JPH02141237A - Rubber laminate - Google Patents
Rubber laminateInfo
- Publication number
- JPH02141237A JPH02141237A JP29358588A JP29358588A JPH02141237A JP H02141237 A JPH02141237 A JP H02141237A JP 29358588 A JP29358588 A JP 29358588A JP 29358588 A JP29358588 A JP 29358588A JP H02141237 A JPH02141237 A JP H02141237A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- sulfur
- chlorinated polyethylene
- composition
- weight
- 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 title claims abstract description 51
- 239000005060 rubber Substances 0.000 title claims abstract description 51
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 10
- 229920003244 diene elastomer Polymers 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 238000013040 rubber vulcanization Methods 0.000 claims description 8
- 230000001603 reducing effect Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 19
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 4
- 229910000765 intermetallic Inorganic materials 0.000 abstract 4
- 125000002897 diene group Chemical group 0.000 abstract 3
- 238000013329 compounding Methods 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- 238000009472 formulation Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- -1 triazinethiol compound Chemical class 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000358 iron sulfate Inorganic materials 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229940120693 copper naphthenate Drugs 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000010058 rubber compounding Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010059 sulfur vulcanization Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-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
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-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
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-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
- 239000004135 Bone phosphate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- RMMPZDDLWLALLJ-UHFFFAOYSA-N Thermophillin Chemical compound COC1=CC(=O)C(OC)=CC1=O RMMPZDDLWLALLJ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical class N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- YFRNYWVKHCQRPE-UHFFFAOYSA-N buta-1,3-diene;prop-2-enoic acid Chemical compound C=CC=C.OC(=O)C=C YFRNYWVKHCQRPE-UHFFFAOYSA-N 0.000 description 1
- UJYLYGDHTIVYRI-UHFFFAOYSA-N cadmium(2+);ethane Chemical compound [Cd+2].[CH2-]C.[CH2-]C UJYLYGDHTIVYRI-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- PRJQLUNGZQZONS-UHFFFAOYSA-N chloro(diethyl)borane Chemical compound CCB(Cl)CC PRJQLUNGZQZONS-UHFFFAOYSA-N 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- VLAGSAGYAIGJSU-UHFFFAOYSA-N hexanoyl hexaneperoxoate Chemical compound CCCCCC(=O)OOC(=O)CCCCC VLAGSAGYAIGJSU-UHFFFAOYSA-N 0.000 description 1
- ZHFOZEBDSIVYQP-UHFFFAOYSA-N hydrogen peroxide;methane Chemical compound C.OO ZHFOZEBDSIVYQP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 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 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はゴム積層体に関する。詳しくは塩素化ポリエチ
レン組成物と硫黄加硫可能なジエン系ゴム組成物から成
るゴム積層体に関する。更に詳しくは塩素化ポリエチレ
ン組成物と硫黄加硫可能なジエン系ゴム組成物の層間が
極めて強固に加硫接着されるゴム積層体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rubber laminate. Specifically, the present invention relates to a rubber laminate comprising a chlorinated polyethylene composition and a sulfur-vulcanizable diene rubber composition. More specifically, the present invention relates to a rubber laminate in which the layers of a chlorinated polyethylene composition and a sulfur-vulcanizable diene rubber composition are bonded together by extremely strong vulcanization.
そして本発明のゴム積層体はゴムライニング、ゴムロー
ル、ゴムライニング、ゴムマット、ゴムケーブル、ゴム
磁石等のゴム製品として使用される。The rubber laminate of the present invention is used as rubber products such as rubber linings, rubber rolls, rubber linings, rubber mats, rubber cables, and rubber magnets.
