CN109890612B - 橡胶层压体及使用其的柔性软管 - Google Patents
橡胶层压体及使用其的柔性软管 Download PDFInfo
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- CN109890612B CN109890612B CN201780064912.7A CN201780064912A CN109890612B CN 109890612 B CN109890612 B CN 109890612B CN 201780064912 A CN201780064912 A CN 201780064912A CN 109890612 B CN109890612 B CN 109890612B
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- Prior art keywords
- rubber
- ethylene
- containing layer
- propylene
- weight
- Prior art date
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 79
- 239000005060 rubber Substances 0.000 title claims abstract description 79
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 71
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 63
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 62
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 229920001083 polybutene Polymers 0.000 claims description 9
- 150000001451 organic peroxides Chemical class 0.000 claims description 7
- -1 polybutylene Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 229920001748 polybutylene Polymers 0.000 claims 1
- 239000003431 cross linking reagent Substances 0.000 abstract description 19
- 239000005011 phenolic resin Substances 0.000 abstract description 15
- 239000010687 lubricating oil Substances 0.000 abstract description 13
- 229920000098 polyolefin Polymers 0.000 abstract description 12
- 238000004378 air conditioning Methods 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 238000010030 laminating Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000010485 coping Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 131
- 239000000203 mixture Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 12
- 239000003507 refrigerant Substances 0.000 description 11
