KR101696995B1 - Extruded plastics - Google Patents
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- KR101696995B1 KR101696995B1 KR1020150017153A KR20150017153A KR101696995B1 KR 101696995 B1 KR101696995 B1 KR 101696995B1 KR 1020150017153 A KR1020150017153 A KR 1020150017153A KR 20150017153 A KR20150017153 A KR 20150017153A KR 101696995 B1 KR101696995 B1 KR 101696995B1
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- 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
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Abstract
본 발명은 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물에 관한 것으로서, 더욱 상세하게는 SBS(스티렌-부타디엔-스티렌 블록공중합체)와 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체)의 혼합물에 가공조제를 혼합하여, 물성 및 가공성을 향상시킨 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물에 관한 것이다.
본 발명의 바람직한 일 실시예는 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체) 100 중량부에 대하여, SBS(스티렌-부타디엔-스티렌 블록공중합체) 30~85중량부; 파라핀 오일 15~70중량부; 가공조제를 0.4~4.0 중량부를 포함하여 구성된다.The present invention relates to a composition comprising polyester elastomer and SBS and an extrusion molding using the same. More particularly, the present invention relates to a composition comprising SBS (styrene-butadiene-styrene block copolymer) and TPEE (thermoplastic polyester elastomer: polyester type block copolymer ), A polyester elastomer having improved physical properties and processability and SBS, and an extrusion molding using the same.
In one preferred embodiment of the present invention, 30 to 85 parts by weight of SBS (styrene-butadiene-styrene block copolymer) is added to 100 parts by weight of TPEE (Thermoplastic polyesterelastomer: polyester type block copolymer) 15 to 70 parts by weight of paraffin oil; And 0.4 to 4.0 parts by weight of a processing aid.
Description
본 발명은 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물에 관한 것으로서, 더욱 상세하게는 SBS(styrene - butadiene styrene block copolymer:스티렌-부타디엔-스티렌 블록공중합체)와 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체)의 혼합물에 가공조제를 혼합하여 물성 및 가공성을 향상시킨 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물에 관한 것이다.The present invention relates to a composition comprising polyester elastomer and SBS and an extrusion molding using the same. More particularly, the present invention relates to a composition comprising a styrene-butadiene styrene block copolymer (SBS) and a thermoplastic polyester elastomer : Polyester type block copolymer), and a mixture of a polyester elastomer and SBS, which has improved physical properties and processability, and an extrusion molding using the same.
일반적으로 PVC는 내후성, 인장강도, 신장율, 긁킴성, 접착성, 내마모성 등의 우수한 물성과 가공성으로 압출제품 원료로 광범위하게 사용하여 왔으나 최근 환경적인 문제로 점차 사용이 제한되고 있다. 사출제품은 여러 가지 수지원료 개발로 많은 부분 PVC제품 대체에 성공하고 있다. 압출제품도 올레핀계(PE,PP등)나 폴리우레탄계 수지로 상당부분 대체가 이루어 졌으나 아직도 미흡한 단계에 있다. In general, PVC has been extensively used as a raw material for extruded products due to excellent physical properties and processability such as weatherability, tensile strength, elongation, scratching property, adhesiveness and abrasion resistance, but its use has been gradually restricted due to environmental problems. Injection products have succeeded in replacing many PVC products due to the development of various resin materials. Extruded products have been largely replaced by olefin-based (PE, PP, etc.) or polyurethane-based resins, but are still in an insufficient stage.
일반적으로 SBS는 가공유와 활제, PS(폴리스티렌)나 PP(폴리프로피렌)등 다른 수지와 혼합하여 콤파운드 과정(압출 후 절단)을 거친 후 주로 사출용 제품 원료로 이용 되고 있으며, TPEE는 콤파운드 과정 없이 바로 제품원료로 이용되고 있다. SBS는 우수한 내한성, 탄성, 내수성, 가공성을 보유한 고무와 유사한 장점을 가지고 있으나 내유성, 내후성, 내마모성, 내열성이 불량하고 압출가공성이 좋지 않은 단점이 있다. TPEE는 내열성, 내후성, 내한성, 내유성, 탄성을 보유한 우수한 TPE(Thermoplastic elastomer)이나, 불량한 압출가공성과 개질를 위한 불량한 컴파운 가공성, 특히 저경도화(D 경도 40이하의 연질화)에 어려움이 있다.In general, SBS is mixed with other resins such as processed oil and lubricant, PS (polystyrene) or PP (polypropylene), and is used mainly as raw material for injection products after compound process (cutting after extrusion). TPEE is used without compound process It is used as raw material for the product. SBS has similar advantages to rubber with excellent cold resistance, elasticity, water resistance and processability, but it has disadvantages such as poor oil resistance, weather resistance, abrasion resistance, heat resistance and poor extrusion processability. TPEE has a problem in TPE (Thermoplastic elastomer) which is excellent in heat resistance, weather resistance, cold resistance, oil resistance and elasticity, poor processability for poor extrusion processability and poor compaction processability, in particular hardness (softness of D hardness of 40 or less).