（従来の技術）
塩素化ポリエチレンは、耐候性、耐熱老化性、耐オゾン
性、難燃性、明色性等の化学的、物理的性質の優れたゴ
ムである。一方、硫黄加硫可能な各種のジエン系ゴムは
塩素化ポリエチレンに比べて、ゴム弾性が高い、圧縮永
久歪が小さい、引裂き抵抗が大きい、屈曲亀裂抵抗性が
ある、或いはガス透過が小さい等の特徴を有するが、耐
候性、耐熱老化性、耐オゾン性、難燃性、明色性等の点
で劣る。このことから、硫黄加硫可能なジエン系ゴムの
優れた性質と塩素化ポリエチレンの優れた性質を供えた
ゴム製品を得るために、塩素化ボリエチレンを外側の保
護層とし、硫黄加硫可能なジエン系ゴムを内層としたゴ
ム積層体のゴム製品が製造されている。またゴム製品に
特殊な物理的あるいは機械的性質を持たせるたるために
、塩素化ポリエチレン層と硫黄加硫可能なジエン系ゴム
層の多層から成るゴム積層体製品が製造されている。(Prior Art) Chlorinated polyethylene is a rubber with excellent chemical and physical properties such as weather resistance, heat aging resistance, ozone resistance, flame retardance, and brightness. On the other hand, various diene rubbers that can be sulfur-vulcanized have higher rubber elasticity, lower compression set, higher tear resistance, flex crack resistance, or lower gas permeation than chlorinated polyethylene. However, it is inferior in terms of weather resistance, heat aging resistance, ozone resistance, flame retardance, brightness, etc. Therefore, in order to obtain rubber products that have the excellent properties of sulfur-vulcanizable diene-based rubber and the excellent properties of chlorinated polyethylene, we used chlorinated polyethylene as an outer protective layer and used sulfur-vulcanizable diene rubber as an outer protective layer. Rubber products are manufactured in the form of rubber laminates with an inner layer of rubber. In addition, in order to impart special physical or mechanical properties to rubber products, rubber laminate products are manufactured which consist of multiple layers of chlorinated polyethylene layers and sulfur-vulcanizable diene rubber layers.
一般に、塩素化ポリエチレンの加硫系はチオウレア系加
硫促進剤と金属化合物の系、有機過酸化物と金属化合物
の系、あるいはトリアジンチオール化合物と金属化合物
の系で加硫される。硫黄加硫可能なジエン系ゴムは硫黄
とゴム用加硫促進剤の系或いは有機過酸化物を使用して
加硫される。Generally, chlorinated polyethylene is vulcanized using a thiourea vulcanization accelerator and a metal compound, an organic peroxide and a metal compound, or a triazinethiol compound and a metal compound. Sulfur vulcanizable diene rubbers are vulcanized using a sulfur and rubber vulcanization accelerator system or an organic peroxide.
この塩素化ポリエチレンと硫黄加硫可能なジエン系ゴム
を接管加硫するに際し、塩素化ポリエチレンの加硫系と
硫黄加硫可能なジエン系ゴムの加硫系の如何なる加硫系
の組合せにおいても、加硫接着した後の層間の剥離強度
は極めて弱い。When vulcanizing this chlorinated polyethylene and sulfur-vulcanizable diene rubber in a pipe, no matter what combination of vulcanization systems, chlorinated polyethylene vulcanization system and sulfur-curable diene rubber vulcanization system, The peel strength between the layers after vulcanization adhesion is extremely weak.
このためゴム積層体の層間の剥離によりゴム製品の化学
的、物理的あるいは機械的性質が劣り、ゴム積層体とし
て満足されるものは得られていないのである。掛ること
から、塩素化ポリエチレン層と硫黄加硫可能なジエン系
ゴム層を加硫接着した後の層間の剥離強度が極めて強い
ゴム積層体の出現が強く望まれているのが現状である。For this reason, the chemical, physical, or mechanical properties of the rubber product are deteriorated due to delamination between the layers of the rubber laminate, and a satisfactory rubber laminate cannot be obtained. Therefore, there is currently a strong desire for a rubber laminate that has extremely strong interlayer peel strength after vulcanization bonding of a chlorinated polyethylene layer and a sulfur-vulcanizable diene rubber layer.
（発明が解決しようとする課題）
本発明者らは、上記問題点の解消と要望に答えるべく鋭
意研究の結果、本発明の塩素化ポリエチレン組成物と硫
黄加硫可能なジエン系ゴム組成物から成るゴム積層体を
提供するものである。(Problems to be Solved by the Invention) As a result of intensive research to solve the above problems and meet the demands, the present inventors have developed a chlorinated polyethylene composition of the present invention and a sulfur-vulcanizable diene rubber composition. The present invention provides a rubber laminate consisting of:
本発明は上述したごときに、層間の剥離強度が極めて弱
いものであった塩素化ポリエチレン層と硫黄加硫可能な
ジエン系ゴム層の層間の剥離強度を極めて強固な剥離強
度としたゴム積層体を提供するものである。As described above, the present invention provides a rubber laminate that has an extremely strong peel strength between a chlorinated polyethylene layer and a sulfur-vulcanizable diene rubber layer, which had an extremely weak peel strength. This is what we provide.