- 229920000459 Nitrile rubber Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920005555 halobutyl Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
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- 239000002344 surface layer Substances 0.000 description 2
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- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- MPJPKEMZYOAIRN-UHFFFAOYSA-N 1,3,5-tris(2-methylprop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound CC(=C)CN1C(=O)N(CC(C)=C)C(=O)N(CC(C)=C)C1=O MPJPKEMZYOAIRN-UHFFFAOYSA-N 0.000 description 1
- HQGYGGZHZWXFSI-UHFFFAOYSA-N 1,4-cycloheptadiene Chemical compound C1CC=CCC=C1 HQGYGGZHZWXFSI-UHFFFAOYSA-N 0.000 description 1
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- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 description 1
- RIIWOXJAAGZDLD-UHFFFAOYSA-N 2-pentyl-3,8-dithiatricyclo[5.1.0.02,4]oct-5-en-4-ol Chemical compound C1=CC2SC2C2(CCCCC)SC21O RIIWOXJAAGZDLD-UHFFFAOYSA-N 0.000 description 1
- LFXNEGVBUADMEB-UHFFFAOYSA-N 3-methylocta-1,7-diene Chemical compound C=CC(C)CCCC=C LFXNEGVBUADMEB-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- HBPSHRBTXIZBDI-UHFFFAOYSA-N 4-ethylidene-8-methylnona-1,7-diene Chemical compound C=CCC(=CC)CCC=C(C)C HBPSHRBTXIZBDI-UHFFFAOYSA-N 0.000 description 1
- OJVSJOBJBMTKIW-UHFFFAOYSA-N 5-methylhepta-1,5-diene Chemical compound CC=C(C)CCC=C OJVSJOBJBMTKIW-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BXIQXYOPGBXIEM-UHFFFAOYSA-N butyl 4,4-bis(tert-butylperoxy)pentanoate Chemical compound CCCCOC(=O)CCC(C)(OOC(C)(C)C)OOC(C)(C)C BXIQXYOPGBXIEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- JRVYFDBNSAHSKS-UHFFFAOYSA-N cyclododeca-1,6-diene Chemical compound C1CCC=CCCCC=CCC1 JRVYFDBNSAHSKS-UHFFFAOYSA-N 0.000 description 1
