JPH02135244A - Polypropylene composition - Google Patents
Polypropylene compositionInfo
- Publication number
- JPH02135244A JPH02135244A JP28923488A JP28923488A JPH02135244A JP H02135244 A JPH02135244 A JP H02135244A JP 28923488 A JP28923488 A JP 28923488A JP 28923488 A JP28923488 A JP 28923488A JP H02135244 A JPH02135244 A JP H02135244A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- mol
- copolymer
- pref
- ethylene
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 21
- -1 Polypropylene Polymers 0.000 title claims description 25
- 239000004743 Polypropylene Substances 0.000 title claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 33
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 27
- 239000010936 titanium Substances 0.000 description 25
- 229910052719 titanium Inorganic materials 0.000 description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000314 lubricant Substances 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical class [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 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
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、透明性、耐低温衝撃性、ヒートシール性な
どに優れたポリプロピレン組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a polypropylene composition having excellent transparency, low-temperature impact resistance, heat sealability, etc.
ポリプロピレンの耐低温衝撃性およびヒートシール性を
改良する方法として、ポリプロピレンにエチレン・プロ
ピレン共重合体あるいはエチレン・１−ブテン共重合体
などを添加する方法が良く知られている。しかしこの組
成物は、透明性の改良効果が十分ではない、またフィル
ムに成形した場合には、低温でのヒートシールは可能と
なるが、ヒートシール強度が低下するという問題点があ
る。A well-known method for improving the low-temperature impact resistance and heat sealability of polypropylene is to add an ethylene/propylene copolymer or an ethylene/1-butene copolymer to polypropylene. However, this composition has problems in that the effect of improving transparency is not sufficient, and when formed into a film, heat sealing is possible at low temperatures, but the heat sealing strength is reduced.
また、ポリプロピレンの透明性を改良する方法として、
ポリプロピレンにプロピレン・１−ブテン共重合体を添
加する方法が提案されている（特公昭５７−２４３７４
）。しかしこの組成物は耐低温衝撃性の点で、なお改良
が望まれている。In addition, as a method to improve the transparency of polypropylene,
A method of adding a propylene/1-butene copolymer to polypropylene has been proposed (Japanese Patent Publication No. 57-24374).
). However, it is still desired to improve this composition in terms of low-temperature impact resistance.
本発明の目的は、上記のような問題点を解決し。 An object of the present invention is to solve the above problems.
透明性、耐低温衝撃性、低温ヒートシール性ならびにヒ
ートシール強度などに優れたプロピレン組成物を提供す
ることである。An object of the present invention is to provide a propylene composition that has excellent transparency, low-temperature impact resistance, low-temperature heat-sealability, heat-seal strength, and the like.
本発明は、（Ａ）高結晶性プロピレン重合体４０ないし
９５重量％、ならびに
（Ｂ）プロピレンに由来する繰り返し単位（ａ）、エチ
レンに由来する繰り返し単位（ｂ）、および炭素原子数
が４ないし２０のα−オレフィンに由来する繰り返し単
位（ｃ）からなるプロピレン系共重合体であって、
（ｉ）プロピレンに由来する繰り返し単位（ａ）が４０
ないし８０モル％、エチレンに由来する繰り返し単位（
ｂ）が２ないし４０モル％、および上記α−オレフィン
に由来する繰り返し単位（ｃ）がＯないし４０モル％で
、かつ２０＜（ｂ＋ｃ）＜６０モル％の範囲にあり、
（ｉ）デカリン中で１３５℃で測定した極限粘度〔η〕
が０．１ないし７ｄｆｌ／ｇの範囲にあり、（ｉｉ）
Ｘ線回折法によって測定した結晶化度が４０％以下の範
囲にある
プロピレン系共重合体５ないし６０重量％からなること
を特徴とするポリプロピレン組成物である。The present invention comprises (A) 40 to 95% by weight of a highly crystalline propylene polymer, and (B) repeating units derived from propylene (a), repeating units derived from ethylene (b), and having 4 to 4 carbon atoms. A propylene-based copolymer consisting of repeating units (c) derived from 20 α-olefins, wherein (i) the repeating units (a) derived from propylene are 40
80 mol% of repeating units derived from ethylene (
b) is 2 to 40 mol%, and the repeating unit (c) derived from the α-olefin is O to 40 mol%, and in the range of 20<(b+c)<60 mol%, (i) in decalin. Intrinsic viscosity [η] measured at 135°C
is in the range of 0.1 to 7 dfl/g, (ii)
A polypropylene composition characterized by comprising 5 to 60% by weight of a propylene copolymer having a crystallinity of 40% or less as measured by X-ray diffraction.
本発明のポリプロピレン組成物において、 （Ａ）成分
の高結晶性プロピレン重合体は、プロピレンの単独重合
体、あるいはプロピレンと１０モル％以下の炭素原子数
２または４ないし２０の α−オレフィンとの高結晶性
共重合体であり、重合体のＭＦＲ（Ｌ）（ＡＳＴＭ ０
１２３８（Ｌ））が０．１ないし２００ｇ／ ｌｏｍｉ
ｎ、好ましくは０．３ないし１００ｇ／１０ｍ１ｎ、デ
カリン中１３５℃で測定した極限粘度〔η〕が１．０な
いし５．ＯｄＱ／ｇ、好ましくは１．２ないし４．Ｏｄ
Ｑ／ｇの範囲のものが好ましし１１１
上記のα−オレフィンとしては、エチレン、１−ブテン
、１−ペンテン、 １−ヘキセン、４−メチル−１−ペ
ンテン、３−メチル−１−ペンテン、ｌ−ヘプテン、１
−オクテン、１−ノネン、１−デセン、■−ドデセン、
■−テトラデセン、■−オクタデセンなどが例示でき、
これらは１種単独で、または２種以上組み合わせて共重
合させることができる。In the polypropylene composition of the present invention, the highly crystalline propylene polymer of component (A) is a homopolymer of propylene or a polymer of propylene and 10 mol% or less of an α-olefin having 2 or 4 to 20 carbon atoms. It is a crystalline copolymer, and the MFR (L) of the polymer (ASTM 0
1238(L)) is 0.1 to 200g/ lomi
n, preferably 0.3 to 100 g/10 m1n, and the intrinsic viscosity [η] measured in decalin at 135°C is 1.0 to 5. OdQ/g, preferably 1.2 to 4. Od
Preferably, those in the range of Q/g are 111. Examples of the above α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, l-heptene, 1
-octene, 1-nonene, 1-decene, ■-dodecene,
Examples include ■-tetradecene, ■-octadecene, etc.