또한, 상기와 같은 SBS와 TPEE의 불량한 압출가공성으로 인하여 이형제품, 비닐 쉬트, 필름, 비닐 레쟈 등 압출제품제조에 어려움이 있어 PVC제품 대체를 이루지 못하는 문제점이 있었다. Also, due to the poor extrusion processability of SBS and TPEE as described above, it is difficult to produce extruded products such as mold release products, vinyl sheets, films, and vinyl lieers, thus failing to replace PVC products.
본 발명의 배경이 되는 기술로는 특허등록 제1004614호 "ＰＶＣ와 유사한 성형성을 갖는 ＰＥＴＧ계 성형용데코시트"(특허문헌 1)이 있다. 상기 배경기술에서는 '폴리에틸렌테레프탈레이트글리콜(PETG) 수지에 엘라스토머(elastomer) 수지를 용융혼합(alloy)한 PETG 얼로이 수지를 포함하고, 엘라스토머 수지가 폴리부틸렌테레프탈레이트(PBT) 수지에 폴리에테르 글리콜(Polyether Glycol)을 공중합한 엘라스토머 수지인 것을 특징으로 하는 데코시트.'를 제안한다. As a background of the present invention, there is a patent registration No. 1004614 entitled " PETG-based molding decorative sheet having moldability similar to PVC "(patent document 1). In the background art, a PETG alloy resin in which an elastomer resin is alloyed with a polyethylene terephthalate glycol (PETG) resin is used, and an elastomer resin is mixed with a polyether glycol (PBT) (Polyether Glycol). ≪ / RTI >
그러나 상기 배경기술은 ＰＶＣ와 유사한 성형성을 갖도록 하나 주로 경질시트, 품용기 등으로 이용되고 있으나 연질화(softening)의 어려움으로 연질필름이나 연질시트 제조에 어려운 문제점이 있었다.However, the background art has a similar formability to that of PVC but is mainly used as a hard sheet or a container. However, it is difficult to produce a soft film or a soft sheet because of difficulty in softening.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물은 상용성이 우수하고 가공이 양호한 TPEE수지와 SBS수지를 혼합하여 조성물을 형성하도록 하여, TPEE는 우수한 물성과 SBS와 혼합성이 양호하여 SBS 단점인 내후성, 내열성, 내유성을 TPEE를 혼합하여 개선 할 수 있으며 TPEE 단점인 저경도화(softening)의 어려움을 극복 할 수 있고 TPEE에 비하여 비교적 가격이 저렴한 SBS를 혼합함으로서 원가절감 효과도 이룰 수 있는 효과가 있으며, PTFE(polytetrafluoroethylene)수지 계통의 가공조제를 혼합하여, TPEE와 SBS의 혼합물의 용융점도를 높이고 용융강도를 강화하여 가공성을 향상시키도록 하여 연질 PVC원료로 제조된 이형압출제품이나 연질 비닐시트, 비닐레쟈, 타포린 같은 압출 제품 대체품 가공이 가능하도록 하는 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물을 제공하는데 그 목적이 있다.Disclosure of the Invention The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a composition comprising a mixture of polyester elastomer and SBS, and an extrusion molding using the same, to form a composition by mixing TPEE resin and SBS resin, TPEE has superior properties and good mixing with SBS, which can improve the weatherability, heat resistance and oil resistance of SBS by mixing TPEE and overcome the difficulty of softening, which is a disadvantage of TPEE, It is possible to reduce the cost by mixing SBS with low price. It improves the processability by increasing the melt viscosity of melt mixture of TPEE and SBS by mixing processing aid of PTFE (polytetrafluoroethylene) resin system. Extrusion products made of soft PVC raw materials or alternatives to extruded products such as soft vinyl sheets, vinyl laggers and tarpaulins To provide a ball polyester elastomer extrudate and a mixture of SBS and a composition using the same that enable it is an object.