- ZLLMHFVWHQSIIV-UHFFFAOYSA-N cyclododeca-1,7-diene Chemical compound C1CCC=CCCCCC=CC1 ZLLMHFVWHQSIIV-UHFFFAOYSA-N 0.000 description 1
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 1
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
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Abstract
本发明的课题在于,不混合异种橡胶成分或不使用粘合剂而将2种橡胶层交联粘合,且形成保持各橡胶层所具有的特性的橡胶层压体,同时,作为空调用软管,也可应对POE类润滑油,并保持振动吸收特性。作为解决办法,提供一种未交联的橡胶层压体,为丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层层压而成,其特征在于,所述乙丙二烯橡胶及/或乙丙橡胶含有层为含有低分子量聚烯烃、酚类树脂以及交联剂的橡胶含有层,相对于100重量份乙丙二烯橡胶及/或乙丙橡胶的合计,含有40~70重量份低分子量聚烯烃、1~4重量份酚类树脂以及1重量份以上交联剂。
Description
技术领域
本发明涉及橡胶层压体及使用其的柔性软管。
背景技术
作为汽车等的制冷剂输送用软管,通常适当选择专利文献1、2所揭示的结构的软管来使用。
并且,目前在混合动力车等环保车中多数搭载了电动压缩机作为空调系统,但作为其润滑油,并非使用以往所用的聚亚烷基二醇(以下称PAG)类,而是多使用多元醇酯(以下称POE)类。在此,就专利文献1所揭示的最内层由聚酰胺树脂构成的软管来说,即便使用POE类的润滑油也没有特别问题,但就专利文献2所揭示的最内层由丁基橡胶(以下有时称IIR)构成的软管来说,由于POE类的润滑油与IIR的相容性差,当使用POE类的润滑油时,最内层的IIR发生溶胀,因而引起故障的可能性升高。但是专利文献2所揭示的结构(内管:橡胶层)的软管相对于专利文献1所揭示的结构(内管:树脂层+橡胶层)的软管,由于非常柔软,振动吸收特性、安装作业性等优异,因此内管仅由橡胶层构成的软管的需求依然很高。
因此,可以考虑如下:使用耐POE油性(耐POE润滑油性)高且价廉的丁腈橡胶(以下称NBR),针对专利文献2所揭示的结构的软管的最内层IIR,通过混合NBR使耐POE油性升高,或者将由NBR构成的层作为保护层设置在内部流体侧即软管的最内层侧。但是,在IIR中混合NBR时,难以同时保持IIR的阻气性和NBR的耐POE油性的特性,因此,优选将由NBR构成的层作为独立的保护层设置在内部流体侧,同时与IIR层进行层压。
在此,作为将这些独立的2层进行层压时的粘合方法之一,就通过粘合剂使IIR层与NBR层进行粘合的方法来说,在需要由粘合剂参与的粘合步骤的同时,有时并不能获得充分的粘合力。因此,可考虑使IIR层与NBR层进行交联粘合,但是由于IIR与NBR的SP值(表示溶解性的值)差异大因而相溶性非常差,所以以往并不存在使该两者进行交联粘合而获得橡胶层压体的技术。为了解决此种问题,专利文献3中,在由独立的2层橡胶组合物构成的层压体中,通过使与其中一种橡胶组合物中所含的橡胶同种的橡胶也包含于另一种橡胶组合物中,之后进行交联粘合,从而使相溶性差的橡胶层彼此粘合。
此外,专利文献4中记载了如下燃料电池车用氢燃料输送软管:在具有内侧橡胶层和外侧橡胶层的橡胶软管中,内侧橡胶层及外侧橡胶层分别由卤化丁基橡胶、卤化丁基橡胶与丁基橡胶的混合以及乙丙类橡胶中的任意一种构成,在使用丁基橡胶的情况下,必须含有卤化丁基橡胶成分,其结果是不会污染氢燃料。
并且,专利文献5记载如下:将由含有乙烯-丙烯-二烯橡胶、液状聚丁烯、过氧化物交联剂的组合物制得的层作为内层,作为外层可采用以丁基橡胶为首的各种材料,其结果是作为燃料电池用软管提高了耐透水性及耐气性。
此外,也需要能够应对新的制冷剂HFO-1234yf等的软管,专利文献6中记载如下:作为可对应此种制冷剂的空调软管,其最内层由含有丁基类橡胶和特定的丙烯腈-丁二烯类共聚橡胶以及鳞片状填料的组合物构成;并且专利文献7记载了在橡胶层的内面侧形成由聚酰胺、聚乙烯、聚丙烯构成的内面层的制冷剂输送软管,该内面层的与该橡胶层接触的一侧具有特定的弹性率。