（課題を解決するための手段）
本発明の特徴は塩素化ポリエチレンに有機過酸化物と金
属化合物を配合した組成物と硫黄加硫可能なジエン系ゴ
ムに還元作用を何する無機及び／又は自゛機の金属塩と
金属化合物を配合したわ１成物からなるゴム積層体にあ
る。(Means for Solving the Problems) The present invention is characterized by a composition in which chlorinated polyethylene is blended with an organic peroxide and a metal compound, and an inorganic and/or organic compound that has a reducing effect on a sulfur-vulcanizable diene rubber. This is a rubber laminate made of a mixture of organic metal salts and metal compounds.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において使用される塩素化ポリエチレンとは、ポ
リエチレン、エチレン−ブテン−１共重合体、エチレン
−プロピレン共重合体、エチレン−酢酸ビニル共重合体
等に塩素を導入しゴム状にしたものである。塩素の導入
は該記ポリマーの粉末又は粒子を水に懸濁させて、塩素
ガスを吹込み塩素化するか、該記ポリマーを四塩化炭素
等の有機溶剤に溶解し塩素ガスを吹込み塩素化する方法
によって塩素が導入される。塩素化ポリエチレンはゴム
状であれば特に塩素量は限定されないが、塩素量が１５
〜５５重菅％、好ましくは３０〜４０重量％の塩素化ポ
リエチレンがゴム状にある。The chlorinated polyethylene used in the present invention is polyethylene, ethylene-butene-1 copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, etc., made into rubber by introducing chlorine. . Chlorine can be introduced by suspending the powder or particles of the polymer in water and blowing chlorine gas into it to chlorinate it, or by dissolving the polymer in an organic solvent such as carbon tetrachloride and blowing chlorine gas into it to chlorinate it. Chlorine is introduced by the following method. The amount of chlorine in chlorinated polyethylene is not particularly limited as long as it is rubbery, but if the amount of chlorine is 15
~55% by weight, preferably 30-40% by weight of chlorinated polyethylene is in rubbery form.
本発明の塩素化ポリエチレンに配合される有機過酸化物
としては、ケトンパーオキサイド、ハイドロパーオキサ
イド、ジアルキルパーオキサイド、ジアシルパーオキサ
イド、パーオキシエステル類等であって、例えばメチル
エチルケトンパーオキサイド、シクロヘキサンパーオキ
サイド、ケトンパーオキサイド、ｔ−ブチルハイドロパ
ーオキサイド、クメンハイドロパーオキサイド、ジ−イ
ソプロピルベンゼンハイ！・ドロパーオキサイド、Ｐメ
タンハイドロパーオキサイド、２．５−ジメチルヘキサ
ン−２，５−シバイドロバ−オキサイド、ジ−ｔ−ブチ
ルパーオキサイド、ｔ−ブチルクミルパーオキサイド、
ジ−クミルパーオキサイド、２，５−ジーメチルージ（
ｔ−ブチルパーオキシ）ヘキサン、アセチルパーオキサ
イド、プロピオニルパーオキサイド、イソ−ブチルパー
オキサイド、オクタノイルパーオキサイド、デカノイル
パーオキサイド、ラウロイルパーオキサイド、ステアロ
イルパーオキサイド、３，３．５−１−リーメチルヘキ
サノイルバーオキサイド、ベンゾイルパーオキサイド、
ｐ−クロロベンゾイルパーオキサイド、２．４−ジ−ク
ロロベンゾイルパーオキサイド、ｔ−ブチルパーオキシ
アセテ−１・、を−ブチルパーオキシイソブチレート、
ｔ−ブチルパーオキシビバレート、ｔ−ブチルパーオキ
シラウレート等が挙げられる。これらは塩素化ポリエチ
レンにｔｌｔ独または混合して配合される。配合される
有機過酸化物の量は、塩素化ポリエチレン１００ｆｆｉ
量部当たり０．１〜２５重量部、好ましくは０．５〜１
５重量部、更に好ましくは１〜１０市は部の範囲におい
て使用される。有機過酸化物０．１重量部未満では塩素
化ポリエチレンの加硫に長い時間を要し実用性に欠ける
。２５重量部を越えて配合した場合、塩素化ポリエチレ
ンの機械的性質が劣り好ましくないのである。Examples of organic peroxides to be blended into the chlorinated polyethylene of the present invention include ketone peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxy esters, such as methyl ethyl ketone peroxide and cyclohexane peroxide. , ketone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene!・Droperoxide, P methane hydroperoxide, 2,5-dimethylhexane-2,5-sibide roberoxide, di-t-butyl peroxide, t-butylcumyl peroxide,
Dicumyl peroxide, 2,5-dimethyldi(
t-butyl peroxide) hexane, acetyl peroxide, propionyl peroxide, iso-butyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 3,3.5-1-lymethyl hexanoyl peroxide, benzoyl peroxide,
p-chlorobenzoyl peroxide, 2,4-di-chlorobenzoyl peroxide, t-butylperoxyacetate-1, -butylperoxyisobutyrate,
Examples include t-butyl peroxybivalate and t-butyl peroxylaurate. These are blended into chlorinated polyethylene either alone or as a mixture. The amount of organic peroxide blended is 100ffi of chlorinated polyethylene.
