JPH0366467B2 - - Google Patents
Info
- Publication number
- JPH0366467B2 JPH0366467B2 JP58201632A JP20163283A JPH0366467B2 JP H0366467 B2 JPH0366467 B2 JP H0366467B2 JP 58201632 A JP58201632 A JP 58201632A JP 20163283 A JP20163283 A JP 20163283A JP H0366467 B2 JPH0366467 B2 JP H0366467B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- olefin
- titanium
- copolymer
- compounds
- 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.)
- Expired - Lifetime
Links
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 27
- 239000004711 α-olefin Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000011949 solid catalyst Substances 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 description 19
- -1 aluminum compound Chemical class 0.000 description 16
- 150000003609 titanium compounds Chemical class 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 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
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BDBNCVOMHKVOST-UHFFFAOYSA-K CCCCCO[Ti](Cl)(Cl)Cl Chemical compound CCCCCO[Ti](Cl)(Cl)Cl BDBNCVOMHKVOST-UHFFFAOYSA-K 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Steps, Ramps, And Handrails (AREA)
Description
本発明はすべり止め部材、さらに詳しくは特定
のエチレン・α−オレフイン共重合体を用いた階
段、手すり、床等のすべり止め部材に関する。
従来よりすべり止めの機能を有する部材は種々
知られているが、その大部分はポリ塩化ビニル樹
脂（以下、PVCと呼称）、エチレン−酢酸ビニル
共重合体（以下、EVAと呼称）およびゴムを主
体とするものであり、これらのなかでも特に軟質
PVCが最も多く用いられている。しかしながら
軟質PVCには可塑剤が多量に配合されており長
期間の使用による可塑剤の移行に伴う表面フイー
リング性の悪化や柔軟性が欠如して脆くなり、特
にこれらの傾向は低温ではなはだしく、実用が困
難になる。さらにPVCは焼却時塩化水素が発生
するという欠点もある。
EVAはその中に含有される酢酸ビニル含量に
よつて性質が変化するが、すべり止め部材は柔軟
性も要求されるため比較的高酢酸ビニル含量のも
のが用いられているが酢酸ビニル含量の高い共重
合体は酢酸臭が強く成形加工時の作業性を悪くし
ている。また吸湿性があり高温下にさらされると
加水分解作用を受けやすく、耐候性が十分ではな
い。ゴムは加工素練り時に多種類の加工助剤の添
加や加硫などの複雑な工程を必要とすることから
省エネルギーの面からも好ましいものではない。
本発明は前記の樹脂等の欠点を解決し、あわせ
て軽量で耐候性、熱安定性、耐熱性、加工性にす
ぐれ、架橋も必要としない等すぐれた性能を有す
るエチレン・α−オレフイン共重合体からなるす
べり止め部材を提供することを目的とするもので
ある。
すなわち本発明は、少なくともマグネシウムお
よびチタンを含有する固体触媒成分と有機アルミ
ニウム化合物からなる触媒の存在下、エチレンと
α−オレフインを共重合させて得られる下記の(a)
〜(d)の性状を有するエチレン・α−オレフイン共
重合体からなるすべり止め部材に関する。
(a) メルトインデツクスが0.01〜100ｇ／10min、
好ましくは0.1〜50ｇ／10min、
(b) 密度が0.860〜0.910ｇ／cm3、好ましくは0.880
〜0.900ｇ／cm3、
(c) 示差走査熱量測定法（DSC）においてその
最大ピークの温度（Tm）が100℃以上、好ま
しくは110℃以上、
(d) 沸騰ｎ−ヘキサン不溶分が10重量％以上、
好ましくは30〜85重量％。
本発明で用いるエチレン・α−オレフイン共重
合体は上記(a)〜(d)の条件をすべて満足するもので
なければならない。
［条件ａ］
(a)のメルトインデツクス（JIS K6760）が0.01
ｇ／10min未満であると加工性が悪くなり、100
ｇ／10minを越えると成形品の表面がべたついた
り、機械的強度が低下するので好ましくない。
［条件ｂ］
(b)の密度（JIS Ｋ 6760）が0.860ｇ／cm3未満
であると融点が下がるため高温下では使用でき
ず、また機械的強度等も劣るため好ましくない。
［条件ｃ］
(c)のDSCの最大ピーク温度（Tm）は結晶形態
と相関する値であり、Tmが100℃未満であると
すべり止め部材の耐熱性、表面強度が不足し、成
形品を高温下で使用する時塑性変形を起しやすく
なり好ましくない。
［条件ｄ］
つぎに、沸騰ｎ−ヘキサン不溶分は、非晶質部
分の割合および低分子量成分の含有率の目安とな
るものであり、不溶分が10重量％未満であるとき
は、非晶質部分および低分子量成分が多くなり強
度低下による性能や不足や表面がべたつきごみが
付着しやすくなるなどの問題が生ずるとともに、
すべり止め部材自体の形状維持が困難となる。
なお、本発明における沸騰ｎ−ヘキサン不溶分
およびDSCの測定方法はつぎのとおりである。
［沸騰ｎ−ヘキサン不溶分の測定法］
熱プレスを用いて、厚さ200μｍのシートを成
形し、そこから縦横それぞれ20mm×30mmのシート
を３枚切り取り、それを２重管式ソツクルレー抽
出器を用いて、沸騰ｎ−ヘキサンで５時間抽出を
行なう。ｎ−ヘキサン不溶分を取り出し、真空乾
燥（７時間、真空下、50℃）後、次式により沸騰
ｎ−ヘキサン不溶分を算出する。
沸騰ｎ−ヘキサン不溶分（重量％）
