KR20060136221A - A composition of environmental-friendly high specific gravity rubber - Google Patents
A composition of environmental-friendly high specific gravity rubber Download PDFInfo
- Publication number
- KR20060136221A KR20060136221A KR1020050055832A KR20050055832A KR20060136221A KR 20060136221 A KR20060136221 A KR 20060136221A KR 1020050055832 A KR1020050055832 A KR 1020050055832A KR 20050055832 A KR20050055832 A KR 20050055832A KR 20060136221 A KR20060136221 A KR 20060136221A
- Authority
- KR
- South Korea
- Prior art keywords
- rubber
- specific gravity
- high specific
- weight
- parts
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 70
- 239000005060 rubber Substances 0.000 title claims abstract description 64
- 230000005484 gravity Effects 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 41
- 238000004132 cross linking Methods 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000003014 reinforcing Effects 0.000 claims abstract description 9
- 230000000996 additive Effects 0.000 claims abstract description 8
- 238000005452 bending Methods 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 13
- 229920002857 polybutadiene Polymers 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 8
- 240000008528 Hevea brasiliensis Species 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
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- 239000010949 copper Substances 0.000 claims description 6
- 239000000806 elastomer Substances 0.000 claims description 6
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- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 229920005549 butyl rubber Polymers 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229920003049 isoprene rubber Polymers 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
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- 239000010936 titanium Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
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- 239000002184 metal Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- VHOQXEIFYTTXJU-UHFFFAOYSA-N 2-methylbuta-1,3-diene;2-methylprop-1-ene Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 claims 1
- DKQVJMREABFYNT-UHFFFAOYSA-N C=C.C=C Chemical compound C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- QABZOJKEJLITJL-UHFFFAOYSA-N but-3-enoic acid;ethenyl acetate Chemical compound CC(=O)OC=C.OC(=O)CC=C QABZOJKEJLITJL-UHFFFAOYSA-N 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- HXDBMSZZSWTGKB-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylidenebutanoic acid Chemical compound CCOC(=O)C=C.CCC(=C)C(O)=O HXDBMSZZSWTGKB-UHFFFAOYSA-N 0.000 claims 1
- CWEFIMQKSZFZNY-UHFFFAOYSA-N pentyl 2-[4-[[4-[4-[[4-[[4-(pentoxycarbonylamino)phenyl]methyl]phenyl]carbamoyloxy]butoxycarbonylamino]phenyl]methyl]phenyl]acetate Chemical compound C1=CC(CC(=O)OCCCCC)=CC=C1CC(C=C1)=CC=C1NC(=O)OCCCCOC(=O)NC(C=C1)=CC=C1CC1=CC=C(NC(=O)OCCCCC)C=C1 CWEFIMQKSZFZNY-UHFFFAOYSA-N 0.000 claims 1
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 210000001138 Tears Anatomy 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium(0) Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
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- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JWOACSMESNKGGJ-UHFFFAOYSA-N 2-ethenyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)C=C JWOACSMESNKGGJ-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-M 2-tert-butylperoxypropan-2-yl carbonate Chemical compound CC(C)(C)OOC(C)(C)OC([O-])=O BQARUDWASOOSRH-UHFFFAOYSA-M 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
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- DZCCLNYLUGNUKQ-UHFFFAOYSA-N N-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N Nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 Chemical class O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
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- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
본 발명은 환경친화적이며 내굴곡성이 우수한 고비중 고무 조성물에 관한 것으로서, 더욱 상세하게는 탄성체 기재에 환경친화적인 고비중 충전제, 보강성 충전제, 통상적인 고무용 첨가제, 가교제 외에 고비중 충전제와 고무 기재간 친화력을 증대시킬 수 있는 특수 기능성 수지를 혼합하고 가교 성형하여 고비중 고무를 제조하는 환경친화적이며 굴곡성 및 가공성이 우수한 고비중 고무 조성물에 관한 것이다.The present invention relates to a high specific gravity rubber composition that is environmentally friendly and excellent in flex resistance, and more particularly, an environmentally friendly high specific gravity filler, a reinforcing filler, an additive for conventional rubber, a crosslinking agent, and a high specific gravity filler and a rubber substrate. The present invention relates to a high specific gravity rubber composition which is environmentally friendly and has excellent flexibility and processability by mixing and crosslinking a special functional resin capable of increasing liver affinity.
특히 고비중 충전제와 고무 기재간 친화력을 증대시킬 수 있는 특수 기능성 수지를 첨가함에 따라 굴곡성과 가공성의 개선은 물론이고, 인장강도를 위시한 기계적 강도가 우수하여 내구성이 개선된 고비중 고무 조성물을 제공함을 그 목적으로 한다.In particular, by adding a special functional resin that can increase the affinity between the high specific gravity filler and the rubber substrate, as well as improving the bendability and workability, as well as excellent mechanical strength including tensile strength to provide a high specific gravity rubber composition with improved durability. For that purpose.
또한 상기와 같이 제조된 고무 성형물은 탄성 고분자 소재를 기재로 설계됨으로써 질감을 위시한 감성품질이 우수하고 특히 굴곡피로저항이 우수하여 신발의 고중량화를 위한 인서트솔과 같이 지속적인 굴곡피로에 대한 안정성이 요구되는 스포츠용품, 생활용품, 완구 등 다양한 용도에 적용이 가능하다.In addition, the rubber molded product manufactured as described above has excellent emotional quality including texture, and is particularly excellent in fatigue fatigue resistance because it is designed based on an elastic polymer material, and thus requires stability for continuous bending fatigue such as an insert sole for high weight of shoes. It can be applied to various uses such as sports goods, household goods, toys.