These can be copolymerized singly or in combination of two or more.
本発明のポリプロピレン組成物において、（Ｂ）成分の
プロピレン系共重合体は、プロピレン成分（プロピレン
に由来する繰り返し単位（ａ））が４０ないし８０モル
％、好ましくは５０ないし８０モル％、より好ましくは
５０ないし７０モル％、エチレン成分（エチレンに由来
する繰り返し単位（ｂ））が２ないし４０モル％、好ま
しくは５ないし４０モル％、より好ましくはＩＯないし
３５モル％、および炭素原子数が４ないし２０のα−オ
レフィン成分（炭素原子数が４ないし２０のα−オレフ
ィンに由来する繰り返し単位（ｃ））がＯないし４０モ
ル％、好ましくは１０ないし３５モル％、より好ましく
は１５ないし３０モル％の範囲のものである。In the polypropylene composition of the present invention, the propylene copolymer as component (B) contains 40 to 80 mol%, preferably 50 to 80 mol%, more preferably 50 to 80 mol% of the propylene component (repeating unit (a) derived from propylene). is 50 to 70 mol%, the ethylene component (repeating unit (b) derived from ethylene) is 2 to 40 mol%, preferably 5 to 40 mol%, more preferably IO to 35 mol%, and the number of carbon atoms is 4. to 20 α-olefin components (repeating units (c) derived from α-olefins having 4 to 20 carbon atoms) are O to 40 mol%, preferably 10 to 35 mol%, more preferably 15 to 30 mol% % range.
炭素原子数が４ないし２０のα−オレフィンとしては１
−ブテン、１−ペンテン、１−ヘキセン、４−メチル−
１−ペンテン、３−メチル−１−ペンテン、１−ヘプテ
ン、１−オクテン、１−ノネン、１−デセン、■−ドデ
セン、ｌ−テトラデセン、１−オクタデセンなど炭素数
１８以下のものが好適であり、とくに炭素数４ないし１
０のものが好適である。As an α-olefin having 4 to 20 carbon atoms, 1
-butene, 1-pentene, 1-hexene, 4-methyl-
Those having 18 or less carbon atoms are preferable, such as 1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, ■-dodecene, 1-tetradecene, and 1-octadecene. , especially carbon number 4 to 1
A value of 0 is preferred.
（８）成分中のプロピレン成分が８０モル％より大きく
なると融点が高く、耐衝撃性、ヒートシール性は充分で
ない、プロピレン成分が４０モル％より小さくなると融
点、結晶化度が低く、ブロッキング性が大きくなる。ま
た、 （Ｂ）成分中のエチレン成分が４０モル％より大
きくなると重合体が不均一となり、透明性が充分でなく
なる。エチレン成分が２モル％より小さくなると融点、
結晶化度が高く、耐衝撃性は充分でない。またさらにＣ
Ｂ）成分中の上記α−オレフィン成分が４０モル％より
大きくなると、融点、結晶化度が低く、ブロッキング性
が大きくなる。ここで共重合体成分の組成はプレスフィ
ルムの赤外線吸収スペクトルから求められる。(8) If the propylene component in the ingredients is more than 80 mol%, the melting point will be high, and the impact resistance and heat sealability will be insufficient. If the propylene component is less than 40 mol%, the melting point and crystallinity will be low, and the blocking property will be poor. growing. Furthermore, if the ethylene component in component (B) exceeds 40 mol %, the polymer will become non-uniform and its transparency will not be sufficient. When the ethylene component is less than 2 mol%, the melting point
High crystallinity and insufficient impact resistance. Furthermore, C
If the α-olefin component in component B) exceeds 40 mol%, the melting point and crystallinity will be low and the blocking property will be high. Here, the composition of the copolymer component is determined from the infrared absorption spectrum of the pressed film.
（Ｂ）成分のプロピレン系共重合体のデカリン中１３５
℃中で測定した極限粘度〔η〕は０．１ないし７ｄＱ／
ｇ、好ましくは０．２ないし５ｄＱ／ｇの範囲である。135 in decalin of propylene copolymer as component (B)
The intrinsic viscosity [η] measured at °C is 0.1 to 7 dQ/
g, preferably in the range of 0.2 to 5 dQ/g.
この特性値は（Ｂ）成分のプロピレン系共重合体の分子
量を示す尺度であり、他の特性値と結合することにより
、前述の優れた性質のプロピレン系共重合体の提供に役
立っている。This characteristic value is a measure of the molecular weight of the propylene copolymer of component (B), and when combined with other characteristic values, it is useful in providing the above-mentioned propylene copolymer with excellent properties.
（Ｂ）成分のプロピレン系共重合体のＸ線回折法によっ
て測定した結晶化度は４０％以下、好ましくは３０％以
下の範囲である。この特性値は（Ｂ）成分のプロピレン
系共重合体が耐衝撃性に優れることを示す尺度であり、
他の特性値と結合することにより前述の優れた性質のプ
ロピレン系共重合体の提供に役立っている。結晶化度は
成形後２０時間経過後の厚さ１ 、５ｍｍのプレスシー
トのＸ線回折測定により求められる。The crystallinity of the propylene copolymer as component (B) measured by X-ray diffraction is in the range of 40% or less, preferably 30% or less. This characteristic value is a measure showing that the propylene copolymer of component (B) has excellent impact resistance.