＝抽出済シート重量／未抽出シート重量×100（重量
％）
［DSCによる測定法］
熱プレス成形した厚さ100μｍのフイルムから
約５mgの試料を精秤し、それをDSC装置にセツ
トし、170℃に昇温してその温度で15min保持し
た後降温速度2.5℃／minで０℃まで冷却する。
次に、この状態から昇温速度10℃／minで170℃
まで昇温して測定を行う。０℃から170℃に昇温
する間に現われたピーク最大ピークの頂点の位置
の温度をもつてTmとする。
本発明におけるエチレン・α−オレフイン共重
合体は上記の諸特性をすべて満たすことによつ
て、所望の性能を発揮することができる。
エチレンと共重合するα−オレフインは炭素数
３〜12のものである。具体的には、プロピレン、
ブテン−１、４−メチルペンテン−１、ヘキセン
−１、オクテン−１、デセン−１、ドデセン−１
などを挙げることができる。これらのうち特に好
ましいのは、プロピレンとブテン−１である。エ
チレン−α−オレフイン共重合体中のα−オレフ
イン含有量は５〜40モル％であることが好まし
い。
以下に、本発明において用いるエチレンとα−
オレフインの共重合体の製造法について説明す
る。
まず使用する触媒系は、少なくともマグネシウ
ムおよびチタンを含有する固体触媒成分に有機ア
ルミニウム化合物を組み合わせたもので、該固体
触媒成分としてはたとえば金属マグネシウム、水
酸化マグネシウム、炭酸マグネシウム、酸化マグ
ネシウム、塩化マグネシウムなど、またケイ素、
アルミニウム、カルシウムから選ばれる金属とマ
グネシウム原子とを含有する複塩、複酸化物、炭
酸塩、塩化物あるいは水酸化物など、さらにはこ
れらの無機質固体化合物を含酸素化合物、含硫黄
化合物、芳香族炭化水素、ハロゲン含有物質で処
理又は反応させたもの等のマグネシウムを含む無
機質固体化合物にチタン化合物を公知の方法によ
り担持させたものが挙げられる。
上記の含酸素化合物としては、例えば水、アル
コール、フエノール、ケトン、アルデヒド、カル
ボン酸、エステル、ポリシロキサン、酸アミド等
の有機含酸素化合物、金属アルコキシド、金属の
オキシ塩化物等の無機含酸素化合物を例示するこ
とができる。含硫黄化合物としては、チオール、
チオエーテルの如き有機含硫黄化合物、二酸化硫
黄、三酸化硫黄、硫酸の如き無機硫黄化合物を例
示することができる。芳香族炭化水素としては、
ベンゼン、トルエン、キシレン、アントラセン、
フエナンスレンの如き各種単環および多環の芳香
族炭化水素化合物を例示することができる。ハロ
ゲン含有物質としては、塩素、塩化水素、金属塩
化物、有機ハロゲン化物の如き化合物等を例示す
ることができる。
チタン化合物としては、チタンのハロゲン化
物、アルコキシハロゲン化物、アルコキシド、ハ
ロゲン化酸化物等を挙げることができる。チタン
化合物としては４価のチタン化合物と３価のチタ
ン化合物が好適であり、４価のチタン化合物とし
ては具体的には一般式Ti（OR）nX4-o（ここでＲ
は炭素数１〜20のアルキル基、アリール基または
アラルキル基を示し、Ｘはハロゲン原子を示す。
ｎは０≦ｎ≦４である。）示されるものが好まし
く、四塩化チタン、四臭化チタン、四ヨウ化チタ
ン、モノメトキシトリクロロチタン、ジメトキシ
ジクロロチタン、トリメトキシモノクロロチタ
ン、テトラメトキシチタン、モノエトキシトリク
ロロチタン、ジエトキシジクロロチタン、トリエ
トキシモノクロロチタン、テトラエトキシチタ
ン、モノイソプロポキシトリクロロチタン、ジイ
ソプロポキシジクロロチタン、トリイソプロポキ
シモノクロロチタン、テトライソプロポキシチタ
ン、モノブトキシトリクロロチタン、ジブトキシ
ジクロロチタン、モノペントキシトリクロロチタ
ン、モノフエノキシトリクロロチタン、ジフエノ
キシジクロロチタン、トリフエノキシモノクロロ
チタン、テトラフエノキシチタン等を挙げること
ができる。３価のチタン化合物としては、四塩化
チタン、四臭化チタン等の四ハロゲン化チタンを
水素、アルミニウム、チタンあるいは周期率〜
族金属の有機金属化合物により還元して得られ
る三ハロゲン化チタンが挙げられる。また一般式
Ti（OR）mX4-n（ここではＲは炭素数１〜20のア
ルキル基、アリール基またはアラルキル基を示
し、Ｘはハロゲン原子を示す。ｍは０＜ｍ＜４で
ある。）で示される４価のハロゲン化アルコキシ
チタンを周期率表〜族金属の有機金属化合物
により還元して得られる３価のチタン化合物が挙
げられる。
これらのチタン化合物のうち、４価のチタン化
合物が特に好ましい。
これらの触媒の具体的なものとしては、たとえ
ばMgO−RX−TiCl4系（特公昭51−3514号公
報）、Mg−SiCl4−ROH−TiCl4系（特公昭50−
23864号公報）、MgCl2−Al（OR）3−TiCl4系（特
公昭51−152号公報、特公昭52−15111号公報）、
MgCl2−SiCl4−ROH−TiCl4系（特公昭49−
106581号公報）、
Mg（OOCR）2−Al（OR）3−TiCl4系（特公昭52−
11710号公報）、
Mg−POCl3−TiCl4系（特公昭51−153号公報）、
MgCl2−AlOCl−TiCl4系（特公昭54−15316号公
報）、MgCl2−Al（OR）nX3−ｎ−Si（OR′）
mX4-n−TiCl4系（特開昭56−95909号公報）な
どの固体触媒成分（前記式中において、Ｒ、
R′は有機残基、Ｘはハロゲン原子を示す）に有
機アルミニウム化合物を組み合わせたものが好ま
しい触媒系の例としてあれられる。
他の触媒系の例としては固体触媒成分として、
いわゆるグリニヤ化合物などの有機マグネシウム
化合物とチタン化合物との反応生成物を用い、こ
れに有機アルミニウム化合物を組み合わせた触媒
系を例示することができる。有機マグネシウム化
合物としては、たとえば、一般式RMgX、
R2Mg、RMg（OR）などの有機マグネシウム化
合物（ここで、Ｒは炭素数１〜20の有機残基、Ｘ
はハロゲンを示す）およびこれらのエーテル錯合
体、またはこれらの有機マグネシウム化合物をさ
らに、他の有機金属化合物たとえば有機ナトリウ
ム、有機リチウム、有機カリウム、有機ホウ素、
有機カルシウム、有機亜鉛などの各種化合物を加
えて変性したものを用いることができる。
これらの触媒系の具体的な例としては、例えば
RMgX−TiCl4系（特公昭50−39470号公報）、
RMgX−フエノールTiCl4系（特公昭54−12953
号公報）、RMgX−ハロゲン化フエノール−
TiCl4系（特公昭54−12954号公報）、RMgx−
CO2−TiCl4（特開昭57−73009号公報）等の固体
触媒成分に有機アルミニウム化合物を組み合わせ
たものを挙げることができる。
また他の触媒系の例としては固体触媒成分とし
て、SiO2、Al2O3等の無機酸化物と前記の少なく