고비중, 고무, 환경친화성, 내굴곡성, 충전제 High specific gravity, rubber, environmental friendliness, flex resistance, filler
Description
본 발명은 환경친화적이며 내굴곡성이 우수한 고비중 고무 조성물에 관한 것으로서, 더욱 상세하게는 탄성체 기재에 고비중 충전제, 보강성 충전제, 통상적인 고무용 첨가제, 가교제 및 특수 기능성 수지를 혼합하고 가교 성형하여 제작하는 고비중 고무에 관한 것이다.The present invention relates to a high specific gravity rubber composition which is environmentally friendly and excellent in bending resistance, and more particularly, by mixing and crosslinking a high specific gravity filler, a reinforcing filler, a conventional rubber additive, a crosslinking agent, and a special functional resin to an elastomer substrate. It relates to a high specific gravity rubber to be produced.
고비중 고무 조성물은 고비중 충전제인 중금속(heavy metal)을 고무에 부가하여 제조되며 이때 사용되는 중금속은 비중이 4∼5 이상인 중금속을 통칭한다. 중금속 중 비소(As), 납(Pb), 베릴륨(Be), 카드뮴(Cd), 크롬(Cr), 셀레늄(Se) 및 수은(Hg) 등은 낮은 농도에서도 인체에 유해하고 환경을 오염시키는 환경공해물질이기 때문에 세계보건기구(WHO), 미국식품의약청(FDA) 등과 같은 기관에서 규제 대상물질에 포함시켰으며 점차 그 규제가 심화되고 있다.The high specific gravity rubber composition is prepared by adding heavy metal (heavy metal), which is a high specific gravity filler, to the heavy metal used at this time. Among heavy metals, arsenic (As), lead (Pb), beryllium (Be), cadmium (Cd), chromium (Cr), selenium (Se) and mercury (Hg) are harmful to humans and pollute the environment even at low concentrations. Because it is a pollutant, organizations such as the World Health Organization (WHO) and the US Food and Drug Administration (FDA) have included it as a regulated substance, and the regulation is intensifying.
이러한 비환경친화적인 중금속 외에 산화철(Fe2O3) 분말, 산화아연(ZnO) 분말, 몰리브덴(Mo) 분말, 구리(Cu) 분말 및 바륨 설페이트(BaSO4) 등과 같은 금속분말 또는 산화금속분말이 고비중 충전제로 사용될 수 있다.In addition to these non-environmentally friendly heavy metals, metal powders or metal oxide powders such as iron oxide (Fe 2 O 3 ) powder, zinc oxide (ZnO) powder, molybdenum (Mo) powder, copper (Cu) powder and barium sulfate (BaSO 4 ) It can be used as a high specific gravity filler.
그러나 고무 기재 100 중량부를 기준으로 상기의 고비중 충전제를 100 중량부 이상 부가할 경우, 유기물인 고무와 무기물인 고비중 충전제의 계면에서 상호 친화성을 기대할 수 없기 때문에 지속적인 굴곡피로(flexual fatigue)에 대한 저항이 열악하여 균열(crack)이 발생하고, 결국 파단되는 문제점을 나타낸다. 따라서 상기와 같은 고비중 고무 조성물은 장기적인 굴곡피로에 노출되는 적용분야에서는 사용될 수 없는 것이다.However, when 100 parts by weight or more of the high specific filler is added based on 100 parts by weight of the rubber substrate, mutual affinity cannot be expected at the interface between the organic rubber and the high specific filler. Insufficient resistance to cracking causes cracking and eventually breakage. Therefore, such high specific gravity rubber compositions cannot be used in applications that are exposed to long term flexion fatigue.
또한 고무기재 100 중량부를 기준으로 고비중 충전제를 200 중량부 이상 부가할 경우 고무 조성물 혼련과 쉬트 제조에 필수적으로 사용되는 오픈롤밀(open roll-mill) 및 카렌다 작업 시 고무의 자체하중에 의해 혼련물이 처지거나 심한 경우 장비로부터 바닥으로 낙하하여 정상적인 가공이 불가능한 문제점을 나타낸다.In addition, when 200 parts by weight or more of the high specific filler is added based on 100 parts by weight of the rubber base, the kneaded material is subjected to the self-loading of rubber during open roll mill and calender work, which are essential for kneading the rubber composition and preparing the sheet. This sagging or severe fall from the equipment to the floor represents a problem that normal machining is impossible.
이에 본 발명은 상기와 같은 문제점들을 해결하기 위하여 안출된 것으로서, 탄성체 기재에 환경친화적인 고비중 충전제, 보강성충전제, 통상적인 고무용 첨가 제, 가교제 외에 고비중 충전제와 고무 기재간 친화력을 증대시킬 수 있는 특수 기능성 수지를 혼합하고 가교 성형하여 고비중 고무를 제조하는 환경친화적이며 굴곡성 및 가공성이 우수한 고비중 고무 조성물을 제공하는 것을 목적으로 한다.Accordingly, the present invention has been made in order to solve the above problems, environmentally friendly high specific gravity fillers, reinforcing fillers, conventional rubber additives, crosslinking agents in addition to the high specific gravity filler and rubber substrate to increase the affinity between the rubber substrate. It is an object of the present invention to provide a high specific gravity rubber composition which is environmentally friendly and has excellent flexibility and processability by mixing and crosslinking a special functional resin capable of producing a high specific gravity rubber.
