JPH0112780B2 - - Google Patents
Info
- Publication number
- JPH0112780B2 JPH0112780B2 JP58132954A JP13295483A JPH0112780B2 JP H0112780 B2 JPH0112780 B2 JP H0112780B2 JP 58132954 A JP58132954 A JP 58132954A JP 13295483 A JP13295483 A JP 13295483A JP H0112780 B2 JPH0112780 B2 JP H0112780B2
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- molecular weight
- polymerization
- composition
- density
- 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
Links
- -1 polyethylene Polymers 0.000 claims description 93
- 229920000573 polyethylene Polymers 0.000 claims description 88
- 239000004698 Polyethylene Substances 0.000 claims description 87
- 238000006116 polymerization reaction Methods 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 46
- 239000003054 catalyst Substances 0.000 claims description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 19
- 239000010408 film Substances 0.000 description 18
- 230000000704 physical effect Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000002734 organomagnesium group Chemical group 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- PQKMPXAXUORKSU-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+] Chemical compound P(=O)([O-])([O-])[O-].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+].C(CCCCCCCCCCCCCCCCC)[Ca+] PQKMPXAXUORKSU-UHFFFAOYSA-K 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- RNDIHDKIZRODRW-UHFFFAOYSA-L magnesium;chloride;hydroxide Chemical compound [OH-].[Mg+2].[Cl-] RNDIHDKIZRODRW-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 125000005374 siloxide group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 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 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、優れた成形加工性と成形品物性を有
するポリエチレン組成物に関し、溶融伸張性、溶
融粘弾性、薄膜加工性等の成形加工性および耐衝
撃性等の物性に優れたフイルム成形、延伸成形用
途等に通したポリエチレン組成物に関する。
ポリエチレンのフイルム用途等では、分子量が
比較的高く、分子量分布の比較的広いポリマーが
適している。
分子量分布の広いポリエチレンの製造方法とし
て、幾つかの方法が提案されている。
１つの方法として、高分子量ポリエチレンと低
分子量ポリエチレンとを混合する方法が提案され