ともマグネシウムおよびチタンを含有する固体触
媒成分を接触させて得られる固体物質を用い、こ
れに有機アルミニウム化合物を組み合わせてもの
を例示することができる。無機酸化物としては
SiO2、Al2O3の他にCaO、B2O3、SnO2等を挙げ
ることができ、またこれらの酸化物の複酸化物も
なんら支障なく使用できる。これら各種の無機酸
化物とマグネシウムおよびチタンを含有する固体
触媒成分を接触させる方法としては公知の方法を
採用することができる。すなわち、不活性触媒の
存在下あるいは不存在下に温度20〜400℃、好ま
しくは50〜300℃で通常５分〜20時間反応させる
方法、共粉砕処理による方法、あるいはこれらの
方法を適宜組み合わせることにより反応させても
よい。
これらの触媒系の具体的な例としては、例え
ば、SiO2−ROH−MgCl2−TiCl4系（特開昭56−
47407号公報）、SiO2−Ｒ−Ｏ−R′−MgO−AlCl3
−TiCl4系（特開昭57−187305号公報）、SiO2−
MgCl2−Al（OR）3−TiCl4−Si（OR′）4系（特開昭
58−21405号公報）（前記式中においてＲ、R′は
炭化水素残基を示す。）等に有機アルミニウム化
合物を組み合わせたものを挙げることができる。
これらの触媒系において、チタン化合物を有機
カルボン酸エステルとの付加物として使用するこ
ともでき、また前記したマグネシウムを含む無機
固体化合物を有機カルボン酸エステルと接触処理
させたのち使用することもできる。また、有機ア
ルミニウム化合物を有機カルボン酸エステルとの
付加物として使用して何ら支障がない。さらに
は、あらゆる場合において、有機カルボン酸エス
テルの存在下に調整された触媒系を使用すること
も何ら支障なく実施できる。
ここで有機カルボン酸エステルとしては各種の
脂肪族、脂環族、芳香族カルボン酸エステルが用
いられ、好ましくは炭素数７〜12の芳香族カルボ
ン酸エステルが用いられる。具体的な例としては
安息香酸、アニス酸、トルイル酸のメチル、エチ
ルなどのアルキルエステルをあげることができ
る。
上記した固体触媒成分と組み合わせるべき有機
アルミニウム化合物の具体的な例としては一般式
R3Al、R2AlX、RAlX2、R2AlOR、RAl（OR）
ＸおよびR3Al2X3の有機アルミニウム化合物（こ
こでＲは炭素数１〜20のアルキル基、アリール基
またはアラルキル基、Ｘはハロゲン原子を示し、
Ｒは同一でもまた異なつてもよい）で示される化
合物が好ましく、トリエチルアルミニウム、トリ
イソブチルアルミニウム、トリヘキシルアルミニ
ウム、トリオクチルアルミニウム、ジエチルアル
ミニウムクロリド、ジエチルアルミニウムエトキ
シド、エチルアルミニウムセスキクロリド、およ
びこれらの混合物等があげられる。
有機アルミニウム化合物の使用量はとくに制限
されないが通常チタン化合物に対して0.1〜1000
モル倍使用することができる。
また、前記の触媒系をα−オレフインと接触さ
せたのち重合反応に用いることによつて、その重
合活性を大巾に向上させ、未処理の場合によりも
一層安定に運転することもできる。このとき使用
するα−オレフインとしては種々のものが使用可
能であるが、好ましくは炭素数３〜12のα−オレ
フインであり、さらに好ましくは炭素数３〜８の
α−オレフインが望ましい。これらのα−オレフ
インの例としてはたとえばプロピレン、ブテン−
１、ペンテン−１、４−メチルペンテン−１、ヘ
キセン−１、オクテン−１、デセン−１、ドデセ
ン−１等およびこれらの混合物などをあげること
ができる。触媒系とα−オレフインとの接触時の
温度、時間は広い範囲で選ぶことができ、たとえ
ば０〜200℃、好ましくは０〜110℃で１分〜24時
間で接触処理させることができる。接触させるα
−オレフインの量も広い範囲で選べるが、通常、
前記固体触媒成分１ｇ当り１ｇ〜50000ｇ、好ま
しくは５ｇ〜30000ｇ程度のα−オレフインで処
理し、前記固体触媒成分１ｇ当り１ｇ〜500ｇの
α−オレフインを反応させることが望ましい。こ
のとき、接触時の圧力は任意に選ぶことができる
が通常、−１〜100Kg／cm2・Ｇの圧力下に接触させ
ることが望ましい。
α−オレフイン処理の際、使用する有機アルミ
ニウム化合物を全量、前記固体触媒成分と組み合
わせたのちα−オレフインと接触させてもよい
し、また、使用する有機アルミニウム化合物のう
ち一部を前記固体触媒成分と組み合わせたのちα
−オレフインと接触させ、残りの有機アルミニウ
ム化合物を重合のさいに別途添加して重合反応を
行なつてもよい。また、触媒系とα−オレフイン
との接触時に、水素ガスが共存しても支障なく、
また、窒素、アルゴン、ヘリウムなどその他の不
活性ガスが共存しても何ら支障ない。
重合反応は通常のチグラー型触媒によるオレフ
インの重合反応と同様にして行われる。すなわち
反応はすべて実質的に酸素、粋などを絶つた状態
で、気相、または不活性溶媒の存在下、またはモ
ノマー自体を溶媒として行われる。オレフインの
重合条件は温度は20〜300℃、好ましくは40〜200
℃であり、圧力は常圧ないし70Kg／cm2・Ｇ、好ま
しくは２Kg／cm2・Ｇないし60Kg／cm2・Ｇである。
分子量の調節は重合温度、触媒のモル比などの重
合条件を変えることによつてもある程度調節でき
るが、重合系中に水素を添加することにより効果
的に行われる。もちろん、水素濃度、重合温度な
どの重合条件の異なつた２段階ないしそれ以上の
多段階の重合反応も何ら支障なく実施できる。
以上の如く、少なくともマグネシウムおよびチ
タンを含有する固体触媒成分と有機アルミニウム
化合物とからなる触媒の存在下、エチレンと炭素
数３〜12のα−オレフイを共重合させて得られた
特定のエチレン・α−オレフイン共重合体によ
り、すぐれた特性を有するすべり止め部材を提供
できたことは、まつたく予期できないことであり
驚くべきことであつた。
本発明のエチレン・α−オレフイン共重合体
と、固体触媒成分としてバナジウムを含有するも
のを使用して得られるエチレン・α−オレフイン
共重合体とは明確に区別される。
両者は共重合体を構成するモノマーが同一の場
合であつて、かつ密度が同一であつても、DSC
によるTmは本発明の共重合体の方が高く、沸騰
ｎ−ヘキサン不溶分は本発明の共重合体は10重量
％以上であるのに対し後者は不溶分は存在しない
か、存在してもごく微量である。このような共重
合体自体の相違に起因して、本発明のすべり止め
部材としての用途に使用したときには、本発明の
共重合体は後者に比較して、耐熱性および強度が
すぐれているとともに、すべり止め部材の用途に
要求される諸性能のバランスがすぐれている。さ
らに解媒残渣として共重合体に存在するバナジウ
ムはチタンとは異なり毒性が問題となるため、触