특히 상기와 같이 제조된 고무 조성물은 탄성 고분자 소재를 기재로 설계됨으로써 질감을 위시한 감성품질이 우수하고 특히 굴곡피로저항이 우수하여 신발의 고중량화를 위한 인서트솔과 같이 지속적인 굴곡피로에 대한 안정성이 요구되는 분야에 적용 가능한 고무조성물을 제공할 수 있다.In particular, the rubber composition prepared as described above has excellent emotional quality including texture, and is particularly excellent in fatigue fatigue resistance, because it is designed based on an elastic polymer material, and thus requires stability for continuous fatigue fatigue such as insert sole for high weight of shoes. It is possible to provide a rubber composition applicable to the field.
더불어 가공성이 우수하기 때문에 통상적인 고무 혼련 및 쉬트 제조 장비인 오픈롤밀이나 카렌다에서 원활한 작업이 가능하다.In addition, because of its excellent workability, it is possible to work smoothly in open roll mills or calenders, which are conventional rubber kneading and sheet manufacturing equipment.
또한 고비중 충전제와 고무 기재간 친화력을 증대시킬 수 있는 특수 기능성 수지를 첨가함에 따라 굴곡성과 가공성의 개선은 물론이고, 인장강도를 위시한 기계적 강도가 우수하여 내구성이 개선된 고비중 고무 조성물을 제공함을 그 목적으로 한다.In addition, by adding a special functional resin that can increase the affinity between the high specific gravity filler and the rubber substrate, as well as improving the bendability and workability, as well as excellent mechanical strength, including tensile strength to provide a high specific gravity rubber composition with improved durability. For that purpose.
이하 본 발명에 따른 바람직한 실시 예를 상세히 설명하면 다음과 같다. 하기의 설명에서는 본 발명의 제조방법을 이해하는데 필요한 부분만이 설명되며, 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.Hereinafter, a preferred embodiment according to the present invention will be described in detail. It should be noted that in the following description, only parts necessary for understanding the manufacturing method of the present invention will be described, and descriptions of other parts will be omitted so as not to distract from the gist of the present invention.
본 발명은 탄성체를 기재로 하고 여기에 고비중 충전제와 보강성 충전제, 통상적인 고무용 첨가제, 가교제 및 특수 기능성 수지를 혼합하여 성형하는 고비중 고무 조성물에 있어서, 상기 기재로 사용되는 탄성체로는 천연고무(NR), 부타디엔고무(BR), 스티렌-부타디엔 고무(SBR)와 같은 범용고무를 위시하여 이소프렌고무(IR), 니트릴 고무(NBR), 클로로프렌 고무(CR), 부틸고무(IIR), 에틸렌-프로필렌 고무(EPM 또는 EPDM), 클로로술폰화폴리에틸렌(CSM), 아크릴고무, 우레탄 고무 중에서 한 가지 또는 그 이상을 선택하여 사용한다. 이 때 상기에서 언급된 기재 구성 탄성체에 대하여 내구성 향상을 위해 수첨 반응을 이용하여 제조된 유도체로 수첨 스티렌-부타디엔 고무(HSBR), 수첨니트릴 고무(HNBR)를 사용해도 무방하다.The present invention is a high specific gravity rubber composition which is formed by mixing a high specific gravity filler with a reinforcing filler, a conventional rubber additive, a crosslinking agent, and a special functional resin. Isoprene rubber (IR), nitrile rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), ethylene, including general purpose rubber such as rubber (NR), butadiene rubber (BR) and styrene-butadiene rubber (SBR). -Select one or more of propylene rubber (EPM or EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber and urethane rubber. At this time, a hydrogenated styrene-butadiene rubber (HSBR) or a hydrogenated nitrile rubber (HNBR) may be used as a derivative prepared by using a hydrogenation reaction for improving durability of the above-mentioned substrate constituent elastomer.
상기의 고비중 충전제로는 아연(Zn), 철(Fe), 몰리브덴(Mo), 텅스텐(W), 구리(Cu), 바륨(Ba), 칼슘(Ca), 알루미늄(Al), 마그네슘(Mg), 규소(Si), 티탄(Ti)과 같은 무기성분을 함유하는 산화물, 황화물, 탄화물 및 금속분말로 구성되는 충전제를 포함하며, 비환경친화적인 비소(As), 납(Pb), 베릴륨(Be), 카드뮴(Cd), 크롬(Cr), 셀레늄(Se) 및 수은(Hg)을 함유하는 것은 제외된다. 충전제의 비중이 2.0 이상이면 사용할 수 있고, 바람직하게는 5.0 이상의 것을 한 가지 또는 그 이상 선택하여 기재 100 중량부에 대하여 100∼1200 중량부, 바람직하게는 200∼1000 중량부 사용할 수 있다. 100 중량부 미만에서는 비중의 효과적인 증가가 어렵고 1200 중량부를 초과되면 충전제의 혼입이 어렵고 경도가 급격히 상승하며 성형물이 부스러지기 쉬워져(brittle) 바람직하지 않다.The high specific gravity fillers include zinc (Zn), iron (Fe), molybdenum (Mo), tungsten (W), copper (Cu), barium (Ba), calcium (Ca), aluminum (Al), magnesium (Mg) ), Fillers composed of oxides, sulfides, carbides and metal powders containing inorganic components such as silicon (Si) and titanium (Ti), and are made of non-environmentally friendly arsenic (As), lead (Pb) and beryllium ( Be, cadmium (Cd), chromium (Cr), selenium (Se) and mercury (Hg) are excluded. If the specific gravity of a filler is 2.0 or more, it can be used, Preferably it selects one or more of 5.0 or more, and can use 100-1200 weight part with respect to 100 weight part of base materials, Preferably it can use 200-1000 weight part. If it is less than 100 parts by weight, an effective increase in specific gravity is difficult, and if it is more than 1200 parts by weight, it is not preferable that the incorporation of the filler is difficult, the hardness rises sharply, and the molding is brittle.