본 발명은 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체) 100 중량부에 대하여, SBS(스티렌-부타디엔-스티렌 블록공중합체) 30~85중량부; 파라핀 오일 15~70중량부; 가공조제를 0.4~4.0 중량부; 화학발포제를 0.2~10중량부 및 충진제를 10~30중량부를 함유하는 것을 특징으로 하는 폴리에스터에라스토머와 SBS를 혼합한 조성물.The present invention relates to a thermoplastic polyester elastomer (TPEE) composition comprising 30 to 85 parts by weight of SBS (styrene-butadiene-styrene block copolymer), 100 parts by weight of a thermoplastic polyester elastomer (polyester type block copolymer) 15 to 70 parts by weight of paraffin oil; 0.4 to 4.0 parts by weight of a processing aid; 0.2 to 10 parts by weight of a chemical foaming agent, and 10 to 30 parts by weight of a filler is mixed with a polyester elastomer and SBS.
상기 가공조제는 PTFE(polytetrafluoroethylene)수지계 인 것을 특징으로 하는 폴리에스터에라스토머와 SBS를 혼합한 조성물.Wherein the processing aid is a PTFE (polytetrafluoroethylene) resin-based polyester elastomer and SBS.
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상기 폴리에스터에라스토머와 SBS를 혼합한 조성물을 압출성형기로 압출하여 형성되는 압출 성형물.An extruder formed by extruding a composition obtained by mixing the polyester elastomer and SBS with an extrusion molding machine.
본 발명의 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물은 상용성이 우수하고 가공이 양호한 TPEE수지와 SBS수지를 혼합하여 조성물을 형성하도록 하여, TPEE는 우수한 물성과 SBS와 혼합성이 양호하여 SBS 단점인 내후성, 내열성, 내유성을 TPEE를 혼합하여 개선 할 수 있으며 TPEE 단점인 저경도화(softening)의 어려움을 극복 할 수 있고 TPEE에 비하여 비교적 가격이 저렴한 SBS를 혼합함으로서 원가절감 효과도 이룰 수 있는 효과가 있다. The composition obtained by mixing the polyester elastomer and the SBS of the present invention and the extruded product using the same, and the TPEE resin having excellent compatibility and good processing are mixed with the SBS resin to form a composition, and TPEE is mixed with SBS It is possible to improve the weather resistance, heat resistance and oil resistance which are the weak points of SBS by mixing with TPEE. It is possible to overcome the difficulty of softening, which is a disadvantage of TPEE, and it is possible to reduce cost by mixing SBS, which is comparatively less expensive than TPEE There is an effect that can be achieved.
또한, PTFE(polytetrafluoroethylene)수지 계통의 가공조제를 혼합하여, TPEE와 SBS의 혼합물의 용융점도를 높이고 용융강도를 강화하여 가공성을 향상시키도록 하여 연질 PVC원료로 제조된 이형압출제품이나 연질 비닐시트, 비닐레쟈, 타포린 같은 압출 제품 대체품 가공이 가능하도록 하는 매우 유용한 효과가 있다.In addition, a molding extruded product made of a soft PVC raw material or a soft vinyl sheet made of a soft PVC material is prepared by mixing a processing aid of a PTFE (polytetrafluoroethylene) resin system to enhance the melt viscosity of a mixture of TPEE and SBS, There is a very useful effect that enables processing of extruded products such as vinyl lieer and tarpaulin.
아래에서 본 발명은 첨부된 도면에 제시된 실시예를 참조하여 상세하게 설명이 되지만 제시된 실시예는 본 발명의 명확한 이해를 위한 예시적인 것으로 본 발명은 이에 제한되지 않는다. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the embodiments shown in the accompanying drawings, but the present invention is not limited thereto.
이하 바람직한 실시예에 따라 본 발명의 기술적 구성을 상세히 설명하면 다음과 같다.Hereinafter, the technical structure of the present invention will be described in detail with reference to the preferred embodiments.