媒除去工程が不可欠であるのに対し、本発明のご
とくチタンを使用する場合には触媒残渣の毒性問
題は生ぜず、マグネシウム担体と組み合わせた高
活性触媒を使用する本発明の共重合体では触媒除
去工程が不要となるので極めて経済的である。
本発明の共重合体は充填剤を加えずに成形加工
して使用しても差しつかえないが、好ましくは無
機および／または有機充填剤を配合した組成物と
して使用する。
無機および／または有機充填剤としては炭酸カ
ルシウム、水酸化アルミニウム、マグネシア、タ
ルク、クレー、チタニア、カーボンブラツク、微
細シリカ、ガラス繊維、フエノール樹脂、石油樹
脂、合成繊維（ポリアミド）等があげられる。本
発明の共重合体と充填剤を配合するには公知の方
法が使用できる。またこの時、通常のポリオレフ
インと同様に各種の安定剤、発泡剤、発泡助剤、
難燃剤、顔料等を添加してもよい。また成形品は
エンボス加工等の二次加工を行なつてもよい。
本発明のすべり止め部材を施工した手段、手す
り等は、その大きい摩擦係数に基くすべり止め効
果が大きく、また、その表面に凹凸などの加工を
行なつてもよくきわめて低密度のため軽量で施工
しやすく、成形後の加硫、架橋等の工程も必要と
せずきわめて経済的である。また、樹脂の基本的
構造から明らかなように不飽和結合を含まず、さ
らに低分子量のいわゆるワツクス分も含まないた
め耐候性にすぐれ、屋外のみならず屋外の階段、
手すり、大型機械設備のステツプ、タラツプ等に
もなんら問題なく使用できるものである。
本発明の共重合体は結晶性部分を適度に含有す
るため従来からの他の樹脂やゴム等には見られな
い弾性があり、施工後はクツシヨン性があり表面
フイーリング性もすぐれたものである。
ゴムと比較した場合、本発明の特定のエチレ
ン・α−オレフイン共重合体を用いたすべり止め
部材は複雑な加工工程を必要とせず、着色も自由
に行えるなどのすぐれた性能を有する。
以下に実施例により本発明を具体的に説明する
が本発明はこれらに制限されるものではない。
実施例および比較例に使用するポリマーは次の
とおりである。
実施例 １
実質的に無水の塩化マグネシウム、１、２−ジ
クロルエタンおよび四塩化チタンから得られた固
体触媒成分とトリエチルアルミニウムからなる触
媒を用いてエチレンとブテン−１を共重合して得
られたエチレン・ブテン−１共重合体。
このエチレン・ブテン−１共重合体のエチレン
含量は91.5モル％、メルトインデツクスは0.5
ｇ／10min、密度は0.904ｇ／cm3、DSCの最大ピ
ーク温度は120.5℃、沸騰ｎ−ヘキサン不溶分は
94重量％であつた。
実施例 ２
実質的に無水の塩化マグネシウム、アントラセ
ンおよび四塩化チタンから得られた固体触媒成分
とトリエチルアルミニウムからなる触媒を用いて
エチレンとプロピレンを共重合して得られたエチ
レン・プロピレン共重合体。
このエチレン・プロピレン共重合体のエチレン
含量は81.5モル％、メルトインデツクスは1.0
ｇ／10min、密度は0.890ｇ／cm3、DSCの最大ピ
ーク温度は121.6℃、沸騰ｎ−ヘキサン不溶分は
58重量％であつた。
実施例 ３
実質的に無水の塩化マグネシウム、1.2−ジク
ロルエタンおよび四塩化チタンから得られた固体
触媒成分とトリエチルアルミニウムからなる触媒
を用いてエチレンとプロピレンを共重合して得ら
れたエチレン・プロピレン共重合体。
このエチレン・プロピレン共重合体のエチレン
含量は87モル％、メルトインデツクスは11.0ｇ／
10min、密度が0.897ｇ／cm3、DSCの最大ピーク
温度は122.5℃、沸騰ｎ−ヘキサン不溶分は85重
量％であつた。
実施例 ４
エチレン含量は87.0モル％、メルトインデツク
スは2.3ｇ／10min、密度は0.839ｇ／cm3、DSCの
最大ピーク温度は119.3℃、沸騰ｎ−ヘキサン不
溶分は78重量％である、実施例−１と同様の方法
で得られたエチレン−ブテン−１共重合体。
比較例 １
エチレン−酢酸ビニル共重合体（酢酸ビニル含
量５重量％）、メルトインデツクス2.1ｇ／
10min、密度0.926ｇ／cm3。
比較例 ２
エチレン酢酸ビニル共重合体（酢酸ビニル含量
15重量％）、メルトインデツクス3.5ｇ／10min、
密度0.934ｇ／cm3。
比較例 ３
バナジウム系触媒により得られたエチレン−ブ
テン−１強重合体。メルトインデツクス3.8ｇ／
10min、密度0.887ｇ／cm3、DSCの最大ピークの
温度67.1℃、沸騰ｎ−ヘキサン不溶分0.0％。
上述の実施例１〜４、比較例１〜３のポリマー
を６mmの厚さのシートに成形し、動摩擦係数を求
めた。その結果を表１に示した。
The present invention relates to an anti-slip member, and more particularly to an anti-slip member for stairs, handrails, floors, etc., using a specific ethylene/α-olefin copolymer. Various members with anti-slip functions have been known, but most of them are made of polyvinyl chloride resin (hereinafter referred to as PVC), ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), and rubber. Among these, especially soft
PVC is the most commonly used. However, soft PVC contains a large amount of plasticizer, and as a result of long-term use, the plasticizer migrates, resulting in deterioration of the surface feeling and lack of flexibility, resulting in brittleness.These tendencies are particularly pronounced at low temperatures, making it difficult to put into practical use. becomes difficult. Another disadvantage of PVC is that it generates hydrogen chloride when incinerated. The properties of EVA change depending on the vinyl