KR20150073662A - Athermoplastic elastomer composition and a method thereof - Google Patents
Athermoplastic elastomer composition and a method thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229920001971 elastomer Polymers 0.000 title description 3
- 239000000806 elastomer Substances 0.000 title description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 31
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims abstract description 22
- 229920006132 styrene block copolymer Polymers 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- -1 polybutylene terephthalate Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002397 thermoplastic olefin Polymers 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
본발명은 열가소성 탄성체 조성물 및 이의제조방법에 관한 것으로, 전체 조성물의 중량에 대하여, 스티렌계블록공중합체 5 내지 20 중량부; 및 열가소성 폴리에스테르 탄성체 50 내지 70 중량부를 포함하는 열가소성 탄성체 조성물을 포함하고, 오일 5 내지 20 중량부 및 충진제 5 내지 25 중량부를 추가로 포함하는 열가소성 탄성체 조성물 및 이의 제조방법을 제공한다. 본 발명에 따른 조성물은 MI가 크고, 인장강도가 높지 않으며 적정의 신율을 가져서, 작업성이 좋고, PC 오버몰딩용으로 적합하고, 이종재질간의 접합력이 우수하다. The present invention relates to a thermoplastic elastomer composition and a process for producing the same, wherein the thermoplastic elastomer composition comprises 5 to 20 parts by weight of a styrenic block copolymer, And 50 to 70 parts by weight of a thermoplastic polyester elastomer, wherein the thermoplastic elastomer composition further comprises 5 to 20 parts by weight of an oil and 5 to 25 parts by weight of a filler, and a process for producing the same. The composition according to the present invention has a large MI, a high tensile strength and an appropriate elongation, and is excellent in workability, suitable for PC overmolding, and excellent in bonding strength between dissimilar materials.
Description
본 발명은 열가소성 탄성체조성물 및 이의제조방법에 관한 것이다.
The present invention relates to a thermoplastic elastomer composition and a process for producing the same.
열가소성탄성체 (Thermoplastic Elastomer,TPE) 는 세계각국에서 독창적인 기술 또는 제품개발을 위한 신소재연구개발이 진행중인 가운데 열가소성 엘라스토머(TPE)는 향후 수요 증가가 기대되는 신소재로 관심이 높아지고 있다. 또한, 점차 환경문제에 대한 인식이 확산되면서 재활용이 가능한 열가소성 엘라스토머에 대한 용도 개발이 추진되고 있다. 상기 TPE는 플라스틱과 동일하게 성형가공이 가능하면서 재활용성등의 특성을 가지고 있으며, 다양한 물성을 얻을 수 있는 장점이 있다. Thermoplastic Elastomer (TPE) is a new material that is expected to increase in demand in the future, while research and development of new material for developing original technology or product is going on in the world. In addition, as the awareness of environmental problems has gradually spread, development of applications for recyclable thermoplastic elastomers has been promoted. The TPE has properties such as moldability and recyclability that can be molded and processed in the same manner as plastic, and has the advantage of obtaining various physical properties.
한국공개특허 제10-2011-0054698호에 따르면, 열가소성 올레핀계 수지 조성물 15 내지 65 중량%, 그리고 α-올레핀계 고무 조성물 35 내지 85 중량%로 이루어져 있으며, α-올레핀계 고무 조성물은 100 중량부에 대하여 0.1 내지 10 중량부로 가교제인 유기과산화물이 첨가되어 있으며, α-올레핀계 고무 조성물과 상기 유기과산화물은 상호 혼합한 후 동적가교를 거친 다음 상기 열가소성 올레핀계 수지조성물과 혼련하여 동적가교를 통해 제조하는 방법을 제공하지만, 다양한 물성을 가지지 못하는 단점이 있다.According to Korean Patent Laid-Open No. 10-2011-0054698, the composition is composed of 15 to 65% by weight of a thermoplastic olefin resin composition and 35 to 85% by weight of an? -Olefin-based rubber composition, wherein the? -Olefin- Olefin-based rubber composition and the organic peroxide are mixed with each other and then subjected to dynamic cross-linking, followed by kneading with the thermoplastic olefin-based resin composition, followed by dynamic cross-linking However, it has disadvantages of not having various physical properties.