0.1 to 25 parts by weight per part, preferably 0.5 to 1 part by weight
A range of 5 parts by weight, more preferably 1 to 10 parts, is used. If the amount of organic peroxide is less than 0.1 part by weight, vulcanization of the chlorinated polyethylene takes a long time and is impractical. If more than 25 parts by weight is added, the mechanical properties of the chlorinated polyethylene will deteriorate, which is not preferable.
塩素化ポリエチレンに配合される金属化合物とは塩素化
ポリエチレンの加硫時に遊離する塩酸を捕捉するもので
あって、金属酸化物、有機鉛化合物、金属水酸化物、脂
肪酸金属石鹸類があり、例えば酸化マグネシウム、酸化
カルシウム、酸化亜鉛、−酸化鉛、四三酸化鉛、三塩基
性マレイン酸鉛、二塩基性フタル酸鉛、三塩基性硫酸鉛
、二塩基性亜燐酸鉛、水酸化カルシウム、ステアリン酸
ソーダ、ステアリン酸マグネシウム、ステアリン酸カル
シウム、ステアリン酸鉛等が挙げられる。The metal compounds added to chlorinated polyethylene are those that capture hydrochloric acid liberated during vulcanization of chlorinated polyethylene, and include metal oxides, organic lead compounds, metal hydroxides, and fatty acid metal soaps. Magnesium oxide, calcium oxide, zinc oxide, -lead oxide, trilead tetroxide, tribasic lead maleate, dibasic lead phthalate, tribasic lead sulfate, dibasic lead phosphite, calcium hydroxide, stearin Examples include acid soda, magnesium stearate, calcium stearate, lead stearate, and the like.
これらは単独もしくは混合して配合される。配合される
量は塩素化ポリエチレン１００重４部当たり０．１〜３
０ｆｆｆ量部、好ましくは５〜２０重量部が配合される
。この配合される量は塩素化ポリエチレンに極く一般的
に使用される量である。These may be used alone or in combination. The amount to be blended is 0.1 to 3 per 4 parts by weight of chlorinated polyethylene.
0fff parts, preferably 5 to 20 parts by weight. This amount is the amount commonly used for chlorinated polyethylene.
本発明の硫黄加硫可能なジエン系ゴムとは一般に硫黄と
ゴム用加硫促進剤によって加硫される硫黄加硫可能なジ
エン系ゴムであって、これらには天然ゴムおよび共役二
重結合をもつ単量体を主体として造られた重合体および
共重合体、例えばインプレンゴム、スチレン−ブタジェ
ンゴム、ブタジェンゴム、インブチレン−イソプレンゴ
ム、アクリルニトリル−ブタジェンゴム、アクリレート
−ブタジェンゴム等がある。そして本発明に使用される
硫黄加硫可能なジエン系ゴムは硫黄とコム用加硫促進剤
によって加硫される。The sulfur-vulcanizable diene rubber of the present invention is generally a sulfur-vulcanizable diene rubber that is vulcanized with sulfur and a rubber vulcanization accelerator, and includes natural rubber and a conjugated double bond. There are polymers and copolymers made mainly from monomers having the following properties, such as imprene rubber, styrene-butadiene rubber, butadiene rubber, imbutylene-isoprene rubber, acrylonitrile-butadiene rubber, and acrylate-butadiene rubber. The sulfur-vulcanizable diene rubber used in the present invention is vulcanized with sulfur and a comb vulcanization accelerator.
本発明の硫黄加硫可能なジエン系ゴムに配合される硫黄
とは、ジエン系ゴムの加硫剤として使用される硫黄或い
は硫黄化合物であって、例えば粉末硫黄、硫黄華、沈降
硫黄、コロイド硫黄、塩化硫黄、二塩化硫黄、モルホリ
ン・ジサルファイド、アルキル・フェノール・ジサルフ
ァイド等が挙げられる。これらはｊド独または混合して
使用される。The sulfur compounded in the sulfur-curable diene rubber of the present invention is sulfur or a sulfur compound used as a vulcanizing agent for diene rubber, such as powdered sulfur, sulfur flower, precipitated sulfur, and colloidal sulfur. , sulfur chloride, sulfur dichloride, morpholine disulfide, alkyl phenol disulfide, and the like. These are used in combination or in combination.