acetate content contained in it, but anti-slip materials require flexibility, so those with a relatively high vinyl acetate content are used. Copolymers have a strong acetic acid odor, which impairs workability during molding. Furthermore, it is hygroscopic and susceptible to hydrolysis when exposed to high temperatures, so it does not have sufficient weather resistance. Rubber is not preferred in terms of energy saving because it requires complicated steps such as addition of various processing aids and vulcanization during mastication. The present invention solves the drawbacks of the above-mentioned resins, etc., and also has an ethylene/α-olefin copolymer that is lightweight, has excellent weather resistance, thermal stability, heat resistance, processability, and does not require crosslinking. The object of the present invention is to provide an anti-slip member made of an integrated structure. That is, the present invention provides the following (a) obtained by copolymerizing ethylene and α-olefin in the presence of a catalyst consisting of a solid catalyst component containing at least magnesium and titanium and an organoaluminum compound.
The present invention relates to an anti-slip member made of an ethylene/α-olefin copolymer having the properties described in (d). (a) Melt index is 0.01 to 100g/10min,
Preferably 0.1-50g/10min, (b) Density 0.860-0.910g/cm 3 , preferably 0.880
~0.900 g/cm 3 , (c) The temperature (Tm) of the maximum peak in differential scanning calorimetry (DSC) is 100°C or higher, preferably 110°C or higher, (d) Boiling n-hexane insoluble matter is 10% by weight % or more, preferably 30-85% by weight. The ethylene/α-olefin copolymer used in the present invention must satisfy all of the above conditions (a) to (d). [Condition a] Melt index (JIS K6760) of (a) is 0.01
If it is less than 10g/10min, the workability will be poor and the
If it exceeds g/10 min, the surface of the molded product becomes sticky and the mechanical strength decreases, which is not preferable. [Condition b] If the density (JIS K 6760) of (b) is less than 0.860 g/cm 3 , the melting point will be lowered, so it cannot be used at high temperatures, and the mechanical strength etc. will also be poor, which is not preferable. [Condition c] The maximum peak temperature (Tm) of DSC in (c) is a value that correlates with the crystal morphology. If Tm is less than 100℃, the heat resistance and surface strength of the anti-slip member will be insufficient, and the molded product will be damaged. When used at high temperatures, plastic deformation tends to occur, which is undesirable. [Condition d] Next, the boiling n-hexane insoluble content is a guideline for the proportion of amorphous parts and the content of low molecular weight components, and when the insoluble content is less than 10% by weight, This results in problems such as poor performance due to decreased strength and a sticky surface, which makes it easier for dirt to adhere.
