CN110446607A - 层叠体 - Google Patents
层叠体 Download PDFInfo
- Publication number
- CN110446607A CN110446607A CN201880019415.XA CN201880019415A CN110446607A CN 110446607 A CN110446607 A CN 110446607A CN 201880019415 A CN201880019415 A CN 201880019415A CN 110446607 A CN110446607 A CN 110446607A
- Authority
- CN
- China
- Prior art keywords
- layer
- rubber
- halogen
- mass parts
- laminated body
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 claims abstract description 137
- 239000005060 rubber Substances 0.000 claims abstract description 132
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 87
- 150000002367 halogens Chemical class 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 45
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 29
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- -1 hydrotalcite Compound Chemical class 0.000 claims description 32
- 229920005558 epichlorohydrin rubber Polymers 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 150000005846 sugar alcohols Polymers 0.000 claims description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229960001545 hydrotalcite Drugs 0.000 claims description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 99
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 52
- 238000000034 method Methods 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 32
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 238000004132 cross linking Methods 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000003712 anti-aging effect Effects 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- 239000004902 Softening Agent Substances 0.000 description 10
- 229920006270 hydrocarbon resin Polymers 0.000 description 10
- 150000001451 organic peroxides Chemical class 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 8
- 239000013032 Hydrocarbon resin Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 229920000800 acrylic rubber Polymers 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 235000012222 talc Nutrition 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- DXKZQNUSKZOLTC-UHFFFAOYSA-N 1,3,5-trichloro-2-[chloro-(2,4,6-trichlorophenoxy)phosphoryl]oxybenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1OP(Cl)(=O)OC1=C(Cl)C=C(Cl)C=C1Cl DXKZQNUSKZOLTC-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 240000001548 Camellia japonica Species 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 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