配合される量は、硫黄加硫可能なジエン系ゴム１００市
巳部当たり０．１〜５重量部が配合される。この量は硫
黄加硫可能なジエン系ゴムに極く一般的に使用される量
である。The amount to be blended is 0.1 to 5 parts by weight per 100 parts of sulfur-vulcanizable diene rubber. This amount is the amount most commonly used for sulfur vulcanizable diene rubbers.
又、硫黄加硫可能なジエン系ゴム配合されるゴム用加硫
促進剤とは、硫黄と共に硫黄加硫可能なジエン系ゴムに
極く一般的に使用ゴム用加硫促進剤であって、例えばヘ
キサメチレン・テ！・ラミン、ジフェニル・グアニジン
、２−メルカプト・ベンゾチアゾール、ジベンゾチアジ
ル・ダイサルファイド、Ｎ−シクロヘキシル・ベンゾチ
アジル−２−スルフェンアミド、Ｎ−オキシ・ジエチレ
ン争ベンゾチアジルー２−スルフェンアミド、テトラメ
チル・チウラム・ダイサルファイド、テトラエチル・チ
ウラム・ダイサルファイド、テトラメチル・チウラム・
モノサルファイド、ジメチル・ジチオカルバミン酸亜鉛
、ジエチル・ジチオカルバミン酸亜鉛、ジ−ローブチル
・ジチオカルバミン酸亜鉛、ブチル・ザントゲン酸亜鉛
等が挙げられる。これらは（１を独又は混合して使用さ
れる。配合される量は、硫黄加硫可能なジエン系ゴム１
００重量部当たり０．１〜５重量部が配合される。Further, the rubber vulcanization accelerator that is mixed with sulfur-vulcanizable diene rubber is a rubber vulcanization accelerator that is very commonly used in sulfur-vulcanizable diene rubber together with sulfur, and includes, for example, Hexamethylene te!・Lamine, diphenyl guanidine, 2-mercapto benzothiazole, dibenzothiazyl disulfide, N-cyclohexyl benzothiazyl-2-sulfenamide, N-oxydiethylene benzothiazyl-2-sulfenamide, tetramethyl thiuram・Disulfide, Tetraethyl thiuram ・Disulfide, Tetramethyl thiuram ・
Examples include monosulfide, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibutyl dithiocarbamate, and zinc butyl xanthogenate. These (1) can be used alone or in a mixture.The amount to be blended is 1 1
0.1 to 5 parts by weight per 00 parts by weight.
この瓜は硫黄加硫可能なジエン系ゴムに極く一般的に使
用される皿である。This melon is a very commonly used dish for sulfur vulcanizable diene rubber.
本発明の硫黄加硫可能なジエン系ゴムに配合される還元
作用を有する無機及び／又は有機の金属塩とは、他の物
質に電子を与えたり、他の物質から酸素原子を奪うこと
の出来る無機及び／又は何機の金属塩であって、例えば
アルミニウム粉、鉄粉、コバルト粉、亜鉛粉、銅粉、錫
粉、塩化アルミニウム、塩化マンガン、塩化鉄、塩化コ
バルト、塩化亜鉛、塩化銅、塩化マンガン、塩化錫、亜
硫酸水素ナトリウム、亜硫酸すトリウム、硫酸すトリウ
ム、硫酸アルミニウム、硫酸鉄、硫酸亜鉛、硫酸銅、ｆ
１ｂ酸鉛、ジエチルアルミニウム、ジエチル亜鉛、ジエ
チルカドミニウム、ジエチルクロロ硼素、トリエチル硼
素、トリエチルアルミニウム、ナフテン酸鉄、ナフテン
酸コバルト、ナフテン酸銅、ナフテン酸鉛等が挙げられ
る。これらは単独または混合して使用される。配合され
る量は硫黄加硫可能なジエン系ゴム１００重量部当たり
０．０１〜２０ｆｆｉ量部、好ましくは０．１〜１０重
量部、更に好ましくは０．３〜５重量部が配合される。The inorganic and/or organic metal salts having a reducing action that are blended into the sulfur-vulcanizable diene rubber of the present invention are capable of donating electrons to other substances or depriving oxygen atoms from other substances. Inorganic and/or metal salts, such as aluminum powder, iron powder, cobalt powder, zinc powder, copper powder, tin powder, aluminum chloride, manganese chloride, iron chloride, cobalt chloride, zinc chloride, copper chloride, Manganese chloride, tin chloride, sodium bisulfite, sodium sulfite, sodium sulfate, aluminum sulfate, iron sulfate, zinc sulfate, copper sulfate, f
Examples include lead 1b acid, diethylaluminum, diethylzinc, diethylcadmium, diethylchloroboron, triethylboron, triethylaluminum, iron naphthenate, cobalt naphthenate, copper naphthenate, and lead naphthenate. These may be used alone or in combination. The amount to be blended is 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight per 100 parts by weight of the sulfur-vulcanizable diene rubber.