现有技术文献
专利文献
专利文献1日本特许第3891718号
专利文献2日本特许第3372475号
专利文献3日本特开2007-98900号公报
专利文献4日本特开2003-278958号公报
专利文献5日本特开2006-32106号公报
专利文献6日本特开2013-228081号公报
专利文献7日本特开2013-217445号公报
然而,如专利文献3的方法,由于在一种及/或另一种橡胶组合物中混合异种橡胶成分,有时会使各橡胶层所具有的特性(例如一种橡胶的耐油性、另一种橡胶的阻气性)难以发挥或下降。
另外,如专利文献4~6中所记载,当做为燃料输送用或空调用的软管使用时,需要具有耐燃料性的同时不污染燃料,且需要针对新型制冷剂不溶胀、不溶解,具有各种稳定性。
并且,由于发动机或车身的振动会通过燃料输送用或空调用的软管进行传播,因此有防止车内的噪音增大的需求。
本发明的目的在于,不配合异种橡胶成分或不使用粘合剂而将2种橡胶层交联粘合,且形成保持各橡胶层所具有的特性的橡胶层压体,同时,作为空调用软管,也可应对POE类润滑油,并保持振动吸收特性。
为了解决上述课题,本发明采用以下结构。
1.一种未交联的橡胶层压体,为丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层层压而成,其特征在于,所述乙丙二烯橡胶及/或乙丙橡胶含有层为含有低分子量聚烯烃、酚类树脂以及交联剂的橡胶含有层,相对于100重量份乙丙二烯橡胶及/或乙丙橡胶的合计,含有40~70重量份低分子量聚烯烃、1~4重量份酚类树脂以及1重量份以上交联剂。
2.根据上述1项所述的未交联的橡胶层压体,其特征在于,所述低分子量聚烯烃为聚丁烯,所述交联剂为有机过氧化物。
3.一种已交联的橡胶层压体,为丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层层压而成,其特征在于,所述乙丙二烯橡胶及/或乙丙橡胶含有层为含有低分子量聚烯烃、酚类树脂,且被过氧化物交联的橡胶含有层,相对于100重量份的乙丙二烯橡胶及/或乙丙橡胶的合计,含有40~70重量份低分子量聚烯烃以及1~4重量份酚类树脂,且所述丁基橡胶含有层与所述乙丙二烯橡胶及/或乙丙橡胶含有层被交联粘合。
4.一种柔性软管,其特征在于,具有上述3项所述的上述橡胶层压体的结构。
5.根据上述4项所述的柔性软管,其特征在于,所述柔性软管的最内层侧由所述乙丙二烯橡胶及/或乙丙橡胶含有层构成,所述丁基橡胶含有层的厚度为1.1mm以上,且相对于所述乙丙二烯橡胶及/或乙丙橡胶含有层的厚度,所述丁基橡胶含有层的厚度为1.4倍以上。
根据本发明,可将含有丁基橡胶的层与含有乙丙二烯橡胶(以下有时称EPDM)及/或乙丙橡胶(以下有时称EPM)的层在强力粘合状态下相互粘合,从而可得到耐热性、耐POE油性以及机械强度优异,且保持振动吸收特性的橡胶层压体及柔性软管。
具体实施方式
本发明是基于以下内容的发明:使丁基橡胶含有层与含有低分子量聚烯烃、酚类树脂以及交联剂的乙丙二烯橡胶及/或乙丙橡胶含有层层压而成为层压体,以及将这些层相互交联粘合而成为橡胶层压体。
以下将对本发明的优选实施方式进行详细说明。
[丁基橡胶含有层]
作为本发明中所使用的丁基橡胶,可从公知的丁基橡胶中任意选择。
其中,从机械强度等橡胶特性考虑,作为丁基橡胶优选采用卤化丁基橡胶。
在不失丁基橡胶特性且不损害本发明的效果的范围内,本发明的丁基橡胶含有层中,可适当添加其他橡胶或树脂以及公知的添加于橡胶组合物中的各种添加剂,例如:碳黑、填充剂、共交联剂、交联促进剂、交联助剂、软化剂、增塑剂、抗老化剂、稳定剂以及加工助剂等。
[乙丙二烯橡胶及/或乙丙橡胶含有层]
(乙丙二烯橡胶)
作为本发明中所使用的乙丙二烯橡胶,可从公知的乙丙二烯橡胶中任意选择。其中,优选乙基含量为50~70重量%。作为构成EPDM的二烯,可列举1,4-己二烯、1,5-己二烯、1,6-庚二烯、甲基四氢化茚、4-甲基-1,4-己二烯、5-甲基-1,4-己二烯、5-甲基-1,5-庚二烯、6-甲基-1,5-庚二烯、6-甲基-1,7-辛二烯及7-甲基-1,6-辛二烯等链状非共轭二烯;二聚环戊二烯、1,5-环辛二烯、1,1-环辛二烯、1,6-环十二烷二烯、1,7-环十二烷二烯、1,5,9-环十二烷三烯、1,4-环庚二烯、1,4-环己二烯、5-亚乙基-2-降冰片烯、5-丙叉基-5-降冰片烯、5-乙烯-2-降冰片烯、5-亚甲基-2-降冰片烯、5-异丙叉基-2-降冰片烯以及降冰片二烯等环状二烯;2,3-二异丙叉基-5-降冰片烯及4-亚乙基-8-甲基-1,7-壬二烯等。