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 2
- 235000018597 common camellia Nutrition 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- IFBDFMPSOCGRKA-UHFFFAOYSA-N 1-octadecoxyoctadecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC IFBDFMPSOCGRKA-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- JUVDEAXMLQQRFP-UHFFFAOYSA-N 1h-imidazol-2-yl(phenyl)methanone Chemical class C=1C=CC=CC=1C(=O)C1=NC=CN1 JUVDEAXMLQQRFP-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-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
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- BQARUDWASOOSRH-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-yl hydrogen carbonate Chemical compound CC(C)(C)OOC(C)(C)OC(O)=O BQARUDWASOOSRH-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
-
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Abstract
本发明的课题在于获得接合强度优异的不同种类的含卤素橡胶(聚合物)的层叠体,本发明涉及一种层叠体,其是下述层(1)和下述层(2)直接接合而成的。层(1):由包含卤素系橡胶(A)〔其中,氟系橡胶除外〕100质量份和无机化合物(B)10~30质量份的组合物形成的层,所述无机化合物(B)含有选自第2族元素和第13族元素中的至少1种元素及氧。层(2):由含卤素聚合物(C)〔其中,层(1)的卤素系橡胶除外。〕形成的层。
Description
技术领域
本发明涉及粘接性优异的不同种类的含卤素橡胶接合而成的层叠体。
背景技术
氟系橡胶的耐热性、耐油性、耐试剂性、耐候性等优异,在工业用材料、其他领域中是有用的。然而氟系橡胶昂贵,而且在这些领域中普遍使用时不能忽视经济性,因此现状是虽然氟系橡胶具有卓越性能,但是也不能期待其使用量有飞跃性增加。
另一方面,丙烯酸酯的均聚物或作为丙烯酸酯与2-氯乙基乙烯基醚的共聚物的丙烯酸类橡胶(ACM)、表氯醇橡胶(ECO)等含卤素橡胶的耐油性、耐热性、耐候性等优异,因此在以汽车用途为中心的各种密封材、垫圈、垫片、油软管、空气软管等耐热、耐油软管等功能部件中被广泛使用。
近年来,对于汽车而言,以提高性能、提高燃料效率为目的,发动机室内的温度日益高温化,要求与以往的耐热、耐油软管相比耐热性能提高了的材料。
这样的耐热、耐油软管等工业用软管要求强度、柔软性、耐热性、耐弯曲性、耐溶剂性等各种物性,因此难以利用1种橡胶来满足所要求的全部特性。因此,尝试了将具有不同性质的橡胶,例如上述氟系橡胶与含卤素橡胶层叠来使用。
然而,由于氟系橡胶与含卤素橡胶的粘接性差,因此例如提出了下述方法:在丙烯酸系弹性体中配合过氧化物、溴化季铵、环氧化脂肪酸酯等的方法(专利文献1);在氟系橡胶中配合二氧化硅系填充剂和有机过氧化物,在丙烯酸类橡胶中配合二氧化硅系填充剂、有机过氧化物和硅烷偶联剂的方法(专利文献2);在氟系橡胶或含卤素橡胶的任一者中配合金属氧化物的方法(专利文献3)等各种方法。
然而,对于在耐热、耐油软管中使用而言,无论采用哪一种方法,氟系橡胶与含卤素橡胶的粘接强度都仍然不充分。
现有技术文献
专利文献
专利文献1:日本特开昭61-189934号公报
专利文献2:日本特开平1-152060号公报
专利文献3:国际公开第2003/039858号
发明内容
发明所要解决的课题
本发明的目的在于获得接合强度优异的不同种类的含卤素橡胶(聚合物)的层叠体。
用于解决课题的方法
本发明涉及一种层叠体,其是下述层(1)与下述层(2)直接接合而成的。
层(1):由包含卤素系橡胶(A)〔其中,氟系橡胶除外〕100质量份和无机化合物(B)10~30质量份的组合物形成的层,所述无机化合物(B)含有选自第2族元素和第13族元素中的至少1种元素及氧。
层(2):由含卤素聚合物(C)〔其中,层(1)的卤素系橡胶除外。〕形成的层。
发明的效果
以往,即使将包含表氯醇橡胶(ECO)和丙烯酸类橡胶(ACM)等卤素系橡胶(A)的层与包含氟系橡胶等含卤素聚合物(C)的层直接接合,也未能获得具有牢固的粘接强度(剥离强度)的层叠体,但在本发明的层叠体中,包含表氯醇橡胶(ECO)和丙烯酸类橡胶(ACM)等卤素系橡胶(A)的层与包含氟系橡胶等含卤素聚合物(C)的层牢固地接合,因此能够适用于耐热、耐油软管等用途。
具体实施方式
<层(1)>
构成本发明的层叠体的层(1)是由组合物形成的层,所述组合物包含卤素系橡胶(A)以及含有选自第2族元素和第13族元素中的至少1种元素及氧的无机化合物(B)〔以下,有时简称为“无机化合物(B)”。〕,相对于卤素系橡胶(A)100质量份,无机化合物(B)为10~30质量份。
<卤素系橡胶(A)>
