KR20130068687A - Thermoplastic elastomer composition for door side extrusion - Google Patents
Thermoplastic elastomer composition for door side extrusion Download PDFInfo
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- KR20130068687A KR20130068687A KR1020110136010A KR20110136010A KR20130068687A KR 20130068687 A KR20130068687 A KR 20130068687A KR 1020110136010 A KR1020110136010 A KR 1020110136010A KR 20110136010 A KR20110136010 A KR 20110136010A KR 20130068687 A KR20130068687 A KR 20130068687A
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- doorside
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- 238000001125 extrusion Methods 0.000 title claims abstract description 64
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 32
- 229920002545 silicone oil Polymers 0.000 claims abstract description 29
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 27
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 24
- 239000004743 Polypropylene Substances 0.000 claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 claims abstract description 23
- -1 polypropylene Polymers 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 239000005662 Paraffin oil Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- 229920001400 block copolymer Polymers 0.000 claims abstract description 3
- 239000000155 melt Substances 0.000 claims abstract description 3
- 150000002978 peroxides Chemical group 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 239000012860 organic pigment Substances 0.000 claims description 10
- 239000001023 inorganic pigment Substances 0.000 claims description 9
- 239000006229 carbon black Substances 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 235000019241 carbon black Nutrition 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005299 abrasion Methods 0.000 abstract description 4
- 239000003086 colorant Substances 0.000 abstract description 3
- 125000002081 peroxide group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000011109 contamination Methods 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000005187 foaming Methods 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 241000220259 Raphanus Species 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229930000044 secondary metabolite Natural products 0.000 description 2
- 229920006342 thermoplastic vulcanizate Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000357292 Monodactylus Species 0.000 description 1
- 235000002791 Panax Nutrition 0.000 description 1
- 241000208343 Panax Species 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 235000006140 Raphanus sativus var sativus Nutrition 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; 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
- C08L91/06—Waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Seal Device For Vehicle (AREA)
Abstract
Description
본 발명은 차량용 웨더스트립 중 도어사이드 압출성형용 열가소성 엘라스토머 조성물에 관한 것으로, 보다 상세하게는 재활용이 가능한 열가소성 엘라스토머 소재를 이용하여 내유 및 내열 특성이 증진되고, 친환경적이며 다양한 색상발현이 가능하고, 기존 고무재 제품과 달리 재활용이 가능한 도어사이드 압출성형용 열가소성 엘라스토머 조성물에 관한 것이다.
The present invention relates to a thermoplastic elastomer composition for doorside extrusion molding in a vehicle weather strip, and more specifically, to improve oil and heat resistance characteristics by using a recyclable thermoplastic elastomer material, and to be environmentally friendly and express various colors. Unlike rubber products, the present invention relates to a thermoplastic elastomer composition for doorside extrusion.
차량용 웨더스트립(Weather strip)이란 기밀재로서 창문이나 출입문의 개폐부에 부착되어 외풍이나 먼지 등의 침입을 방지하는 것으로서, 간단하게 표현하자면 누수방지용 고무라 할 수 있다.A weather strip for a vehicle is an airtight material, which is attached to an opening or closing part of a window or a door to prevent invasion of air, dust, and the like, and is simply a rubber for preventing leakage.
일반적으로 도어(Door)의 기밀재로 사용되는 도어사이드 압출성형부의 압출소재의 경우 에틸렌 프로필렌 디엔 모노머(Ethylene propylene diene monomer, EPDM) 고무로 제조되며, 제조방법은 압출 성형 후 가황공정 및 발포공정을 거치는 것이 일반적이다. 그러나 최근 고객의 요구에 따라 친환경적이면서도 제품의 강도 및 내구성이 향상된 신재료 개발의 요구가 대두되고 있다.In general, the extruded material of the door-side extrusion molded part used as the airtight material of the door is made of ethylene propylene diene monomer (EPDM) rubber, and the manufacturing method is a vulcanization process and a foaming process after extrusion molding. It is common to go through. Recently, however, there is a demand for developing new materials that are environmentally friendly and have improved strength and durability.
자동차 웨더스트립에 대하여 EPDM 고무를 함유하는 조성물에 안료를 첨가한 등록특허공보 제10-0792886호가 있으나, EPDM 및 SEBS를 사용한 열가소성 엘라스토머 조성물에 안료를 적용한 조성물은 알려진 바가 없다.
Patent Publication No. 10-0792886, which adds a pigment to a composition containing EPDM rubber for automotive weatherstrips, has not known a composition in which the pigment is applied to a thermoplastic elastomer composition using EPDM and SEBS.
본 발명자들은 도어사이드 압출성형용 소재로서 고무대신 열가소성 엘라스토머를 사용하게 되면 제품의 물성을 개선시킬 수 있으며, 작업 효율성도 높일 수 있음을 발견하였다. The inventors have found that the use of thermoplastic elastomers instead of rubber as the material for doorside extrusion can improve the physical properties of the product and increase the working efficiency.
따라서, 본 발명은 강도, 내구성 등이 향상되며 재활용이 가능한 도어사이드 압출성형용 열가소성 엘라스토머 조성물을 제공하는 것을 목적으로 한다.
Accordingly, an object of the present invention is to provide a thermoplastic elastomer composition for doorside extrusion which is improved in strength, durability, and can be recycled.
본 발명은 에틸렌 프로필렌 디엔 모노머(ethylene propylene diene monomer; EPDM), 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(Styrene-Ethylene/Butylene-Styrene Copolymer; SEBS), 폴리프로필렌(polypropylene; PP), 고점도 파라핀 오일, 실리콘 오일, 퍼옥사이드 가교제, 산화방지제, 기타 첨가제로 이루어 진다. The present invention is ethylene propylene diene monomer (EPDM), styrene ethylene butadiene styrene copolymer (Styrene-Ethylene / Butylene-Styrene Copolymer (SEBS), polypropylene (PP), high viscosity paraffin oil, silicone oil, Peroxide crosslinker, antioxidant, and other additives.