(乙丙橡胶)
作为本发明中所使用的乙丙橡胶,可从公知的乙丙橡胶中任意选择。
作为EPM中的乙基含量,优选为30~80重量%。
[低分子量聚烯烃]
作为本发明中添加于乙丙二烯橡胶及/或乙丙橡胶含有层的低分子量聚烯烃,例如可列举:石蜡油、环烷油、液状IR、液状EPDM、液状SBR、液状聚丁二烯、液状聚丁烯等,优选使用液状聚丁烯,其数均分子量为300~4000,优选为1000~3000。
此外,为了提高与橡胶的反应性,低分子量聚烯烃也可为马来酸改性、环氧改性、羟基末端。
相对于100重量份的乙丙二烯橡胶及/或乙丙橡胶,乙丙二烯橡胶及/或乙丙橡胶含有层中的低分子量聚烯烃的含量为40~70重量份,优选为45~65重量份,进一步优选为50~60重量份。当含量小于40重量份时,耐POE油性变差,进而由于与POE油接触而使溶胀等可能性升高。当含量超过70重量份时,机械强度变差,且在交联前的滚动作业时存在引起橡胶组合物粘附到滚筒上等故障的风险。
[酚类树脂]
本发明中所使用的酚类树脂,被用作乙丙二烯橡胶及/或乙丙橡胶含有层与丁基橡胶含有层的粘合剂。作为此种酚类树脂,例如可列举:甲阶酚醛型酚树脂、酚醛型酚树脂等。
相对于100重量份的乙丙二烯橡胶及/或乙丙橡胶,乙丙二烯橡胶及/或乙丙橡胶含有层中的酚类树脂的含量为1~4重量份,优选为1~3重量份,进一步优选为1~2重量份。当含量小于1重量份时,与丁基橡胶含有层之间的粘合性变差的可能性升高;当含量超过4重量份时,交联后乙丙二烯橡胶及/或乙丙橡胶含有层的耐热性和机械强度下降。且在交联前的滚动作业时存在引起橡胶组合物粘附到滚筒上等故障的风险。
[交联剂]
为了得到本发明的橡胶层压体及柔性软管,可预先将交联剂添加于乙丙二烯橡胶及/或乙丙橡胶含有层中,使其在与丁基橡胶含有层层压后进行交联。
作为该交联剂,可采用硫黄或有机过氧化物等。
且这些交联剂中可无限定地使用有机过氧化物。作为具体例可列举:过氧化苯甲酰、过氧化二异丙苯、2,5-二甲基-2,5-二(叔丁基过氧基)已烷、1,1’-二(叔丁基过氧基)二异丙基苯、正丁基-4,4-二(叔丁基过氧基)戊酸酯、1,1-二(叔丁基过氧基)环已烷等,优选使用2,5-二甲基-2,5-二(叔丁基过氧基)已烷、1,1’-二(叔丁基过氧基)二异丙基苯。
在未交联状态下,相对于100重量份的乙丙二烯橡胶及/或乙丙橡胶,乙丙二烯橡胶及/或乙丙橡胶含有层中的交联剂的含量为1重量份以上,优选为1.5重量份以上,进一步优选为2重量份以上。当含量小于1重量份时,机械强度变差的可能性升高。
[碳黑]
在本发明中的乙丙二烯橡胶及/或乙丙橡胶含有层中可由公知的添加于橡胶组合物中的碳黑中任意选择而使用。
本发明中的乙丙二烯橡胶及/或乙丙橡胶含有层中,可从公知的添加于橡胶组合物的共交联剂或交联助剂中任意选择使用。作为具体例可列举:三烯丙基氰尿酸酯、三烯丙基异氰脲酸酯、三甲代烯丙基异氰脲酸酯、乙二醇二甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯、1,2-聚丁二烯、丙烯酸镁、丙烯酸锌、甲基丙烯酸镁、甲基丙烯酸锌、六亚甲基二胺脲酸酯、对苯醌二肟、对,对’-二苯甲酰苯醌二肟、N,N’-间苯双马来酰亚胺、戊基苯酚二硫聚合物、硫黄等,优选使用三烯丙基异氰脲酸酯。
本发明中的乙丙二烯橡胶及/或乙丙橡胶含有层中,在不失乙丙二烯橡胶及/或乙丙橡胶含有层特性,且不损害本发明的效果的范围内,可适当添加其他橡胶或树脂以及公知的添加于橡胶组合物中的各种添加剂,例如:共交联剂、填充剂、交联促进剂、软化剂、增塑剂、抗老化剂、稳定剂以及加工助剂等。
[橡胶层压体]
本发明的未交联的或已交联的橡胶层压体的形状,没有特别限定,可列举片状、棒状、管状、软管状等,特别优选制成最内层侧为乙丙二烯橡胶及/或乙丙橡胶含有层的柔性软管。
且该软管等可用于接触POE类等润滑油和制冷剂的用途。