本发明的层叠体的形成层(1)的卤素系橡胶(A)是分子中包含卤原子的橡胶〔其中,氟系橡胶除外〕,优选为具有来源于含卤素单体的构成单元的橡胶。
作为卤原子,可举出氯原子、溴原子、碘原子等,作为卤素系橡胶,优选为包含氯原子的橡胶。
作为本发明涉及的卤素系橡胶(A),具体而言,可举出表氯醇橡胶(ECO)、丙烯酸类橡胶(ACM)、氯化聚乙烯、氯丁橡胶(CR)、氯化丁基橡胶(CIIR)、溴化丁基橡胶(BIIR)等。
在这些卤素系橡胶(A)中,表氯醇橡胶(ECO)和丙烯酸类橡胶(ACM)能够获得耐热、耐油性优异的层叠体,因此优选。
<无机化合物(B)>
本发明的层叠体的形成层(1)的卤素系橡胶(A)中所配合的无机化合物(B)为含有选自第2族元素和第13族元素中的至少1种元素及氧的无机化合物。
本发明涉及的无机化合物(B)只要是含有选自第2族元素和第13族元素中的至少1种元素及氧的无机化合物,就没有特别限制,可举出例如,包含选自第2族元素和第13族元素中的至少1种元素的氧化物、氢氧化物、碳酸盐、水滑石类化合物。
作为选自第2族元素和第13族元素中的至少1种元素,可举出例如选自Mg、Ca、Ba和Al中的至少1种元素。
作为本发明涉及的无机化合物(B),可以使用市售品,可举出例如,“KYOWAMAG150”(协和化学工业株式会社制,氧化镁)、“DHT-4A”(协和化学工业株式会社制,水滑石类化合物:Mg4.3Al2(OH)12.6CO3·mH2O)。
相对于上述卤素系橡胶(A)100质量份,以1~30质量份、优选为2~30质量份、进一步优选为5~30质量份的范围包含本发明涉及的无机化合物(B)。
通过以上述范围包含无机化合物(B),从而能够获得形成层(1)的卤素系橡胶(A)与层(2)的粘接强度(剥离强度)优异的层叠体。
此外,形成层(1)的卤素系橡胶(A)也可以进一步以10~30质量份、更优选为15~30质量份的范围包含无机化合物(B)。如果包含无机化合物(B)10质量份以上,则从热稳定性方面来看是优选的,此外,如果包含15质量份以上,则从热稳定性和加工性方面来看是优选的。
<其他配合剂>
本发明涉及的形成层(1)的卤素系橡胶(A)中,除了上述无机化合物(B)以外,能够添加通常在橡胶中配合的各种添加剂。
作为其他添加剂,可以例示例如,以下添加剂。
更具体而言,可举出有机过氧化物、炭黑、防老剂、软化剂、金属氧化物、交联助剂、盐等。
《有机过氧化物》
作为本发明涉及的有机过氧化物的具体例,可举出二枯基过氧化物、二叔丁基过氧化物、2,5-二(叔丁基过氧化)己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、2,5-二甲基-2,5-二(叔丁基过氧化)己炔-3、1,3-双(叔丁基过氧化异丙基)苯、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷、正丁基-4,4-双(叔丁基过氧化)戊酸酯、过氧化苯甲酰、对氯过氧化苯甲酰、2,4-二氯过氧化苯甲酰、叔丁基过氧化苯甲酸酯、叔丁基过氧化异丙基碳酸酯、二乙酰基过氧化物、月桂酰基过氧化物、叔丁基枯基过氧化物等。
本发明涉及的有机过氧化物可以单独使用1种,也可以组合使用2种以上。
在将本发明涉及的有机过氧化物配合至上述卤素系橡胶(A)的情况下,通常期望相对于卤素系橡胶(A)100质量份,以0.1~5质量份、优选为0.5~5质量份、进一步优选为0.5~4质量份的范围来使用。如果有机过氧化物的配合量在上述范围内,则在层叠体的表面的起霜少,层(1)显示优异的交联特性,因此优选。
《炭黑》
作为本发明涉及的炭黑,具体而言,可举出SRF、GPF、FEF、MAF、HAF、ISAF、SAF、FT、MT等各种炭黑;将这些炭黑用硅烷偶联剂等进行表面处理后的表面处理炭黑等。
在将本发明涉及的炭黑配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,炭黑的配合量通常可以设为10~300质量份,优选为10~200质量份,更优选为10~100质量份左右。
如果在上述范围内含有炭黑,则能够获得提高了抗拉强度和耐摩耗性等机械性质的层叠体,能够提高层叠体的硬度而不损害它的其他物性,因此优选。
《防老剂》
本发明涉及的形成层(1)的卤素系橡胶(A)如果含有防老剂,则能够延长所得的层叠体的产品寿命。作为本发明涉及的防老剂,可以使用以往公知的防老剂,例如胺系防老剂、酚系防老剂、硫系防老剂等。
作为本发明涉及的防老剂,具体而言,可举出苯基丁基胺、N,N-二(2-萘基)对苯二胺、4,4’-双(α,α-二甲基苄基)二苯基胺(又称:4,4’-二枯基-二苯基胺(4,4’-Dicumyl-diphenylamine))等芳香族仲胺系防老剂、2,2,4-三甲基-1,2-二氢喹啉聚合物等胺系防老剂、二丁基羟基甲苯、四[亚甲基(3,5-二叔丁基-4-羟基)氢化肉桂酸酯]甲烷等酚系防老剂;双[2-甲基-4-(3-正烷基硫代丙酰氧基)-5-叔丁基苯基]硫醚等硫醚系防老剂;二丁基二硫代氨基甲酸镍等二硫代氨基甲酸盐系防老剂;2-巯基苯甲酰咪唑、2-巯基苯并咪唑的锌盐、二月桂基硫代二丙酸酯、二硬脂基硫代二丙酸酯等硫系防老剂等。
这些防老剂可以单独使用1种,也可以组合使用2种以上。
在将本发明涉及的防老剂配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,防老剂的配合量通常为0.5~5.0质量份,优选为0.5~4.5质量份,更优选为0.5~4.0质量份。如果在上述范围内,则所得的层叠体的耐热老化性优异,因此优选。
《软化剂》
作为本发明涉及的软化剂,能够广泛使用作为以往在橡胶中配合的软化剂、加工助剂等已知的成分。
