택된 흐름성 개선제 5 ∼ 50 중량부, 충전제로서 실리카 3 ∼ 50 중량부, 내마모성 향상제 0.5 ∼ 20 중량부 및 실란 커플링제 0.2 ∼ 20 중량부가 함유되어 있는 신발용 열가소성 탄성체 조성물을 그 특징으로 한다.The substrate may include styrene-based thermoplastic elastomers alone, or polystyrene-based resins 5 to 30 selected from 70 to 95 parts by weight of styrene-based thermoplastic elastomers, and general purpose polystyrene (GPPS) and high impact polystyrene (HIPS). Blended parts blended by weight are used, and 5 to 50 parts by weight of a flow improver selected from polyolefin resins and plasticizers, 3 to 50 parts by weight of silica as a filler, 0.5 to 20 parts by weight of abrasion resistance improver, and silane based on 100 parts by weight of the substrate. It is characterized by the thermoplastic elastomer composition for shoes which contains 0.2-20 weight part of coupling agents.

이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명에서 열가소성 탄성체를 이용한 신발용 조성물을 제조하기 위하여 스티렌계 열가소성 탄성체를 단독으로 사용하거나, 또는 내후성이 우수한 스티렌계 열가소성 탄성체와 폴리스티렌 수지인 통상적으로 사용되는 폴리스티렌(general purpose polystyrene: GPPS) 및 고내충격성 폴리스티렌(high impact polystyrene: HIPS) 중에서 선택된 것을 블렌드하여 사용한다. 즉, 본 발명에 따른 열가소성 탄성체 조성물에 기재로서는 스티렌계 열가소성 탄성체를 단독으로 사용하거나, 또는 경도조절을 위하여 스티렌계 열가소성 탄성체 70 ∼ 95 중량부와 폴리스티렌계 수지 5 ∼ 30 중량부를 블렌드하여 사용할 수 있다. 이때, 상기 스티렌계 열가소성 탄성체의 함량이 상기 범위 미만이면 경도상승의 효과가 미비하고, 반면 상기 범위를 초과하면 흐름성 저하 및 경도가 탄성범위를 벗어나는 문제가 있다.In the present invention, in order to prepare a shoe composition using a thermoplastic elastomer, a styrene-based thermoplastic elastomer is used alone, or a polystyrene (general purpose polystyrene (GPPS)) and a high temperature which are styrene-based thermoplastic elastomer and a polystyrene resin having excellent weather resistance. Blends selected from high impact polystyrene (HIPS) are used. That is, as the substrate in the thermoplastic elastomer composition according to the present invention, a styrene-based thermoplastic elastomer may be used alone, or 70 to 95 parts by weight of a styrene-based thermoplastic elastomer and 5 to 30 parts by weight of a polystyrene resin may be used for hardness control. . At this time, if the content of the styrene-based thermoplastic elastomer is less than the range, the effect of increasing the hardness is insignificant, whereas if the content of the styrene-based thermoplastic elastomer exceeds the above range, there is a problem that the flowability and hardness is out of the elastic range.

본 발명에서는 사출성형시 가공성 향상을 위하여 흐름성 개선제로서 폴리올레핀계 수지 및 가소제 중에서 선택하여 사용하는 것이 가능하다. 폴리올레핀계 수지로는 폴리프로필렌 수지, 폴리에틸렌 수지, 에틸렌-비닐 아세테이트 수지, 에틸렌-α올레핀 수지 중에서 선택하여 사용하며, 가소제로는 파라핀계 오일, 나프텐계 오일, 방향족계 오일 및 이들의 혼합물 중에서 선택하여 사용할 수 있다.In the present invention, in order to improve processability during injection molding, it is possible to use a polyolefin resin and a plasticizer as a flow improving agent. The polyolefin resin may be selected from polypropylene resin, polyethylene resin, ethylene-vinyl acetate resin, and ethylene-αolefin resin, and the plasticizer may be selected from paraffinic oil, naphthenic oil, aromatic oil, and mixtures thereof. Can be used.