ている（特公昭45−3215、特公昭45−22007、特
開昭54−100444、特開昭54−100445、特開昭54−
161657、特開昭55−60542、特開昭55−60543、特
開昭56−57841、特開昭57−133136）。
又、別の方法として、２段以上の多段重合方法
が試みられてきた（特公昭46−11349、特公昭48
−42716、特開昭51−47079、特開昭52−19788）。
本願発明者らは、上記混合、重合の方法による
ポリエチレンを詳細に検討してみると、分子量分
布が広いために押出性が優れていることなどは確
認出来るものの、一方、溶融伸張性が低い、薄膜
加工性に難点がある、薄膜フイルムの耐衝撃性が
必ずしも十分でない等幾多の欠点があることが分
つた。
本願発明は、低分子量部と高分子量部とからな
るポリエチレンのこれらの欠点を改良し、加工性
および物性に優れた、とくに薄膜フイルム用途、
延伸用途等に適したポリエチレン組成物を提供す
るものである。
すなわち、本発明はエチレンの単独重合体およ
びエチレンとα−オレフインの共重合体の群から
選ばれるポリエチレン(A)および(B)とから成るポリ
エチレン組成物であり、
(i) ポリエチレン(A)は分子量が0.5万から５万の
低分子量部（Ａ−Ｌ）と分子量が10万から150
万の高分子量部（Ａ−Ｈ）とから成り、（Ａ−
Ｈ）の分子量／（Ａ−Ｌ）の分子量が５〜200
であり、且つ、（Ａ−Ｌ）の量対（Ａ−Ｈ）の
量が重量比で、60対40から40対60の範囲であ
り、
(ii) ポリエチレン(B)はチーグラー型触媒により重
合されたものであり、(B)の分子量は３万から８
万であり、密度が0.94ｇ／cm3を越え０・97ｇ／
cm3以下であり、組成物中の(B)の量は２重量％か
ら15重量％であり、
(iii) 組成物のメルトインデツクスが0.001ｇ／
10minから10ｇ／10minである。
本発明によれば、工業的に適用範囲の広い、優
れた溶融伸張性、薄膜フイルム加工性および薄膜
フイルムの耐衝撃性等を有し、とくにフイルム成
形、延伸成形用途等に適したポリエチレン組成物
が与えられる。
以下、本発明を詳細に説明する。
本発明の構成成分であるポリエチレン(A)と(B)は
エチレンの単独重合体およびエチレンとα−オレ
フインとの共重合体の群から選ばれる。
共重合に用いるα−オレフインは炭素数３〜14
のもので、例えば、プロピレン、ブテン、ペンテ
ン、ヘキセン、４−メチルペンテン−１、オクテ
ン、デセン等が挙げられる。
ポリエチレン(A)は低分子量部（Ａ−Ｌ）と高分
子量部（Ａ−Ｈ）とから成るポリマーであるが、
（Ａ−Ｌ）の分子量（MWA-L）は0.5万から５万
であり、（Ａ−Ｈ）の分子量（MWA-H）は10万か
ら150万である。MWA-Lが0.5万未満では、各成
分の均一分散性および物性が低下し、一方５万を
越えると組成物の分子量が適度な範囲で分子量分
布を広げにくくなり、加工性が低下する。より好
ましくは１万から４万である。一方MWA-Hが10
万未満では組成物の分子量が低下し、耐衝撃性も
低下する。150万を越えるとフイツシユアイが発
生したり、組成物中の各成分の均一分散性が低下
するなど、加工性、物性ともにバランスが悪くな
る。より好ましくは15万〜100万である。
また、MWA-HとMWA-Lとの比（MWA-H／
MWA-L）は５〜200であり、５未満では分子量分
布が狭く加工性が低く、本発明の秀れた物性が得
られ難い。一方、200を越えても、成形性、物性
を向上させる上で何らの利点もなく、かつ製造上
も不利となる。より好ましくは７〜150である。
また、（Ａ−Ｌ）の密度は0.91〜０・98ｇ／cm3
で、（Ａ−Ｈ）の密度は0.91〜０・97ｇ／cm3であ
る。とくに（Ａ−Ｈ）の密度が（Ａ−Ｌ）及びポ
リエチレン(B)の密度のいずれよりも低く、0.91〜
０・95ｇ／cm3のときは、押出性フイルム製膜性等
の加工性、耐衝撃性等の物性がともに良くなり好
ましい。
ポリエチレン(A)中の（Ａ−Ｌ）の量対（Ａ−
Ｈ）の量は60対40から40対60の範囲である。Ａ−
ＬまたはＡ−Ｈの量が60％を越えると分子量分布
が狭くなり、加工性、物性のバランスが悪くなる
と共に、フイツシユアイの発生が多くなる。
該ポリエチレン(A)はあらかじめつくつた該低分
子量部と該高分子量部とを混合する方法、あるい
は該低分子量部と該高分子量部とを２段重合等の
方法でつくることが出来る。工業的には、２段重
合の方法が好ましい。