具体而言,可举出石蜡系操作油、环烷系操作油、芳香系操作油等石油系软化剂;合成油系软化剂;乙烯与α-烯烃的共低聚物;固体石蜡;液体石蜡;白油(white oil);矿脂;煤焦油、煤焦油沥青等煤焦油系软化剂;蓖麻油、棉籽油、亚麻籽油、菜籽油、椰油、棕榈油、大豆油、花生油、木蜡、松香、松树油、松油精、松焦油、妥尔油等植物油系软化剂;黑色硫化油膏、白色硫化油膏、半透明硫化油膏等硫化油膏(油膏);蜂蜡、巴西棕榈蜡、羊毛脂等蜡类;蓖麻油酸、棕榈酸、硬脂酸、亚油酸、月桂酸、肉豆蔻酸、硬脂酸钡、硬脂酸钙、硬脂酸镁、硬脂酸锌、月桂酸锌等脂肪酸、脂肪酸盐和酯类;邻苯二甲酸二辛酯、己二酸二辛酯、癸二酸二辛酯等酯系增塑剂;香豆酮-茚树脂;苯酚-甲醛树脂;萜烯-酚醛树脂;多萜树脂;合成多萜树脂、芳香族系烃树脂、脂肪族系烃树脂、脂肪族系环状烃树脂、脂肪族-脂环族系石油树脂、脂肪族-芳香族系石油树脂、氢化改性脂环族系烃树脂、氢化烃树脂、液体聚丁烯、液体聚丁二烯、无规立构聚丙烯等石油系烃树脂等。
其中,优选为脂肪酸、石油系软化剂、苯酚-甲醛树脂、石油系烃树脂,进一步优选为脂肪酸、石油系软化剂、石油系烃树脂,特别优选为脂肪酸、石油系软化剂。
在上述石油系软化剂中,优选为石油系操作油,其中,进一步优选为石蜡系操作油、环烷系操作油、芳香系操作油等,特别优选为石蜡系操作油。此外,在石油系烃树脂中,优选为脂肪族系环状烃树脂。这些软化剂中,特别优选为石蜡系操作油。
这些软化剂可以单独使用1种,也可以组合使用2种以上。
在将本发明涉及的软化剂配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,通常为小于200质量份的量,优选为0~100质量份,更优选为0~80质量份,进一步优选为0~70质量份,特别优选为0~60质量份。
《金属氧化物》
作为本发明涉及的金属氧化物,可以根据层叠体的用途来适当选择,可以单独使用也可以混合使用2种以上。作为金属氧化物的具体例,可举出锌白(例如META-Z102)(商品名:井上石灰工业株式会社制等的氧化锌)、氧化镁等。
在将本发明涉及的金属氧化物配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,通常为0.5~20质量份,优选为0.5~15质量份,更优选为0.5~10质量份,进一步优选为0.5~5质量份。
《交联助剂》
作为本发明涉及的交联助剂,可举出硫;对醌二肟等醌二肟系化合物;多官能性单体,例如三羟甲基丙烷三丙烯酸酯、聚乙二醇二甲基丙烯酸酯等(甲基)丙烯酸酯系化合物;二烯丙基邻苯二甲酸酯、三烯丙基氰脲酸酯等烯丙基系化合物;间亚苯基双马来酰亚胺等马来酰亚胺系化合物;二乙烯基苯等。本发明涉及的交联助剂可以单独使用一种,也可以组合使用2种以上。
在将本发明涉及的交联助剂配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,通常为0~4.0质量份,优选为0~3.5质量份,更优选为0~3.0质量份,进一步优选为0.1~3.0质量份。此外,也期望交联助剂的配合量相对于上述有机过氧化物1摩尔优选为0.5~2摩尔,更优选为大致等摩尔的量。
《盐》
作为本发明涉及的盐,可举出例如,季铵盐、季盐、氧盐、锍盐、环状胺、1官能性胺化合物等,其中,优选为季铵盐、季盐。
本发明涉及的盐可以单独使用一种,也可以组合使用2种以上。
作为上述季铵盐,没有特别限定,可举出例如,二烷基(C14-18)二甲基氯化铵、1,8-二氮杂双环[5,4,0]十一碳-7-烯盐、8-甲基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵、8-甲基-1,8-二氮杂双环[5,4,0]十一碳-7-烯碘化铵、8-甲基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氢氧化铵、8-甲基-1,8-二氮杂双环[5,4,0]十一碳-7-烯甲基硫酸铵、8-乙基-1,8-二氮杂双环[5,4,0]十一碳-7-烯溴化铵、8-丙基-1,8-二氮杂双环[5,4,0]十一碳-7-烯溴化铵、8-十二烷基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵、8-十二烷基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氢氧化铵、8-二十烷基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵、8-二十四烷基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵、8-苄基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵(以下,称为DBU-B)、8-苄基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氢氧化铵、8-苯乙基-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵、8-(3-苯基丙基)-1,8-二氮杂双环[5,4,0]十一碳-7-烯氯化铵等。其中,优选为二烷基(C14-18)二甲基氯化铵。
此外,作为季盐,没有特别限定,可举出例如,四丁基氯化苄基三苯基氯化(以下,称为BTPPC)、苄基三甲基氯化苄基三丁基氯化三丁基烯丙基氯化三丁基-2-甲氧基丙基氯化苄基苯基(二甲基氨基)氯化等,其中,从硫化性、硫化物的物性方面考虑,优选为苄基三苯基氯化(BTPPC)。
此外,也可以使用季铵盐、季盐与双酚AF的固溶体、日本特开平11-147891号公报所公开的化合物。
此外,作为胺化合物,可举出例如,六亚甲基二胺氨基甲酸盐、N,N’-二亚肉桂基-1,6-六亚甲基二胺、4,4’-双(氨基环己基)甲烷氨基甲酸盐等。其中,优选为N,N’-二亚肉桂基-1,6-六亚甲基二胺。