본 발명의 폴리에스터에라스토머(TPEE)와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물은 SBS(스티렌-부타디엔-스티렌 블록공중합체)와 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체)의 혼합물에 가공조제를 혼합하여 물성 및 가공성을 향상시켜 우수한 내후성, 인장강도, 신장율, 긁킴성(anti-scratch), 접착성, 내마모성 및 내한성, 내열성, 내유성과 친환경성도 보유하도록 한다.The composition obtained by mixing the polyester elastomer (TPEE) and SBS of the present invention and the extruded product using the same is a mixture of SBS (styrene-butadiene-styrene block copolymer) and TPEE (thermoplastic polyesterelastomer: polyester type block copolymer) It has excellent weatherability, tensile strength, elongation, anti-scratch, adhesion, abrasion resistance and cold resistance, heat resistance, oil resistance and environment friendliness by mixing processing aids.
본 발명에서 사용되는 기재 수지인 TPEE수지는 우수한 가공성과 성형성, 인쇄성이 우수하고 수축으로 인한 변형이 없으며 ,내후성이 우수하고 소각 또는 화재발생시 염소가스가 발생하지 않고 환경 호르몬 등의 유해성분이 전혀 없는 특성이 있고 어느 정도의 경도(Hardness)조절이 가능하나 D경도40이하의 연질TPEE수지의 제조는 어렵다.The TPEE resin, which is a base resin used in the present invention, is excellent in processability, moldability, and printability, has no deformation due to shrinkage, is excellent in weatherability, and does not generate chlorine gas when incinerated or when a fire occurs and harmful substances such as environmental hormones But it is difficult to manufacture soft TPEE resin with D hardness of 40 or less.
SBS수지는 내열성, 내후성, 내유성이 불량하나 내한성은 아주 우수하고 가공성도 양호한, 비교적 가격도 저렴한 수지로 경도조절이 용이한 수지로 TPEE와의 상용성도 아주 양호한 수지이다. SBS resin is a resin which is excellent in heat resistance, weatherability and oil resistance, but has excellent cold resistance, good processability, comparatively low price, easy hardness control and compatibility with TPEE.
따라서, TPEE는 우수한 물성과 SBS와 혼합성이 양호하여 SBS 단점인 내후성, 내열성, 내유성을 TPEE를 혼합하여 개선 할 수 있으며 TPEE 단점인 저경도화(softening)의 어려움을 극복 할 수 있도록 하고, TPEE에 비하여 비교적 가격이 저렴한 SBS를 혼합함으로서 원가절감 효과도 이룰 수 있으면서도, PVC를 대체할 수 있도록 한다.Therefore, TPEE has excellent physical properties and good mixing with SBS, which can improve the weatherability, heat resistance and oil resistance of SBS by mixing TPEE, and overcome the difficulty of softening, which is a disadvantage of TPEE. By mixing SBS, which is relatively inexpensive compared to PVC, it is possible to reduce cost, but it can replace PVC.
본 발명은 TPEE(Thermoplastic polyesterelastomer:폴리에스테르형 블록공중합체) 100 중량부에 대하여, SBS(스티렌-부타디엔-스티렌 블록공중합체) 30~85중량부; 파라핀 오일 15~70중량부; 가공조제를 0.4~4.0 중량부를 함유하는 것을 특징으로 한다.The present invention relates to a thermoplastic polyester elastomer (TPEE) composition comprising 30 to 85 parts by weight of SBS (styrene-butadiene-styrene block copolymer), 100 parts by weight of a thermoplastic polyester elastomer (polyester type block copolymer) 15 to 70 parts by weight of paraffin oil; And 0.4 to 4.0 parts by weight of a processing aid.
연질플라스틱 압출가공성을 결정하는 중요한 요인중 하나가 용융지수이다. One of the important factors determining the extrusion processability of soft plastics is the melt index.
일반적으로 사출성형은 가공성을 향상시키기 위하여 가능한 용융지수가 높은 플라스틱원료가 좋으나 연질플라스틱 압출성형에서는 용융지수가 낮은 플라스틱 원료를 선호한다. 특히 이형제품이나 발포제품은 용융지수가 높은 플라스틱 원료는 성형자체가 불가능 하며 발포제품은 성형 후 수축도 고려하여야 한다. In general, injection molding is preferable to a plastic raw material having a high melting index in order to improve workability, but in a plastic extrusion molding, a plastic raw material having a low melt index is preferred. In particular, mold release products and foamed products are not capable of forming plastic materials having a high melt index, and shrinkage after molding should be taken into account.