０．０１重量部未満では、還元作用を有する無機及び／
又は有機の金属塩の効果が小さく、強固な加硫液１１を
示さないのである。２０重量部を越えて配合しても、０
．０１〜２０重量部範囲内で配合した場合での強固な加
硫接着以上にはならず、配合する価値がない。If it is less than 0.01 part by weight, inorganic and/or
Alternatively, the effect of the organic metal salt is small and the vulcanizing liquid 11 is not strong. Even if it is added in excess of 20 parts by weight, 0
．． It does not provide stronger vulcanized adhesion than that achieved when blended within the range of 0.01 to 20 parts by weight, and is not worth blending.
硫黄加硫可能なジエン系ゴムに配合される金属化合物と
は、該記した塩素化ポリエチレンに配合される金属化合
物と同様のものであって、塩素化ポリエチレンが加硫接
着の際に発生させる塩酸を捕捉するために配合される。The metal compound compounded in the sulfur-vulcanizable diene rubber is the same as the metal compound compounded in the chlorinated polyethylene mentioned above, and is free from hydrochloric acid generated when chlorinated polyethylene is vulcanized and bonded. Formulated to capture.
配合される量は０．１〜２０重量部で、０．１重量部未
満では充分な塩酸捕捉を示さず、加硫接着する層間の剥
離強度の低下および硫黄加硫可能なジエン系ゴムの機械
的強度の低下を示す。２０重量部を越えて配合しても、
脱塩酸捕捉効果は、０．１〜２０重量部範囲の効果と同
じであり、２０重二部を越えて配合する価値がなく、逆
にジエン系ゴムの機械的性質が低下し、好ましくないの
である。The amount to be blended is 0.1 to 20 parts by weight; if it is less than 0.1 part by weight, sufficient hydrochloric acid scavenging will not be achieved, resulting in a decrease in peel strength between vulcanized and bonded layers, and problems with sulfur-vulcanizable diene rubber machines. This indicates a decrease in the strength of the target. Even if it is blended in excess of 20 parts by weight,
The dehydrochloric acid scavenging effect is the same as the effect in the range of 0.1 to 20 parts by weight, so it is not worth blending more than 20 parts by weight, and on the contrary, the mechanical properties of the diene rubber deteriorate, which is not preferable. be.
本発明の塩素化ポリエチレン組成物と硫黄加硫可能なジ
エン系ゴム組成物には、必要に応じてゴム用配合剤、例
えば加硫剤、加硫促進剤、老化防止剤、粘着付与剤、可
塑剤、軟化剤、補強剤、増量剤等が配合される。本発明
のゴム積層体の製造法は特に制限されるものではなく、
各組成物は例えば練りロール機、インターナルミキサー
、双腕型ニーダ−等の混線機で混練配合される。次に加
圧成形機、例えばロール成形機、押出成形機、圧縮成形
機、射出成形機カレンダーロール等で積層され、得られ
たゴム積層体は高温下の加硫機、例えば加硫缶、熱風循
環加硫機、圧縮成形加硫機、射出成形加硫機、流動床加
硫機等で成形および／または加硫接着される。The chlorinated polyethylene composition and the sulfur-vulcanizable diene rubber composition of the present invention may optionally contain rubber compounding agents, such as vulcanizing agents, vulcanization accelerators, anti-aging agents, tackifiers, plasticizers, etc. Agents, softeners, reinforcing agents, fillers, etc. are added. The method for manufacturing the rubber laminate of the present invention is not particularly limited,
Each composition is kneaded and blended using a mixing machine such as a kneading roll machine, an internal mixer, or a double-arm kneader. Next, the rubber laminate is laminated using a pressure molding machine, such as a roll molding machine, an extrusion molding machine, a compression molding machine, an injection molding machine, and a calender roll. Molding and/or vulcanization bonding is performed using a circulating vulcanizer, compression molding vulcanizer, injection molding vulcanizer, fluidized bed vulcanizer, etc.
（実施例）
次に、実施例により本発明を説明するが、本発明はこれ
らの実施例のみに限定されるものではない。(Examples) Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.
実施例及び比較例に使用した塩素化ポリエチレンは、以
下の方法で製造した。The chlorinated polyethylene used in Examples and Comparative Examples was manufactured by the following method.