상기와 같은 문제점을 해결하기 위하여, 이에 작업온도 범위가 광범위하고, TPEE를 소재로 활용한 본 발명을 완성하였다.
In order to solve the above problems, the present invention has been completed by using TPEE as a material, which has a wide working temperature range.
본 발명은 MI가 크고, 인장강도가 높지 않으며 적정의 신율을 가져서, 작업성이 좋은 열가소성 탄성체 조성물을 제조하기 위하여, 전체 조성물의 중량에 대하여, 스티렌계블록공중합체5 내지 20 중량부; 및 열가소성 폴리에스테르 탄성체 50 내지 70 중량부를 포함하는 열가소성 탄성체 조성물 및 이의 제조방법을 제공하는 것을 목적으로 한다.
In order to produce a thermoplastic elastomer composition having a high MI, a high tensile strength and an appropriate elongation, and having good workability, the present invention provides a thermoplastic elastomer composition comprising 5 to 20 parts by weight of a styrenic block copolymer, And 50 to 70 parts by weight of a thermoplastic polyester elastomer, and a process for producing the same.
본원에 기재된 다양한 구체예가 도면을 참조로 기재된다. 하기설명에서, 본발명의 완전한 이해를 위해서, 다양한 특이적 상세 사항, 예컨대, 특이적 형태, 조성물, 및 공정등이 기재되어 있다. 그러나, 특정의 구체예는 이들 특이적 상세 사항 중 하나 이상 없이, 또는 다른 공지된 방법 및 형태와 함께 실행될 수 있다. 다른 예에서, 공지된 공정 및 제조기술은 본 발명을 불필요하게 모호하게 하지 않게하기 위해서, 특정의 상세사항으로 기재되지 않는다. "한 가지 구체예" 또는 "일 구체예"에 대한 본 명세서 전체를 통한 참조는 구체예와 결부되어 기재된 특별한 특징, 형태, 조성 또는 특성이 본 발명의 하나 이상의 구체예에 포함됨을 의미한다. 따라서, 본 명세서 전체에 걸친 다양한 위치에서 표현 "한가지 구체예에서" 또는 "구체예"의 상황은 반드시 본 발명의 동일한 구체예를 나타내지는 않는다. 추가로, 특별한 특징, 형태, 조성, 또는 특성은 하나 이상의 구체예에서 어떠한 적합한 방법으로 조합될 수 있다.
Various embodiments described herein are described with reference to the drawings. In the following description, for purposes of complete understanding of the present invention, various specific details are set forth, such as specific forms, compositions, and processes, and the like. However, certain embodiments may be practiced without one or more of these specific details, or with other known methods and forms. In other instances, well-known processes and techniques of manufacture are not described in any detail, in order not to unnecessarily obscure the present invention. Reference throughout this specification to "one embodiment" or "one embodiment" means that a particular feature, form, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Accordingly, the appearances of the phrase "in one embodiment" or "an embodiment" in various places throughout this specification are not necessarily indicative of the same embodiment of the present invention. In addition, a particular feature, form, composition, or characteristic may be combined in any suitable manner in one or more embodiments.