By combining this with other characteristic values, it is useful to provide a propylene copolymer with the above-mentioned excellent properties. The degree of crystallinity is determined by X-ray diffraction measurement of a pressed sheet with a thickness of 1.5 mm 20 hours after molding.
本発明のポリプロピレン組成物は、上記の高結晶性プロ
ピレン重合体（Ａ）を４０ないし９５重量％、好ましく
は５０ないし９０重量％、および上記のプロピレン系共
重合体（Ｂ）を５ないし６０重量％、好ましくはＩＯな
いし５０重量％の割合で配合したものである。低結晶性
プロピレン系共重合体（Ｂ）の配合割合が５重量％未満
では耐低温衝撃性およびヒートシール性の改善が十分で
なく、６０重量％を超えると耐熱性が悪くなる。The polypropylene composition of the present invention contains the above-mentioned highly crystalline propylene polymer (A) in an amount of 40 to 95% by weight, preferably 50 to 90% by weight, and the above-mentioned propylene copolymer (B) in an amount of 5 to 60% by weight. %, preferably IO to 50% by weight. If the proportion of the low-crystalline propylene copolymer (B) is less than 5% by weight, the improvement in low-temperature impact resistance and heat sealability will not be sufficient, and if it exceeds 60% by weight, the heat resistance will deteriorate.
本発明のポリプロピレン組成物は、上記（Ａ）成分と（
Ｂ）成分を必須成分とするものであるが、これらの必須
成分のほかに本発明の目的に反しない範囲で、他の樹脂
、耐熱安定剤、耐候安定剤、帯電防止剤、スリップ剤、
アンチブロッキング剤、防曇剤、滑剤、染料、顔料、充
填剤、天然油、合成油、ワックスなどの配合剤を配合す
ることができ、その配合割合は適宜量である。The polypropylene composition of the present invention comprises the above component (A) and (
Component B) is an essential component, but in addition to these essential components, other resins, heat stabilizers, weather stabilizers, antistatic agents, slip agents,
Compounding agents such as anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, fillers, natural oils, synthetic oils, and waxes can be blended, and the blending ratios thereof are appropriate.
次に（Ｂ）成分のプロピレン系共重合体の製造方法につ
いて説明する。Next, a method for producing the propylene copolymer as component (B) will be explained.
（Ｂ）成分のプロピレン系共重合体の製造方法は、特開
昭６２−２４１９１０号に示されているように、■マグ
ネシウム、チタン、ハロゲンおよび電子供与体を必須成
分として含有する高立体規則性のチタン触媒成分、
■有機アルミニウム化合物触媒成分、および■電子供与
体触媒成分
から形成される触媒の存在下で、プロピレン、エチレン
および炭素原子数が４ないし２０の α−オレフィンを
共重合させることにより製造することができる。As shown in JP-A No. 62-241910, the method for producing the propylene copolymer of component (B) is as follows: by copolymerizing propylene, ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a catalyst formed from a titanium catalyst component, an organoaluminum compound catalyst component, and an electron donor catalyst component. can be manufactured.
（Ｂ）成分の製造に用いられる上記■の高活性、高立体
規則性固体状チタン触媒成分はマグネシウム、チタン、
ハロゲンおよび電子供与体を必須成分として含有するも
ので、マグネシウム／チタン（原子比）が１より大きく
、好ましくは３ないし５０、とくに好ましくは６ないし
３０、ハロゲン／チタン（原子比）が好ましくは４ない
し１００、 とくに好ましくは６ないし４０．電子供与
体／チタン（モル比）が好ましくは０．１ないし１０、
とくに好ましくは０．２ないし６の範囲にあるのが望ま
しい、その比表面積は好ましくは３ｍ２／ｇ以上、−層
好ましくは４０１１＋２／ｇ以上、さらに好ましくは１
００ないし８００ｍ”／ｇである。固体状チタン触媒成
分■は、平均粒径がたとえば１ないし２００μｍ、好ま
しくは３ないし１００μ■、とくに好ましくは６ないし
５０μ曹であって、粒度分布の幾何標準偏差がたとえば
２．１未満、好ましくは１．９以下、さらに好ましくは
１．７以下であるのが望ましい。The highly active and highly stereoregular solid titanium catalyst component (①) used in the production of component (B) is magnesium, titanium,
It contains a halogen and an electron donor as essential components, and the magnesium/titanium (atomic ratio) is greater than 1, preferably 3 to 50, particularly preferably 6 to 30, and the halogen/titanium (atomic ratio) is preferably 4. from 100 to 100, particularly preferably from 6 to 40. electron donor/titanium (molar ratio) preferably from 0.1 to 10;
The specific surface area is particularly preferably in the range of 0.2 to 6. The specific surface area is preferably 3 m2/g or more, preferably 4011+2/g or more, and more preferably 1
00 to 800 m"/g. The solid titanium catalyst component has an average particle diameter of, for example, 1 to 200 μm, preferably 3 to 100 μm, particularly preferably 6 to 50 μm, and the geometric standard deviation of the particle size distribution. is preferably less than 2.1, preferably 1.9 or less, more preferably 1.7 or less.
このような条件を全て満足するようなチタン触媒成分■
は、たとえば平均粒子径および粒度分布。A titanium catalyst component that satisfies all of these conditions■
is, for example, the average particle size and particle size distribution.
さらに好ましくは形状が前述のような範囲にあるような
マグネシウム化合物を形成した後触媒調製を行う方法、
あるいは液状のマグネシウム化合物と液状のチタン化合
物を接触させて前記のような粒子性状となるように固体
状触媒を形成させる方法などによって得ることができる
。このような方法はたとえば特開昭５５−１３５１０２
号、同５５−１３５１０３号、同５６−８１１号、同５
６−６７３１１号、同５８−８３００６号などに開示さ
れている。More preferably, a method in which a catalyst is prepared after forming a magnesium compound having a shape within the above-mentioned range;
Alternatively, it can be obtained by a method in which a liquid magnesium compound and a liquid titanium compound are brought into contact to form a solid catalyst having the particle properties as described above. Such a method is described, for example, in Japanese Patent Application Laid-Open No. 55-135102.