상기한 목적을 달성하기 위하여 본 발명은 에틸렌 프로필렌 디엔 모노머(EPDM) 60~90 중량부, 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS)는150~170 중량부, 폴리프로필렌 10~20 중량부, 고점도 파라핀 오일 120~140 중량부, 실리콘 오일 30~40 중량부, 퍼옥사이드 가교제 0.6~0.9 중량부, 산화방지제 0.6~0.9 중량부 및 기타 첨가제 0.3~0.5 중량부를 함유 하는 도어사이드 압출성형용 열가소성 엘라스토머 조성물을 제공한다.In order to achieve the above object, the present invention is 60 to 90 parts by weight of ethylene propylene diene monomer (EPDM), styrene ethylene butadiene styrene copolymer (SEBS) is 150 to 170 parts by weight, polypropylene 10 to 20 parts by weight, high viscosity paraffin oil Provided is a thermoplastic elastomer composition for doorside extrusion molding containing 120 to 140 parts by weight, silicone oil 30 to 40 parts by weight, peroxide crosslinking agent 0.6 to 0.9 parts by weight, antioxidant 0.6 to 0.9 parts by weight and other additives 0.3 to 0.5 parts by weight. do.
바람직하게는 에틸렌 프로필렌 디엔 모노머(EPDM) 90 중량부, 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS) 160 중량부, 폴리프로필렌(PP) 17 중량부, 고점도 파라핀 오일 125 중량부, 실리콘 오일 40 중량부, 퍼옥사이드 가교제 0.85 중량부, 산화방지제 0.9중량부 및 기타 첨가제 0.5중량부를 함유 한다.Preferably, 90 parts by weight of ethylene propylene diene monomer (EPDM), 160 parts by weight of styrene ethylene butadiene styrene copolymer (SEBS), 17 parts by weight of polypropylene (PP), 125 parts by weight of high viscosity paraffin oil, 40 parts by weight of silicone oil, fur 0.85 parts by weight of oxide crosslinker, 0.9 parts by weight of antioxidant and 0.5 parts by weight of other additives.
본 발명의 조성물에 사용되는 에틸렌 프로필렌 디엔 모노머(EPDM)은 도어사이드 압출성형부의 우수한 압출(Extrusion) 성형성, 복원률 등을 개선시켜 주며 내후성 및 내열특성을 강화시켜 준다. 본 발명의 조성물에서 상기 에틸렌 프로필렌 디엔 모노머(EPDM)는 60~90중량부의 양으로 함유된다. 함량이 60중량부 미만일 경우에는 압출(Extrusion) 성형 시 제품 흐름성 불량이 생겨 치수 안정성 및 성형이 어려우며, 제품의 복원률이 떨어진다. 90중량부 초과일 경우에는 완제품 경도 상승으로 인해 도어사이드 성능에 큰 영향을 주는 압축하중 및 영구압축줄음율 특성 저하와 도어(Door)에 최종제품 장착 시 작업의 어려움이 있다.The ethylene propylene diene monomer (EPDM) used in the composition of the present invention improves the excellent extrusion moldability, recovery rate, etc. of the doorside extrusion molding, and enhances weather resistance and heat resistance characteristics. In the composition of the present invention, the ethylene propylene diene monomer (EPDM) is contained in an amount of 60 to 90 parts by weight. When the content is less than 60 parts by weight, product flowability defects occur during extrusion molding, which makes dimensional stability and molding difficult, and the recovery rate of the product is reduced. In the case of more than 90 parts by weight, there is a problem of deterioration of the compression load and permanent compression rate characteristics which greatly affect the doorside performance due to the increase of the hardness of the finished product, and the difficulty of work when the final product is mounted on the door.
본 발명의 조성물에 사용되는 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS)는 우수한 내마모특성을 가지며 외력에 대한 형상 복원능력이 뛰어나다. 본 발명의 조성물에서 상기 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS)는 150~170 중량부의 양으로 함유된다.Styrene ethylene butadiene styrene copolymer (SEBS) used in the composition of the present invention has excellent wear resistance and excellent shape resilience to external forces. In the composition of the present invention, the styrene ethylene butadiene styrene copolymer (SEBS) is contained in an amount of 150 to 170 parts by weight.
함량이 150중량부 미만일 경우에는 Door 개폐 시 제품의 탄성이 떨어져 형상복원이 불리하며, 170중량부 초과일 경우에는 밀폐(Sealing)성은 좋으나, 경도 및 점도 저하, 토출량의 불균일로 인해 압출 시 맥동현상이 발생하는 등 치수 안정성 및 압출 성형성이 불리하며, 재료강성 저하로 인해 찢어짐 등 장기 내구성에 불리하다.If the content is less than 150 parts by weight, the elasticity of the product is inferior when the door is opened and closed, which is disadvantageous.If the content is more than 170 parts by weight, the sealing property is good, but the pulsation phenomenon during extrusion due to the decrease in hardness, viscosity, and discharge amount This is disadvantageous in terms of dimensional stability and extrusion moldability, and is disadvantageous in long-term durability such as tearing due to a decrease in material rigidity.