It becomes difficult to maintain the shape of the anti-slip member itself. The method for measuring the boiling n-hexane insoluble matter and DSC in the present invention is as follows. [Measurement method for boiling n-hexane insoluble matter] A sheet with a thickness of 200 μm was formed using a heat press, and three sheets of 20 mm x 30 mm in length and width were cut from the sheet, and the sheets were placed in a double-tube Sotsukurray extractor. Extraction is carried out using boiling n-hexane for 5 hours. After taking out the n-hexane insoluble matter and vacuum drying (7 hours under vacuum, 50° C.), the boiling n-hexane insoluble matter is calculated using the following formula. Boiling n-hexane insoluble content (weight %) = Extracted sheet weight / unextracted sheet weight x 100 (weight %) [Measurement method by DSC] Precisely weigh approximately 5 mg of sample from a 100 μm thick hot press-molded film. The sample was set in a DSC device, heated to 170°C, held at that temperature for 15 minutes, and then cooled to 0°C at a cooling rate of 2.5°C/min.
Next, from this state, increase the temperature to 170°C at a rate of 10°C/min.
Measurement is performed by raising the temperature to . The temperature at the peak position of the maximum peak that appeared during the temperature increase from 0°C to 170°C is defined as Tm. The ethylene/α-olefin copolymer of the present invention can exhibit desired performance by satisfying all of the above-mentioned properties. The α-olefin copolymerized with ethylene has 3 to 12 carbon atoms. Specifically, propylene,
Butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1
etc. can be mentioned. Particularly preferred among these are propylene and butene-1. The α-olefin content in the ethylene-α-olefin copolymer is preferably 5 to 40 mol%. Below, ethylene used in the present invention and α-
A method for producing an olefin copolymer will be explained. First, the catalyst system used is one in which an organic aluminum compound is combined with a solid catalyst component containing at least magnesium and titanium, and examples of the solid catalyst component include magnesium metal, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, etc. , also silicon,
Double salts, double oxides, carbonates, chlorides, or hydroxides containing metals selected from aluminum and calcium and magnesium atoms, and furthermore, these inorganic solid compounds can be used as oxygen-containing compounds, sulfur-containing compounds, and aromatic compounds. Examples include those in which a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, such as one treated or reacted with a hydrocarbon or halogen-containing substance. Examples of the above oxygen-containing compounds include organic oxygen-containing compounds such as water, alcohol, phenol, ketone, aldehyde, carboxylic acid, ester, polysiloxane, and acid amide, and inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. can be exemplified. Examples of sulfur-containing compounds include thiol,
Examples include organic sulfur-containing compounds such as thioethers, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. As aromatic hydrocarbons,
benzene, toluene, xylene, anthracene,
Examples include various monocyclic and polycyclic aromatic hydrocarbon compounds such as phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides, and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable. Specifically, as a tetravalent titanium compound, the general formula Ti(OR)nX 4-o (here R
represents an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom.
n is 0≦n≦4. ) Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, trichlorotitanium Ethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxy Examples include trichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium. As trivalent titanium compounds, titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide are combined with hydrogen, aluminum, titanium, or periodicity ~
Examples include titanium trihalides obtained by reduction with organometallic compounds of group metals. Also general formula
Ti(OR)mX 4-n (here, R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms; Examples include trivalent titanium compounds obtained by reducing tetravalent alkoxy titanium halide with an organometallic compound of a group metal of the periodic table. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. Specific examples of these catalysts include, for example, MgO-RX-TiCl 4 system (Japanese Patent Publication No. 51-3514), Mg-SiCl 4 -ROH-TiCl 4 system (Japanese Patent Publication No. 51-3514),
23864), MgCl 2 −Al(OR) 3 −TiCl 4 system (Japanese Patent Publication No. 51-152, Japanese Patent Publication No. 52-15111),
MgCl 2 −SiCl 4 −ROH−TiCl 4 system
106581), Mg (OOCR) 2 -Al (OR) 3 -TiCl 4 system (Special Publication No. 1972-
11710), Mg-POCl 3 -TiCl 4 system (Japanese Patent Publication No. 51-153), MgCl 2 -AlOCl-TiCl 4 system (Japanese Patent Publication No. 54-15316), MgCl 2 -Al(OR)nX 3 −n−Si(OR′)
Solid catalyst components such as mX 4-n -TiCl 4 system (JP-A-56-95909) (in the above formula, R,
An example of a preferred catalyst system is one in which R' is an organic residue and X is a halogen atom) in combination with an organoaluminum compound. Examples of other catalyst systems include solid catalyst components such as
An example is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound is used in combination with an organoaluminum compound. Examples of organomagnesium compounds include general formula RMgX,
Organomagnesium compounds such as R 2 Mg, RMg (OR) (where R is an organic residue having 1 to 20 carbon atoms,
represents a halogen) and their ether complexes, or these organomagnesium compounds may be further combined with other organometallic compounds such as organosodium, organolithium, organopotassium, organoboron,
Those modified by adding various compounds such as organic calcium and organic zinc can be used. Specific examples of these catalyst systems include, for example:
RMgX-TiCl 4 system (Special Publication No. 50-39470),
RMgX-Phenol TiCl 4 series (Special Publication No. 1984-12953)
(No. Publication), RMgX-Halogenated Phenol-
TiCl 4 series (Special Publication No. 12954/1983), RMgx−
Examples include combinations of organoaluminum compounds with solid catalyst components such as CO 2 -TiCl 4 (Japanese Unexamined Patent Publication No. 57-73009). In addition, as an example of another catalyst system, a solid substance obtained by contacting an inorganic oxide such as SiO 2 or Al 2 O 3 with a solid catalyst component containing at least magnesium and titanium is used as a solid catalyst component, An example of this can be combined with an organoaluminum compound. As an inorganic oxide
In addition to SiO 2 and Al 2 O 3 , CaO, B 2 O 3 , SnO 2 and the like can be used, and double oxides of these oxides can also be used without any problem. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium. That is, a method of reacting in the presence or absence of an inert catalyst at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or a combination of these methods as appropriate. The reaction may be carried out by Specific examples of these catalyst systems include, for example, the SiO 2 -ROH-MgCl 2 -TiCl 4 system (Japanese Patent Application Laid-Open No.