No. 55-135103, No. 56-811, No. 5
It is disclosed in No. 6-67311, No. 58-83006, etc.
チタン触媒成分■の調製に用いられるマグネシウム化合
物としては、酸化マグネシウム、水酸化マグネシウム、
へイドロタルサイト、マグネシウムのカルボン酸塩、ア
ルコキシマグネシウム、アリロキシマグネシウム、アル
コキシマグネシウムハライド、アリロキシマグネシウム
ハライド、マグネシウムシバライド、有機マグネシウム
化合物、有機マグネシウム化合物と電子供与体、ハロシ
ラン、アルコキシシラン、シラノール、アルミニウム化
合物などとの反応物などを例示することができる。上記
チタン触媒成分■の調製に用いられることのある有機ア
ルミニウム化合物としては、後述する有機アルミニウム
化合物■の中から選ぶことができる。さらにチタン触媒
成分■の調製に用いられることのあるハロゲン含有ケイ
素化合物としては、テトラハロゲン化ケイ素、アルコキ
シハロゲン化ケイ素、アルキルハロゲン化ケイ素、ハロ
ポリシロキサンなどが例示できる。Magnesium compounds used in the preparation of titanium catalyst component ■ include magnesium oxide, magnesium hydroxide,
Hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium cybaride, organomagnesium compounds, organomagnesium compounds and electron donors, halosilanes, alkoxysilanes, silanols, Examples include reactants with aluminum compounds and the like. The organoaluminum compound that may be used in the preparation of the titanium catalyst component (1) can be selected from the organoaluminum compounds (2) described below. Furthermore, examples of halogen-containing silicon compounds that may be used in the preparation of titanium catalyst component (1) include silicon tetrahalides, silicon alkoxy halides, silicon alkyl halides, and halopolysiloxanes.
チタン触媒成分■の調製に用いられるチタン化合物の例
としては、テトラハロゲン化チタン、アルコキシチタン
ハライド、アリロキシチタンハライド、アルコキシチタ
ン、アリロキシチタンなどが例示でき、とくにテトラハ
ロゲン化チタン、中でも四塩化チタンが好ましい。Examples of titanium compounds used in the preparation of titanium catalyst component (III) include titanium tetrahalide, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium, and especially titanium tetrahalide, especially tetrachloride titanium. Titanium is preferred.
チタン触媒成分■の調製に用いることのできる電子供与
体としては、アルコール、フェノール類、ケトン、アル
デヒド、カルボン酸、有機酸または無機酸のエステル、
エーテル、酸アミド、酸無水物のアルコキシシランのよ
うな含酸素電子供与体、アンモニア、アミン、ニトリル
、イソシアネートのような含窒素電子供与体などを例示
することができる。Electron donors that can be used in the preparation of the titanium catalyst component (■) include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids,
Examples include oxygen-containing electron donors such as alkoxysilanes such as ethers, acid amides, and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.
（Ｂ）成分の製造に用いられる前記■の有機アルミニウ
ム化合物触媒成分の好適なものは有機アルミニウム化合
物であって、少なくとも分子内に１個のアルミニウムー
炭素結合を有する化合物が利用でき、たとえば、（ｉ）
−儀式Ｒ”、Ａｌ（ＯＲ”）ｎ／ＨｐＸｑ（ここで８１
およびＲ２は炭素原子通常工ないし１５個、好ましくは
１ないし４個を含む炭化水素基で互いに同一でも異なっ
てもよい。Ｘはハロゲン、ｍは０＜ｍ≦３、ｎはＯ≦ｎ
（３、ｐは０≦ｐ ＜ ３、ｑはＯ≦ｑ ＜ ３の数
であって、しかもｍ ＋ ｎ ＋ ｐ＋９＝３である）
で表わされる有機アルミニウム化合物、 （ｉ）−形式
Ｍ”ＡＩＲ”４ （ここでＭｌはＬｉ、 Ｎａ、Ｋであ
り、Ｒ１は前記と同じ）で表わされる周期律表第１族に
属する金属とアルミニウムとの錯アルキル化物などをあ
げることができる。Preferably, the organoaluminum compound catalyst component (2) used in the production of component (B) is an organoaluminum compound, and a compound having at least one aluminum-carbon bond in the molecule can be used. For example, ( i)
- Ritual R”, Al(OR”)n/HpXq (where 81
and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. X is halogen, m is 0<m≦3, n is O≦n
(3, p is a number such that 0≦p<3, q is a number such that O≦q<3, and m + n + p+9 = 3)
an organoaluminum compound represented by (i) - a metal belonging to Group 1 of the periodic table represented by the form M"AIR"4 (where Ml is Li, Na, K, and R1 is the same as above) and aluminum; Examples include complex alkylated products with.
前記（ｉ）に属する有機アルミニウム化合物としては、
−儀式Ｒ’、、Ａｌ（ＯＲ２）、、（ここでＲ１および
Ｒ２は前記と同じ。ｍは好ましくは１．５≦ｍ≦３の数
である）、−儀式Ｒ１，ＡＩＸａ−（： コテＲ１は前
記と同じ。Ｘはハロゲン、ｍは好ましくはＯ＜ ｍ ＜
３である）、−儀式Ｒ”、Ａ１１（３−、（ここでＲ
１は前記と同じ。ｍは好ましくは２≦ｍ＜３である）、
−儀式Ｒ１ｊＩ （ＯＲ” ） ｎＸ’ｌ （ここでＲ
１およびＲ２は前記と同じ。As the organoaluminum compounds belonging to the above (i),
-Ritual R',,Al(OR2),, (where R1 and R2 are the same as above.m is preferably a number of 1.5≦m≦3), -Ritual R1, AIXa-(: Kote R1 is the same as above. X is halogen, m is preferably O<m<
3), -ritual R'', A11(3-, (where R
1 is the same as above. m is preferably 2≦m<3),
-Ritual R1jI (OR”) nX'l (where R
1 and R2 are the same as above.