본 발명의 조성물에 사용되는 폴리프로필렌(PP)은 에틸렌 프로필렌 디엔 모노머(EPDM) 및 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS)의 Matrix를 형성하는 역할을 하며 내유 및 내역특성을 강화시켜 준다. 본 발명의 조성물에서 사용되는 폴리프로필렌은 10~20중량부의 양으로 함유된다. 함량이 10중량부 미만일 경우에는 낮은 흐름성으로 인한 압출 성형이 어려우며, 20중량부 초과일 경우에는 완제품 경도 상승으로 인해 성능저하 및 도어사이드 압출성형부 장착 시 작업이 어려움 점이 있다. 또한 본 발명에서 폴리프로필렌은 도어사이드 압출성형부의 우수한 압출(Extrusion) 성형성 및 고강도, 고충격, 내유성 등의 개선을 위해 용융 흐름 지수(Melt Flow Index)가 230℃, 2.16kg 에서 0.5g/10min 이하인 고 결정성 블록 코폴리머를 블랜드하여 제조한 것을 사용한다.Polypropylene (PP) used in the composition of the present invention serves to form a matrix of ethylene propylene diene monomer (EPDM) and styrene ethylene butadiene styrene copolymer (SEBS) and enhance oil and oil resistance characteristics. The polypropylene used in the composition of the present invention is contained in an amount of 10 to 20 parts by weight. If the content is less than 10 parts by weight, it is difficult to extrude due to low flowability, and if it is more than 20 parts by weight, there is a difficulty in lowering the performance and installing the doorside extrusion part due to the increase in hardness of the finished product. Also, in the present invention, the polypropylene has a melt flow index of 0.5 g / 10 min at 230 ° C. and 2.16 kg in order to improve the extrusion property of the doorside extrusion part and improve the high strength, high impact, oil resistance, and the like. The thing manufactured by blending the following high crystalline block copolymer is used.
본 발명의 조성물에 사용되는 고점도 파라핀 오일은 열가소성 엘라스토머 제조 시 가공성을 촉진시키며, 또한, 열가소성 엘라스토머의 경도를 감소시켜, 가소성 및 성형성을 증가시키는 역할을 한다. 본 발명의 조성물에서 상기 고점도 파라핀 오일은 120~140중량부의 양으로 함유된다. 함량이 120중량부 미만일 경우에는 압출(Extrusion) 성형 시 흐름성이 낮아 다이스 버르(Dies Burr)에 의한 성형 불량 및 작업 불량의 원인이 되며, 140중량부 초과일 경우에는 흐름성이 증가하여 압출(Extrusion) 성형 시 압출 조건에 의한 민감한 반응을 보여 제품 두께 편차가 발생한다. 또한 상기 고점도 파라핀 오일은 40℃ 동점도(Kinematic Viscosity)의 범위가 170 cSt 이상인 것이 바람직하다. The high viscosity paraffin oil used in the composition of the present invention promotes workability in preparing thermoplastic elastomers, and also serves to reduce the hardness of the thermoplastic elastomer, thereby increasing plasticity and formability. In the composition of the present invention, the high viscosity paraffin oil is contained in an amount of 120 to 140 parts by weight. If the content is less than 120 parts by weight, the flowability during extrusion molding is low, which causes mold failure and work failure by dies burr. If the content is more than 140 parts by weight, the flowability increases and the extrusion ( Extrusion During molding, the product exhibits a sensitive reaction due to extrusion conditions, resulting in product thickness variations. In addition, the high viscosity paraffin oil is preferably in the range of 40 ℃ kinematic viscosity (Kinematic Viscosity) of 170 cSt or more.
본 발명의 조성물에 사용되는 실리콘 오일은 자기윤활성 및 내마모성 향상을 위한 재료로서 20~40 중량부의 양으로 함유된다. 함량이 20 중량부 미만일 경우에는 자기윤활성이 떨어져 마모가 쉽게 발생되며, 40 중량부 초과일 경우에는 재료물성 저하 및 과도한 자기윤활성으로 인해 2차 오염을 발생 시키며 또한 장착 시 과도한 슬립으로 인해 장착 어려움이 발생된다. 또한 본 발명에서 상기 실리콘 오일은 바람직하게는 분자량 3,000인 실리콘 오일과 분자량 10,000인 실리콘 오일을 동시에 함유하며, 초기 이행성을 높이기 위해 분자량 3,000인 실리콘 오일을 15~30 중량부 및 경시변화에 따른 지속적인 이행성을 부여하기 위해 분자량 10,000인 실리콘 오일을 5~10 중량부를 함유한다. 보다 바람직하게는 분자량 3,000인 실리콘 오일 30중량부 및 분자량 10,000인 실리콘 오일 10중량부를 함유한다.The silicone oil used in the composition of the present invention is contained in an amount of 20 to 40 parts by weight as a material for improving self-lubrication and wear resistance. If the content is less than 20 parts by weight, the self-lubrication is poor and wear is easily generated. If the content is more than 40 parts by weight, secondary contamination occurs due to deterioration of material properties and excessive self-lubrication. Is generated. In addition, the silicone oil in the present invention preferably contains a silicone oil having a molecular weight of 3,000 and a silicone oil having a molecular weight of 10,000 at the same time, 15 to 30 parts by weight of the silicone oil having a molecular weight of 3,000 in order to increase the initial transferability and continuous with change over time In order to impart transferability, the silicone oil having a molecular weight of 10,000 is contained 5 to 10 parts by weight. More preferably, it contains 30 weight part of silicone oils with a molecular weight of 3,000, and 10 weight part of silicone oils with a molecular weight of 10,000.
본 발명의 조성물에 사용되는 퍼옥사이드는 열가소성 엘라스토머의 물성을 나타낼 수 있도록 에틸렌 프로필렌 디엔 모노머(EPDM)을 가교시키는 역할을 한다. 이를 위해 이축압출기(트윈압출기)를 사용하여 동적 가교를 시켜 고무와 같은 점성과 탄성의 성질을 보유하도록 제조한다. 이 때 열가소성 엘라스토머 가교를 위한 가교제의 경우 페놀 수지 가교제와 퍼옥사이드 가교제가 주로 사용되는데, 페놀 수지 가교제의 경우 친수성 재료, 즉 수분에 상당히 민감한 화학 물질이므로 수분 흡습에 따른 압출 시 표면불량(Fish Eye) 문제점과 사용 및 보관 시 제습을 위한 건조설비가 반드시 필요하나, 퍼옥사이드 가교제의 경우 소수성 재료로서 페놀수지 대비 수분 흡수에 따른 문제점이 없기 때문에 본 발명에서는 퍼옥사이드 가교제를 사용하였다. 그러나, 사용 가능한 가교제가 퍼옥사이드 가교제로 한정되지는 않는다.The peroxide used in the composition of the present invention serves to crosslink ethylene propylene diene monomer (EPDM) to exhibit the physical properties of the thermoplastic elastomer. To this end, a biaxial extruder (twin extruder) is used for the dynamic crosslinking to produce rubber-like viscosity and elastic properties. In this case, a phenolic resin crosslinking agent and a peroxide crosslinking agent are mainly used for the crosslinking agent for thermoplastic elastomer crosslinking. In the case of the phenolic resin crosslinking agent, a hydrophilic material, that is, a chemical substance that is highly sensitive to moisture, causes surface defects during extrusion due to moisture absorption. Problems and drying facilities for dehumidification during use and storage are necessary, but peroxide crosslinking agents are used in the present invention because peroxide crosslinking agents do not have problems due to water absorption as compared to phenolic resins as hydrophobic materials. However, the crosslinking agent which can be used is not limited to a peroxide crosslinking agent.