본 발명의 일 구체예에서, 전체 조성물의 중량에 대하여, 스티렌계블록공중합체5 내지 20 중량부; 및 열가소성 폴리에스테르 탄성체 50 내지 70 중량부를 포함하는 열가소성 탄성체 조성물을 제공한다. 상기 구체예에서, 오일 5 내지 20 중량부를 추가로 포함하는 열가소성 탄성체 조성물을 제공하고, 충진제 5 내지 25 중량부를 추가로 포함하는 열가소성 탄성체 조성물을 제공하며, 스티렌계 블록공중합체는 스트렌 함량이 13 내지 33 중량%이거나, 평균 분자량이 50,000 내지 300,000g/mol인 열가소성 탄성체 조성물을 제공한다. 이때, 열가소성 폴리에스테르 탄성체(TPEE)는 하기 화학식 1인 열가소성 탄성체 조성물로 이들의 평균 분자량은 대략 300,000-400,000g/mol이다.In one embodiment of the present invention, 5 to 20 parts by weight, based on the weight of the total composition, of a styrenic block copolymer; And 50 to 70 parts by weight of a thermoplastic polyester elastomer. In this embodiment, a thermoplastic elastomer composition is provided, further comprising 5 to 20 parts by weight of an oil, wherein the thermoplastic elastomer composition further comprises 5 to 25 parts by weight of a filler, wherein the styrene block copolymer has a styrene content of 13 To 33% by weight, or an average molecular weight of 50,000 to 300,000 g / mol. The thermoplastic polyester elastomer (TPEE) is a thermoplastic elastomer composition represented by the following formula (1), and the average molecular weight thereof is approximately 300,000-400,000 g / mol.
[화학식 1][Chemical Formula 1]
여기서, x, 및 y는 목적하는 물성의 조성물에 따라서 적합하게 조절할 수 있다.
Here, x and y can be suitably adjusted according to the composition of the desired physical properties.
본 발명의 일 구체예에서, 열가소성 폴리에스테르 탄성체는 하드 세그먼트인 결정성 폴리부틸렌텔레프탈레이트(PBT)와 소프트 세그먼트인 비결정성 폴리에테르 그룹과의 중합체로서 TPE계열 화합물중에서는 가장 우수한 내열특성과 더불어 TPU보다 우수한 저온 탄성특성을 가지고 있다. 즉, 하드세그먼트 영역에서는 기계적 강성, 내열성, 내화학성, 내오일성 및 성형 가공성 특성을 부여하는 반면에 소프트 세그먼트에서는 유연성 과 내충격 및 내한성이 우수한 저온 특성, 반발탄성 특성을 가지고 있다. 그러나 열가소성폴리에스테르 탄성체 자체가 가지고 있는 높은 경도로 인하여 낮은 경도의 제품 개발이 어려울 뿐만 아니라 가공조건에 따라 기계적 특성이 큰 편차를 나타내므로 보다 정확한 가공조건의 확보가 필요하였다. 상기 구체예에서, 우수한 기계적 특성을 가졌음에도 불구하고 좁은 영역대의 가공조건을 가지는 열가소성 폴리에스테르 탄성체를 이용하여 스틸렌계 블록공중합체(SEBS)와의 컴파운딩을 통하여 다양한 물성과 함께 좀 더 용이한 작업조건에서의 가공성을 향상시킬 수 있었다. 상기 구체예에서 사용된 열가소성 폴리에스테르 탄성체는 이에 한정하지는 않지만 Keyflex 1030D (LG화학) 또는 Triel 5250SP (삼양사)를 사용할 수 있다. 이들의 주요 물성으로는 경도 (Shore A) 70-80, 비중 1.05-1.07, 용융지수(MI; 230℃, 2.16kgf) 25-30g/10min 정도이며, Izod 충격강도는 상온 및 저온에서도 균일 없으며 (균일 무 @ 23℃, - 40℃), 신율은 400-800% 이상이었다.
In one embodiment of the present invention, the thermoplastic polyester elastomer is a polymer of a crystalline polybutylene terephthalate (PBT) which is a hard segment and an amorphous polyether group which is a soft segment, and has the best heat resistance characteristics among the TPE series compounds It has low temperature elasticity property superior to TPU. That is, in the hard segment area, mechanical stiffness, heat resistance, chemical resistance, oil resistance and molding processability are given, while soft segment has low temperature property and rebound resilience property which is excellent in flexibility, impact resistance and cold resistance. However, due to the high hardness of the thermoplastic polyester elastomer itself, it is difficult to develop a product having a low hardness, and since the mechanical characteristics show large deviations depending on processing conditions, it is necessary to secure more accurate processing conditions. In the above specific examples, although having excellent mechanical properties, the thermoplastic polyester elastomer having the processing conditions of the narrow region band is used to make compounding with the styrene block copolymer (SEBS) It is possible to improve the processability in the process. The thermoplastic polyester elastomer used in the above embodiments is not limited thereto, but Keyflex 1030D (LG Chem) or Triel 5250SP (Samyang Corp.) may be used. The Izod impact strength is not uniform even at room temperature and low temperature (for example, the hardness is about 70-80, the specific gravity is about 1.05-1.07, the melting point is about 25-30g / 10min, Uniformity @ 23 ° C, -40 ° C) and the elongation was over 400-800%.