Ｘはハロゲン、Ｏ＜ｍ≦３，０≦ｎ＜３．０≦ｑ〈３で
、ｍ ＋ ｎ ＋ ｑ ＝ ３である）で表わされるも
のなどを例示できる。For example, X is a halogen, O<m≦3, 0≦n<3.0≦q<3, and m + n + q = 3).
前記（ｉ）に属する化合物としては、ＬｉＡ１（ｃ２Ｈ
Ｇ）４、ＬｉＡｌ（ｃ，Ｈ工、）４などを例示できる。As a compound belonging to the above (i), LiA1(c2H
Examples include G) 4, LiAl(c, H engineering,) 4, and the like.
これらの中では、とくにトリアルキルアルミニウム、ま
たはトリアルキルアルミニウムとアルキルアルミニウム
ハライドもしくはアルミニウムハライドとの混合物を用
いるのが好ましい。Among these, it is particularly preferable to use trialkylaluminum or a mixture of trialkylaluminum and alkyl aluminum halide or aluminum halide.
（Ｂ）成分の製造に用いられる前記■の電子供与体触媒
成分の例としては、アミン類、アミド類、エーテル類、
ケトン類、ニトリル類、ホスフィン類、スチビン類、ア
ルシン類、ホスホルアミド類、エステル類、チオエーテ
ル類、チオエステル類、酸無水物類、酸ハライド類、ア
ルデヒド類、アルコレート類、アルコキシ（アリロキシ
）シラン類、有機酸類および周期律表の第１族ないし第
４族に属する金属のアミド類および塩類などがある。Examples of the electron donor catalyst component (2) used in the production of component (B) include amines, amides, ethers,
Ketones, nitriles, phosphines, stibines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, These include organic acids and amides and salts of metals belonging to Groups 1 to 4 of the periodic table.
（Ｂ）成分のプロピレン系共重合体の製造は、前記■の
チタン触媒成分、■の有機アルミニウム化合物触媒成分
および■の電子供与体触媒成分から形成される触媒の存
在下に不活性炭化水素溶媒中で、または溶媒を用いない
でプロピレン、エチレンおよび炭素原子数が４ないし２
０のα−オレフィンを共重合させることにより行われる
。この場合不活性炭化水素溶媒中で生成する共重合体が
溶解する条件下で共重合反応を行う方法を採用するのが
とくに好ましい。The propylene copolymer as component (B) is produced in an inert hydrocarbon solvent in the presence of a catalyst formed from the titanium catalyst component (1), the organoaluminum compound catalyst component (2), and the electron donor catalyst component (2). Propylene, ethylene and C4 to C2 in or without solvent
This is carried out by copolymerizing 0 α-olefins. In this case, it is particularly preferable to employ a method in which the copolymerization reaction is carried out under conditions in which the copolymer produced in an inert hydrocarbon solvent is dissolved.
共重合反応を行う場合、前記■のチタン触媒成分１ｇに
対して、 １００ないし１００，０００ｇ、好ましくは
１５０ないし２０，０００ｇ、より好ましくは２００な
いし１０．０００ｇのプロピレン、エチレンおよび炭素
原子数が４ないし２０のα−オレフィンを共重合させる
のが望ましい。When carrying out a copolymerization reaction, 100 to 100,000 g, preferably 150 to 20,000 g, more preferably 200 to 10.000 g of propylene, ethylene, and carbon atoms each having a carbon number of 4 are added to 1 g of the titanium catalyst component (2) above. It is desirable to copolymerize from 1 to 20 α-olefins.
共重合反応において不活性溶媒を使用するときは、不活
性溶媒１ａ当り、■のチタン触媒成分をチタン原子に換
算して０．００１ないし５００ミリモル、とくに好まし
くはｏ、ｏｏｓないし２００ミリモルとするのが好まし
く、また■の有機アルミニウム化合物触媒成分をＡｔ／
Ｔｉ （ＦＡ子比）が０．１ないし１０００、とくに好
ましくは０．５ないし５００となるような割合で用いる
のが好ましい、また■の電子供与体触媒成分は、■のチ
タン触媒成分に担持されていてもよく、■の有機アルミ
ニウム化合物触媒成分に付加して用いてもよく、また遊
離の状態で重合系に添加してもよい、いずれにしても■
の電子供与体触媒成分は、チタン原子１モル当り０．１
ないし２００モル、とくに好ましくは０．２ないし５０
モル程度存在させればよい。When an inert solvent is used in the copolymerization reaction, the amount of the titanium catalyst component (2) in terms of titanium atoms is 0.001 to 500 mmol, particularly preferably o, oos to 200 mmol, per 1a of the inert solvent. is preferable, and the organoaluminum compound catalyst component (①) is preferably At/
It is preferable to use Ti (FA ratio) in a proportion of 0.1 to 1000, particularly preferably 0.5 to 500, and the electron donor catalyst component (2) is supported on the titanium catalyst component (2). It may be added to the organoaluminum compound catalyst component of (■), or it may be added to the polymerization system in a free state.
The electron donor catalyst component of is 0.1 per mole of titanium atom.
200 mol to 200 mol, particularly preferably 0.2 to 50 mol
It is sufficient if it is present in a molar amount.
共重合反応に用いられる不活性炭化水素溶媒としては、
プロパン、ブタン、ｎ−ペンタン、イソペンタン、ｎ−
ヘキサン、イソヘキサン、ｎ−へブタン、ｎ−オクタン
、イソオクタン、ｎ−デカン、ｎ−ドデカン、灯油など
の脂肪族炭化水素、シクロペンタン、メチルシクロペン
タン、シクロヘキサン、メチルシクロヘキサンのような
脂環族炭化水素、ベンゼン、トルエン、キシレンのよう
な芳香族炭化水素、メチレンクロリド、エチルクロリド
、エチレンクロリド、クロルベンゼンのようなハロゲン
化炭化水素などを例示することができ、中でも脂肪族炭
化水素、とくに炭素数４ないし１０の脂肪族炭化水素が
好ましい。Inert hydrocarbon solvents used in copolymerization reactions include:
Propane, butane, n-pentane, isopentane, n-
Aliphatic hydrocarbons such as hexane, isohexane, n-hebutane, n-octane, isooctane, n-decane, n-dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane , aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as methylene chloride, ethyl chloride, ethylene chloride, and chlorobenzene. Among them, aliphatic hydrocarbons, especially those having 4 carbon atoms, to 10 aliphatic hydrocarbons are preferred.