또한, 본 발명에서 열가소성 탄성체 조성물의 내마모성 향상을 위하여 보강성 충전제를 사용할 수 있으며, 이러한 충전제로는 입자크기가 아주 작아 조성물에 고르게 분산되어 물성을 저하시키지 않아야 하기 때문에 일반적으로 건식법 실리카가 가장 적합하다. 건식법 실리카는 사용량에 따라 열가소성 탄성체 조성물의 경도와 물리적 특성을 좌우하는데, 건식법 실리카의 경우 그 사용량은 기재 100 중량부에 대하여 3 ∼ 50 중량부로 사용하는 것이 바람직하다. 이때, 상기 충전제로 사용되는 실리카의 함량이 3 중량부 미만으로 사용할 때는 물성향상 효과가 나타나지 않고, 반면 50 중량부를 초과하여 사용시 경도가 높게 나타나는 문제가 있다.In addition, in the present invention, reinforcing fillers may be used to improve abrasion resistance of the thermoplastic elastomer composition. As such fillers, generally, dry silica is most suitable because the particle size is so small that it should be uniformly dispersed in the composition so as not to degrade physical properties. . Dry silica determines the hardness and physical properties of the thermoplastic elastomer composition depending on the amount of use. In the case of dry silica, the amount is preferably 3 to 50 parts by weight based on 100 parts by weight of the substrate. At this time, when the content of the silica used as the filler is less than 3 parts by weight does not appear to improve the physical properties, while when used in excess of 50 parts by weight there is a problem that the hardness is high.

또한, 본 발명은 열가소성 탄성체 조성물의 내마모성 향상을 위하여 내마모 향상제로서 폴리옥테나머, 불소고무, 테프론 파우더, 스테아린산 아미드, 황화몰리브덴, 실리콘 고무 및 실리콘 오일 중에서 선택하여 단독 또는 혼합 사용할 수 있다. 그 사용함량은 기재 100 중량부에 대하여 0.5 ∼ 20 중량부로 사용하며, 이때 상기 범위를 한정하는 이유는 상기 범위 미만이면 충분한 효과를 얻을 수 없으며, 상기 범위를 초과하면 내마모성 향상효과가 없으면서 제반 물성도 저하되기때문이다.In addition, the present invention can be used alone or in combination of polyoctenamer, fluorine rubber, teflon powder, stearic acid amide, molybdenum sulfide, silicone rubber and silicone oil as an anti-wear enhancer for improving the wear resistance of the thermoplastic elastomer composition. The content is used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the base material, and the reason for limiting the above range is not enough effect to be obtained if it is less than the above range. Because it is degraded.

본 발명은 열가소성 탄성체의 내구성 향상을 위하여 통상의 열안정제, 산화방지제 및 자외선 안정제를 단독 또는 혼합 사용할 수 있다.The present invention may be used alone or in combination of conventional heat stabilizers, antioxidants and ultraviolet stabilizers to improve the durability of the thermoplastic elastomer.

이러한 열안정제로는 카드뮴(Cd), 바륨(Ba), 아연(Zn) 및 칼슘(Ca) 중에서 선택된 금속을 함유하고 있는 금속 스테아레이트로서 기재 100 중량부에 대하여 0.1 ∼ 3 중량부로 사용할 수 있다.As such a heat stabilizer, a metal stearate containing a metal selected from cadmium (Cd), barium (Ba), zinc (Zn), and calcium (Ca) may be used in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the substrate.

산화방지제로는 페놀계 및 아릴아민계 산화방지제 중에서 선택된 1차 산화방지제와, 포스파이트계 및 티오에스터계 산화방지제 중에서 선택된 2차 산화방지제 중에서 선택하여 기재 100 중량부에 대하여 0.1 ∼ 5 중량부로 사용될 수 있다.The antioxidant may be selected from primary antioxidants selected from phenolic and arylamine antioxidants and secondary antioxidants selected from phosphite and thioester antioxidants and used as 0.1 to 5 parts by weight based on 100 parts by weight of the substrate. Can be.

또한, 자외선 안정제로는 하이드록시 벤조페논계, 하이드록시페닐 벤조트리아졸계, 살리실레이트, 벤조에이트 및 시아노아크릴레이트계의 자외선 흡수제, 니켈화합물을 이용한 퀀처(guencher), 하이드로퍼옥사이드 분해제, 라디칼 포착제인 할스(HALS, Hindered Amine Light Stabilizer)가 기재 100 중량부에 대하여 0.1 ∼ 5 중량부로 사용될 수 있다.In addition, UV stabilizers include hydroxy benzophenone-based, hydroxyphenyl benzotriazole-based, salicylate, benzoate and cyanoacrylate-based ultraviolet absorbers, quenchers using nickel compounds, hydroperoxide decomposers, A radical scavenger HLS (Hindered Amine Light Stabilizer) may be used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the substrate.