본 발명의 일 구체예에서, 전체 조성물의 중량에 대하여, 스티렌계블록공중합체5 내지 20 중량부 및 열가소성 폴리에스테르 탄성체 50 내지 70 중량부를 용융혼합하여 열가소성 탄성체를 제조하는 방법을 제공한다. 상기 구체예에서, 오일 5 내지 20 중량부 및 충진제 5 내지 25 중량부를 추가로 용융혼합하여 열가소성 탄성체를 제조하는 방법을 제공하고, 스티렌계 블록공중합체는 스트렌 함량이 13 내지 33 중량%이거나, 평균 분자량이 50,000 내지 300,000g/mol인 열가소성 탄성체를 제조하는 방법을 제공하며, 열가소성 폴리에스테르 탄성체는 상기 화학식 1인 열가소성 탄성체를 제조하는 방법을 제공한다.
In one embodiment of the present invention, there is provided a method for producing a thermoplastic elastomer by melt mixing 5 to 20 parts by weight of a styrenic block copolymer and 50 to 70 parts by weight of a thermoplastic polyester elastomer, based on the weight of the entire composition. Wherein the styrene-based block copolymer has a styrene content of 13 to 33% by weight or a styrene-based block copolymer having a styrene content of 5 to 20% by weight and a filler of 5 to 25% by weight, A thermoplastic elastomer having an average molecular weight of 50,000 to 300,000 g / mol, wherein the thermoplastic polyester elastomer provides a method for producing the thermoplastic elastomer of Formula 1 above.
본 발명의 일 구체예에서, 수첨스티렌계블록공중합체는 이에 한정하지 않지만,스티렌-에틸렌-부틸렌-스티렌블록공중합체(SEBS: styrene-b-ethylene-b-butadiene-b-styrene), 스티렌-에틸렌-프로필렌-스티렌블록공중합체(SEPS) 및스티렌-에틸렌-에틸렌-프로필렌-스티렌(SEEPS) 등이있다. 상기스티렌함량은 전체 중량에 대하여 약중량부 13 ~33 중량부이고, 중량평균분자량(Mw)이 50,000g/mol 내지 300,000g/mol 이어야 목적하는 물성을 가진다.
In one embodiment of the present invention, the hydrogenated styrenic block copolymer includes, but is not limited to, styrene-ethylene-butylene-b-styrene (SEBS) -Ethylene-propylene-styrene block copolymer (SEPS) and styrene-ethylene-ethylene-propylene-styrene (SEEPS). The styrene content is about 13 to 33 parts by weight based on the total weight and the weight average molecular weight (Mw) is 50,000 g / mol to 300,000 g / mol.
본 발명의 일 구체예에서, 미네랄오일은 동점도(40℃, cSt)가 20 이상, 인화점이 180℃이상인 유동파라핀으로 이루어지며, 오일은 조성물의 경도 및 흐름성 조절등을 위해 사용된다.
In one embodiment of the present invention, the mineral oil is composed of liquid paraffin having a kinematic viscosity (40 DEG C, cSt) of 20 or more and a flash point of 180 DEG C or more, and the oil is used for controlling the hardness and flowability of the composition.