47407), SiO2 -R-O-R'-MgO- AlCl3
−TiCl 4 system (JP-A-57-187305), SiO 2 −
MgCl 2 −Al(OR) 3 −TiCl 4 −Si(OR′) 4 series (JP-A-Sho
58-21405) (in the above formula, R and R' represent hydrocarbon residues), in combination with an organic aluminum compound. In these catalyst systems, a titanium compound can be used as an adduct with an organic carboxylic acid ester, or the above-described magnesium-containing inorganic solid compound can be used after being brought into contact with an organic carboxylic acid ester. Further, there is no problem in using the organoaluminum compound as an adduct with the organic carboxylic acid ester. Furthermore, in all cases it is also possible to use catalyst systems prepared in the presence of organic carboxylic acid esters without any problems. Here, various aliphatic, alicyclic, and aromatic carboxylic esters are used as the organic carboxylic ester, and aromatic carboxylic esters having 7 to 12 carbon atoms are preferably used. Specific examples include alkyl esters of benzoic acid, anisic acid, toluic acid, such as methyl and ethyl. A specific example of an organoaluminum compound to be combined with the above-mentioned solid catalyst component is the general formula
R 3 Al, R 2 AlX, RAlX 2 , R 2 AlOR, RAl(OR)
An organoaluminum compound of X and R 3 Al 2 X 3 (where R is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms,
(R may be the same or different) Compounds represented by triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof are preferred. etc. can be mentioned. The amount of organoaluminum compound used is not particularly limited, but is usually 0.1 to 1000% of the titanium compound.
Molar times can be used. In addition, by bringing the above-mentioned catalyst system into contact with an α-olefin and then using it in the polymerization reaction, the polymerization activity can be greatly improved, and the system can be operated more stably than when untreated. Various α-olefins can be used at this time, but α-olefins having 3 to 12 carbon atoms are preferred, and α-olefins having 3 to 8 carbon atoms are more preferred. Examples of these α-olefins include propylene, butene-
Examples include 1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and mixtures thereof. The temperature and time during contact between the catalyst system and the α-olefin can be selected within a wide range, for example, the contact treatment can be carried out at 0 to 200°C, preferably 0 to 110°C, for 1 minute to 24 hours. α to contact
-The amount of olefin can be selected from a wide range, but usually
It is desirable to treat 1 g of the solid catalyst component with 1 g to 50,000 g, preferably 5 g to 30,000 g of α-olefin, and react with 1 g to 500 g of α-olefin per 1 g of the solid catalyst component. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to contact under a pressure of -1 to 100 kg/cm 2 ·G. During the α-olefin treatment, the entire amount of the organoaluminum compound used may be combined with the solid catalyst component and then brought into contact with the α-olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component. After combining with α
- The polymerization reaction may be carried out by contacting with the olefin and adding the remaining organoaluminum compound separately during the polymerization. Furthermore, there is no problem even if hydrogen gas coexists during contact between the catalyst system and α-olefin.
Further, there is no problem even if other inert gases such as nitrogen, argon, and helium coexist. The polymerization reaction is carried out in the same manner as the polymerization reaction of olefins using ordinary Ziegler type catalysts. That is, all reactions are carried out in a gas phase, in the presence of an inert solvent, or in the presence of the monomer itself as a solvent, substantially free of oxygen and other substances. The polymerization conditions for olefin are temperatures of 20 to 300℃, preferably 40 to 200℃.
℃, and the pressure is normal pressure to 70 kg/cm 2 ·G, preferably 2 kg/cm 2 ·G to 60 kg/cm 2 ·G.
Although the molecular weight can be controlled to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-stage or more multi-stage polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem. As described above, specific ethylene and - It was completely unexpected and surprising that an anti-slip member with excellent properties could be provided using an olefin copolymer. The ethylene/α-olefin copolymer of the present invention is clearly distinguished from the ethylene/α-olefin copolymer obtained by using one containing vanadium as a solid catalyst component. Even if the monomers constituting the copolymer are the same and the density is the same, DSC
The copolymer of the present invention has a higher Tm than that of the copolymer of the present invention, and the insoluble matter in boiling n-hexane is 10% by weight or more in the copolymer of the present invention, whereas the latter has no insoluble matter or even if it exists, The amount is extremely small. Due to these differences in the copolymers themselves, when used as the anti-slip member of the present invention, the copolymers of the present invention have superior heat resistance and strength as well as superior strength compared to the latter. , has an excellent balance of various performances required for use as anti-slip members. Furthermore, unlike titanium, vanadium present in the copolymer as a desolvent residue poses a toxicity problem, so a catalyst removal step is essential.However, when titanium is used as in the present invention, the toxicity of the catalyst residue No problems arise and the copolymers of the present invention, which use a highly active catalyst in combination with a magnesium support, are extremely economical since no catalyst removal step is required. Although the copolymer of the present invention may be used after being molded without adding a filler, it is preferably used as a composition containing an inorganic and/or organic filler. Inorganic and/or organic fillers include calcium carbonate, aluminum hydroxide, magnesia, talc, clay, titania, carbon black, fine silica, glass fiber, phenolic resin, petroleum resin, synthetic fiber (polyamide), and the like. Known methods can be used to blend the copolymer of the present invention and filler. At this time, as well as ordinary polyolefins, various stabilizers, foaming agents, foaming aids,
Flame retardants, pigments, etc. may also be added. Further, the molded product may be subjected to secondary processing such as embossing. The means, handrails, etc. to which the anti-slip member of the present invention is applied have a large anti-slip effect due to its large coefficient of friction, and the surface can be processed with irregularities, etc., and has an extremely low density, so it is lightweight and easy to construct. It is easy to mold, does not require any steps such as vulcanization and crosslinking after molding, and is extremely economical. In addition, as is clear from the basic structure of the resin, it does not contain unsaturated bonds and does not contain low molecular weight so-called wax components, so it has excellent weather resistance and can be used not only outdoors but also on outdoor stairs.