３０リツターの反応器に、四塩化炭素１７．５リツター
と、Ｊ Ｉ Ｓ Ｋ −６７６０に従って、温度１９
０℃、荷重２１６０ｇで測定されたメルトインデックス
が５６２の高密度ポリエチレン２．８Ｋｇを入れ、撹拌
しなから１００℃に昇温し、高密度ポリエチレンを四塩
化炭素に溶解させた。次に塩素ガスを２．８リツタ一／
分の割合で反応器下部から吹込み、塩素含量が３５重量
９６の塩素化ポリエチレンの四塩化炭素溶液を得た。こ
の溶液からドラムドライヤーにより四塩化炭素を取除き
、固形の塩素化ポリエチレンを得た。A 30 liter reactor was charged with 17.5 liters of carbon tetrachloride and a temperature of 19 liters according to JIS K-6760.
2.8 kg of high-density polyethylene with a melt index of 562 measured at 0° C. under a load of 2160 g was added, and the temperature was raised to 100° C. without stirring to dissolve the high-density polyethylene in carbon tetrachloride. Next, add 2.8 liters of chlorine gas/
A carbon tetrachloride solution of chlorinated polyethylene having a chlorine content of 35% by weight and 96% by weight was obtained. Carbon tetrachloride was removed from this solution using a drum dryer to obtain solid chlorinated polyethylene.
実施例−１〜４および比較例−１〜４
表−１に実施例および比較例に使用した配合を示す。表
中の実施例および比較例の配合Ａは塩素化ポリエチレン
の配合であり、配合Ｂは硫黄加硫可能なジエン系ゴムの
配合である。配合Ａおよび配合Ｂを、（株）東洋精機製
作所製８インチロールを使用して混練り後、厚さＩＩＩ
ＩＬｌのシートに分出し、縦１５ｃｍ、横１５ｃｍのシ
ート に裁断した。Examples 1 to 4 and Comparative Examples 1 to 4 Table 1 shows the formulations used in the Examples and Comparative Examples. In the examples and comparative examples in the table, formulation A is a chlorinated polyethylene formulation, and formulation B is a sulfur-vulcanizable diene rubber formulation. After kneading Formulation A and Formulation B using an 8-inch roll manufactured by Toyo Seiki Seisakusho Co., Ltd., the thickness of
It was divided into ILl sheets and cut into sheets 15 cm long and 15 cm wide.
裁断した配合Ａのシートと配合Ｂのシートを重ね合せ、
この配合Ａと配合Ｂから成る積層体をキャビィティが縦
１５ｃｍ、横１５ｃｍ、厚さ２ ｍｍ の加硫用金型
に入れ、圧縮成形加硫機を使用して圧力５０Ｋｇ／ｃｍ
２、温度１６０℃で３０分間、加硫接着を行った。Layer the cut sheet of composition A and sheet of composition B,
The laminate consisting of formulation A and formulation B was placed in a vulcanization mold with a cavity of 15 cm in length, 15 cm in width, and 2 mm in thickness, and was heated to a pressure of 50 kg/cm using a compression molding vulcanizer.
2. Vulcanization adhesion was performed at a temperature of 160° C. for 30 minutes.
次に、得られたゴム積層体をｉｌ Ｉ Ｉｎｃｈ の
タンザク状に裁断し、ＪＩＳ Ｋ ６３０１に従っ
て、引張速度５０ Ｃｍ／ｌ１ｉｎ ｓ 試験温度２
３℃で１８０度剥離試験を行った。実施例１〜４および
比較例１〜４の試験結果表−１に示す。Next, the obtained rubber laminate was cut into a tanzak shape of il I Inch, and according to JIS K 6301, the tensile speed was 50 Cm/l in s and the test temperature was 2.
A 180 degree peel test was conducted at 3°C. Test results of Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1.
表−１から分るように、実施例−１〜４は比較例に比べ
て、層間の剥離強度が大きく、塩素化ポリエチレンと硫
黄加硫可能なジエン系ゴムのゴム積層体の層間が極めて
強固に加硫液４′Ｔシていることが分る。As can be seen from Table 1, Examples 1 to 4 have greater interlayer peel strength than Comparative Examples, and the interlayers of the rubber laminate made of chlorinated polyethylene and sulfur-vulcanizable diene rubber are extremely strong. It can be seen that the vulcanizing liquid 4'T is present.