본 발명의 일 구체예에서, 열가소성탄성체(TPE)는 올레핀계 TPE 및올레핀계 TPV(thermoplastic vulcanizate), 스티렌계 TPE, 우레탄계 TPE(TPU), 불소계 TPE, 폴리에스테르계 TPE, PVC계 TPE, 폴리아미드계 TPE 등으로 다양하게 세분화되며, 열가소성수지의 우수한 가공성 및 재활용성과 가황고무의 탄성의 장점을 동시에 지닌 경량 소재로서, 전산업분야에 적용범위가 급속도로 확대되고 있으며 향후 가황고무를 완벽히 대체할수 있는 신소재로 부상하고 있다.이러한 열가소성 탄성체는 소재에따라 올레핀계, 스티렌계, 아미드계, 에스터계, 우레탄계, PVC계등으로나눌수있으며 이중에서 스티렌계 및 올레핀계 열가소성탄성체는 범용적으로 사용되고 있다. 특히, 열가소성 폴리에스테르 탄성체(TPEE)는 폴리에스테를 기본으로 엔지니어링 플라스틱(Engineering Plastic) 특성이 강한 엘라스토머이며, 기계적강도를비롯한 내열성, 내유성, 내약품성, 가공성이 우수하며 특히 자동차 부품중 C.V.J.(등속조인트) 부츠용으로 대체되고 있어 기존 가황고무타입의 CR(Chloroprene Rubber)의 대체소재 분야에서 사용된다. 또한, TPEE는고무와 엔지니어링플라그틱의특성을 모두 가지고 있으며 특히 다른 열가소성 엘라스토머와 비교해 볼때 사용가능한 온도영역이 넓고, 또한 내열성 및 내유성이 우수하여 자동차부품소재 분야나전기 전자분야의 신소재로서 사용된다.In one embodiment of the present invention, the thermoplastic elastomer (TPE) is selected from the group consisting of olefinic TPE and thermoplastic vulcanizate, styrene TPE, urethane TPE, fluorinated TPE, polyester TPE, PVC TPE, Based TPE. It is a lightweight material with excellent processability and recyclability of thermoplastic resin and elasticity of vulcanized rubber, and its application range has been expanding rapidly in all industrial fields. It can be completely replaced with vulcanized rubber in the future. Such as olefin, styrene, amide, ester, urethane, PVC, etc. Among these thermoplastic elastomers, styrene-based and olefin-based thermoplastic elastomers are commonly used. Particularly, the thermoplastic polyester elastomer (TPEE) is an elastomer having a strong engineering plastic property based on polyester, and has excellent heat resistance, oil resistance, chemical resistance and processability including mechanical strength, and especially CVJ ) Is used for boots, and is used in the field of alternative materials for CR (chloroprene rubber), which is a conventional vulcanized rubber type. In addition, TPEE has both the properties of rubber and engineering plastics. Especially, when compared with other thermoplastic elastomers, it has a wide temperature range, and is excellent in heat resistance and oil resistance, so it is used as a new material for automobile parts and electric and electronic fields.
TPEE는 하드세그먼트의 구성비율이 높은 경우에는 엔지니어링 플라스틱의 특성인 강도, 강성, 내열, 내약품성등이 우수한 반면, 소프트가 높은 경우에는 탄성체로서의 특성인 반발탄성, 유연성, 내충격성, 제음성등이 우수한 특징이 나타내기때문에 분자설계, 각세그먼트의 종류, 중합방법, 분자량, 분자량분포, 가교구조등에의해 수요특성에 맞는 물성구현이 가능하며 임계성능을 극복할 수 있다.
TPEE has excellent strength, stiffness, heat resistance and chemical resistance, which are characteristics of engineering plastics when the hard segment ratio is high. On the other hand, when the softness is high, the elastic properties such as rebound resilience, flexibility, impact resistance, It is possible to realize physical properties according to demand characteristics by molecular design, kind of each segment, polymerization method, molecular weight, molecular weight distribution, crosslinked structure, etc., and it is possible to overcome the critical performance.
본 발명에 따른 조성물은 MI가 크고, 인장강도가 높지 않으며 적정의 신율을 가져서, 작업성이 좋고, PC /ABS 오버몰딩용으로 적합하고, 이종재질간의 접합력이 우수하다.