상기의 보강성 충전제로는 카본블랙, 실리카, 탄산칼슘, 탈크와 같은 미네랄 충전제를 포함하여 기재 100 중량부에 대하여 3∼100 중량부 사용할 수 있다.The reinforcing filler may be used in an amount of 3 to 100 parts by weight based on 100 parts by weight of the base, including mineral fillers such as carbon black, silica, calcium carbonate, and talc.
3중량부 미만이면, 보강효과가 나타나지 않고, 100 중량부를 초과할 경우에는 충전제의 혼입이 어렵고 경도가 급격히 상승하기 때문에 바람직하지 않다.If it is less than 3 parts by weight, the reinforcing effect does not appear, and if it exceeds 100 parts by weight, it is not preferable because the mixing of the filler is difficult and the hardness rises sharply.
또한 본 발명에서는 통상적인 고무용 첨가제로 점착부여제, 연장유, 산화방지제, 오존화방지제 및 색상을 고려하여 다양한 안료를 사용할 수 있다.In addition, in the present invention, various pigments may be used in consideration of a tackifier, an extended oil, an antioxidant, an ozonation inhibitor, and a color as a conventional rubber additive.
상기 점착부여제로 부여제로는 로진유도체, 터펜계 수지, 석유 수지, 쿠마론 수지, 스티렌계 수지, 페놀수지 중에서 한 가지 또는 그 이상 선택하여 1∼50 중량부 사용할 수 있다. 1중량부 미만이면, 점착부여 성능이 나타나지 않고, 50 중량부를 초과할 경우에는 물성이 급격히 저하되고 가공 장비에 점착되기 때문에 바람직하지 않다. The tackifier may be used in the amount of 1 to 50 parts by weight of one or more selected from rosin derivatives, terpene resins, petroleum resins, coumarone resins, styrene resins, and phenol resins. If it is less than 1 part by weight, the tackifying performance does not appear, and if it exceeds 50 parts by weight, it is not preferable because the physical properties are drastically lowered and adhered to the processing equipment.
상기 연장유로는 나프텐계, 방향족계 및 파라핀계와 같은 탄화수소계 가공유와 채종유, 피마자유와 같은 천연유 중에서 한 가지 또는 그 이상 선택하여 기재 100 중량부에 대하여 1∼50 중량부 사용할 수 있다. 1중량부 미만이면 가공성 향상 및 증량효과를 기대하기 어렵고, 50 중량부를 초과할 경우에는 물성이 급격히 저하되기 때문에 바람직하지 않다.The extension oil may be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of one or more selected from hydrocarbon-based processing oils such as naphthenic, aromatic and paraffin-based oils, and natural oils such as rapeseed oil and castor oil. If it is less than 1 part by weight, it is difficult to expect an improvement in workability and an increase effect, and if it exceeds 50 parts by weight, the physical properties are sharply lowered, which is not preferable.
일반적으로 상기와 같은 기재로 이루어진 고분자 블렌드물은 물리적 성질, 성능 및 내구성을 위해 가교 결합될 수 있으며, 이러한 특성들은 가교 반응 도중에 형성된 가교 결합의 수 및 형태와 직접 연관된다.Generally, polymer blends made of such substrates can be crosslinked for physical properties, performance and durability, and these properties are directly related to the number and form of crosslinks formed during the crosslinking reaction.
본 발명에서 사용될 수 있는 가교형태로는 황가교 기구, 유기과산화물 가교기구 및 레진 가교기구 중에서 한 가지 또는 상기의 가교기구 중 두 가지 이상을 혼성해서 사용할 수 있다.As the crosslinking form that can be used in the present invention, one of a sulfur crosslinking mechanism, an organic peroxide crosslinking mechanism and a resin crosslinking mechanism, or two or more of the above crosslinking mechanisms may be mixed and used.
상기 황가교 기구에서는 황 또는 불용성 황을 기재 100 중량부에 대하여 0.1∼10 중량부, 가황촉진제를 기재 100 중량부에 대하여 0.01∼8 중량부 첨가하는 것이 바람직하다.In the sulfur crosslinking mechanism, it is preferable to add sulfur or insoluble sulfur to 0.1 to 10 parts by weight based on 100 parts by weight of the substrate, and 0.01 to 8 parts by weight of a vulcanization accelerator based on 100 parts by weight of the substrate.
상기에서 황 또는 불용성황의 사용량이 1중량부 미만이면, 효과적인 가교가 어렵기 때문에 성형물 제조가 어렵고, 10 중량부를 초과할 경우에는 조기가황이 나타나고 성형물의 경도가 급격히 상승하기 때문에 바람직하지 않다.When the amount of sulfur or insoluble sulfur is less than 1 part by weight, it is difficult to manufacture a molded product because it is difficult to effectively crosslink, and when it exceeds 10 parts by weight, it is not preferable because early vulcanization appears and the hardness of the molded product rises rapidly.
그리고 가황촉진제의 사용량이 0.01중량부 미만이면, 효과적인 촉진효과를 기대하기 어렵고, 8 중량부를 초과할 경우에는 조기가황이 나타나고 성형물의 경도가 급 격히 상승하기 때문에 바람직하지 않다.If the amount of the vulcanization accelerator is less than 0.01 part by weight, it is difficult to expect an effective promoting effect. If the amount of the vulcanization accelerator is more than 8 parts by weight, it is not preferable because early vulcanization appears and the hardness of the molded article rises rapidly.
이 때 사용되는 가황촉진제로는 알데히드·암모니아류, 알데히드·아민류, 구아니딘류, 티오우레아류, 티아졸류, 술펜아미드류, 티우람류 및 디티오카르바민산염류 등으로부터 한 가지 또는 그 이상 선택하여 사용할 수 있다.The vulcanization accelerator used in this case may be selected from aldehydes, ammonias, aldehydes, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams and dithiocarbamates. Can be used.