ポリエチレン(B)はそ分子量（MWB）が３万か
ら８万の範囲である。組成物の成形加工性、物性
のバランスを良くするために、とくに望ましい態
様は、MWBが４万から７万でMWB／MWA-Lが
1.5以上であり、MWA-H／MWBが1.5以上である。
(B)の密度は0.94ｇ／cm3を越え０・97ｇ／cm3以下で
ある。密度が低いと、組成物の剛性が下り、引張
強度等も下り、好ましくない。
また、組成物中のポリエチレン(B)の量は、重量
で２〜15％の範囲にあり、好ましくは４％以上13
％以下である。(B)の量が２％未満の時は、加工
性、衝撃強度が改善されない。一方15％を越える
と組成物の分子量が低くなり、フイルムの製膜加
工性、物性が低くなり、本願発明のポリエチレン
組成物の特徴が損なわれる。
該ポリエチレン(A)は、チーグラー型触媒、クロ
ム化合物系触媒等遷移金属系触媒によつて重合さ
れたものである。(A)の低分子量部、高分子量部と
もに、同種の遷移金属系触媒によつて重合された
もの、低分子量部と高分子量部とが互いに異なる
種類の遷移金属系触媒によつて重合されたものの
群から選択されるが、とくに好ましいのは、マグ
ネシウム化合物系チーグラー型触媒によつて、低
分子量部、高分子量部ともにつくられたものであ
る。
該ポリエチレン(B)は、チーグラー型触媒によつ
てつくられるが、とくに好ましいのは、脱触媒工
程が省略出来るマグネシウム化合物系チーグラー
型触媒によつてつくられたものである。マグネシ
ウム化合物系チーグラー型触媒によつてつくられ
たポリエチレン(B)は、分子量分布が比較的狭いこ
とを特徴とし、このために本願の目的とする効果
が大きくなる。
マグネシウム化合物系チーグラー型触媒として
無機マグネシウム、有機マグネシウムに基くいず
れの系も用いることができる。
例えば、塩化マグネシウム、ヒドロキシマグネ
シウムクロリド、酸化マグネシウム、水酸化マグ
ネシウム、炭酸マグネシウム、マグネシウムアル
コキシド、マグネシウムの有機酸塩、又はこれら
とアルコール、有機酸エステル等の電子供与性化
合物との錯合体あるいはこれらの混合物、炭素−
マグネシウム結合を有する有機マグネシウム化合
物、たとえば、ジアルキルマグネシウム、アルキ
ルマグネシウムクロリド、アルキルマグネシウム
アルコキシド、アルキルマグネシウムシロキシ
ド、又はこれらの有機マグネシウム化合物とエー
テル等の電子供与体と錯合体、あるいはこれらの
有機マグネシウム成分とハロゲン化物、たとえ
ば、塩酸、クロル化炭化水素、四塩化ケイ素、四
塩化スズとの反応生成物をマグネシウム成分とし
て用い、これとチタンおよび／又はバナジウム化
合物とを反応させた成分と有機金属化合物とから
成る触媒が用いられる。
チーグラー型触媒の中で、とくに好ましいマグ
ネシウム化合物系触媒としては、たとえば、次の
ものがある。
(1) 一般式
MαMgβR1 pR2 qXrYs
（式中、αは０または０より大きい数、ｐ、ｑ、
ｒ、ｓは０または０より大きい数で、ｐ＋ｑ＋ｒ
＋ｓ＝mα＋2βの関係を有し、Ｍは周期律表第
族ないし第族に属する金属元素、R1、R2は同
一または異なつた炭素原子数の炭化水素基、Ｘ、
Ｙは同一または異なつた基であり、ハロゲン、
OR3、OSiR4R5R6、NR7R8、SR9なる基を表わ
し、R3、R4、R5、R6、R7、R8は水素原子または
炭化水素基、R9は炭化水素基を表わす）で示さ
れる有機マグネシウム化合物と、(ii)少なくとも１
個のハロゲン原子を含有するチタンまたはバナジ
ウム化合物と、(iii)Al、Ｂ、Si、Ge、Sn、Te、
Sbのハライド化合物の(i)〜(iii)のうち(i)と(ii)ある
いは(i)と(ii)と(iii)とを反応させてなる固体触媒成分
〔Ａ〕と有機金属化合物〔Ｂ〕からなるものであ
る。有機金属化合物〔Ｂ〕としては、周期律表第
〜族の化合物で、特に有機アルミニウム化合
物および有機マグネシウムを含む錯体が好まし
い。
触媒成分〔Ａ〕と有機金属化合物〔Ｂ〕成分の
反応は、重合系内に両成分を添加し、重合条件下
に重合の進行とともに行わせることも可能であ
り、あらかじめ重合に先立つて実施してもよい。
また触媒成分の反応比率は、〔Ａ〕成分１ｇに対
し〔Ｂ〕成分１〜3000ｍmolの範囲で行なうこと
が好ましい。触媒成分〔Ａ〕の代りに、無機の
Mg化合物にTi化合物を担持したものでもよい。
これらの触媒系の中でも、工業的に脱触媒工程
を省略出来るためにとくに望ましいものとして、