橡胶层压体在加工成上述任意形状后,可根据由公知的交联条件中所选择的条件进行交联。其结果,未交联的橡胶层压体中所含的有机过氧化物等交联剂被消耗,其几乎未残存于交联的橡胶层压体中。
与此同时,丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层被相互强力交联粘合。
此外,根据需要可在丁基橡胶含有层侧的外周形成有机纤维等的补强层,进一步可在补强层的外周形成橡胶组合物等的外层。
[软管的制造方法]
作为制造本发明的柔性软管的方法,可采用如下方法:将本发明的橡胶层压体通过2层挤出机等挤出成型,在管芯的外周覆盖成软管用的圆筒形状,并通过将该橡胶层压体加热而进行交联。
此外,通过将EPDM及/或EPM含有层用橡胶组合物挤出成型,形成柔性软管最内层侧用的圆筒形状,然后再通过将IIR含有层用橡胶组合物挤出成型,形成第2层用的圆筒形状,并在EPDM及/或EPM含有层的外周进行层压,此后通过将该橡胶层压体加热而进行交联。此外,在挤出成型(层压)步骤之后,根据需要,也可在IIR含有层的外周形成纤维补强层以及最外层的橡胶层。
通过加热,在EPDM及/或EPM含有层,EPDM及/或EPM通过交联制备交联的EPDM及/或EPM含有层的同时,在IIR含有层用橡胶组合物中,IIR通过交联制备交联的IIR含有层,与此同时,该2层以具有强力的粘合强度而被层压。
此外,可将该软管制成具有振动吸收特性的柔性软管。并且,在制成柔性软管的情况下,例如也可用作车辆用空调软管。
可制成当软管内部流通的流体为POE类润滑油或制冷剂时所使用的软管。并且将软管的最内层侧作成将本发明中的EPDM及/或EPM含有层交联而成的层,在EPDM及/或EPM含有层的外周可设置将IIR含有层交联而形成的层。
虽然将EPDM及/或EPM含有层交联形成的层,设定为比IIR含有层薄的肉厚,但只要具备某种程度的肉厚,即可充分具备对内部流通的POE系润滑油及制冷剂的耐受性,而不妨碍其外周的IIR含有层的阻气性等特性。且EPDM及/或EPM含有层与IIR含有层的合计厚度为1.9mm的情况下,相对于EPDM及/或EPM含有层,IIR含有层为1.4倍以上、优选为2.0倍以上、进一步优选为3.0倍以上的肉厚,由此,作为软管整体,可兼具针对POE类润滑油及制冷剂的耐受性和振动吸收特性。
此外,当EPDM及/或EPM含有层与IIR含有层的合计厚度超过1.9mm而在实际使用上不存在问题的情况下,IIR含有层的厚度也可为1.1mm以上及/或EPDM及/或EPM含有层的厚度可为0.8mm以上。
实施例
接下来基于实施例进一步对本发明进行具体说明,但本发明并不仅限于此。
形成含有下述表1中所示各成分的EPDM含有层,除此之外,形成IIR含有层,然后制作如下试验片。
针对所得试验片,测定以下角度的特性。
(EPDM与IIR的粘合性)
将厚度2mm的未交联的EPDM橡胶片与厚度为2mm的未交联的IIR橡胶片(相对于氯化丁基橡胶而含有碳黑、交联剂、交联促进剂、交联助剂、抗老化剂、填充剂等市售配合剂的橡胶组合物)通过冲压加热进行交联粘合,然后切成宽10mm×长100mm的尺寸,从而制成试验片。
试验方法是按照JIS K6256-1“硫化橡胶及热可塑性橡胶-粘合性的求法-第1部:与布的剥离强度”,以50mm/分的剥离速度进行90°剥离,并基于下述标准评价粘合力。
○:1.5N/mm以上
×:小于1.5N/mm
(耐热性)
将厚度2mm的未交联的EPDM橡胶片通过冲压加热进行交联,然后制成JIS K6251中所规定的哑铃状3号形试验片。
按照JIS K6257“硫化橡胶及热可塑性橡胶-热老化特性的求法”,在100℃的环境下放置70小时后,基于下述标准评价伸长变化率。
○:-20%以上
×:小于-20%
(耐POE油性)
将厚度2mm的未交联的EPDM橡胶片通过冲压加热进行交联,然后切成宽20mm×长50mm的尺寸,从而制成试验片。
按照JIS K6258“硫化橡胶及热可塑性橡胶-耐液性的求法”,在100℃的环境下放置70小时后,基于下述标准评价体积变化率。试验油使用POE类润滑油。
○:±5%的范围内
×:±5%的范围外
(机械强度(系数))