TPEE는 물성이 좋기 때문에 SBS를 30중량부를 초과하여 혼합하면 물성이 저하되고, 85중량부 미만으로 혼합하면 저경도화(softening)의 어려움을 극복 할 수 없기 때문에, TPEE 100중량부에 대하여 SBS 30~85 중량부를 혼합하는 것이 바람직하다.Since TPEE has good physical properties, when the SBS is mixed in an amount of more than 30 parts by weight, the physical properties thereof deteriorate. When the TPEE is mixed at less than 85 parts by weight, the difficulty of softening can not be overcome. 85 parts by weight are preferably mixed.
파라핀 오일은 경도조절과 가공성을 향상시키기 위하여 혼합하는데 15중량부 미만으로 혼합시에는 경도가 높아지고, 70중량부를 초과하여 혼합할 경우에는 점착성이 높게 나타나는 등의 문제가 있기 때문에, TPEE 100중량부에 대하여 15~70중량부를 혼합하는 것이 바람직하다.Paraffin oil is mixed to improve hardness and processability. When it is mixed in an amount of less than 15 parts by weight, the hardness is increased. When it is mixed more than 70 parts by weight, By weight based on the total weight of the composition.
상기 오일로는 식물 또는 식물의 씨로부터 추출된 오일로, 팜 오일, 코코넛 오일, 피마자 오일, 포도씨 오일, 호호바 오일, 홍화 오일, 마카데미아너츠 오일, 올리브씨 오일 등이 사용될 수 있으며, 특히 파라핀 오일을 사용할 수 있다.The oil may be palm oil, coconut oil, castor oil, grape seed oil, jojoba oil, safflower oil, macadamia nut oil, olive seed oil and the like, Oil can be used.
상기와 같이, 파라핀 오일을 혼합하면 용융지수가 높아지고 용융강도(melt strength)가 약해져 압출가공이 어려워 지기 때문에, 가공조제를 더 혼합하여 가공성을 향상시키도록 한다.
As described above, when the paraffin oil is mixed, the melt index is increased and the melt strength is weakened, so that extrusion processing becomes difficult. Therefore, the processing aid is further mixed to improve the processability.
<실험예 1> <Experimental Example 1>
표 1에서와 같이 TPEE와 SBS, 파라핀오일의 혼합물에 가공조제의 함량을 실시예 2에서 실시예 7까지 0.1%에서 2.5%까지 단계적으로 증량하여 혼합한 결과 용융지수가 6.4g/cc 0.2g/cc 까지 상당한 변화를 보였다.As shown in Table 1, when the content of the processing aid in the mixture of TPEE, SBS, and paraffin oil was increased stepwise from 0.1% to 2.5% from Example 2 to Example 7, the melt index was increased from 6.4 g / cc to 0.2 g / cc.
ingredient
연질PVC의 경우 보통 용융지수가 1g/cc이하이면 이형제품 가공이 가능한데 가공조제가 혼합되지 않은 조성예1은 용융지수가 6.4 정도이며 가공조제 2%혼합된 조성예6의 용융지수는 0.3g/cc로 이형제품을 가공하기 좋은 조건이며 호스와 같은 원형제품의 경우 보통 3g/cc이하이면 가능하며 이형제품의 경우 용융지수가 1.0이하는 되어야 가능한 것으로 생각된다. 표 1의 예에서 보는 봐와 같이 가공조제를 혼합함으로서 가공이 불가능 하였던 이형제품도 가능하게 되었다. In the case of soft PVC, it is usually possible to process a release product when the melt index is less than 1 g / cc. The melt index of Composition Example 1 in which the processing aid is not mixed has a melt index of 6.4 and the melt index of Composition Example 6 mixed with 2% cc, it is possible to process the mold release product. In the case of circular product such as hose, it is usually possible to be 3g / cc or less. In case of mold release product, the melt index should be below 1.0. As shown in the example of Table 1, it is also possible to manufacture a mold release product which could not be processed by mixing the processing aid.