特公昭52−36788、52−36790、52−36791、52−
36792、52−50070、52−36794、52−36795、52−
36796、52−36915、52−36917、53−6019、特開
昭50−21876、50−31835、50−72044、50−
788619、53−40696号のものがある。
該ポリエチレン(A)、(B)は懸濁重合、溶液重合、
気相重合等の方法でつくられる。
該ポリエチレン(A)は２段重合によつてつくるの
が、工業的には好ましいが、２段重合の方法はす
でに機つか提案されている。本願発明において使
用される好ましい方法の例を以下に説明する。
重合は炭素原子数４〜10個を有する飽和炭化水
素中で行なう。重合の順序は（Ａ−Ｌ）−（Ａ−
Ｈ）あるいは（Ａ−Ｈ）−（Ａ−Ｌ）のいずれでも
よい。
簡単のために（Ａ−Ｌ）−（Ａ−Ｈ）のパターン
を図面を参照しながら説明する。
低分子量部（Ａ−Ｌ）は、重合圧力１〜30Kg／
cm2Ｇ、好ましくは３〜25Kg／cm2Ｇで、重合温度は
60〜100℃、好ましくは70〜90℃で行なう。高分
子量部（Ａ−Ｈ）は、重合圧力0.5〜30Kg／cm2Ｇ、
好ましくは0.5〜20Kg／cm2Ｇで、重合温度は40〜
110℃、好ましくは60〜90℃で行なう。
重合器１ではライン２よりエチレン、ヘキサ
ン、水素、触媒成分等が供給され、低分子量のポ
リエチレン（Ａ−Ｌ）が重合される。重合器１内
のスラリーはフラツシユドラム３に導かれ、未反
応のエチレン、水素が除かれる。除去されたエチ
レン、水素はコンプレツサー４により昇圧され重
合器１に戻される。一方、フラツシユドラム３内
のスラリーは、ポンプ５により２段目の重合器６
に導入される。重合器６はライン７よりエチレ
ン、コモノマー、ヘキサン、触媒成分等が供給さ
れ、高分子量のポリエチレン（Ａ−Ｈ）の重合が
行なわれ、重合器６内のポリマーが製品として後
処理工程を経てとり出される。
以上説明したフローは、本発明の代表的な例の
一つであり、場合によつては重合器１で高分子量
部（Ａ−Ｈ）を重合し、重合器６で低分子量部
（Ａ−Ｌ）を重合してもよい。そろ際には、フラ
ツシユドラム３を省略することが可能である。さ
らに後段の重合器６から前段の重合器１に重合器
内容物を循環してもよい。
このようなフローシートにより連続的にポリエ
チレン(A)の重合を行なうことができる。
該ポリエチレン(A)と(B)とは、混合、混練して目
的とするポリエチレン組成物になされる。
ポリエチレン(A)と(B)の混合方法は、パウダー状
能、スラリー状態、ペレツト状態等通常の方法が
用いられる。混練する場合は150〜300℃の温度
で、一軸、二軸の押出機、混練機等で行なわれ
る。
このようにして、製造されるポリエチレン組成
物のメルトインデツクス（以下、MIと言う）は
0.001ｇ／10minから10ｇ／10minの範囲より、用
途によつて選択される。とくに加工性、物性とも
に総合的に秀れたフイルム用組成物としては、
MIが0.01ｇ／10minから１ｇ／10minの範囲にあ
り、密度が0.935ｇ／cm3から０・965ｇ／cm3の範囲
にある。
該ポリエチレン組成物は、熱安定剤、酸化防止
剤、紫外線吸収剤、顔料、帯電防止剤、滑剤、充
填剤、他のポリオレフイン、熱可塑性樹脂、ゴム
等、通常ポリオレフインに添加、ブレンドされ得
る物質は、必要に応じて使用されることは可能で
ある。また、発泡剤を混入させて発泡成形するこ
とも可能である。
以上に詳述したように、本願発明によつて得ら
れるポリエチレン組成物は下記の如き特徴を有す
る。
(1) 溶融時の流動特性、溶融伸張性、溶融粘弾性
などの加工特性のバランスが良く、また、耐衝
撃性、引張強度、表面光択などの物性等にも秀
れる。
(2) フイルムの用途では、従来困難とされてい
た、６ミクロン以下の非常に薄いフイルムを、
100ｍ／min以上の超高速で加工出来る。
(3) 成形品の剛性、耐衝撃性、耐環境応力亀裂性
に秀れ、これらの全ての特性が実用的によくバ
ランスしている。とくに、薄肉成形品ですぐれ
た耐衝撃性を与える。
(4) 物性、加工性ともに秀れているため、薄肉成
形品がつくり易い。このため、省資源、省エネ
ルギー時代に適合する。
(5) 容易に製造出来る。
(6) 中空、押出、射出、回転および発泡などの各
種成形用途にも適用出来る。
以下、実施例を挙げて、本願発明をさらに詳細
に説明するが、本願発明はこれらの実施例によつ
て何ら制限されるものではない。
本実施例、比較例において示す記号、測定方法