더욱이 본 발명에서는 물성 향상을 위해서 실란 커플링제를 사용할 수 있는데, 본 발명에서 사용되는 실란 커플링제의 종류로는 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리클로로실란, 비닐트리(2-메톡시에톡시)실란, 3-아미노프로필에톡시실란, 머캅토프로필트리메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸트리메톡시실란, 3-글리시딜옥시프로필트리메톡시실란, 3-글리시딜옥시프로필메틸디에톡시실란 및 비스-(3-(트리에톡시실릴)-프로필)테트라설파이드 중에서 선택된 것을사용할 수 있다. 상기 실란 커플링제의 사용량은 기재 100 중량부에 대하여 0.2 ∼ 20 중량부로 사용하는 것이 바람직하다. 이때, 실란 커플링제를 0.2 중량부 미만으로 사용할 경우 첨가 효과가 없으며, 반면 20 중량부를 넘을 경우 첨가량에 비해 물성향상이 미비하여 경제성면에서 불리하게 된다.In addition, in the present invention, a silane coupling agent may be used to improve physical properties, and examples of the silane coupling agent used in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, and vinyltri (2- Methoxyethoxy) silane, 3-aminopropylethoxysilane, mercaptopropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxy Any selected from silane, 3-glycidyloxypropylmethyldiethoxysilane and bis- (3- (triethoxysilyl) -propyl) tetrasulfide can be used. It is preferable to use the usage-amount of the said silane coupling agent at 0.2-20 weight part with respect to 100 weight part of base materials. In this case, when the silane coupling agent is used in less than 0.2 parts by weight, there is no addition effect, whereas when it exceeds 20 parts by weight, the physical properties are not improved compared to the added amount, which is disadvantageous in terms of economics.

이상에서 설명한 바와 같은 조성성분들을 이용하여 통상의 열가소성 탄성체 성형방법인 사출, 압출, 압축 또는 이송(transfer) 성형에 의해 신발창을 제조할 수 있다.The shoe sole may be manufactured by injection, extrusion, compression, or transfer molding, which is a conventional thermoplastic elastomer molding method using the composition components as described above.

이하 본 발명을 실시예에 의거하여 상세히 설명하겠는바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by Examples.

실시예 1 ∼ 3 및 비교예 1Examples 1-3 and Comparative Example 1

다음 표 1과 같은 조성과 함량으로 다음과 같은 방법을 이용하여 열가소성 탄성체 조성물을 제조하였다.Next, the thermoplastic elastomer composition was prepared by using the following composition and content as shown in Table 1 below.

스티렌계 열가소성 탄성체(TPE LG 475 및 TPE KTR 201) 폴리머 복합체에 파라핀계 오일, 테프론 파우더, 실리콘 오일, 산화방지제, 자외선 안정제, 산화티탄, 카본블랙을 첨가하여 110 ∼ 120 ℃ 온도의 니이더에서 약 15분간 혼련한 후, 다이가 140 ℃, 실린더가 130 ℃, 호퍼가 100 ℃인 압출기에 혼련물을 투입하여 펠렛상의 시료를 제조하였다. 이렇게 제조된 조성물을 배럴(barrel) 온도가 140 ∼ 190 ℃이고, 금형이 실온인 조건에서 사출공정을 통해 시편을 제조하였다.Addition of paraffinic oil, Teflon powder, silicone oil, antioxidants, UV stabilizer, titanium oxide, and carbon black to styrene thermoplastic elastomer (TPE LG 475 and TPE KTR 201) polymer composite After kneading for 15 minutes, the kneaded material was thrown into the extruder which is 140 degreeC of die, 130 degreeC of cylinder, and 100 degreeC of hopper, and prepared the pellet sample. In the composition thus prepared, a specimen was prepared by an injection process under a condition in which the barrel temperature is 140 to 190 ° C. and the mold is at room temperature.

상기 시편에 대하여 다음과 방법으로 물성을 측정하여 그 결과를 다음 표 2에 나타내었다.The physical properties of the specimens were measured by the following method, and the results are shown in Table 2 below.

[시험방법][Test Methods]

① 경도: 에스커 에이(Asker A) 타입의 경도계로 ASTM D-224 방법에 준하여 측정하였다.① Hardness: It was measured according to ASTM D-224 method with an Escker A type hardness tester.

② 인장강도 및 신장율: 제조된 시이트(sheet)를 다이(die) A 틀칼로 시험편을 제작하여 ASTM D-412에 준하여 인장강도와 신장율을 측정하였다. 이때, 동일 시험에 사용한 시험편은 5개로 하였다.② Tensile strength and elongation rate: The prepared sheet (sheet) was made with a die A die knife to measure the tensile strength and elongation rate according to ASTM D-412. At this time, five test pieces were used for the same test.

③ 인열강도: ASTM D-634에 준하여 측정을 하였으며, 5회 반복 시험한 후, 중간값에서 20% 이상 벗어나는 시편은 제외시키고 평균을 내어 측정하였다.③ Tear strength: measured in accordance with ASTM D-634, and after five repeated tests, the average was measured by excluding the specimen deviating more than 20% from the median value.