It can be used for handrails, steps of large mechanical equipment, ramps, etc. without any problems. Since the copolymer of the present invention contains a moderate amount of crystalline portion, it has elasticity not found in other conventional resins or rubbers, and after application, it has cushioning properties and excellent surface feeling. . When compared to rubber, the anti-slip member using the specific ethylene/α-olefin copolymer of the present invention does not require complicated processing steps and has excellent performance such as being able to be colored freely. The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. The polymers used in Examples and Comparative Examples are as follows. Example 1 Ethylene obtained by copolymerizing ethylene and butene-1 using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride, and a catalyst consisting of triethylaluminum.・Butene-1 copolymer. The ethylene content of this ethylene-butene-1 copolymer is 91.5 mol%, and the melt index is 0.5.
g/10min, density is 0.904g/cm 3 , maximum peak temperature of DSC is 120.5℃, boiling n-hexane insoluble content is
It was 94% by weight. Example 2 An ethylene-propylene copolymer obtained by copolymerizing ethylene and propylene using a solid catalyst component obtained from substantially anhydrous magnesium chloride, anthracene, and titanium tetrachloride and a catalyst consisting of triethylaluminum. The ethylene content of this ethylene-propylene copolymer is 81.5 mol%, and the melt index is 1.0.
g/10min, density is 0.890g/cm 3 , maximum peak temperature of DSC is 121.6℃, boiling n-hexane insoluble content is
It was 58% by weight. Example 3 Ethylene-propylene copolymer obtained by copolymerizing ethylene and propylene using a solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride, and a catalyst consisting of triethylaluminum. Combined. The ethylene content of this ethylene-propylene copolymer is 87 mol%, and the melt index is 11.0 g/
10 min, the density was 0.897 g/cm 3 , the maximum peak temperature of DSC was 122.5° C., and the content insoluble in boiling n-hexane was 85% by weight. Example 4 Ethylene content is 87.0 mol%, melt index is 2.3 g/10 min, density is 0.839 g/cm 3 , maximum peak temperature of DSC is 119.3°C, boiling n-hexane insoluble content is 78 wt%. Ethylene-butene-1 copolymer obtained in the same manner as Example-1. Comparative Example 1 Ethylene-vinyl acetate copolymer (vinyl acetate content 5% by weight), melt index 2.1g/
10min, density 0.926g/cm 3 . Comparative Example 2 Ethylene vinyl acetate copolymer (vinyl acetate content
15% by weight), melt index 3.5g/10min,
Density 0.934g/cm 3 . Comparative Example 3 Ethylene-butene-1 strong polymer obtained using a vanadium catalyst. Melt index 3.8g/
10 min, density 0.887 g/cm 3 , DSC maximum peak temperature 67.1°C, boiling n-hexane insoluble content 0.0%. The polymers of Examples 1 to 4 and Comparative Examples 1 to 3 described above were molded into sheets with a thickness of 6 mm, and the coefficient of dynamic friction was determined. The results are shown in Table 1.
【表】【table】
Claims (1)
する固体触媒成分と有機アルミニウム化合物から
なる触媒の存在下、エチレンとα−オレフインを
共重合させて得られる下記の(a)〜(d)の性状を有す
るエチレン・α−オレフイン共重合体からなるす
べり止め部材： (a) メルトインデツクス 0.01〜100ｇ／10min、 (b) 密度 0.860〜0.910ｇ／cm3、 (c) 示差走査熱量測定法（DSC）においてその
最大ピークの温度が100℃以上、 (d) 沸騰ｎ−ヘキサン不溶分が10重量％以上。 ２ 前記α−オレフインが炭素数３〜12のα−オ
レフインであることを特徴とする特許請求の範囲
第１項記載のすべり止め部材。[Claims] 1. The following (a) to (d) obtained by copolymerizing ethylene and α-olefin in the presence of a solid catalyst component containing at least magnesium and titanium and a catalyst consisting of an organoaluminum compound. Anti-slip member made of ethylene/α-olefin copolymer with properties: (a) Melt index 0.01-100g/10min, (b) Density 0.860-0.910g/ cm3 , (c) Differential scanning calorimetry ( DSC), the maximum peak temperature is 100°C or higher; (d) Boiling n-hexane insoluble content is 10% by weight or higher. 2. The anti-slip member according to claim 1, wherein the α-olefin is an α-olefin having 3 to 12 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58201632A JPS6095062A (en) | 1983-10-27 | 1983-10-27 | Anti-slip member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58201632A JPS6095062A (en) | 1983-10-27 | 1983-10-27 | Anti-slip member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6095062A JPS6095062A (en) | 1985-05-28 |
| JPH0366467B2 true JPH0366467B2 (en) | 1991-10-17 |
Family
ID=16444288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58201632A Granted JPS6095062A (en) | 1983-10-27 | 1983-10-27 | Anti-slip member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6095062A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753778B2 (en) * | 1985-10-14 | 1995-06-07 | 日本石油株式会社 | Roofing material and its sheet |
-
1983
- 1983-10-27 JP JP58201632A patent/JPS6095062A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6095062A (en) | 1985-05-28 |
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