본 발명에서 사용되는 퍼옥사이드 가교제는 0.6~0.9 중량부의 양으로 함유된다. 함량이 0.6 중량부 미만일 경우에는 가교가 충분하게 이루어지지 않게 되어 완제품의 물성저하, 탄성 및 내후성이 저하되고, 0.9 중량부 초과일 경우에는 높은 가교도로 인해 외관에 피시아이(Fish Eye)와 같은 이물질이 관찰될 수 있으며 압출 성형 시 외관 불량 및 성형성 불량의 원인이 될 수 있다.The peroxide crosslinking agent used in the present invention is contained in an amount of 0.6 to 0.9 parts by weight. If the content is less than 0.6 parts by weight, the crosslinking is not sufficient, resulting in deterioration of physical properties, elasticity and weather resistance of the finished product, and if it is more than 0.9 parts by weight, foreign substances such as fish eyes may appear on the appearance due to the high degree of crosslinking. This may be observed and may be a cause of poor appearance and poor moldability during extrusion.
일반적으로 열가소성 엘라스토머 소재를 제조할 경우 이축압출기(트윈압출기)를 사용하여 동적가교를 통해 제조하며, 이 경우 가공온도가 200℃ 이상이고 높은 전단력이 발생한다. 이 때 열가소성 엘라스토머 소재 산화 방지를 목적으로 산화방지제를 사용한다. 또한, 완제품의 경우 열에 의한 분해를 방지하기 위하여 산화방지제를 사용한다.In general, when manufacturing a thermoplastic elastomer material is manufactured through a dynamic cross-linking using a twin-screw extruder (twin extruder), in this case the processing temperature is 200 ℃ or more and high shear force occurs. At this time, an antioxidant is used for the purpose of preventing oxidation of the thermoplastic elastomer material. In addition, in the case of finished products, antioxidants are used to prevent decomposition by heat.
본 발명의 조성물에 사용되는 산화방지제는 0.6~0.9 중량부의 양으로 함유된다. 함량이 0.6 중량부 미만일 경우에는 제조 후 조성물의 물성이 저하되고 완제품을 장기간 사용시 성능이 저하되며, 0.9 중량부 초과일 경우에는 제품의 제조단가가 상승하고 반응하지 못한 산화방지제가 제품 표면으로 블루밍(Blooming)되는 문제점을 발생시키게 된다.The antioxidant used in the composition of the present invention is contained in an amount of 0.6 to 0.9 parts by weight. If the content is less than 0.6 parts by weight, the physical properties of the composition after the production is lowered, the performance is degraded when using the finished product for a long time, and if it is more than 0.9 parts by weight, the manufacturing cost of the product rises and the unreacted antioxidants bloom on the surface of the product ( It causes a problem of blooming.
본 발명의 조성물에 사용되는 기타 첨가제는 0.3~0.5 중량부의 양으로 함유된다. 또한 상기 기타 첨가제는 도어사이드 압출성형부의 표면 슬립성 개선 및 내마모성 증가시키기 위하여 폴리프로필렌계 왁스를 사용하는 것이 바람직하지만, 이에 한정되는 것은 아니다.Other additives used in the composition of the present invention are contained in an amount of 0.3 to 0.5 parts by weight. In addition, the other additives, but it is preferable to use a polypropylene wax to improve the surface slip properties and increase the wear resistance of the door-side extrusion molded parts, but is not limited thereto.
본 발명의 조성물에는 안료를 더 포함할 수 있으며, 상기 안료는 무기 안료 또는 유기안료를 사용할 수 있다. 상기 무기안료 또는 유기안료는 당업계에서 통상적으로 사용되는 것을 사용할 수 있으며, 무기안료 및 유기안료 중 1종 이상을 함께 사용할 수 있다. 구체적인 예를 들면 상기 무기안료는 산화물, 수산화물, 황화물, 크롬산염, 규산염, 탄산염, 이산화 티탄, 산화철, 탈크, 탄산칼슘, 카본블랙 등을 사용할 수 있으며, 유기 안료로는 아조계, 프탈로시아닌계, 니트로계, 축합다환 안료, 프탈로시아닌 그린, 프탈로시아닌 블루, 키나크리든 레드, 이소인돌린 옐로우 등을 사용할 수 있으나 이에 한정되는 것은 아니다. 이들 안료는 색상, 착색력, 내후성등을 고려하여 보완적으로 사용한다. The composition of the present invention may further comprise a pigment, the pigment may be used an inorganic pigment or an organic pigment. The inorganic pigments or organic pigments may be used that are commonly used in the art, may be used together with one or more of inorganic pigments and organic pigments. Specific examples of the inorganic pigments include oxides, hydroxides, sulfides, chromates, silicates, carbonates, titanium dioxide, iron oxides, talc, calcium carbonates, carbon black, and the like, and organic pigments include azo, phthalocyanine, and nitro. System, condensed polycyclic pigments, phthalocyanine green, phthalocyanine blue, kinacrden red, isoindolin yellow and the like can be used, but is not limited thereto. These pigments are used complementarily in consideration of color, coloring power, weather resistance, and the like.