④ 마모도: NBS 마모도와 아크론 마모도를 각각 측정하였다.④ Abrasion degree: NBS wear and Akron wear were measured, respectively.

(가) NBS 마모도 - ASTM 1630에 준하여 규격화된 시편을 5개 시험한 후, 최대ㆍ최소값을 제외하고 평균을 내어 측정하였으며, 이때 사용한 NBS 마모도(%)는 다음 식에 의해 계산하였다.(A) NBS Abrasion-After testing five specimens standardized according to ASTM 1630, the average was measured except for the maximum and minimum values. The NBS wear (%) used at this time was calculated by the following equation.

(나) 아크론 마모도 - KSM 6624에 준하여 측정하였고, 다음 식에 의해 계산하였다.(B) Akron wear-It was measured according to KSM 6624 and calculated by the following equation.

⑤ 용융지수(MI) : ASTM D-1238에 준하여 3회 시험한 후, 평균을 내어 측정하였다.⑤ Melt Index (MI): After testing three times according to ASTM D-1238, the average was measured.

이상에서 설명한 바와 같이, 본 발명의 열가소성 탄성체 조성물은 스티렌계 열가소성 탄성체와 각종 수지와의 블렌드물을 기재로 하고 여기에 흐름성 개선제, 충전제, 내마모 향상제 및 통상의 첨가제를 투입하여 사출, 압출 및 열프레스 성형함으로써, 내마모성, 내구성 및 제반물성이 뛰어나고 흐름성이 높아 성형이 용이하고, 전기ㆍ전자재, 자동차재 및 장식재 등의 다양한 용도로 사용하기에 적합할 뿐만 아니라, 특히 신발 겉창용 소재로서 내마모성이 우수하여 스포츠화용 겉창으로 사용할 수 있는 조성물을 제공하는 것이 가능하다.As described above, the thermoplastic elastomer composition of the present invention is based on a blend of a styrene-based thermoplastic elastomer and various resins, and is injected, extruded, and injected with a flow improver, a filler, an anti-wear enhancer, and a conventional additive. The hot press molding provides excellent abrasion resistance, durability and various physical properties, high flowability, and easy molding, and is not only suitable for use in various applications such as electric and electronic materials, automobile materials and decorative materials, but also particularly as a shoe outsole material. It is possible to provide a composition which is excellent in wear resistance and can be used as an outsole for sports shoes.

Claims (5)