作为本发明涉及的盐,可以使用市售品,可以使用例如,“LIPOQUAD2HT FLAKE”(Lion-Specialty-Chemicals株式会社制,二烷基(C14-18)二甲基氯化铵)。
在将本发明涉及的盐配合至上述卤素系橡胶(A)的情况下,通常,相对于卤素系橡胶(A)100质量份,优选为0.2质量份以上,更优选为0.2质量份以上10质量份以下,进一步优选为0.5质量份以上8质量份以下。如果以上述范围使用本发明涉及的盐,且与上述无机化合物(B)并用,则与层(2)的粘接强度得到进一步改良。
《其他成分》
在本发明涉及的形成层(1)的卤素系橡胶(A)中,除了上述添加剂以外,可以配合以下添加剂。
作为本发明涉及的其他成分,可举出填充剂、发泡剂、抗氧化剂、加工助剂、表面活性剂、耐候剂等通常被添加至橡胶组合物的各种添加剂成分。此外,也可以根据需要含有卤素系橡胶(A)以外的树脂或橡胶成分。
〈填充剂〉
作为本发明涉及的填充剂,可举出二氧化硅、活化碳酸钙、轻质碳酸钙、重质碳酸钙、微粉滑石、滑石、微粉硅酸、粘土等无机填充剂等。相对于卤素系橡胶(A)100质量份,这些填充剂通常可以设为0~300质量份,优选为0~200质量份左右。通过使用填充剂,从而能够获得提高了抗拉强度、撕裂强度和耐摩耗性等机械性质的层叠体,能够提高层叠体的硬度而不损害它的其他物性。
〈抗氧化剂〉
作为本发明涉及的抗氧化剂,具体而言,可举出:
苯基萘胺、4,4’-(α,α-二甲基苄基)二苯基胺、N,N’-二(2-萘基)对苯二胺等芳香族仲胺系稳定剂;
2,6-二叔丁基-4-甲基苯酚、四[亚甲基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯]甲烷等酚系稳定剂;
双[2-甲基-4-(3-正烷基硫代丙酰氧基)-5-叔丁基苯基]硫醚等硫醚系稳定剂;2-巯基苯并咪唑等苯并咪唑系稳定剂;
二丁基二硫代氨基甲酸镍等二硫代氨基甲酸盐系稳定剂;
2,2,4-三甲基-1,2-二氢喹啉的聚合物等喹啉系稳定剂等。它们可以单独使用,或可以组合使用2种以上。
在将本发明涉及的抗氧化剂配合至上述卤素系橡胶(A)的情况下,通常相对于卤素系橡胶(A)100质量份,可以以例如5质量份以下、优选为3质量份以下的量来使用。
〈表面活性剂〉
作为本发明涉及的表面活性剂,具体而言,可举出二正丁基胺、二环己基胺、单乙醇胺、三乙醇胺、“ACTING B(吉富制药株式会社制)、“ACTING SL(吉富制药株式会社制)等胺类、聚乙二醇、二甘醇、聚乙二醇、卵磷脂、偏苯三酸三烯丙酯、脂肪族和芳香族羧酸的锌化合物(例如:“Struktol activator 73”、“Struktol IB 531”、“Struktol FA541”Schill&Seilacher公司制)、“ZEONET ZP”(日本ZEON株式会社制)、十八烷基三甲基溴化铵、合成水滑石、特殊季铵化合物(例如:“LIPOQUAD 2HTF”(Lion-Specialty-Chemicals株式会社制、二烷基(C14-18)二甲基氯化铵)等。作为表面活性剂,最优选为LIPOQUAD 2HTF。
在将本发明涉及的表面活性剂配合至上述卤素系橡胶(A)的情况下,通常相对于卤素系橡胶(A)100质量份,例如为0.2~10质量份,优选为0.3~8质量份,进一步优选为0.3~7质量份,特别优选为0.5~7质量份,最优选为1~6质量份。表面活性剂可以根据其用途来适当选择,可以单独使用,也可以混合使用2种以上。
〈假凝胶防止剂〉
作为本发明涉及的假凝胶防止剂,可举出例如,“NHM-007”(三井化学公司制)。
在将本发明涉及的假凝胶防止剂配合至上述卤素系橡胶(A)的情况下,相对于卤素系橡胶(A)100质量份,通常为0.1~15质量份,优选为0.5~12质量份,进一步优选为1.0~10质量份。
在形成本发明涉及的层(1)的卤素系橡胶(A)中,可以根据需要进一步配合其他添加剂。作为其他添加剂,可举出耐热稳定剂、耐候稳定剂、抗静电剂、着色剂、润滑剂和增稠剂等。
<含卤素聚合物(C)>
形成本发明的层叠体的层(2)的含卤素聚合物(C)是排除了上述形成层(1)的卤素系橡胶(A)的聚合物。
本发明涉及的含卤素聚合物(C)为分子中包含卤原子的聚合物,优选为具有来源于含卤素单体的构成单元的聚合物。
作为本发明涉及的含卤素聚合物(C),优选为含氟原子的聚合物,进一步优选为氟系橡胶。
作为形成层(2)的含卤素聚合物(C),如果使用氟系橡胶,则能够获得耐热、耐油性优异的层叠体,因此优选。
《氟系橡胶》
作为本发明涉及的氟系橡胶,可举出例如1,1-二氟乙烯(VdF)/六氟丙烯(HFP)共聚物、VdF/四氟乙烯(TFE)/HFP共聚物、VdF/TFE/全氟(烷基乙烯基醚)(PAVE)共聚物、VdF/氯三氟乙烯(CTFE)共聚物等VdF/全卤代烯烃系弹性体;TFE/丙烯/VdF共聚物、HFP/乙烯/VdF共聚物等VdF/非全卤代烯烃系弹性体;TFE/PAVE共聚物等全氟弹性体;TFE/丙烯共聚物、HFP/乙烯共聚物等非全氟弹性体;氟硅橡胶等。
上述氟(烷基乙烯基醚)可以包含多个醚键。进一步优选氟系橡胶的分子量以数均分子量计为20,000~300,000,优选为50,000~200,000。
其中,从耐热性、耐油性、耐试剂性方面考虑,优选为VdF/HFP共聚物、VdF/TFE/HFP共聚物、VdF/TFE/PAVE共聚物、TFE/丙烯/VdF共聚物、HFP/乙烯/VdF共聚物、TFE/丙烯共聚物、HFP/乙烯共聚物的弹性体,特别优选为VdF/HFP共聚物、VdF/TFE/HFP共聚物的弹性体。