본 발명에 의한 열가소성 엘라스토머 조성물은 차량용 웨더스트립에 사용되는 도어사이드 압출성형용으로서 제조되며, 제조방법이 특별히 제한되는 것은 아니지만, 바람직하게는 압출(Extrusion)성형 방법으로 제조될 수 있다.The thermoplastic elastomer composition according to the present invention is prepared for doorside extrusion for use in a vehicle weather strip, and the production method is not particularly limited, but may preferably be produced by an extrusion molding method.
도어사이드 압출성형부의 제조공정에 있어서, 일반적으로 고무로 제품을 제조하는 경우 고무 소재의 특성상 탄성을 부여하기 위해서 가교공정 및 발포공정이 필요한 반면, 열가소성 엘라스토머의 경우 제품 성형시에 가교공정 및 발포공정이 필요하지 않고 제품을 성형 설비에서 바로 생산할 수 있다. 또한 고무 재료를 이용하여 도어사이드 압출성형부를 제조할 경우에는 압출공정은 ① 소재공급, ② 압출, ③ 가교 및 발포, ④ 냉각, ⑤ 인취, ⑥ 열경화 코팅, ⑦ 건조, ⑧ 천공, ⑨ 절단, ⑩ 조인트, ⑪ 사상, ⑫ 검사 공정으로 이루어진다.In the manufacturing process of the door-side extrusion part, in general, when a product is manufactured from rubber, a crosslinking process and a foaming process are required to impart elasticity due to the characteristics of the rubber material, while in the case of thermoplastic elastomers, a crosslinking process and a foaming process at the time of molding a product This is not necessary and the product can be produced directly at the molding facility. Also, in the case of manufacturing doorside extrusion using rubber material, the extrusion process is ① material supply, ② extrusion, ③ crosslinking and foaming, ④ cooling, ⑤ withdrawal, ⑥ thermosetting coating, ⑦ drying, ⑧ perforation, ⑨ cutting, ⑩ joint, ⑪ mapping, ⑫ inspection process.
반면, 본 발명에 의한 열가소성 엘라스토머 소재를 사용하여 압출(Extrusion)성형 공정을 거치게 되면 ① 소재공급, ② 압출, ③ 냉각, ④ 인취, ⑤ 건조 ⑥ 천공, ⑦ 절단, ⑧ 조인트, ⑨ 사상, ⑩ 검사 공정으로 이루어져 가교 및 발포 공정, 열경화 코팅 공정이 필요하지 않기 때문에 빠른 시간 이내에 모든 공정을 완료할 수 있으므로, 기존에 일반적으로 사용되는 방법인 압출성형 방법으로 제조할 경우와 비교하여 공정을 줄일 수 있다.On the other hand, when the extrusion molding process using the thermoplastic elastomer material according to the present invention is carried out ① material supply, ② extrusion, ③ cooling, ④ withdrawal, ⑤ dry ⑥ perforation, ⑦ cutting, ⑧ joint, ⑨ finishing, ⑩ inspection Because the process does not require cross-linking, foaming, and thermosetting coating processes, all processes can be completed in a short time. Therefore, the process can be reduced compared to manufacturing by extrusion method, which is a commonly used method. have.
또한, 본 발명의 열가소성 엘라스토머 조성물은 재활용이 가능하므로, 압출성형의 방법으로 제품의 제조 시 발생되는 및 성형불량품을 실시간으로 분쇄하여 재활용할 수 있어 환경보호 및 비용절감 효과를 제공할 수 있으며 기존 고무소재에서 행하던 가교 및 발포공정을 줄일 수 있어 작업인원 감원 감소 및 전체 작업 시간을 줄일 수 있다.
In addition, since the thermoplastic elastomer composition of the present invention can be recycled, it can be recycled by real-time crushing and molding defects generated during the manufacture of the product by the extrusion molding method can provide environmental protection and cost-saving effect and existing rubber The crosslinking and foaming process used in the material can be reduced, which can reduce the number of workers and reduce the total work time.
본 발명에서는 재활용이 가능한 열가소성 엘라스토머 소재를 적용한 도어사이드 압출성형부의 경우 비발포(Solid) 압출성형 방법을 적용하여 기존 고무재 제품와 비교하여 발포제 및 기타 화학약품의 배제로 친환경적이며, 유기 및 무기 안료를 포함하여도 강도가 우수하고, 압출성형이 가능하며, 압축줄음율, 내오존성, 내열성 및 내마모성이 뛰어난 물성에 영향이 없어 안료와의 상용성이 우수하며, 다양한 색상 발현이 가능하므로 소비자 감성에 맞춘 도어사이드 생산이 가능하다. 또한 폴리프로필렌을 첨가하여 내유, 내열특성까지 보강되며, 성형불량품을 실시간으로 분쇄하여 재활용이 가능하다.
In the present invention, in the case of the door-side extrusion molded part to which the recyclable thermoplastic elastomer material is applied, it is eco-friendly by excluding foaming agent and other chemicals by applying the non-foaming (Solid) extrusion method and compared to the conventional rubber product, and using organic and inorganic pigments It is excellent in strength even though it is included, and can be extruded, and it has excellent compatibility with pigments because it does not affect the properties of compression shrinkage, ozone resistance, heat resistance, and abrasion resistance. Doorside production is possible. In addition, polypropylene is added to reinforce oil and heat resistance characteristics, and it is possible to recycle by molding the defective parts in real time.
이하 실시예 및 시험예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 이들 실시예 및 시험예는 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예 및 시험예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. These examples and test examples are for illustrating the present invention more specifically, but the scope of the present invention is not limited by these examples and test examples.