比較例−１は実施例−１の配合Ｂから還元作用を持つ無
機金属塩（硫酸鉄）を除いたゴム積層体の剥離強度であ
り、比較例−２は実施例−２の配合Ｂから還元作用を持
つ無機金属塩（硫酸銅）を除いたゴム積層体の剥離強度
である。比較例−３は実施例−３の配合Ｂから還元作用
を持つ無機金属塩（塩化銅）を除いたゴム積層体の剥離
強度である。比較例−４は実施例−４の配合Ｂから有機
金属塩（ナフテン酸銅）を除き、更に配合の硫黄とゴム
用加硫促進剤の加硫系を有機過酸化物の系にしたゴム積
層体の剥離強度である。即ち、実施例に示すように、塩
素化ポリエチレンをａ機過酸化物の加硫系とし、硫黄加
硫可能なジエン系ゴムを一般に使用されている硫黄とゴ
ム用加硫促進剤の系とし、更に還元作用を持つ無機及び
／又は有機の金属塩、及び金属化合物を配合することに
より、本発明升目的とする層間が極めて強固に加硫接着
したゴム積層体が得られるのである。Comparative Example-1 is the peel strength of a rubber laminate obtained by removing the reducing inorganic metal salt (iron sulfate) from Formulation B of Example-1, and Comparative Example-2 is the peel strength of a rubber laminate obtained by removing the reducing inorganic metal salt (iron sulfate) from Formulation B of Example-2. This is the peel strength of a rubber laminate excluding the active inorganic metal salt (copper sulfate). Comparative Example-3 is the peel strength of a rubber laminate obtained by removing the inorganic metal salt (copper chloride) having a reducing action from Formulation B of Example-3. Comparative Example-4 is a rubber laminate in which the organic metal salt (copper naphthenate) is removed from Formulation B of Example-4, and the vulcanization system of the sulfur and rubber vulcanization accelerator is an organic peroxide system. It is the peel strength of the body. That is, as shown in the examples, chlorinated polyethylene is used as a vulcanization system using a peroxide, sulfur-vulcanizable diene rubber is used as a vulcanization system containing commonly used sulfur and a rubber vulcanization accelerator, Further, by blending inorganic and/or organic metal salts and metal compounds with a reducing action, a rubber laminate in which interlayers are extremely strongly vulcanized and bonded, which is the object of the present invention, can be obtained.
（発明の効果）
以上の説明から明らかなように、本発明のゴム積層体は
、強固な加硫接着を示さなかった塩素化ポリエチレン組
成物と硫黄加硫可能なジエン系ゴム組成物の層間の極め
て強固な加硫接着を可能ならしめた、層間の剥離強度の
強いゴム積層体であることが分る。このことから、化学
的、物理的あるいは機械的性質の優れたゴム積層体、あ
るいは特殊な機能を有するゴム積層体を市場に提供出来
る。(Effects of the Invention) As is clear from the above description, the rubber laminate of the present invention has a bond between the layers of the chlorinated polyethylene composition and the sulfur-vulcanizable diene rubber composition, which did not exhibit strong vulcanization adhesion. It can be seen that this is a rubber laminate with strong interlayer peel strength that enables extremely strong vulcanization adhesion. Therefore, rubber laminates with excellent chemical, physical or mechanical properties, or rubber laminates with special functions can be provided on the market.
Claims (1)
物０．１〜２５重量部、及び金属化合物０．１〜３０重
量部を配合した組成物と硫黄加硫可能なジエン系ゴム１
００重量部当たり硫黄０．１〜５重量部、ゴム用加硫促
進剤０．１〜５重量部、及び還元作用を有する無機及び
／又は有機の金属塩０．０１〜２０重量部、及び金属化
合物０．１〜２０重量部を配合した組成物から成るゴム
積層体。1 Composition containing 0.1 to 25 parts by weight of organic peroxide and 0.1 to 30 parts by weight of metal compound per 100 parts by weight of chlorinated polyethylene and sulfur-curable diene rubber 1
0.1 to 5 parts by weight of sulfur, 0.1 to 5 parts by weight of a rubber vulcanization accelerator, and 0.01 to 20 parts by weight of an inorganic and/or organic metal salt having a reducing action, and a metal A rubber laminate comprising a composition containing 0.1 to 20 parts by weight of a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29358588A JP2699479B2 (en) | 1988-11-22 | 1988-11-22 | Rubber laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29358588A JP2699479B2 (en) | 1988-11-22 | 1988-11-22 | Rubber laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02141237A true JPH02141237A (en) | 1990-05-30 |
| JP2699479B2 JP2699479B2 (en) | 1998-01-19 |
Family
ID=17796635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29358588A Expired - Fee Related JP2699479B2 (en) | 1988-11-22 | 1988-11-22 | Rubber laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2699479B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225425A (en) * | 2000-02-15 | 2001-08-21 | Tosoh Corp | Laminate and hose consisting of the same |
-
1988
- 1988-11-22 JP JP29358588A patent/JP2699479B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001225425A (en) * | 2000-02-15 | 2001-08-21 | Tosoh Corp | Laminate and hose consisting of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2699479B2 (en) | 1998-01-19 |
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