표 1 실시예 2는 가공조제의 함량이 적어 실시예 1과 비슷한 용융지수를 나타 났으며 실시예 3은 호스와 같은 원형제품의 가공이 가능할 정도의 용융지수를 보였으며 실시예 6은 이형제품까지도 가공이 가능한 용융지수 이며 실시예7은 가공조제의 함량이 필요이상으로 많아 원가 부담이 될 것으로 생각된다.Example 2 showed a melt index similar to that of Example 1 because the content of the processing aid was small. Example 3 showed a melt index to such an extent that a round product such as a hose could be processed. In Example 6, It is considered that the melt index is a processable melt index, and in Example 7, the content of the processing aid is more than necessary, which is a cost burden.
따라서, 가공조제를 0.4중량부에서 4.0중량부를 포함하는 것이 바람직하다.Therefore, it is preferable that 0.4 to 4.0 parts by weight of the processing aid is included.
특히, 가공조제는 다양한 제품을 사용할 수 있으며, 특히 PTFE수지로 구성되는 것이 바람직하다. 폴리테트라플루오로에틸렌(Polytetrafluoroethylene, PTFE) 수지는 열 안정성과 내화학성이 뛰어나 용융강도와 점도가 높아 가공성이 뛰어나다.Particularly, a variety of products can be used as the processing aid, and it is particularly preferable to be composed of a PTFE resin. Polytetrafluoroethylene (PTFE) resin has excellent heat stability and chemical resistance, and is excellent in workability because of high melt strength and viscosity.
저경도의 연질플라스틱은 일반적으로 용융지수가 높은 관계로 화학발포제를 이용한 발포가 어렵다. 발포가 잘 되더라도 균일한 셀(Cell)를 보유한 발포체를 얻기가 어려우며 냉각 과정에서의 수축으로 균일한 발포제품 제조가 용이치 않으며 특히 발포 압출제품은 거의 불가능 하다.Since soft plastics having low hardness generally have high melt index, foaming using a chemical foaming agent is difficult. It is difficult to obtain a foam having a uniform cell even if it is foamed well and it is difficult to manufacture a uniform foamed product due to shrinkage during the cooling process, and in particular, a foamed extruded product is almost impossible.
따라서, 상기와 같은 본 발명의 폴리에스터에라스토머와 SBS를 혼합한 조성물에 발포제를 더 혼합하도록 할 수 있다.
Therefore, it is possible to further mix the foaming agent in the composition of the polyester elastomer and SBS of the present invention as described above.
<실험예 2> <Experimental Example 2>
아래 표 2에서와 같이 발포제의 조성을 변화시키면 비중 및 혼합상태를 확인하였다.As shown in Table 2 below, the specific gravity and mixing state were confirmed by varying the composition of the foaming agent.
ingredient
표 2의 실시예 1과 같이 TPEE와 SBS와 오일만 혼합한 후 화학발포제(UNICELL-D200L:동진쎄미켐제조)로 발포한 경우에는 제품화 할 수 없을 정도의 불량한 발포 상태였으나 표 2의 조성에서와 같이 가공조제와 같이 혼합하여 압출한 결과 고른 셀과 표면 상태도 양호한 발포체를 제조할 수 있었으며 표 2 실시예 2의 경우 적은 양의 발포제 혼합으로 발포효과가 극히 미약하였으며 실시예 7은 과다한 발포제 투입으로 양호한 발포체를 얻을 수 없었으며 화학발포제의 종류에 따라 상이한 발포형태를 보였다.
When TPEE, SBS and oil alone were blended and foamed with a chemical foaming agent (UNICELL-D200L: manufactured by Dongjin Semichem Co.) as in Example 1 of Table 2, it was in a poorly foamed state to such an extent that it could not be commercialized. As a result, it was possible to produce a foam having good cell and surface condition. In the case of Example 2, the foaming effect was extremely weak due to the mixing of a small amount of foaming agent. Example 7 shows a good foam No foam was obtained and different foaming forms were observed depending on the type of chemical foaming agent.
<실험예 3><Experimental Example 3>
표 2의 발포제 1은 동진쎄미켐 제조 UNICELL-D200L로 ADCA(Azodicarbonamide)계통의 발포제로 발포효력이 좋고 가격도 저가이나 황색이고 발포체에서 냄새가 많이 발생하여 무독무취 제품이나 백색의 발포체의 제조가 불가능하다. OBSH(bezenesulfonyl hydrazide)계의 발포제는 무독, 무취, 백색발포제이나 ADCA계 발포제에 비하여 발포력이 약하고 가격이 높은 단점이 있다. The foaming agent 1 shown in Table 2 is a product of UNICELL-D200L manufactured by Dongjin Semichem, which is a foaming agent of ADCA (azodicarbonamide) system. It is effective in foaming and is inexpensive and yellowish in color and has many odors in foams. . The blowing agent of the OBSH (bezenesulfonyl hydrazide) type has a weak foaming power and a high price as compared with the non-toxic, odorless, white foaming agent or ADCA foaming agent.