关于本发明涉及的氟系橡胶,作为含有交联性基团的单元,可以将具有多个乙烯基、烯丙基的多官能单体、含碘、溴的单体进行共聚。此外,可以通过实施热处理等,促进脱氢氟酸而使分子中生成作为交联点的双键。特别优选为使用碘化烯烃、溴化烯烃作为交联性单元,具有来源于碘化烯烃的构成单元或来源于溴化烯烃的构成单元的氟系橡胶。
此外,氟系橡胶中的交联点含量(例如,在使用溴化烯烃作为交联性单元的情况下,来源于溴化烯烃的构成单元的含量)优选为0.05~5摩尔%,进一步优选为0.15~3摩尔%,特别优选为0.25~2摩尔%。如果交联点低于上述含量,则密封性、粘接强度变得不充分,如果多于上述含量,则伸长率、柔软性变低等,可能会失去橡胶弹性。
〈多元醇系交联剂〉
本发明涉及的形成层(2)的含卤素聚合物(C)优选包含多元醇系交联剂。
作为本发明涉及的多元醇系交联剂,优选为双酚类。具体而言,可举出例如,2,2’-双(4-羟基苯基)丙烷[双酚A]、2,2-双(4-羟基苯基)六氟丙烷[双酚AF]、双(4-羟基苯基)砜[双酚S]、双酚A双(二苯基磷酸酯)、4,4’-二羟基联苯、4,4’-二羟基二苯基甲烷、2,2-双(4-羟基苯基)丁烷[双酚B]等多羟基芳香族化合物。
作为本发明涉及的多元醇系交联剂,可优选使用双酚A、双酚AF。此外,作为多元醇系交联剂,也可以使用上述多羟基芳香族化合物的碱金属盐或碱土金属盐。
此外,作为多元醇系交联剂,可以使用包含原料橡胶和多元醇系交联剂的市售的母料。作为市售的母料,可举出例如Curative VC#30(杜邦陶氏弹性体公司制:含有交联剂〔双酚AF〕50wt%)等。
本发明涉及的多元醇系交联剂可以使用1种或可以组合使用2种以上。
在本发明涉及的形成层(2)的上述含卤素聚合物(C)中配合上述多元醇系交联剂的情况下,相对于含卤素聚合物(C)100质量份,期望以0.5~10质量份、优选为1.0~8.0质量份、进一步优选为1.5~6.0质量份的范围来使用。
如果形成层(2)的上述含卤素聚合物(C)包含上述多元醇系交联剂,则所得的层叠体能够获得与层(1)的剥离强度更优异的层叠体。
本发明涉及的层(2)可以使用包含作为含卤素聚合物的氟系橡胶和上述多元醇系交联剂的市售的组合物来形成。作为包含氟系橡胶和多元醇系交联剂的市售的组合物,可举出例如,DAI-EL DC-2270F、DAI-EL DC-4070(均为大金工业制)。DAI-EL DC-2270F是除了氟系橡胶以外还包含多元醇系交联剂、填充剂、吸酸剂的组合物,DAI-EL DC-4070是除了氟系橡胶以外还包含有机过氧化物、填充剂的组合物。
此外,在本发明涉及的形成层(2)的含卤素聚合物(C)中,与上述卤素系橡胶(A)同样地,能够以上述记载的量添加通常配合至橡胶的各种添加剂。
在本发明涉及的形成层(2)的含卤素聚合物(C)中,作为填充剂,可以使用氢氧化镁、氢氧化铝、氢氧化钙等金属氢氧化物;碳酸镁、碳酸铝、碳酸钙、碳酸钡等碳酸盐;硅酸镁、硅酸钙、硅酸钠、硅酸铝等硅酸盐;硫酸铝、硫酸钙、硫酸钡等硫酸盐;合成水滑石、二硫化钼、硫化铁、硫化铜等金属硫化物;湿式二氧化硅、干式二氧化硅、石英微粉末、玻璃纤维等氧化硅类;硅藻土、石棉、锌钡白(硫化锌/硫化钡)、石墨、炭黑、氟化碳、氟化钙、焦炭、滑石、云母粉末、硅灰石、碳纤维、芳纶纤维、各种晶须等无机填充剂、以及有机增强剂、有机填充剂等。
此外,在含卤素聚合物中,作为其他成分,可以任意配合吸酸剂、紫外线吸收剂、阻燃剂、耐油性改进剂、防焦剂、增粘剂等。
<层叠体>
本发明的层叠体是上述层(1)与上述层(2)直接接合而成的层叠体。
作为构成本发明的层叠体的层(1)和层(2)的厚度,没有特别限定,层(1)通常为1~30mm,优选为1~5mm,层(2)通常为1~30mm,优选为1~5mm。此外,作为层叠体整体的厚度,没有特别限定,通常为5~31mm,优选为5~20mm。
本发明的层叠体只要具有上述层(1)与上述层(2)直接接合而成的层,则不限于仅该层,可以在层(1)的外侧〔没有接合层(2)的面〕、或层(2)的外侧〔没有接合层(1)的面〕层叠其他层。
<层叠体的制造方法>
作为本发明的层叠体的制造方法,没有特别限定,可举出例如通过以下方法(a)~(c)来获得层叠体的方法。另外,通过方法(a)~(c)获得了层叠体之后,可以进行交联工序,或者也可以在一次硫化后利用烘箱等进行二次硫化工序,获得具有包含交联后的聚合物或橡胶的层的层叠体。
(a)将构成层(1)的材料和构成层(2)的材料分别利用捏合机、辊、班伯里密炼机、混炼机等混合机进行混炼,通过利用挤出机同时挤出,从而获得层(1)与层(2)直接接合的层叠体的方法。
(b)将构成层(1)的材料利用捏合机、辊、班伯里密炼机、混炼机等混合机进行混炼,通过利用挤出机进行挤出,从而形成层(1),将构成层(2)的材料利用捏合机、辊、班伯里密炼机、混炼机等混合机进行混炼,通过利用挤出机挤出至层(1)上,从而使层(1)与层(2)直接接合的方法。
(c)将构成层(2)的材料利用捏合机、辊、班伯里密炼机、混炼机等混合机进行混炼,通过利用挤出机进行挤出,从而形成层(2),将构成层(1)的材料利用捏合机、辊、班伯里密炼机、混炼机等混合机进行混炼,通过利用挤出机挤出至层(2)上,从而使层(2)与层(1)直接接合的方法。
另外,在制造层叠体时,从提高层(1)与层(2)的剥离强度的观点考虑,优选对将层(1)和层(2)直接接合而成的层叠体进行加压成型。
(交联工序、一次硫化)
作为交联工序或一次硫化,可举出:对于构成上述层(1)、层(2)的材料预先配合交联剂等交联时所需要的成分,通过加热(例如150~240℃)来进行交联的工序;通过将电子射线(例如具有0.1~10MeV的能量的电子射线)照射于层叠体而进行交联的工序。另外,上述电子射线的照射按照层叠体的吸收剂量通常成为0.5~36Mrad、优选为0.5~20Mrad、更优选为1~10Mrad的方式来进行。