스티렌계 열가소성 탄성체를 기재로 하고, 여기에 산화방지제, 자외선 안정제 및 통상의 첨가제가 함유되어 있는 열가소성 탄성체 조성물에 있어서,In a thermoplastic elastomer composition based on a styrene-based thermoplastic elastomer, which contains an antioxidant, an ultraviolet stabilizer, and a usual additive, 상기 기재로는 스티렌계 열가소성 탄성체 단독, 또는 스티렌계 열가소성 탄성체 70 ∼ 95 중량부와 통상적인 폴리스티렌(general purpose polystyrene: GPPS) 및 고내충격성 폴리스티렌(high impact polystyrene: HIPS) 중에서 선택된 폴리스티렌계 수지 5 ∼ 30 중량부가 블렌드된 블렌드물이 사용되고, 상기 기재 100 중량부에 대하여 폴리올레핀계 수지 및 가소제 중에서 선택된 흐름성 개선제 5 ∼ 50 중량부, 충전제로서 실리카 3 ∼ 50 중량부, 내마모성 향상제 0.5 ∼ 20 중량부 및 실란 커플링제 0.2 ∼ 20 중량부가 함유되어 있는 것임을 특징으로 하는 신발용 열가소성 탄성체 조성물.The substrate may include styrene-based thermoplastic elastomers alone, or polystyrene-based resins 5 to 30 selected from 70 to 95 parts by weight of styrene-based thermoplastic elastomers, and general purpose polystyrene (GPPS) and high impact polystyrene (HIPS). Blended parts blended by weight are used, and 5 to 50 parts by weight of a flow improver selected from polyolefin resins and plasticizers, 3 to 50 parts by weight of silica as a filler, 0.5 to 20 parts by weight of abrasion resistance improver, and silane based on 100 parts by weight of the substrate. The thermoplastic elastomer composition for shoes characterized by containing 0.2-20 weight part of coupling agents. 제 1 항에 있어서, 폴리올레핀계 수지가 폴리에틸렌수지, 폴리프로필렌 수지, 에틸렌-비닐아세테이트 수지 및 에틸렌-α올레핀 수지 중에서 선택된 것임을 특징으로 하는 신발용 열가소성 탄성체 조성물.2. The thermoplastic elastomer composition for shoes according to claim 1, wherein the polyolefin resin is selected from polyethylene resin, polypropylene resin, ethylene-vinylacetate resin and ethylene-? Olefin resin. 제 1 항에 있어서, 상기 가소제가 파라핀계 오일, 나프텐계 오일 및 이들의혼합물 중에서 선택된 것임을 특징으로 하는 신발용 열가소성 탄성체 조성물.The thermoplastic elastomer composition according to claim 1, wherein the plasticizer is selected from paraffinic oil, naphthenic oil, and mixtures thereof. 제 1 항에 있어서, 상기 내마모성 향상제로는 폴리옥테나머, 불소고무, 테프론 파우더, 스테아린산 아미드, 황화 몰리브덴, 실리콘 고무 및 실리콘 중에서 선택된 것을 단독 또는 혼합 사용하는 것임을 특징으로 하는 신발용 열가소성 탄성체 조성물.The method of claim 1, wherein the wear resistance improving agent is a thermoplastic elastomer composition for shoes, characterized in that used alone or mixed selected from polyoctenamer, fluorine rubber, Teflon powder, stearic acid amide, molybdenum sulfide, silicone rubber and silicone. 제 1 항에 있어서, 상기 실란 커플링제가 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리클로로실란, 비닐트리(2-메톡시에톡시)실란, 3-아미노프로필에톡시실란, 머캅토프로필트리메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸트리메톡시실란, 3-글리시딜옥시프로필트리메톡시실란, 3-글리시딜옥시프로필메틸디에톡시실란 및 비스-(3-(트리에톡시실릴)-프로필)테트라설파이드 중에서 선택된 것임을 특징으로 하는 신발용 열가소성 탄성체 조성물.The silane coupling agent according to claim 1, wherein the silane coupling agent is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (2-methoxyethoxy) silane, 3-aminopropylethoxysilane, mercapto Propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and bis- ( Thermoplastic elastomer composition for shoes, characterized in that selected from 3- (triethoxysilyl) -propyl) tetrasulfide.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040050165A (en) * 2002-12-09 2004-06-16 한국신발피혁연구소 Pellet rubber compound for out-sole and its manufacturing method and manufacturing method of out-sole
KR100668039B1 (en) * 2005-02-17 2007-01-15 동서대학교산학협력단 Thermoplastic elastomer compounds for footwear outsole with enhanced abrasion resistance and debris resistance
KR100852972B1 (en) 2007-06-29 2008-08-19 주식회사 트렉스타 Butyl rubber compound with non-marking and non-slip properties for climbing shoe outsole
KR100980028B1 (en) * 2008-08-29 2010-09-03 한국신발피혁연구소 Foam composition having shock absorption at a variety of temperature range
KR101662007B1 (en) * 2015-03-26 2016-10-04 한국신발피혁연구원 An abrasion resistive rubber composition for shoes outsole and method for thereof
KR102092733B1 (en) * 2018-09-19 2020-03-24 한국신발피혁연구원 Injection moulding type composition for outsole of shoes with high sensitive and non slip properties

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WO2006014273A1 (en) * 2004-07-02 2006-02-09 Polyone Corporation Soil-resistant thermoplastic elastomer compositions and related methods

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KR0154397B1 (en) * 1995-10-25 1998-12-01 강대승 Out-sole
JPH11253201A (en) * 1998-03-13 1999-09-21 Aron Kasei Co Ltd Elastomer composition for footgear

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040050165A (en) * 2002-12-09 2004-06-16 한국신발피혁연구소 Pellet rubber compound for out-sole and its manufacturing method and manufacturing method of out-sole
KR100668039B1 (en) * 2005-02-17 2007-01-15 동서대학교산학협력단 Thermoplastic elastomer compounds for footwear outsole with enhanced abrasion resistance and debris resistance
KR100852972B1 (en) 2007-06-29 2008-08-19 주식회사 트렉스타 Butyl rubber compound with non-marking and non-slip properties for climbing shoe outsole
KR100980028B1 (en) * 2008-08-29 2010-09-03 한국신발피혁연구소 Foam composition having shock absorption at a variety of temperature range
KR101662007B1 (en) * 2015-03-26 2016-10-04 한국신발피혁연구원 An abrasion resistive rubber composition for shoes outsole and method for thereof
KR102092733B1 (en) * 2018-09-19 2020-03-24 한국신발피혁연구원 Injection moulding type composition for outsole of shoes with high sensitive and non slip properties

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