共重合温度は適宜に選択でき、好ましくは約２０ないし
約２００℃、−層好ましくは約５０ないし約１８０℃程
度、圧力も適宜に選択でき、大気圧ないし約１００ｋｇ
／ａＪ、 好ましくは大気圧ないし約５０ｋｇ／ａＪ
程度の加圧条件下で行うのが好ましい。The copolymerization temperature can be selected as appropriate, preferably from about 20 to about 200°C, preferably about 50 to about 180°C, and the pressure can be selected as appropriate, from atmospheric pressure to about 100 kg.
/aJ, preferably atmospheric pressure to about 50 kg/aJ
It is preferable to carry out the process under moderate pressure conditions.
分子量の調節は、重合温度、触媒成分の使用割合などの
重合条件を変えることによっである程度調節できるが、
重合系中に水素を添加するのが最も効果的である。The molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and proportion of catalyst components used.
It is most effective to add hydrogen into the polymerization system.
本発明のポリプロピレン組成物は、透明性、耐低温衝撃
性に優れているため、ボトルその他の容器類、およびシ
ートなどの成形品の用途に適している。またヒートシー
ル性に優れ、低温でヒートシールできるとともに、ヒー
トシール強度に優れるため、上記用途のほか、包装用フ
ィルムなどの成形品として広く利用することができる。Since the polypropylene composition of the present invention has excellent transparency and low-temperature impact resistance, it is suitable for use in molded products such as bottles and other containers, and sheets. In addition, it has excellent heat-sealing properties, can be heat-sealed at low temperatures, and has excellent heat-sealing strength, so it can be widely used in molded products such as packaging films in addition to the above-mentioned applications.
本発明によれば、高結晶性プロピレン重合体に特定のプ
ロピレン系共重合体を配合したため、透明性、耐低温衝
撃性、低温ヒートシール性、ヒートシール強度などに優
れたポリプロピレン組成物が得られる。According to the present invention, since a specific propylene-based copolymer is blended with a highly crystalline propylene polymer, a polypropylene composition with excellent transparency, low-temperature impact resistance, low-temperature heat-sealability, heat-seal strength, etc. can be obtained. .
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
参考例１ プロピレン系共重合体（Ｂ）の製造〈チタン
触媒成分の調製〉
無水塩化マグネシウム４．７６ｇ（５０ｍｍｏｌ）、デ
カン２５＋ｕおよび２−エチルヘキシルアルコール２３
．４ｍＭ（１５０ｍｍ＋ｏｌ）を１３０℃で２時間加熱
反応を行い均一溶液とした後、この溶液中に無水フタル
酸１．１１ｇ（７，５ｍｍｏｌ）を添加し、１３０℃に
てさらに１時間攪拌混合を行い、無水フタル酸を上記均
一溶液に溶解させる。このようにして得られた均一溶液
を室温に冷却した後、−２０℃に保持された四塩化チタ
ン２００ｍＱ（１，８ｍｏｌ）中に１時間にわたって全
量滴下注入する。注入終了後、この混合液の温度を４時
間かけて１１０℃に昇温し、１１０℃に達したところで
ジイソブチ／ｌ／７タレート２．６８ｍｆｌ（１２，５
ｍｍｏｌ）を添加し。Reference Example 1 Production of propylene copolymer (B) <Preparation of titanium catalyst component> Anhydrous magnesium chloride 4.76 g (50 mmol), decane 25+u and 2-ethylhexyl alcohol 23
．． 4mM (150mm+ol) was subjected to a heating reaction at 130°C for 2 hours to form a homogeneous solution, then 1.11g (7.5mmol) of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130°C for 1 hour. , phthalic anhydride is dissolved in the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was poured dropwise over 1 hour into 200 mQ (1.8 mol) of titanium tetrachloride maintained at -20°C. After the injection was completed, the temperature of this mixture was raised to 110°C over 4 hours, and when it reached 110°C, 2.68 mfl (12,5
mmol) was added.
撹拌下で２時間１１０℃の温度を保持する。２時間の反
応終了後熱濾過にて固体部を採取し、この固体部を２０
０ｍｆｌのＴｉＣ１，にて再懸濁させた後、再び１１０
℃で２時間加熱反応を行う６反応終了後、再び熱濾過に
て固体部を採取し、１１０℃のデカンおよびヘキサンに
て、洗液中に遊離のチタン化合物が検出されなくなるま
で充分洗浄する。A temperature of 110° C. is maintained for 2 hours under stirring. After 2 hours of reaction, the solid part was collected by hot filtration, and this solid part was
After resuspending in 0 mfl TiC1,
After the completion of the 6 reactions in which the reaction is heated for 2 hours at °C, the solid portion is again collected by hot filtration and thoroughly washed with decane and hexane at 110 °C until no free titanium compound is detected in the washing liquid.
以上の製造方法にて合成されたチタン触媒成分の組成は
チタン３．１重量％、塩素５６．０重量％、マグネシウ
ム１７．０重景％およびジイソブチルフタレート２０．
９重量％であった。The composition of the titanium catalyst component synthesized by the above production method was 3.1% by weight of titanium, 56.0% by weight of chlorine, 17.0% by weight of magnesium, and 20% by weight of diisobutyl phthalate.
It was 9% by weight.