또한 가황촉진제를 활성화시키기 위해 가황촉진조제가 기재 100 중량부에 대하여 0.01∼8 중량부 사용할 수 있으며, 그 사용량이 0.01중량부 미만이면, 가황촉진제의 활성화 효과를 기대하기 어렵고, 8 중량부를 초과할 경우에는 과도한 촉진 활성화로 조기가황이 나타나고 성형물의 경도가 급격히 상승하게 된다.In addition, in order to activate the vulcanization accelerator, the vulcanization accelerator may be used in an amount of 0.01 to 8 parts by weight based on 100 parts by weight of the substrate, and when the amount thereof is less than 0.01 parts by weight, it is difficult to expect the activating effect of the vulcanization accelerator, and may exceed 8 parts by weight. In this case, excessive vulcanization activates preliminary vulcanization, and the hardness of the molding increases rapidly.
가황촉진제는 산화아연과 같은 금속산화물, 스테아린산과 같은 지방산 중에 선택하여 사용할 수 있다.The vulcanization accelerator may be selected from metal oxides such as zinc oxide and fatty acids such as stearic acid.
상기 유기과산화물 가교기구에서는 기재 100 중량부에 대하여 유기과산화물 0.05∼10 중량부 사용할 수 있으며, 0.05 중량부 미만이면 가교가 부족하고, 10 중량부를 초과하면 경도가 급격히 상승한다.In the organic peroxide crosslinking mechanism, 0.05 to 10 parts by weight of the organic peroxide can be used with respect to 100 parts by weight of the base material, and if it is less than 0.05 parts by weight, the crosslinking is insufficient.
본 발명에서 사용 가능한 가교제의 종류로는 유기과산화물로서 사이클로헥사논퍼옥사이드, t-부틸퍼옥시이소프로필카르보네이트, t-부틸퍼옥시라우릴레이트, t-부틸퍼옥시아세테이트, 디-t-부틸디퍼옥시프탈레이트, t-디브틸퍼옥시말레인산, t-부틸큐밀퍼옥사이드, t-부틸하이드로퍼옥사이드, t-부틸퍼옥시벤조에이트, 디벤조일퍼옥사이드, 디큐밀퍼옥사이드, 1,3-비스(t- 부틸퍼옥시이소프로필)벤젠, 메틸에틸케폰퍼옥사이드, 디-(2,4-디클로로벤조일)퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸사이클로헥산, 2,5-디메틸-2,5-(t-벤조일퍼옥시)헥산, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, 디-t-부틸퍼옥사이드, 2,5-디메틸-2,5-(t-부틸퍼옥시)-3-헥신, n-부틸-4,4-비스(t-부틸퍼옥시)발러레이트, a,a'-비스(t-부틸퍼옥시) 디이소프로필벤젠 등으로부터 한 가지 또는 그 이상 선택하여 사용할 수 있다.Examples of the crosslinking agent usable in the present invention include cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxylaurylate, t-butylperoxyacetate, and di-t-butyl as organic peroxides. Diperoxyphthalate, t-dibutyl peroxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t- Butylperoxyisopropyl) benzene, methylethylkeponperoxide, di- (2,4-dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- (t-benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5 -Dimethyl-2,5- (t-butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-butylperoxy) valerate, a, a'-bis (t-butylperoxy ) From diisopropylbenzene or the like or It can be used to select at least.
또한 본 발명에서는 과산화물 가교 시 성형시간 단축과 적절한 가교구조를 얻기 위하여 상기 가교제에 가교조제를 기재 100 중량부에 대하여 0.01∼3 중량부, 바람직하게는 0.05∼2 중량부를 사용할 수 있다.In addition, in the present invention, in order to shorten the molding time during peroxide crosslinking and to obtain an appropriate crosslinking structure, the crosslinking aid may be used in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the substrate.
사용량이 0.05중량부 미만이면, 가교촉진효과가 부족하기 때문에 적절한 가교구조를 얻기 어렵고, 2 중량부를 초과할 경우에는 조기가교가 나타나거나 성형물이 부스러지기 쉽게 되기 때문에 바람직하지 않다.If the amount used is less than 0.05 parts by weight, it is difficult to obtain an appropriate crosslinked structure because the crosslinking promoting effect is insufficient, and when it exceeds 2 parts by weight, it is not preferable because early crosslinking occurs or the molded product is easily broken.
상기 가교조제는 예를 들어 p-퀴논디옥심, p,p-디벤조일퀴논디옥심, N-메틸-N-4-디니트로소아닐린, 니트로소벤젠, 디페닐구아니딘 및 트리메틸올프로판-N, N'-m-페닐렌디말레이미드 등의 퍼옥시 가교조제; 디비닐벤젠, 트리아릴시아누레이트(TAC) 및 트리아릴이소시아누레이트(TAIC); 에틸렌글리콜 디메타크릴레이트, 디에틸렌글리콜 디메타크릴레이트, 폴리에틸렌글리콜 디메타크릴레이트, 트리메틸올프 로판 트리메타크릴레이트 및 비닐스테아레이트 등의 다관능성 비닐 단량체 중에서 한 가지 또는 그 이상 선택하여 사용할 수 있다.The crosslinking aids are, for example, p-quinonedioxime, p, p-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine and trimethylolpropane-N, Peroxy crosslinking aids such as N'-m-phenylenedimaleimide; Divinylbenzene, triarylcyanurate (TAC) and triarylisocyanurate (TAIC); One or more polyfunctional vinyl monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and vinyl stearate can be selected and used. .