另外,在上述交联工序或一次硫化中,从提高层(1)与层(2)的剥离强度的观点考虑,优选在通过加热进行交联时,一边进行加压成型一边进行加热。
(二次硫化)
二次硫化是在上述一次硫化之后进行的工序,是通过进行加热(例如150~200℃),从而充分促进硫化(交联)的工序。
<用途>
本发明的层叠体能够用于各种用途。本发明的层叠体能够作为例如用于汽车、摩托车、工业机械、建设机械或农业机械的构件来使用。作为该构件的具体例,可举出工业用辊、垫片(例如冷凝器垫片)、垫圈、带(例如,绝热传送带、复印机带、运输带)、汽车用软管等软管类(例如,涡轮增压器软管、输水软管、制动液储罐软管、散热器软管、空气软管)、防振橡胶、防振材或减振材(例如,发动机架、电动机架)、消声器吊胶、电缆(点火电缆、包胶电缆、高压电缆)、电线被覆材(高压电线被覆材、低压电线被覆材、船舶用电线被覆材)、窗导槽密封条、彩色表皮材、送纸辊、屋顶板等。
其中,本发明的层叠体可以在汽车用内外装部件、要求耐热性的用途中适当地使用。作为层叠体的用途,例如,可举出具有本发明的层叠体作为至少一部分的软管。作为软管,并不限定其用途,但优选在用于汽车、摩托车、工业机械、建设机械或农业机械的任一用途中使用。更具体而言,可举出涡轮增压器软管、制动液储罐软管、散热器软管等,特别优选用于汽车用涡轮增压器软管。
本发明的软管只要具有本发明的层叠体作为至少一部分即可,也可以为仅由本发明的层叠体形成的软管。
本发明的层叠体适合作为涡轮增压器软管。
本发明的涡轮增压器软管的制造方法没有特别限定,可举出例如如下方法:通过挤出成型、共挤出成型、片状物的卷绕或它们的组合,将具有层状结构的未固化的涡轮增压器软管(层叠体)成型,使用蒸汽等进行加热,从而获得涡轮增压器软管(层叠体)的方法。未固化的涡轮增压器软管优选不进行收缩、变形,保持形状的能力高。
实施例
接下来,对于本发明,示出实施例来进一步详细地说明,但本发明不受这些实施例的限定。
(测定、评价方法)
在以下制造例、实施例和比较例中,各特性的测定和评价方法如下。
(T型剥离试验)
采用以下方法来测定层叠体的剥离强度。
将由实施例、比较例获得的层叠体以测定温度:23.0℃、试验速度:200.0mm/min、试验片宽度:25.0mm实施T型剥离试验,测定剥离强度。
以下示出本发明的实施例和比较例所使用的卤素系橡胶(A)等。
《卤素系橡胶(A)》
〈丙烯酸类橡胶(ACM)〉
Nipol AR-12:以丙烯酸酯作为骨架主成分的丙烯酸类橡胶,日本ZEON公司制
〈表氯醇橡胶(ECO)〉
Epichlomer H:表氯醇橡胶,株式会社大阪soda制
《含卤素聚合物(C)》
〈氟系橡胶〉
DAI-EL DC-2270F:全复合物(full compound),二元多元醇硫化系,比重1.85,ML(1+10)100℃:约115,大金工业(株)制
另外,DAI-EL DC-2270F又称为“多元醇系FKM”。
[实施例1]
《形成层(1)的ACM组合物的制备》
作为第一阶段,使用BB-2型班伯里密炼机(神户制钢所制),将100质量份的ACM素炼30秒,接着在其中加入60质量份的HAF炭黑(旭#70G,旭CARBON(株)公司制)、1质量份的硬脂酸和2质量份的4,4’-双(α,α-二甲基苄基)二苯基胺(NOCRAC CD,大内新兴化学(株)制),在140℃混炼2分钟。然后,使上顶栓(ram)上升进行清洁,进一步,进行1分钟混炼,在约150℃排出,获得了第一阶段的配合物。
接下来,作为第二阶段,将由第一阶段获得的配合物卷绕于8英寸辊(日本ROLL(株)公司制,前辊的表面温度50℃,后辊的表面温度50℃,前辊的转速16rpm,后辊的转速18rpm),添加20质量份的水滑石(DHT-4A,协和化学工业株式会社制)、1质量份的聚氧乙烯硬脂基醚磷酸(PHOSPHANOL PL-210:东邦化学工业(株)制)、0.5质量份的(6-氨基己基)氨基甲酸(Diak No.1:杜邦公司制)、2质量份的1,3-二邻甲苯基胍(NOCCELER DT,大内新兴化学工业(株)制),混炼10分钟,获得了未交联的橡胶组合物(橡胶配合物)(包含ACM的组合物)。
《形成层(2)的氟系橡胶组合物的制备》
(氟系橡胶组合物)
作为氟系橡胶组合物,使用了DAI-EL DC-2270F(大金工业制:多元醇交联型氟系橡胶复合物)。DAI-EL DC-2270F是除了氟系橡胶以外还包含多元醇系交联剂(双酚AF)、交联促进剂(季盐)、填充剂、吸酸剂的组合物。
《层叠体的制备、评价》
(T型剥离试验用的层叠体的制备)
将上述包含ACM的组合物和上述氟系橡胶组合物分别制成片状。接下来将制成的未硫化橡胶片(包含ACM的组合物和氟系橡胶组合物)50g分别单独地利用露米勒(LUMIRROR)(拉伸聚酯(聚对苯二甲酸乙二醇酯)膜)从上下夹持。将上下被露米勒夹持的各未硫化橡胶片使用50吨加压成型机,在120℃加压2分钟,制作t(厚度)=1mm,20cm见方的未硫化橡胶片。
接下来,将进行了上述加压后的、由包含ACM的组合物获得的未硫化橡胶片〔层(1)〕和由氟系橡胶组合物获得的未硫化橡胶片〔层(2)〕分别裁切成后述的正式加压尺寸(15cm×15cm×t=1mm)。裁切之后将上下的露米勒剥离,接下来将各个未硫化橡胶片重叠。重叠时,以在未硫化橡胶片的一部分(宽度3cm,长度15cm:剥离试验时的抓取边缘)夹入特氟隆(注册商标)树脂片(t=0.2mm)的状态,使上述未硫化橡胶片重叠。
使用100吨加压成型机,将在上述一部分夹入了特氟隆(注册商标)树脂片的、重叠后的未硫化橡胶片在180℃加压10分钟(正式加压),制备出厚度2mm的交联橡胶片(层叠体)。
从交联橡胶片(层叠体)将特氟隆(注册商标)树脂片除去,利用上述记载的方法,对交联橡胶片(层叠体)进行了T型剥离试验。
将结果示于表1中。
[实施例2~12]