[[ 제조예Manufacturing example 1] One] 도어사이드Doorside 압출성형용 조성물의 제조 Preparation of Extrusion Molding Composition
하기 표 1의 조성으로 실시예 1~2 및 비교예 1~4의 도어사이드 압출성형용 소재를 제조하였다.To the door 1 in the composition of Tables 1 and 2 and Comparative Examples 1 to 4 were prepared for the door-side extrusion.
- EPDM : 에틸렌 프로필렌 디엔 모노머, 금호폴리켐사, KEP-2480, 125℃ Moony Viscosity 81 -EPDM: Ethylene Propylene Diene Monomer, Kumho Polychem, KEP-2480, 125 ℃ Moony Viscosity 81
- SEBS : 스타일렌 에틸렌 부타디엔 스타일렌 공중합체, 광성플라스틱사, GT-35EX, 용융지수 4g/min (230℃, 2.16kg), 밀도 0.98g -SEBS: Styrene Ethylene Butadiene Styrene Copolymer, Photoplastic Plastics, GT-35EX, Melt Index 4g / min (230 ℃, 2.16kg), Density 0.98g
- 폴리프로필렌 : 대한유화사, BP2000, 용융지수 0.5g/10min (230℃, 2.16kg) -Polypropylene: Daehan Emulsifier, BP2000, Melt Index 0.5g / 10min (230 ℃, 2.16kg)
- 고점도 파라핀 오일 : 서진화학, KL시리즈, 밀도 0.85g/㎤ 동점도(40℃) 170 cSt이상 -High viscosity paraffin oil: Seojin Chemical, KL series, Density 0.85g / cm3 Kinematic viscosity (40 ℃) 170 cSt or more
- 실리콘 오일 : 분자량 3000 - GE Toshiba, TSF-0.3M; 분자량 10000 - GE Toshiba, TSF-1MSilicone oil: molecular weight 3000-GE Toshiba, TSF-0.3M; Molecular Weight 10000-GE Toshiba, TSF-1M
- 퍼옥사이드 가교제 : Pergan사, HX50PS 순도 50% 1분 반감기 170℃ 이상-Peroxide Crosslinker: Pergan, HX50PS Purity 50% 1min Half Life 170 ℃ or higher
- 산화방지제 : 송원화학, S1010 분자량 1150, 녹는점 110℃ -Antioxidant: Songwon Chemical, S1010 Molecular Weight 1150, Melting Point 110 ℃
- 기타첨가제 : 폴리프로필렌 왁스, 라이온켐텍 500 Series, 밀도 0.89g/㎤, 분자량 2000 이상 -Other additives: Polypropylene wax, Lion Chemtech 500 Series, Density 0.89g / cm3, Molecular Weight 2000 or more
상기 표 1의 조성에 따라 퍼옥사이드 가교제, 산화방지제 및 기타 첨가제를 반응기(Super Mixer 150L, 풍광기계)를 이용하여 1Batch 40분, 300~350 rpm에서 드라이블렌드(dry blend) 후 정량공급장치로 일괄 투입하고, 폴리프로필렌, 에틸렌 프로필렌 디엔 모노머 및 고점도 파라핀 오일은 각각을 정량공급장치로 투입하여 이축압출기(Twin Screw Extruder; 독일 Coperion社 (W&P))로 가교 TPV(Thermoplastic Vulcanizate) 컴파운드(1차 컴파운드)를 제조하였다. 1차 컴파운드의 제조 조건은 아래와 같으며, 온도 조건은 하기 표 2와 같다.Peroxide crosslinking agent, antioxidant and other additives according to the composition of Table 1 by using a reactor (Super Mixer 150L, Wind Light Machine) for 1 batch 40 minutes, dry blend at 300 ~ 350 rpm (batch blend) and then batch Polypropylene, ethylene propylene diene monomer, and high viscosity paraffin oil were fed into a fixed-supply device, and then crosslinked with a twin screw extruder (W & P), TPV (Thermoplastic Vulcanizate) compound (primary compound). Was prepared. The manufacturing conditions of the primary compound are as follows, and the temperature conditions are shown in Table 2 below.
- TSE사양 : 70mm / 60D -TSE specification: 70mm / 60D
- Set Point : 350kg/hr-Set Point: 350kg / hr
- Screw RPM : 400-Screw RPM: 400
- 압력 : 7~8Bar-Pressure: 7 ~ 8Bar
상기 1차 컴파운드와 스타일렌 에틸렌 부타디엔 스타일렌 공중합체(SEBS) 및 실리콘 오일(분자량 3,000 및 10,000)을 반응기(Super Mixer 150L, 풍광기계)를 이용하여 1Batch 40분, 300~350 rpm에서 드라이블렌드(dry blend) 후 정량공급장치로 일괄 투입하여 이축압출기(Twin Screw Extruder; 독일 Coperion社 (W&P))로 도어사이드 압출용 컴파운드(2차 컴파운드)를 제조하였다. 2차 컴파운드의 제조 조건은 아래와 같으며, 온도 조건은 하기 표 3와 같다.Dry blend of the primary compound and styrene ethylene butadiene styrene copolymer (SEBS) and silicone oil (molecular weight 3,000 and 10,000) at 1 batch 40 minutes, 300 ~ 350 rpm using a reactor (Super Mixer 150L, Pungwang Machinery) After the batch feed into the metering device, a compound for the doorside extrusion (secondary compound) was manufactured by a twin screw extruder (W & P). The manufacturing conditions of the secondary compound are as follows, and the temperature conditions are shown in Table 3 below.