따라서, 실험예 3에서는 발포제(발포제 2)로 동진쎄미켐의 OHW2를 선정하여 아래 표 3에서와 같이 발포제 2의 조성을 변화시키면 비중 및 혼합상태를 확인하였다.Therefore, in Experimental Example 3, OHW2 of Dongjin Semichem was selected as a foaming agent (foaming agent 2), and specific gravity and mixed state were confirmed by changing the composition of foaming agent 2 as shown in Table 3 below.
ingredient
일반적으로 OBSH계 발포제는 ADCA계 발포제와 비슷한 발포배율를 얻기 위하여는 발포제의 투입량을 ADCA계 발포제에 비하여 5에서 10배정도 증량하여야 한다. 표4에서 보는 봐와 같이 발포제 2의 투입량을 10배정도 증량한 결과 비슷한 비중의 발포체를 구하였으나 표 4 실시예 1은 발포배율이 너무 낮았으며 실시예 6은 발포배율에 비하여 과다한 발포제의 투입으로 경제성이 저하되었다.
In general, in order to obtain a foaming ratio similar to that of the ADCA-based foaming agent, the amount of the foaming agent should be increased by 5 to 10 times that of the ADCA-based foaming agent. As shown in Table 4, when the amount of blowing agent 2 was increased by a factor of 10, foams with similar specific gravity were obtained. However, in Example 1, the foaming magnification was too low. In Example 6, .
따라서, 발포제 0.2중량부 미만으로 혼합시에는 발포효과가 극히 미약하고, 10 중량부를 초과하여 혼합하는 경우 과다한 발포제 투입으로 양호한 발포체를 얻을 수 없기 때문에, 화학발포제를 0.2~10중량부를 더 혼합하는 것이 바람직하다.
Therefore, when mixing is carried out at less than 0.2 part by weight of the foaming agent, the foaming effect is extremely weak. When mixing more than 10 parts by weight, an excellent foaming agent can not be obtained due to excessive foaming agent addition. desirable.
<실험예 4> <Experimental Example 4>
TPE(Thermoplsastic elastomer)중 TPEE는 가격이 높은 에라스토머 중에 하나이다. 높은 가격으로 인하여 사용이 제한적일 수 밖에 없다. 이를 극복하기 위한 방법은 충진제를 혼합하도록 할 수 있다.Among TPE (Thermoplastics elastomer), TPEE is one of the high cost elastomers. Due to the high price, its use is limited. A method to overcome this is to mix the filler.
TPEE는 충진제 혼합이 용이치 않으며 물성저하 현상도 나타나기 때문에, 그 조성범위를 명확하게 한정하여야 하여 아래 표와 같이 충진제의 조성을 변화시키며 실험하였다.TPEE is mixed with filler and shows a property deterioration. Therefore, the composition range should be clearly defined, and the composition of the filler was experimented as shown in the table below.
ingredient
SBS는 충진제 혼합도 용이하고 물성저하 현상도 없어 표4와 같이 충진제(칼슘카보네이트)를 혼합한 결과 다소 비중의 증가 현상이외에는 양호한 혼합결과를 보였으며 상당한 원가절감 효과도 있으나 실시예 5와 6은 비중이 높을 뿐만 아니라 원가절감 효과도 높지 않았다.SBS is easy to mix filler and there is no phenomenon of deterioration of physical properties. As a result of mixing of filler (calcium carbonate) as shown in Table 4, it shows good mixing result except for a somewhat increase in specific gravity and significant cost saving effect. In Examples 5 and 6, And the cost reduction effect was not high.
따라서, 충진제는 10~30중량부를 더 혼합하는 것이 바람직하다.Therefore, 10 to 30 parts by weight of the filler is preferably further mixed.