The composition according to the present invention has a high MI, a high tensile strength and an appropriate elongation, and is excellent in workability, suitable for PC / ABS overmolding, and excellent in bonding strength between different materials.
이하, 본 발명의 구성요소와 기술적 특징을 다음의 실시예들을 통하여 보다 상세하게 설명하고자 한다. 그러나, 하기 실시예들은 본 발명의 내용을 예시하는것일 뿐발명의 범위가 실시예에의해 한정되는 것은 아니다.
Hereinafter, the components and technical features of the present invention will be described in more detail with reference to the following examples. However, the following examples illustrate the contents of the present invention, but the scope of the invention is not limited by the examples.
하기 표 1과 같이, 스티렌계 블록공중합체(SEBS), TPEE를 헨켈혼합기에 넣고 rpm 300-500 정도의 속도로 1분간 혼합한 후, 미네랄 오일을 첨가하고 rpm 100-300 정도의 속도로 혼합하였다. 다음으로 충진제, 안정제를 첨가하고 20초간 혼합하였다.As shown in Table 1, styrene block copolymer (SEBS) and TPEE were placed in a Henkel mixer and mixed at a speed of about 300-500 rpm for 1 minute, followed by addition of mineral oil at a speed of about 100-300 rpm . Next, filler and stabilizer were added and mixed for 20 seconds.
(충진제)Calcium carbonate
(Filler)
(UV 안정제)Bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate
(UV stabilizer)
SEBS 는 분자사슬내의 불포화 이중결합 구조를 가지고 있어 오존 또는 자외선에 의하여 쉽게 황변 또는 크랙이 발생되기 쉬우므로 이를 방지하기 위하여 산화방지제와 UV안정제를 각각 처방하였다. 이때 사용된 1차 산화방지제는 페놀계 산화방지제인 Irganox 1010 (Ciba-Geigy)을, UV 안정제로는 Songlight 7700 (송원산업, Bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate)를 각각 사용하였다. Since SEBS has an unsaturated double bond structure in the molecular chain, it is easy to cause yellowing or cracking due to ozone or ultraviolet ray. Therefore, antioxidant and UV stabilizer are prescribed to prevent this. Irganox 1010 (Ciba-Geigy), a phenolic antioxidant, and Songlight 7700 (bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate) Respectively.
이축압출기(Ø48mm, L/D = 32)로 180∼220℃의 온도 조건에서 수지 조성물을 용융혼합하였다. 이축압출기의 다이스를 통해 압출된 스트랜드(strand)는 냉각수와 air-blower를 거쳐 충분히 냉각을 시키면서 수분을 제거한 후 펠렛타이져를 거쳐 컴파운드 펠렛을 제조하였다. 압출시 작업온도 범위 및 속도등은 하기 표 2와 같다.The resin composition was melt-mixed under a temperature condition of 180 to 220 캜 with a twin-screw extruder (ø48 mm, L / D = 32). The strand extruded through the die of the twin-screw extruder was sufficiently cooled through cooling water and an air-blower to remove moisture, and the compound pellets were produced through a pelletizer. The operating temperature range and speed during extrusion are shown in Table 2 below.
상기 표 2와 같이 제조예 1 내지 3가 대조군에 비하여 작업온도범위가 넓다는 것을 알 수 있었다. 또한, 제조예 1 내지 3의 메쉬는 대략 80 내지 120의 범위이고, 속도(rpm)은 300이었다.
As shown in Table 2, it was found that Production Examples 1 to 3 had a wider working temperature range than the control group. Further, the meshes of Production Examples 1 to 3 were in the range of about 80 to 120, and the speed (rpm) was 300.
표 1에서 본 발명의 제조예 및 대조군에 대하여, 하기 표 3에서와 같은 시험방법으로 각 물성을 측정하였다.In Table 1, the physical properties of the production examples of the present invention and the control group were measured by the test method as shown in Table 3 below.