- TSE사양 : 70mm / 60D -TSE specification: 70mm / 60D
- Set Point : 350kg/hr-Set Point: 350kg / hr
- Screw RPM : 400-Screw RPM: 400
- 압력 : 4~5Bar-Pressure: 4 ~ 5Bar
[[ 시험예Test Example 1] One] 도어사이드Doorside 압출성형용 조성물의 물성 평가 Evaluation of physical properties of the composition for extrusion molding
상기 제조예 1에서 제조한 실시예 1~2 및 비교예 1~3의 도어사이드 압출성형용 조성물의 기본 물성, 내열물성, 압축줄음율, 내오존성, 압출 성형성, 도장판 오염, 내마모성 및 내유성을 평가하였다.Basic physical properties, heat resistance, compressive shrinkage, ozone resistance, extrusion molding, coating plate contamination, abrasion resistance and oil resistance of the doorside extrusion composition of Examples 1 to 2 and Comparative Examples 1 to 3 prepared in Preparation Example 1 Was evaluated.
구체적으로 내열물성은 120℃에서 70시간 경과 후의 물성을 측정하였으며, 내오존성은 오존농도 50pphm, 40℃에서 100시간 경과 후 외면 크랙 유무를 확인하여 결과는 매우좋음(◎), 좋음(○), 보통(△), 좋지 않음(×)으로 평가하였으며, 압출 성형성은 Thermo Haake사 Single Screw Extruder(Φ25)를 사용하여 하기 표 4의 조건에서 시트(Sheet) 압출 후 외관상태를 통하여 압출성을 평가하였다.Specifically, the heat resistance was measured after 70 hours at 120 ℃, the ozone resistance was 50pphm, after 100 hours at 40 ℃ to confirm the presence of external cracks, the results are very good (◎), good (○), It was evaluated as normal (△), not good (×), the extrudability was evaluated by the appearance state after sheet extrusion under the conditions of Table 4 using a Thermo Haake's Single Screw Extruder (Φ25). .
또한 도장판 오염시험은 압출 시트를 80℃에서 70시간 노화 후 항온수조에 50℃, 습도 90%, 24 시간 침적 후 도장판 오염 유무를 확인하였고, 내마모성 평가는 완제품을 100,000만회 실차 도어 개폐 마모평가 후 제품 파열 유무를 확인하였다. 압축줄음율은 70℃에서 24시간 경과 후의 복원력을 측정하였다. 내유성 평가 방법는 ASTM NO.3 오일(Oil)에서 시험온도 120℃, 70시간 침적 후 부피변화를 측정하였다.In addition, the paint plate contamination test confirmed the presence of paint plate contamination after immersion of the extruded sheet at 80 ° C for 70 hours in a constant temperature water bath at 50 ° C, humidity of 90%, and 24 hours. After the rupture of the product was confirmed. Compression decrease was measured for restoring force after 24 hours at 70 ℃. Oil resistance evaluation method measured the change in volume after the deposition temperature of 120 ℃, 70 hours in ASTM NO.3 oil (Oil).
상기 평가 결과를 하기 표 5에 나타내었다.The evaluation results are shown in Table 5 below.
물성basic
Properties
물성Heat resistance
Properties
상기 표 5에 나타난 바와 같이, 본원발명에 의한 도어사이드 압출성형용 소재는 강도가 우수하고, 압출성형이 가능하며, 압축줄음율, 내오존성, 내열성 및 내마모성이 뛰어나다.
As shown in Table 5, the door-side extrusion molding material according to the present invention is excellent in strength, capable of extrusion molding, excellent in compression shrinkage, ozone resistance, heat resistance and wear resistance.
[[ 시험예Test Example 2] 실리콘 오일 함량에 따른 마모 변화 평가 2] Evaluation of Wear Change According to Silicone Oil Content
하기 표 6의 조성으로 도어사이드 압출성형용 조성물을 제조하였다. 비교예 5는 실리콘오일을 첨가하지 않았고, 비교예 6~8은 본 발명의 함량 범위 외의 실리콘 오일을 첨가하였다. EPDM, SEBS, 폴리프로필렌, 고점도 파라핀 오일, 실리콘 오일, 퍼옥사이드 가교제, 산화방지제, 기타첨가제는 시험예 1에서와 동일한 물질을 사용하였다.To the composition of the doorside extrusion molding was prepared in the composition of Table 6. Comparative Example 5 did not add silicone oil, Comparative Examples 6 to 8 added silicone oil outside the content range of the present invention. EPDM, SEBS, polypropylene, high viscosity paraffin oil, silicone oil, peroxide crosslinker, antioxidant, and other additives used the same materials as in Test Example 1.
상기 실시예 3~4 및 비교예 5~8의 조성물에 대하여 상기 시험예 1에서와 동일한 방법으로 기본 물성, 도장판 오염 및 내마모성 평가하여 결과를 아래 표 7에 나타내었다. 내마모성 평가는 완제품을 100,000회 실차 도어 개폐 마모평가 후 제품 파열 유무를 확인하였으며, 제품의 비교 시험에 적합한 DIN53516(가황고무의 마모 시험 방법)에 의한 마모평가를 진행하여 체적손실을 각 시험편을 5개씩 사용하여 실험한 결과의 중간값으로 하기 표 7에 나타내었다. 구체적으로는 표준 기준 물질 (standard reference material SRM )을 사용하여 만든 마모용 기준물로 7~8회 연마지를 체크하며, 표준 시험편은 원반 모양, 직경 φ16.0 ± 0.2mm, 두께 6 ~ 10mm로 제작하였다. 표준 고무 시편으로 테스트 시 무게 감량이 220mg ~ 180mg이어야 한다. 180mg 이하일 경우에는 연마 지를 교환하고 220mg 이상일 경우에는 연마지를 금속판으로 문질러 기준치 내로 관리하였다.The compositions of Examples 3 to 4 and Comparative Examples 5 to 8 were evaluated in the same manner as in Test Example 1 to evaluate basic physical properties, paint plate contamination and wear resistance, and the results are shown in Table 7 below. In the wear resistance evaluation, after the 100,000 times of vehicle door opening and closing wear evaluation of the finished product, it was confirmed whether or not the product was ruptured. It is shown in Table 7 below as the median of the results of experiments. Specifically, the abrasive paper is made by using a standard reference material SRM, and the abrasive paper is checked 7 to 8 times, and the standard test piece is made into a disk shape, a diameter of φ16.0 ± 0.2mm, and a thickness of 6 to 10mm. It was. Standard rubber specimens should weigh 220 mg to 180 mg when tested. In the case of 180 mg or less, the abrasive paper was replaced, and in the case of 220 mg or more, the abrasive paper was rubbed with a metal plate and managed within the reference value.