および測定条件。
(i) MI；メルトインデツクスを表わし、
ASTMD−1238により、温度190℃、荷重216
Kgの条件下で測定した値。
(ii) MIR；MI測定条件において荷重21.6Kgで測
定した値をMIで除した商を意味し、分子量分
布の１つの尺度であり、この値が大きい程分子
量分布が広いことを示す。
(iii) 分子量（MW）；デカリン溶液を用い、135℃
で測定した固有粘度（η）と、ジヤーナル・オ
ブ・ポリマーサイエンス36巻91頁（1957）記載
の式、η＝6.8×10-4MW0.67からMWを求めた。
なお、本願発明における分子量は全てこの方法
によるものである。
(iv) 密度；ASTMD−1505にしたがつて測定し
た。
(v) 溶融伸張性；東洋精機(株)製メルトテンシヨン
テスターを使用し、温度150℃で樹脂を溶融押
出したストランドを引伸ばし、ストランドが破
断しないで引伸ばせる最高の引取速度を、スト
ランドがノズルから出る時の線速度で除した
商。
(iv) フイルム成形加工性；50mm径スクリユー、75
mm径ダイ付インフレーシヨンフイルム成形機
で、温度180℃、ブロー比３倍で、引取速度105
ｍ／minでフイルムを成形し、成形可能な最低
厚さを測定する。
(vii) フイルムの耐衝撃性；上記フイルム成形機、
条件で成形して得た厚さ12ミクロンのフイルム
をASTMD1709で測定する。
(viii) フイルムのフイツシユアイ；上記フイルム成
形機、条件で成形して得た厚さ12ミクロンのフ
イルム700cm2切り取り、その上にある直径0.1ミ
リ以上のフイツシユアイを目視により全数数え
る。
実施例 １−１
(1) ポリエチレン(A)および(B)用の触媒の合成
トリクロルシラン（HSiCl3）１モル／の
ヘキサン溶液２を８のオートクレーブに入
れ、50℃に保つた。これに組成AlMg6.0（C2H5）
2.0（ｎ−C4H9）9.5（OC4H9）3.5の有機アルミニ
ウム−マグネシウム錯体の１モル／のヘキサ
ン溶液２を撹拌下に２時間かけて滴下し、さ
らにこの温度で２時間反応させた。生成した固
体成分を２のヘキサンで２回沈降法によつて
洗浄した。この固体成分を含むスラリーに四塩
化チタン２を仕込み、130℃にて２時間反応
させた後、固体触媒を単離し、遊離のハロゲン
が検出されなくなるまでヘキサンで洗浄した。
この固体触媒は2.1％のチタンを含有していた。
(2) ２段重合によるポリエチレン(A)の製造
まず、低分子量部でつくるために、反応容積
300の重合器１で重合した。重合温度は83℃、
重合圧力は10Kg／cm2Ｇである。この重合器１
に、上記の固体触媒を1.3ｍmol（Ti原子基
準）／Hrの速度で、20ｍmol（金属原子基
準）／Hrの速度でトリエチルアルミニウムを、
40／Hrの速度で精製ヘキサンを供給し、ま
たエチレンを7NM3／Hrと分子量調節剤とし
て水素を、気相の水素濃度が約86モル％になる
ように供給し、重合を行なう。重合器１内のポ
リマースラリー内溶液を圧力１Kg／cm2Ｇ、温度
75℃のフラツシユドラム３に導き、未反応のエ
チレン、水素を分離した後、重合器６にスラリ
ーポンプ５で昇圧し導入する。重合器６では温
度80℃、圧力６Kg／cm2Ｇで重合を行なう。重合
器６は内容積250である。該重合器６にトリ
エチルアルミニウムを7.5ｍmol（金属原子基
準）／Hrの速度で、精製ヘキサンを40／
Hr、エチレンを7.2NM3／Hrの速度でそれぞ
れ供給し、かつ、水素をブテン−１を気相の濃
度がそれぞれ約１モル％、約2.5モル％になる
ように導入し、重合を行なつた。このようにし
て２段重合を行ない重合器６より得られたポリ
エチレン(A)のパウダーのMIは0.12ｇ／10min、
密度は0.956ｇ／cm3であつた。
なお、別に同様の条件で行なつた単独重合の
実験結果から、１段目の重合器１で重合したポ
リエチレン(A)の低分子量部（Ａ−Ｌ）は、分子
量が約15000、密度約0.974ｇ／cm3、２段目の重
合器２で重合したポリエチレン(A)の高分子量部
（Ａ−Ｈ）は分子量が約62万、密度約0.939ｇ／
cm3であるとそれぞれ推定される。
この低分子量部（Ａ−Ｌ）と高分子量部（Ａ
−Ｈ）の比率は、１段目の生成ポリエチレンの
密度と２段目重合器出口の組成物密度から計算
し、（Ａ−Ｌ）：（Ａ−Ｈ）＝50：50と求められ
た。
(3) ポリエチレン(B)の製造
反応容積200の重合器を使用し、単独重合
によつてポリエチレン(B)を製造した。重合温度