본 발명의 폴리에스터에라스토머와 SBS를 혼합한 조성물은 활제, 난연제, 자외선방지제, 자외선흡수제등을 더 포함하도록 하여 기능성 및 물성을 추가하도록 할 수도 있다.The composition obtained by mixing the polyester elastomer and SBS of the present invention may further include a lubricant, a flame retardant, an ultraviolet absorber, and an ultraviolet absorber so as to add functionality and physical properties.
상기와 같이 구성되는 폴리에스터에라스토머와 SBS를 혼합한 조성물은 압출성형기로 압출하여 형성되는 연질 필름이나 시트와 같은 압출 성형물을 형성하도록 할 수 있다.The composition obtained by mixing the polyester elastomer and SBS as described above may be formed into an extruded product such as a soft film or a sheet formed by extrusion using an extrusion molding machine.
상기와 같은 본 발명의 폴리에스터에라스토머와 SBS를 혼합한 조성물 및 이를 이용한 압출 성형물은 상용성이 우수하고 가공이 양호한 TPEE수지와 SBS수지를 혼합하여 조성물을 형성하도록 하여, TPEE는 우수한 물성과 SBS와 혼합성이 양호하여 SBS 단점인 내후성, 내열성, 내유성을 TPEE를 혼합하여 개선 할 수 있으며 TPEE 단점인 저경도화(softening)의 어려움을 극복 할 수 있고 TPEE에 비하여 비교적 가격이 저렴한 SBS를 혼합함으로서 원가절감 효과도 이룰 수 있으며, PTFE(polytetrafluoroethylene)수지 계통의 가공조제를 혼합하여, TPEE와 SBS의 혼합물의 용융점도를 높이고 용융강도를 강화하여 가공성을 향상시키도록 하여 연질 PVC원료로 제조된 이형압출제품이나 연질 비닐시트, 비닐레쟈, 타포린 같은 압출 제품 대체품 가공이 가능하도록 하는 매우 유용한 효과가 있다.The composition comprising the polyester elastomer and SBS of the present invention as described above and the extruded product using the same provide a composition by mixing the TPEE resin and the SBS resin having excellent compatibility and good workability, It is possible to improve the weatherability, heat resistance and oil resistance which are the disadvantages of SBS with TPBS by mixing with SBS. By mixing SBS which can overcome the difficulty of softening which is a disadvantage of TPEE and which is comparatively less expensive than TPEE It is possible to achieve a cost saving effect and it is possible to increase the melt viscosity of the mixture of TPEE and SBS by mixing the processing aid of PTFE (polytetrafluoroethylene) resin system and to improve the workability by strengthening the melt strength, There is a very useful effect that makes it possible to process alternatives such as products or extruded products such as soft vinyl sheets, vinyl rejas and tarpaulins. All.
지금까지 본 발명은 제시된 실시예를 참조하여 상세하게 설명이 되었지만 이 분야에서 통상의 지식을 가진 자는 제시된 실시예를 참조하여 본 발명의 기술적 사상을 벗어나지 않는 범위에서 다양한 변형 및 수정 발명을 만들 수 있을 것이다. 본 발명은 이와 같은 변형 및 수정 발명에 의하여 제한되지 않으며 다만 아래에 첨부된 청구범위에 의하여 제한된다. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the above teachings. will be. The invention is not limited by these variations and modifications, but is limited only by the claims appended hereto.
Claims (5)
SBS(스티렌-부타디엔-스티렌 블록공중합체) 30~85중량부,
파라핀 오일 15~70중량부,
가공조제를 0.4~4.0 중량부, 화학발포제를 0.2~10중량부 및 충진제를 10~30중량부를 함유하는 것을 특징으로 하는 폴리에스터에라스토머와 SBS를 혼합한 조성물.With respect to 100 parts by weight of TPEE (Thermoplastic polyesterelastomer: polyester type block copolymer)
30 to 85 parts by weight of SBS (styrene-butadiene-styrene block copolymer)
15 to 70 parts by weight of paraffin oil,
0.4 to 4.0 parts by weight of a processing aid, 0.2 to 10 parts by weight of a chemical foaming agent and 10 to 30 parts by weight of a filler.
가공조제는 PTFE(polytetrafluoroethylene)수지계 인 것을 특징으로 하는 폴리에스터에라스토머와 SBS를 혼합한 조성물.The method according to claim 1,
Wherein the processing aid is a PTFE (polytetrafluoroethylene) resin-based polyester elastomer and SBS.
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