く重 合〉
内容積２００Ｑの連続重合反応器を用い、脱香精製した
ヘキサンを１００Ｑ／ｈｒ、エチレンを０．５ｋｇ／ｈ
ｒ、プロピレンを５．５ｋｇ／ｈｒ、１−ブテンを６．
０ｋｇ／ｈｒの割合で、また水素を重合反応器中のガス
相濃度が５ｓｏ−１％になるように供給し、一方チタン
触媒成分をチタン原子に換算してり、２ｍｍｏｌ／ｈｒ
、トリイソブチルアルミニウム６０ａ＋ｍｏｌ／ｈｒ、
ジフェニルジメトキシシラン７．２ｍｍｏｌ／ｈｒの割
合で供給し、重合温度７０℃、重合圧力２ｋｇ／ｃＩ１
１２．滞留時間１時間となる条件下で共重合を行った。Polymerization> Using a continuous polymerization reactor with an internal volume of 200Q, deodorized and purified hexane was used at 100Q/hr and ethylene at 0.5kg/hr.
r, propylene at 5.5 kg/hr, 1-butene at 6.
Hydrogen was supplied at a rate of 0 kg/hr, and hydrogen was supplied so that the gas phase concentration in the polymerization reactor was 5so-1%, while the titanium catalyst component was converted to titanium atoms, and hydrogen was supplied at a rate of 2 mmol/hr.
, triisobutylaluminum 60a+mol/hr,
Diphenyldimethoxysilane was supplied at a rate of 7.2 mmol/hr, the polymerization temperature was 70°C, and the polymerization pressure was 2 kg/cI1.
12. Copolymerization was carried out under conditions where the residence time was 1 hour.
得られたプロピレン・エチレン・ｌ−ブテン共重合体（
以下ＦＥＢ−１と記す）の物性は、プロピレン含有量６
４ａ＋ｏ１％、エチレン含有ｆ１４ｍｏ１％、■−ブテ
ン含有量２２ｍｏ１％、極限粘度〔η） ＝ １，５ｄ
Ｑ、／ｇ、結晶化度＝１６％、融点（Ｔｍ） ＝ ６４
℃であった。The obtained propylene/ethylene/l-butene copolymer (
The physical properties of the product (hereinafter referred to as FEB-1) are that the propylene content is 6.
4a+o1%, ethylene content f14mo1%, ■-butene content 22mo1%, intrinsic viscosity [η) = 1,5d
Q, /g, crystallinity = 16%, melting point (Tm) = 64
It was ℃.
実施例１
上記ＦＥＢ−１３０重量％と高結晶性プロピレン・エチ
レンランダム共重合体（ＭＦＲ（Ｌ） ： ２０ｇ／１
０ｍ１ｎ、エチレン含有量： ２．７ｓｏ１％、極限粘
度（ｙ＋ ） ： １．６ｄｆｌ／ｇ、以下ＰＰ−１と
記す）７０重量％をヘンシェルミキサーで混合後、−軸
押出機（設定温度２３０℃）中で溶融混練して組成物ｌ
を得た。Example 1 30% by weight of the above FEB-1 and highly crystalline propylene/ethylene random copolymer (MFR(L): 20g/1
0mln, ethylene content: 2.7so1%, intrinsic viscosity (y+): 1.6dfl/g, hereinafter referred to as PP-1) 70% by weight were mixed in a Henschel mixer, then a -shaft extruder (set temperature 230°C) The composition is melted and kneaded in
I got it.
次いで、この組成物ｌを用いて射出成形機にて、試験片
を成形した。この試験片について１曲げ初期弾性率、Ｉ
ＺＯＤ衝撃強度、ヘイズを下記の方法で測定した。結果
を第１表に示す。Next, a test piece was molded using this composition 1 using an injection molding machine. For this test piece, 1 bending initial elastic modulus, I
ZOD impact strength and haze were measured by the following methods. The results are shown in Table 1.
（１）曲げ初期弾性率（ｋｇｆ／ｃｄ） ： ＡＳＴＭ
Ｄ７９０（２） ＩＺＯＤ衝撃強度（ｋｇ−ｃｎ＋／
ｃｍ） ： ＡＳＴＭ Ｄ２５６（ノツチ付）（３）ヘ
イズ（％） ： ＡＳＴＭ ＤＩＯ０３（２龍厚）比較
例１
実施例１で用いたＦＥＢ−１の代わりに、参考例１に準
じて製造した低結晶性エチレン・１−ブテンランダム共
重合体（ＭＦＲ（Ｅ）： ３．６ｇ／ｌｏｍｉｎ、密度
二０．８８６ｇ／ｊ 、融点；７０℃、■−ブテン含有
量： ｌｌｍｏｌ％、以下ＥＢ−１と記す）を用いる以
外は実施例１と同様に行った。結果を第１表に示す。(1) Initial bending modulus (kgf/cd): ASTM
D790 (2) IZOD impact strength (kg-cn+/
cm) : ASTM D256 (notched) (3) Haze (%) : ASTM DIO03 (2 dragon thickness) Comparative Example 1 Instead of FEB-1 used in Example 1, low crystal produced according to Reference Example 1 ethylene/1-butene random copolymer (MFR(E): 3.6 g/lomin, density 20.886 g/j, melting point: 70°C, ■-butene content: llmol%, hereinafter referred to as EB-1 ) was carried out in the same manner as in Example 1 except for using. The results are shown in Table 1.
比較例２
実施例１で用いたＦＥＢ−１の代わりに、参考例１に準
じて製造した低結晶性プロピレン弓−ブテンランダム共
重合体（ＭＦＲ（Ｌ）： ７．０ｇ／１０ｍ１ｎ、密度
＝０．８８５ｇ／ｃｉ！、融点＝１１０℃、１−ブテン
含有量：２８ｍｏ１％、以下ＰＢ−１と記す）を用いる
以外は実施例１と同様に行った。結果を第１表に示す。Comparative Example 2 Instead of FEB-1 used in Example 1, a low-crystalline propylene bow-butene random copolymer (MFR (L): 7.0 g/10 m1n, density = 0) manufactured according to Reference Example 1 was used. .885 g/ci!, melting point = 110°C, 1-butene content: 28 mo1%, hereinafter referred to as PB-1) was used in the same manner as in Example 1. The results are shown in Table 1.