は83℃、重合圧力11Kg／cm2Ｇ、10.5Kg／Hrの
生成量となるように重合をコントロールした。
触媒は、ポリエチレン(A)と同様のものを使用し
水素を分子量調節剤として使用し、プロピレン
をコモノマーとして使用し、分子量７万、密度
0.955ｇ／cm3、MIは６ｇ／10min、MIR28のポ
リエチレン(B)を製造した。
(4) ポリエチレン組成物の製造と評価
上記の如くして製造したポリエチレン(A)およ
び(B)のパウダーを、重量比で94対６の割合で混
合し、次いでこの混合物に熱、酸化防止剤とし
て、テトラキス〔メチレン−３−（3′，5′−ジ
−ｔ−ブチル−4′−ヒドロキシフエニル）プロ
ピオネート〕メタンを1200ppm、およびジター
シヤリブチルフエノール800ppm、ステアリン
酸カルシウム2500ppmを添加し、ヘンシエルミ
キサー中で、十分撹拌混合し、パウダー状の混
合物をつくり、この混合物をフアレル社製
FCMで220℃の温度で混練し、次いでこの混練
物を一軸押出機で230℃の温度で押出し、ペレ
タイズをし、ポリエチレン組成物を製造した。
このポリエチレン樹脂組成物の性能は第１表に
示す通り、成形加工性及び物性ともに非常に優
れた性能を示す。
実施例 １−２
実施例１−１で製造したポリエチレンパウダー
(A)および(B)を、第１表に示すような配合量にして
混合した以外は、添加剤、混合、混練及び押出条
件などは、実施例１−１と同様にしてポリエチレ
ン組成物を製造し、その性能を評価した結果を第
１表に示す。
比較例 １−１
実施例１−１で製造したポリエチレン(A)のみを
使用した以外は、実施例１−１と同様にしてその
性能を評価した。
比較例 １−２
実施例１−１において、ポリエチレン(B)の代り
に、分子量15万、密度０・960ｇ／cm3、MI0.5
ｇ／10min、MIR34のプロピレンをコモノマーと
するポリエチレンを使用した。
The present invention relates to a polyethylene composition having excellent molding processability and physical properties of molded products, and relates to a polyethylene composition having excellent molding processability such as melt extensibility, melt viscoelasticity, thin film processability, and physical properties such as impact resistance. This invention relates to polyethylene compositions for molding applications and the like. For applications such as polyethylene films, polymers with a relatively high molecular weight and a relatively wide molecular weight distribution are suitable. Several methods have been proposed as methods for producing polyethylene with a wide molecular weight distribution. As one method, a method of mixing high molecular weight polyethylene and low molecular weight polyethylene has been proposed. 1977-
161657, JP 55-60542, JP 55-60543, JP 56-57841, JP 57-133136). In addition, as another method, a multi-stage polymerization method of two or more stages has been attempted (Japanese Patent Publication No. 46-11349, Special Publication No. 11349, No. 48)