상기 표 3에서와 같이, 제조예 1 내지 3은 MI가 크고, 인장강도가 높지 않으며 적정의 신율을 가져서, 작업성이 좋고, PC 오버몰딩용으로 적합하였으며, 이종재질간의 접합력이 우수하다는 것을 알 수 있었다. As shown in Table 3, in Examples 1 to 3, MI was large, tensile strength was not high, proper elongation was good, workability was good, PC was suitable for over molding, and bonding strength between different materials was excellent I could.
TPEE 조성물은 ABS, PC 등과는 매우 우수한 접합력을 가지고 있어 오버몰딩 용으로 사용되지만, PA (nylon)과는 접합력이 없어 오버 몰딩 용으로 부적합하였다. 이 경우 TPEE 단독의 경우는 경도가 80A 정도이므로 그 이하의 경도를 충족하기 위해서는 다른 성분을 추가할 필요가 생기는 것이었다.
The TPEE composition has excellent bonding strength with ABS and PC and is used for overmolding, but it has no bonding strength with PA (nylon) and is not suitable for overmolding. In this case, since TPEE alone has a hardness of about 80 A, it is necessary to add other components in order to satisfy the hardness below that.
지금까지 예시적인 실시태양을 참조하여 본 발명을 기술하여 왔지만, 본 발명의 속하는 기술분야의 당업자는 본 발명의 범주를 벗어나지 않고서도 다양한 변화를 실시할 수 있으며 그의 요소들을 등가물로 대체할 수 있음을 알 수 있을 것이다. 또한, 본 발명의 본질적인 범주를 벗어나지 않고서도 많은 변형을 실시하여 특정 상황 및 재료를 본 발명의 교시내용에 채용할 수 있다. 따라서, 본 발명이 본발명을 실시하는데 계획된 최상의 양식으로서 개시된 특정 실시 태양으로 국한되는것이 아니며, 본 발명이 첨부된 특허청구의 범위에 속하는 모든 실시 태양을 포함하는 것으로 해석되어야 한다.
While the present invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. You will know. In addition, many modifications may be made to adapt a particular situation and material to the teachings of the invention without departing from the essential scope thereof. Accordingly, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention be construed as including all embodiments falling within the scope of the appended claims.
Claims (7)
And 50 to 70 parts by weight of a thermoplastic polyester elastomer based on 15 parts by weight of the styrenic block copolymer.
오일 5 내지 20 중량부를 추가로 포함하는 열가소성 탄성체 조성물.
The method according to claim 1,
And 5 to 20 parts by weight of an oil.
충진제 5 내지 25 중량부를 추가로 포함하는 열가소성 탄성체 조성물.
3. The method of claim 2,
And 5 to 25 parts by weight of a filler.
스티렌계블록공중합체는 스트렌 함량이 13 내지 33 중량%이거나, 평균 분자량이 50,000 내지 300,000g/mol인 열가소성 탄성체 조성물.
The method according to claim 1,
The styrenic block copolymer has a styrene content of 13 to 33% by weight, or an average molecular weight of 50,000 to 300,000 g / mol.
열가소성 폴리에스테르 탄성체 50 내지 70 중량부를 용융혼합하여 열가소성 탄성체를 제조하는 방법.
Based on the weight of the total composition, 5 to 20 parts by weight of the styrenic block copolymer and
And 50 to 70 parts by weight of a thermoplastic polyester elastomer is melt-mixed to produce a thermoplastic elastomer.
오일 5 내지 20 중량부 및 충진제 5 내지 25 중량부를 추가로 용융혼합하여 열가소성 탄성체를 제조하는 방법.
The method according to claim 6,
5 to 20 parts by weight of an oil and 5 to 25 parts by weight of a filler are further melt-mixed to prepare a thermoplastic elastomer.
스티렌계블록공중합체는 스트렌 함량이 13 내지 33 중량%이거나, 평균 분자량이 50,000 내지 300,000g/mol인 열가소성 탄성체를 제조하는 방법.
8. The method of claim 7,
Wherein the styrenic block copolymer has a styrene content of 13 to 33% by weight, or an average molecular weight of 50,000 to 300,000 g / mol.
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