상기 레진 가교기구에서는 기제 100 중량부에 대하여 변성페놀수지를 0.1∼20 중량부 사용할 수 있으며, 그 사용량이 0.1 중량부 미만이면 효과적인 가교반응을 기대하기 어렵고, 20중량부를 초과할 경우에는 변성페놀수지의 혼입이 어렵고 성형물의 경도가 급격히 상승하기 때문에 바람직하지 않다. In the resin crosslinking mechanism, the modified phenolic resin may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the base. If the amount is less than 0.1 parts by weight, it is difficult to expect an effective crosslinking reaction. It is not preferable because of the fact that it is difficult to mix with and the hardness of the molded article rises sharply.
변성페놀수지는 메틸올(methylol) 기를 5∼20% 함유한 것이 바람직하다.It is preferable that a modified phenol resin contains 5 to 20% of methylol groups.
함유량이 5중량% 미만이면 효과적인 가교반응을 기대하기 어렵고, 20 중량%를 초과할 경우에는 가교반응의 제어가 어렵기 때문에 바람직하지 않다.If the content is less than 5% by weight, it is difficult to expect effective crosslinking reaction, and if it exceeds 20% by weight, it is not preferable because the control of the crosslinking reaction is difficult.
또한 본 발명에서는 다량 첨가되는 고비중 첨가제와 탄성체 기재간의 계면 친화력 증대를 위해 특수 기능성 수지를 사용한다.In addition, in the present invention, a special functional resin is used to increase the interfacial affinity between the high specific gravity additive and the elastic substrate added in a large amount.
상기의 특수 기능성 수지는 에틸렌계 공중합체 중에서 한 가지 또는 그 이상 선택하여 기재 100 중량부에 대하여 1∼50 중량부 사용할 수 있다. 사용량이 1중량부 미만이면 계면에서의 친화력 증대 작용을 기대하기 어렵고, 50 중량부를 초과할 경우에는 성형물의 경도가 급격히 상승하고 탄성이 저하되기 때문에 바람직하지 않다. v상기의 에틸렌계 공중합체는 에틸렌(ethylene)과 공중합되는 공단량체로 비닐아세테이트(vinyl acetate), 에틸아크릴레이트(ethyl acrylate), 메타크릴산 (methacrylic acid)중 하나로 제조된 것으로 한정된다.The special functional resin may be selected from one or more of ethylene copolymers and may be used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the substrate. If the amount is less than 1 part by weight, it is difficult to expect an affinity-increasing effect at the interface. If the amount is more than 50 parts by weight, the hardness of the molded article rises rapidly and the elasticity decreases, which is not preferable. v The ethylene-based copolymer is a comonomer copolymerized with ethylene and is limited to one made of vinyl acetate, ethyl acrylate, and methacrylic acid.
특히 특수 기능성 수지는 고비중 충전제의 함량이 300 중량부 이상에서 혼련물 쉬트의 가공성 개선 및 제조된 고비중 고무 성형물의 기계적 특성 개선 효과가 탁월하다.In particular, the special functional resin is excellent in improving the processability of the kneaded sheet and the mechanical properties of the manufactured high-density rubber molding when the content of the high specific filler is 300 parts by weight or more.
이상과 같은 조성 성분들로 이루어진 고비중 고무 조성물을 이용하여 고비중 고무 성형물의 제조 공정을 설명하면 다음과 같다.Referring to the manufacturing process of a high specific gravity rubber molding using a high specific gravity rubber composition composed of the above composition components are as follows.
먼저 고무 탄성체 중에서 한 가지 또는 그 이상 선택한 기재에 고비중 충전제, 보강성 충전제, 통상적인 고무용 첨가제 및 특수 기능성 수지 등을 혼합한 후 가교제를 배합한 컴파운드 조성물을 쉬트상으로 제조하여 밀폐된 금형안에 투입한 후 압축성형기를 이용하여 100∼200℃, 50∼200kg/cm2의 고온·고압 하에서 3∼30분간 성형함으로써 원하는 형태의 고비중 고무 성형물을 제조할 수 있다.First, a high specific gravity filler, a reinforcing filler, a conventional rubber additive, a special functional resin, and the like are mixed with a substrate selected from one or more rubber elastomers. After injecting, a high specific gravity rubber molded article of desired shape can be produced by molding at a high temperature and high pressure of 100 to 200 ° C. and 50 to 200 kg / cm 2 using a compression molding machine for 3 to 30 minutes.
이하 본 발명을 [표1]의 구성으로 제조한 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the examples prepared in the configuration of Table 1, but the present invention is not limited to the examples.
실시예 1Example 1
천연고무 50 중량%, 부타디엔고무 30 중량% 및 스티렌/부타디엔 고무 20 중량%로 이루어진 기재 100 중량부에 대하여 기능성 수지를 15 중량부, 산화아연을 5 중량부, 스테아린산을 2 중량부, 산화철 280 중량부, 산화방지제 1 중량부 및 연장유 5 중량부를 100∼120℃의 밀폐식 혼합기에서 약 15분 동안 혼련한 후 표면 온도가 70∼80℃인 롤밀에서 기재 100 중량부에 대하여 황 1.5 중량부 및 촉진제 2.2 중량부를 투입하여 충분히 혼련 시킨 후 2∼6㎜의 혼련물 쉬트(sheet)를 제조한 후 실온(23℃)에서 24시간 이상 숙성 시킨다. 이렇게 제조된 혼련물 쉬트를 금형의 캐비티 형태로 절단하여 금형에 투입한 후 155℃, 150㎏/㎠의 조건에서 가황시간 측정기로 측정된 최적가황시간(t90) 동안 압축 성형하여 3mm 두께의 고비중 고무 성형물 시편을 제조하였다.15 parts by weight of functional resin, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 2 parts by weight of iron oxide, based on 100 parts by weight of the base consisting of 50% by weight of natural rubber, 30% by weight of butadiene rubber and 20% by weight of styrene / butadiene rubber 1 part by weight of antioxidant and 5 parts by weight of extension oil were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes, and then 1.5 parts by weight of sulfur to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C .; After mixing 2.2 parts by weight of the accelerator and sufficiently kneading, a sheet of 2-6 mm kneaded material was prepared and aged at room temperature (23 ° C.) for at least 24 hours. The kneaded sheet thus prepared is cut into a cavity of a mold and introduced into the mold, and then compression-molded for an optimal vulcanization time (t 90 ) measured by a vulcanization time measuring instrument under conditions of 155 ° C. and 150 kg / cm 2. Heavy rubber molded specimens were prepared.