代替实施例1所使用的形成层(1)的ACM组合物,使用以表1所记载的配合量添加各种配合剂而获得的ACM组合物,除此以外,与实施例1同样地进行,制作层叠体,利用实施例1所记载的方法,进行了T型剥离试验。
将结果示于表1-1和表1-2中。
[比较例1]
代替实施例1所使用的形成层(1)的ACM组合物,以表1-2所记载的配合量〔不配合水滑石等无机化合物(B)〕来使用,除此以外,与实施例1同样地进行,制作层叠体,利用实施例1所记载的方法,进行了T型剥离试验。
将结果示于表1-2中。
[参考例1]
代替实施例1所使用的形成层(1)的ACM组合物,以表1-2所记载的配合量〔不配合水滑石等无机化合物(B)〕来使用,除此以外,与实施例1同样地进行,制作层叠体,利用实施例1所记载的方法,进行了T型剥离试验。
将结果示于表1-2中。
[表1-1]
[表1-2]
[实施例13]
代替实施例1所使用的形成层(1)的ACM组合物,使用由以下方法制备的由包含ECO的组合物形成的层(1),除此以外,与实施例1同样地进行,制作层叠体,利用实施例1所记载的方法,进行了T型剥离试验。
将结果示于表2中。
《形成层(1)的ECO组合物的制备》
作为第一阶段,使用BB-2型班伯里密炼机(神户制钢所制),将100质量份的ECO素炼30秒,接着在其中加入40质量份的MAF炭黑(Seast 116:东海CARBON(株)制)、1质量份的硬脂酸(珠硬脂酸山茶(Beads STEARIC ACID CAMELLIA):日油公司制)、3质量份的氧化镁(KYOWAMAG 150:协和化学工业公司制)、1质量份的二丁基二硫代氨基甲酸镍(NOCRAC NBC:大内新兴化学工业(株)制)、5质量份的碳酸钙(Whiton SB(红):备北粉化工业(株)制),在140℃混炼2分钟。然后,使上顶栓上升,进行清洁,进一步,进行1分钟混炼,在约150℃排出,获得了第一阶段的配合物。
接下来,作为第二阶段,将由第一阶段获得的配合物卷绕于8英寸辊(日本ROLL(株)公司制,前辊的表面温度50℃,后辊的表面温度50℃,前辊的转速16rpm,后辊的转速18rpm),添加20质量份的水滑石(DHT-4A,协和化学工业株式会社制)、1.2质量份的2,4,6-三巯基-S-三嗪(NOCCELER TCA:大内新兴化学工业(株)制)、0.5质量份的四甲基秋兰姆二硫醚(NOCCELER TT:大内新兴化学工业(株)制),混炼10分钟,获得了未交联的橡胶组合物(橡胶配合物)(包含ECO的组合物)。
[实施例14~18]
代替实施例13所使用的形成层(1)的ECO组合物,使用以表2所记载的配合量添加各种配合剂而获得的ECO组合物,除此以外,与实施例1同样地进行,制作层叠体,利用实施例13所记载的方法,进行了T型剥离试验。
将结果示于表2中。
[比较例2]
代替实施例13所使用的形成层(1)的ECO组合物,以表2所记载的配合量〔不配合水滑石等无机化合物(B)〕来使用,除此以外,与实施例5同样地进行,制作层叠体,利用实施例13所记载的方法,进行了T型剥离试验。
将结果示于表2中。
[参考例2]
代替实施例13所使用的形成层(1)的ECO组合物,以表2所记载的配合量〔不配合水滑石等无机化合物(B)〕来使用,除此以外,与实施例5同样地进行,制作层叠体,利用实施例13所记载的方法,进行了T型剥离试验。
将结果示于表2中。
[表2]
〈层叠软管的制造例1〉
使用2台挤出机,对于2层成型用模具,以成为内层(实施例1的氟系橡胶组合物)厚度=1mm,外层(实施例1的ACM组合物)厚度=2mm,软管内径=10mm,软管外径=16mm的方式,以挤出头温度=80℃,挤出速度为2m/分钟~5m/分钟挤出层叠软管。然后,利用蒸汽硫化(150℃~160℃,30分钟~50分钟)进行加热,将层叠软管交联,确认了软管外观平滑并且内层与外层牢固地粘接。
〈层叠软管的制造例2〉
对于实施例2~8所记载的各ACM组合物或ECO组合物,也同样地成型与氟系橡胶的多层软管,确认了软管外观平滑并且内层与外层牢固地粘接。
Claims (10)
1.一种层叠体,其是下述层(1)和下述层(2)直接接合而成的,
层(1):由包含卤素系橡胶(A)100质量份和无机化合物(B)1~30质量份的组合物形成的层,卤素系橡胶(A)中,氟系橡胶除外,所述无机化合物(B)含有选自第2族元素和第13族元素中的至少1种元素及氧,
层(2):由含卤素聚合物(C)形成的层,含卤素聚合物(C)中,层(1)的卤素系橡胶除外。
2.根据权利要求1所述的层叠体,卤素系橡胶(A)为选自表氯醇橡胶(ECO)和丙烯酸类橡胶(ACM)中的1种以上。
3.根据权利要求1所述的层叠体,含卤素聚合物(C)为氟系橡胶。
4.根据权利要求1所述的层叠体,层(2)由多元醇系的交联剂交联而成。
5.根据权利要求1所述的层叠体,无机化合物(B)为包含选自镁、钙、钡、铝中的1种以上元素的化合物。
6.根据权利要求1所述的层叠体,无机化合物(B)为选自氧化镁和水滑石中的1种以上的化合物。
7.一种软管,其至少一部分具有权利要求1~6中任一项所述的层叠体。
8.根据权利要求7所述的软管,其用于汽车用途、摩托车用途、工业机械用途、建设机械用途或农业机械用途中的任一用途。
9.根据权利要求7所述的软管,其用于汽车用涡轮增压器软管。
10.一种层叠体的制造方法,其特征在于:将下述层(1)和下述层(2)直接接合,
层(1):由包含卤素系橡胶(A)100质量份和无机化合物(B)10~30质量份的组合物形成的层,卤素系橡胶(A)中,氟系橡胶除外,所述无机化合物(B)含有选自第2族元素和第13族元素中的至少1种元素及氧,
层(2):由含卤素聚合物(C)形成的层,含卤素聚合物(C)中,层(1)的卤素系橡胶除外。
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