상기 표 7의 결과에서, 비교예 5~6은 실리콘 오일 함량 부족으로 인해 체적손실이 크며 도어 개폐 마모평가에서 찢어짐이 발생하였다. 비교예 7~8의 경우 과량의 실리콘 오일 첨가로 인한 과도한 자기윤활성으로 인해 도장판의 오염이 발생 되었고 기본 물성이 저하되는 것을 알 수 있다. 따라서 본 발명에 따른 적정량의 실리콘 오일을 함유함으로써 우수한 내마모성을 가진 도어사이드 압출성형용 조성물 생산이 가능함을 알 수 있다.
In the results of Table 7, Comparative Examples 5 to 6 had a large volume loss due to lack of silicone oil content, and tearing occurred in the door opening and closing wear evaluation. In Comparative Examples 7 to 8 it can be seen that due to excessive self-lubrication due to the addition of excess silicone oil, the contamination of the coating plate occurred and the basic physical properties are reduced. Therefore, it can be seen that it is possible to produce a composition for doorside extrusion with excellent wear resistance by containing the appropriate amount of silicone oil according to the present invention.
[ [ 시험예Test Example 3] 안료를 적용한 3] applying pigment 도어사이드Doorside 압출성형용 조성물 Extrusion Molding Composition
실시예 5~10에서 하기 표 8과 같은 조성으로 도어사이드 압출성형용 조성물을 제조하였다. 실시예 5는 안료를 첨가하지 않았고, 실시예 6~10은 각각 다른 안료를 첨가하였다. EPDM, SEBS, 폴리프로필렌, 고점도 파라핀 오일, 실리콘 오일, 퍼옥사이드 가교제, 산화방지제, 기타첨가제는 시험예 1에서와 동일한 물질을 사용하였다.In Examples 5 to 10 to prepare a composition for doorside extrusion molding as shown in Table 8. Example 5 did not add a pigment, and Examples 6-10 added the other pigment, respectively. EPDM, SEBS, polypropylene, high viscosity paraffin oil, silicone oil, peroxide crosslinker, antioxidant, and other additives used the same materials as in Test Example 1.
- Black : 우성케미칼 NB 9000 Series(Color M/B), 카본블랙 22%, 용융지수(230℃, 2.16kg) 2.2g/10min, 밀도 0.98g/㎤-Black: Woosung Chemical NB 9000 Series (Color M / B), Carbon Black 22%, Melt Index (230 ℃, 2.16kg) 2.2g / 10min, Density 0.98g / cm3
- Brown : 우성케미칼 NB 7000 Series(Color M/B), 무기안료 16%, 용융지수(230℃, 2.16kg) 2.5g/10min, 밀도 1.2g/㎤-Brown: Woosung Chemical NB 7000 Series (Color M / B), Inorganic Pigment 16%, Melt Index (230 ℃, 2.16kg) 2.5g / 10min, Density 1.2g / cm3
- Yellow : 우성케미칼 NB 2000 Series(Color M/B), 안료 7%, 용융지수(190℃, 2.16kg) 2.6g/10min, 밀도 1.1g/㎤-Yellow: Woosung Chemical NB 2000 Series (Color M / B), Pigment 7%, Melt Index (190 ℃, 2.16kg) 2.6g / 10min, Density 1.1g / cm3
- Blue : 우성케미칼 NB 5000 Series(Color M/B), 유기 안료 19%, 용융지수(190℃, 2.16kg) 1.6g/10min, 밀도 1.4g/㎤-Blue: Woosung Chemical NB 5000 Series (Color M / B), Organic Pigment 19%, Melt Index (190 ℃, 2.16kg) 1.6g / 10min, Density 1.4g / cm3
- Red : 욱성화학, PANAX Red Series, 유기 안료 100%, 밀도 2.0g/㎤
-Red: Uksung Chemical, PANAX Red Series, Organic Pigment 100%, Density 2.0g / cm3
상기 실시예 5~10의 조성물에 대하여 시험예 1에서와 동일한 방법으로 기본 물성, 내열물성, 압축줄음율, 내오존성, 압출 성형성, 도장판 오염, 내마모성 및 내유성을 평가하여 결과를 아래 표 9에 나타내었다.The compositions of Examples 5 to 10 were evaluated in the same manner as in Test Example 1 to evaluate basic physical properties, heat resistance, compressive shrinkage, ozone resistance, extrusion moldability, paint plate contamination, abrasion resistance, and oil resistance. Shown in
물성basic
Properties
물성Heat resistance
Properties
상기 표 9에 나타나는 바와 같이, 본원발명에 의한 도어사이드 압출성형용 조성물은 유기 및 무기 안료를 포함하여도 강도가 우수하고, 압출성형이 가능하며, 압축줄음율, 내오존성, 내열성 및 내마모성이 뛰어난 물성에 영향이 없어 안료와의 상용성이 우수하며, 다양한 색상 발현이 가능하므로 소비자 감성에 맞춘 도어사이드 생산이 가능하다. As shown in Table 9, the composition for doorside extrusion molding according to the present invention is excellent in strength even by the inclusion of organic and inorganic pigments, can be extruded, excellent in compression shrinkage, ozone resistance, heat resistance and wear resistance As it has no influence on physical properties, it has excellent compatibility with pigments, and various colors can be expressed, enabling doorside production according to consumer's sensitivity.
Claims (11)
The thermoplastic elastomer weatherstrip composition for doorside extrusion according to claim 9, wherein the organic pigment is selected from the group consisting of azo, phthalocyanine, nitro and condensed polycyclic pigments.
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