실시예 2Example 2
천연고무 50 중량%, 부타디엔고무 30 중량% 및 스티렌/부타디엔 고무 20 중량%로 이루어진 기재 100 중량부에 대하여 기능성 수지를 15 중량부, 산화아연을 5 중량부, 스테아린산을 2 중량부, 산화철 700 중량부, 산화방지제 1 중량부 및 연장유 5 중량부를 100∼120℃의 밀폐식 혼합기에서 약 15분 동안 혼련한 후 표면 온도가 70∼80℃인 롤밀에서 기재 100 중량부에 대하여 황 1.5 중량부 및 촉진제 2.2 중량부를 투입하여 충분히 혼련 시킨 후 이하 실시예 1과 동일한 방법으로 고비중 고무 성형물 시편을 제조하였다.15 parts by weight of functional resin, 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 700 parts by weight of iron oxide, based on 100 parts by weight of the base composed of 50% by weight of natural rubber, 30% by weight of butadiene rubber and 20% by weight of styrene / butadiene rubber. 1 part by weight of antioxidant and 5 parts by weight of extension oil were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes, and then 1.5 parts by weight of sulfur to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C .; After mixing 2.2 parts by weight of the accelerator and sufficiently kneading, a high specific gravity rubber molded specimen was prepared in the same manner as in Example 1 below.
비교예 1Comparative Example 1
천연고무 50 중량%, 부타디엔고무 30 중량% 및 스티렌/부타디엔 고무 20 중량%로 이루어진 기재 100 중량부에 대하여 산화아연을 5 중량부, 스테아린산을 2 중량부, 실리카 45 중량부, 산화방지제 1 중량부 및 연장유 5 중량부를 100∼120℃의 밀폐식 혼합기에서 약 15분 동안 혼련한 후 표면 온도가 70∼80℃인 롤밀에서 기재 100 중량부에 대하여 황 1.5 중량부 및 촉진제 2.2 중량부를 투입하여 충분히 혼련 시킨 후 이하 실시예 1과 동일한 방법으로 고비중 고무 성형물 시편을 제조하였다.5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 45 parts by weight of silica, 1 part by weight of antioxidant based on 100 parts by weight of the base material consisting of 50% by weight of natural rubber, 30% by weight of butadiene rubber and 20% by weight of styrene / butadiene rubber And 5 parts by weight of extension oil were kneaded in a sealed mixer at 100 to 120 ° C. for about 15 minutes, and then 1.5 parts by weight of sulfur and 2.2 parts by weight of accelerator were added to 100 parts by weight of the substrate in a roll mill having a surface temperature of 70 to 80 ° C. After kneading, a high specific gravity rubber molded specimen was prepared in the same manner as in Example 1 below.
비교예 2Comparative Example 2
천연고무 50 중량%, 부타디엔고무 30 중량% 및 스티렌/부타디엔 고무 20 중량%로 이루어진 기재 100 중량부에 대하여 산화아연을 5 중량부, 스테아린산을 2 중량부, 산화철 700 중량부, 산화방지제 1 중량부 및 연장유 5 중량부를 100∼120℃의 밀폐식 혼합기에서 약 15분 동안 혼련한 후 표면 온도가 70∼80℃인 롤밀에서 가황제 투입작업을 시도하였으나 컴파운드의 비중이 높아 롤밀에 감김성이 부족하여 혼련물 쉬트 제조가 불가능하였다.5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 700 parts by weight of iron oxide, 1 part by weight of antioxidant based on 100 parts by weight of the base material consisting of 50% by weight of natural rubber, 30% by weight of butadiene rubber and 20% by weight of styrene / butadiene rubber And 5 parts by weight of the extension oil were kneaded in a closed mixer at 100 to 120 ° C. for about 15 minutes, and then a vulcanizing agent was introduced into a roll mill having a surface temperature of 70 to 80 ° C., but due to the high specific gravity of the compound, the roll mill was insufficiently wound. Kneaded sheet production was not possible.
[표1]Table 1
[단위 : 중량부] [Unit: parts by weight]
상기 실시예 1∼2 및 비교예 1∼2에 의해 3mm 쉬트로 제조된 고비중 고무 성형물 시편에 대하여 다음과 같은 방법으로 특성을 시험하여 그 결과를 [표 2]에 나타내었다.The properties of the high specific gravity rubber molded specimens prepared in 3 mm sheets according to Examples 1 and 2 and Comparative Examples 1 and 2 were tested in the following manner and the results are shown in [Table 2].
[표 2]TABLE 2
1) 비중 1) Specific gravity
KS M6519에 준하여 우에시마(Ueshima)사의 자동비중 측정 장치인 모델DMA-3을 이용하여 5회 측정하여 그 평균치를 취하였다.In accordance with KS M6519, the measurement was performed 5 times using a model DMA-3, an automatic specific gravity measurement apparatus of Ueshima Corporation, and the average value was taken.