按照JIS K6251“硫化橡胶及热可塑性橡胶-拉伸特性的求法”,基于下述标准评价100%伸长拉伸应力(M100)。试验片使用上述JIS K6251规定的哑铃状3号形。
○:1.8MPa以上
×:小于1.8MPa
[表1]
※1 TAIC WH-60(表1中的值是当除去稀释剂(二氧化硅等)而使三烯丙基异氰脲酸酯为100%时的值。)
※2日油聚丁烯40SH(数均分子量:1400~1800)
※3全丁基P
※4全己基25B-40(表1中的值是当除去稀释剂(二氧化硅等)而使过氧化物交联剂为100%时的值。)
※5 TACKIROL 250-I
根据上述实施例1~9,本发明的橡胶层压体及橡胶组合物的EPDM含有层与IIR含有层的粘合性和耐热性、耐POE油性以及机械强度均优异。
根据该结果,作为柔性软管可具有如下特性:具有充分的机械强度;在耐久性优异的同时在高温环境下耐用;即使在发生振动的环境下使用也具有充分的振动吸收特性;对于POE类润滑油或制冷剂具有充分的耐受性。
相对于此,根据对比例1~3,当聚丁烯的含量少时,由于EPDM含有层与IIR含有层的粘合性不充分,作为柔性软管的耐久性差,且耐POE油性也差。此外,当聚丁烯的含量多时,机械强度变差。
根据对比例4~5,当不含过氧化物时,EPDM含有层不能交联;当过氧化物含量少时,即使交联也会出现机械强度变差的结果。
根据对比例6~8,当酚类树脂的含量少时,由于EPDM含有层与IIR含有层的粘合性不充分,作为柔性软管的耐久性变差;当酚类树脂的含量多时,耐热性及机械强度变差。
使用表1中的实施例6的橡胶组合物,EPDM含有层与IIR含有层的合计厚度为1.9mm,且以成为表2的各种肉厚比例的形式将橡胶层压体挤出成型,然后,使用其制成各种柔性软管。
并且,针对制得的各种柔性软管,分别测定HFC-134a的透过量。测定条件按照社团法人“日本冷冻空调工业会”发行的“汽车空调装置(HFC-134a)用制冷剂软管”的标准“JRA2012-1995 9.制冷剂透过量”。该测定结果示于表2。
[表2]
根据表2的结果可知,当EPDM及/或EPM含有层与IIR含有层的合计厚度为1.9mm,且IIR含有层的厚度为1.1mm以上时,即在此种条件下当上述IIR含有层的厚度相对于上述EPDM及/或EPM含有层的厚度,IIR含有层/EPDM含有层的肉厚比例为1.4倍以上时,HFC-134a的透过量满足JRA标准(1.0g/cm2/year以下)。
而且,根据此结果可理解为:只要IIR含有层的厚度为1.1mm以上,且EPDM含有层的厚度为0.8mm以上(1.9mm-1.1mm=0.8mm),至少可获得超过实施例13的结果的阻透效果,并且满足JRA标准。
Claims (4)
1.一种未交联的橡胶层压体,为丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层层压而成,其特征在于,
所述乙丙二烯橡胶及/或乙丙橡胶含有层为含有数均分子量为300~4000的低分子量聚丁烯、溴化烷基酚树脂以及有机过氧化物的橡胶含有层,相对于100重量份乙丙二烯橡胶及/或乙丙橡胶的合计,
含有40~70重量份数均分子量为300~4000的低分子量聚丁烯、
1~4重量份溴化烷基酚树脂、
以及1重量份以上有机过氧化物。
2.一种已交联的橡胶层压体,为丁基橡胶含有层与乙丙二烯橡胶及/或乙丙橡胶含有层层压而成,其特征在于,
所述乙丙二烯橡胶及/或乙丙橡胶含有层为含有数均分子量为300~4000的低分子量聚丁烯、溴化烷基酚树脂,且被有机过氧化物交联的橡胶含有层,相对于100重量份的乙丙二烯橡胶及/或乙丙橡胶的合计,
含有40~70重量份数均分子量为300~4000的低分子量聚丁烯、
以及1~4重量份溴化烷基酚树脂,且,
所述丁基橡胶含有层与所述乙丙二烯橡胶及/或乙丙橡胶含有层被交联粘合。
3.一种柔性软管,其特征在于,具有权利要求2所述的橡胶层压体的结构。
4.根据权利要求3所述的柔性软管,其特征在于,所述柔性软管的最内层侧由所述乙丙二烯橡胶及/或乙丙橡胶含有层构成,所述丁基橡胶含有层的厚度为1.1mm以上,且相对于所述乙丙二烯橡胶及/或乙丙橡胶含有层的厚度,所述丁基橡胶含有层的厚度为1.4倍以上。
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