第１表
実施例２
実施例１で用いたＦＥＢ−１２０重量％と高結晶性プロ
ピレン・エチレンランダム共重合体（ＭＦＲ（Ｌ） ：
６．５ｇ／１０ｍ１ｎ、エチレン含有量： ４．７ｓｏ
１％、以下ｐｐ−２と記す）８０重量％とをヘンシェル
ミキサーで混合後、この混合組成物よりキャストフィル
ム成形機でＩ［２５０ａ＋ｍ、厚さ５０μｍの試験フィ
ルムを成形した。なお、成形時の樹脂温度は２３０℃、
チルロール温度は２０℃、スクリュ回転数は８０ｒｐｍ
で行った。Table 1 Example 2 20% by weight of FEB-1 used in Example 1 and highly crystalline propylene/ethylene random copolymer (MFR(L):
6.5g/10mln, ethylene content: 4.7so
1% (hereinafter referred to as pp-2)) and 80% by weight were mixed in a Henschel mixer, and a test film of I[250a+m, thickness 50 μm was formed from this mixed composition using a cast film molding machine. The resin temperature during molding was 230°C.
Chill roll temperature is 20℃, screw rotation speed is 80 rpm
I went there.
上記の試験フィルムについて、０℃の衝撃強度。Impact strength at 0°C for the above test films.
ヘイズ、ヒートシール強度を下記の方法で測定した。結
果を第２表に示す。Haze and heat seal strength were measured by the following methods. The results are shown in Table 2.
（１）衝撃強度（ｋｒｅｍ／ｃｍ）： ＡＳＴＭ ０３
４２０（２）ヘイズ（％） ： ＡＳＴＭ ０１００３
（３）ヒートシール強度（ｇ／１５ｍｍ幅）：ヒートシ
ール圧力； ２ｋｇ／ａｌ
ヒートシール時間プ１ ｓｅｃ
引張速度 ； ３００ｍｍ／ｗｉｎ比較例３
実施例２で用いたＰＥＢ−１の代わりに、比較例１で用
いたＥＢ−１を用いる以外は実施例２と同様に行った。(1) Impact strength (krem/cm): ASTM 03
420(2) Haze (%): ASTM 01003
(3) Heat-sealing strength (g/15mm width): Heat-sealing pressure; 2kg/al; Heat-sealing time: 1 sec; Tensile speed; 300mm/win Comparative Example 3 Instead of PEB-1 used in Example 2, Comparative Example Example 2 was carried out in the same manner as in Example 2 except that EB-1 used in Example 1 was used.
結果を第２表に示す６
比較例４
実施例２で用いたＰＥＢ−１の代わりに比較例２で用い
たＰＢ−１を用いる以外は実施例２と同様に行った。結
果を第２表に示す。The results are shown in Table 2.6 Comparative Example 4 The same procedure as in Example 2 was conducted except that PB-1 used in Comparative Example 2 was used instead of PEB-1 used in Example 2. The results are shown in Table 2.
第２表Table 2
Claims (1)
重量％、ならびに （Ｂ）プロピレンに由来する繰り返し単位（ａ）、エチ
レンに由来する繰り返し単位（ｂ）、および炭素原子数
が４ないし２０のα−オレフィンに由来する繰り返し単
位（ｃ）からなるプロピレン系共重合体であって、 （ｉ）プロピレンに由来する繰り返し単位（ａ）が４０
ないし８０モル％、エチレンに由来する繰り返し単位（
ｂ）が２ないし４０モル％、および上記α−オレフィン
に由来する繰り返し単位（ｃ）が０ないし４０モル％で
、かつ２０＜（ｂ＋ｃ）＜６０モル％の範囲にあり、 （ｉｉ）デカリン中で１３５℃で測定した極限粘度〔η
〕が０．１ないし７ｄｌ／ｇの範囲にあり、 （ｉｉｉ）Ｘ線回折法によって測定した結晶化度が４０
％以下の範囲にある プロピレン系共重合体５ないし６０重量％ からなることを特徴とするポリプロピレン組成物。(1) (A) Highly crystalline propylene polymer 40 to 95
% by weight, and (B) propylene consisting of repeating units (a) derived from propylene, repeating units (b) derived from ethylene, and repeating units (c) derived from an α-olefin having 4 to 20 carbon atoms. system copolymer, wherein (i) the repeating unit (a) derived from propylene is 40
80 mol% of repeating units derived from ethylene (
b) is 2 to 40 mol%, and the repeating unit (c) derived from the α-olefin is 0 to 40 mol%, and in the range of 20<(b+c)<60 mol%, (ii) in decalin. Intrinsic viscosity [η
] is in the range of 0.1 to 7 dl/g, and (iii) the degree of crystallinity is 40 as measured by X-ray diffraction method.
A polypropylene composition comprising 5 to 60% by weight of a propylene copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28923488A JP2687503B2 (en) | 1988-11-16 | 1988-11-16 | Polypropylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28923488A JP2687503B2 (en) | 1988-11-16 | 1988-11-16 | Polypropylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02135244A true JPH02135244A (en) | 1990-05-24 |
| JP2687503B2 JP2687503B2 (en) | 1997-12-08 |
Family
ID=17740523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28923488A Expired - Lifetime JP2687503B2 (en) | 1988-11-16 | 1988-11-16 | Polypropylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2687503B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994016009A1 (en) * | 1993-01-11 | 1994-07-21 | Mitsui Petrochemical Industries, Ltd. | Propylene polymer composition |
| US8173748B1 (en) | 2010-12-17 | 2012-05-08 | Exxonmobil Research And Engineering Company | Heat-seal resin and package formed therefrom |
-
1988
- 1988-11-16 JP JP28923488A patent/JP2687503B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994016009A1 (en) * | 1993-01-11 | 1994-07-21 | Mitsui Petrochemical Industries, Ltd. | Propylene polymer composition |
| US8173748B1 (en) | 2010-12-17 | 2012-05-08 | Exxonmobil Research And Engineering Company | Heat-seal resin and package formed therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2687503B2 (en) | 1997-12-08 |
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