2) 경도 2) hardness
KS M6518에 준하여 아스커(Asker) A형 경도계를 사용하여 측정하였다.It measured using the Asker A hardness tester based on KS M6518.
3) 인장강도, 신장율 3) tensile strength, elongation
KS M6518에 준하여 Zwick사의 만능시험기를 사용하여 측정하였다.In accordance with KS M6518 it was measured using a Zwick universal testing machine.
4) 인열강도 4) tear strength
KS M6518에 준하여 Zwick사의 만능시험기를 사용하여 측정하였다.In accordance with KS M6518 it was measured using a Zwick universal testing machine.
5) 굴곡시험(Flex. test) 5) Flex. Test
ASTM D813에 준하여 De Mattia Tester를 사용하여 측정하였다.It measured using De Mattia Tester according to ASTM D813.
상기 [표 2]에 나타낸 바와 같이 실시예 1∼2는 고비중을 나타내는데 반하여 비교예 1은 비중이 낮은 것을 알 수 있다.As shown in Table 2, Examples 1 to 2 show a high specific gravity, whereas Comparative Example 1 shows a low specific gravity.
또한 상기 [표 1]에 나타낸 실시예 1∼2의 배합계와 [표 2]의 비중 결과를 통해 고비중 충진제의 첨가량을 다양하게 조절함으로써 비중이 조절되며, 결국 고비중 고무 성형물의 중량 조절이 가능함을 알 수 있다.In addition, the specific gravity is controlled by variously adjusting the addition amount of the high specific gravity filler through the compounding system of Examples 1 to 2 shown in [Table 1] and the specific gravity result of [Table 2]. It can be seen that.
더불어 비교예 2는 고비중 충전제(산화철)를 과량 첨가함에 따라 롤밀 가공성이 열악하여 정상적인 혼련물 쉬트의 제조가 불가능한 반면, 실시예 2는 동일한 고비중 충전제를 함유하고 있지만 첨가된 기능성 수지가 고비중 충전제와 탄성체 기재간의 계면에서 친화력을 증대시켜 원활한 가공성과 기계적 특성을 부여함으로써 고비중 고무 성형물의 제조가 가능함을 알 수 있다.In addition, Comparative Example 2 is not possible to manufacture a normal kneaded sheet due to poor roll mill workability due to excessive addition of a high specific filler (iron oxide), while Example 2 contains the same high specific filler, but the added functional resin is high specific gravity It can be seen that it is possible to produce a high specific gravity rubber molding by increasing the affinity at the interface between the filler and the elastomer substrate to impart smooth processability and mechanical properties.
또한 굴곡시험 결과 실시예 1과 2 모두 균열(crack)이 발생하지 않은 것으로 보아 내굴곡성이 우수한 것을 알 수 있다.In addition, as a result of the bending test, the cracks did not occur in both Examples 1 and 2, indicating that the bending resistance was excellent.
즉 상기 실시예 1과 실시예 2는 고비중 고무 조성물로 적합함을 알 수 있다.That is, it can be seen that Example 1 and Example 2 are suitable as a high specific gravity rubber composition.
이상에서 설명한 바와 같이 본 발명의 환경친화적이며 굴곡성을 갖는 고비중 고무 조성물은 탄성체 기재에 고비중 충전제, 보강성충전제, 통상적인 고무용 첨가제, 가교제 및 기능성 수지를 혼합하고 가교 성형하여 고무 성형물을 제작함으로써 고비중 충전제의 함량에 따라 중량 조절이 가능한 환경친화적이며 내굴곡성이 우수한 고비중 고무 조성물을 제공하는 것을 특징으로 한다. As described above, the environmentally friendly and flexible high specific gravity rubber composition of the present invention mixes and crosslinks a high specific gravity filler, a reinforcing filler, a conventional rubber additive, a crosslinking agent, and a functional resin to an elastic substrate to produce a rubber molding. It is characterized by providing a high specific gravity rubber composition which can be environmentally friendly and excellent in bending resistance can be adjusted according to the content of the high specific gravity filler.
특히 가공성이 우수하기 때문에 통상적인 고무 혼련 및 쉬트 제조 장비인 오픈롤밀이나 카렌다에서 원활한 작업이 가능하다.In particular, because of its excellent processability, smooth operation is possible in open roll mills and calendars, which are conventional rubber kneading and sheet manufacturing equipment.
더불어 고비중 충전제와 고무 기재간 친화력을 증대시킬 수 있는 특수 기능성 수지를 첨가함에 따라 굴곡성과 가공성의 개선은 물론이고, 인장강도를 위시한 기계적 강도가 우수하여 내구성이 개선된 고비중 고무 조성물을 제공할 수 있다.In addition, by adding a special functional resin that can increase the affinity between the high specific gravity filler and the rubber substrate, as well as improving the bendability and workability, as well as excellent mechanical strength including tensile strength to provide a high specific gravity rubber composition with improved durability. Can be.
또한 상기와 같이 제조된 고무 조성물은 탄성 고분자 소재를 기재로 설계됨으로써 질감을 위시한 감성품질이 우수하고 특히 굴곡피로저항이 우수하여 신발의 고중량화를 위한 인서트솔과 같이 지속적인 굴곡피로에 대한 안정성이 요구되는 스포츠용품, 생활용품, 완구 등 다양한 용도에 적용이 가능하다.In addition, the rubber composition prepared as described above has excellent emotional quality including texture, and is particularly excellent in fatigue fatigue resistance because it is designed based on an elastic polymer material, and requires stability for continuous fatigue fatigue such as insert sole for high weight of shoes. It can be applied to various uses such as sports goods, household goods, toys.
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