-42716, JP-A-51-47079, JP-A-52-19788). The inventors of the present application have examined in detail the polyethylene obtained by the mixing and polymerization methods described above, and have confirmed that it has excellent extrudability due to a wide molecular weight distribution, but on the other hand, it has low melt extensibility. It has been found that there are a number of drawbacks, such as difficulty in thin film processability and insufficient impact resistance of the thin film. The present invention improves these drawbacks of polyethylene consisting of a low molecular weight part and a high molecular weight part, and has excellent processability and physical properties, especially for thin film applications,
The present invention provides a polyethylene composition suitable for stretching purposes. That is, the present invention is a polyethylene composition comprising polyethylene (A) and (B) selected from the group of ethylene homopolymers and copolymers of ethylene and α-olefin, wherein (i) polyethylene (A) is Low molecular weight part (A-L) with a molecular weight of 5,000 to 50,000 and a molecular weight of 100,000 to 150
It consists of 10,000 high molecular weight parts (A-H), (A-
Molecular weight of H)/molecular weight of (A-L) is 5 to 200
and the weight ratio of the amount of (A-L) to the amount of (A-H) is in the range of 60:40 to 40:60, (ii) polyethylene (B) is polymerized by a Ziegler type catalyst. The molecular weight of (B) is from 30,000 to 8
10,000, and the density exceeds 0.94 g/ cm3 and 0.97 g/cm3.
cm3 or less, the amount of (B) in the composition is from 2% to 15% by weight, and (iii) the melt index of the composition is 0.001g/
10g/10min from 10min. According to the present invention, a polyethylene composition has a wide range of industrial applicability, has excellent melt extensibility, thin film processability, thin film impact resistance, etc., and is particularly suitable for film molding, stretch molding, etc. is given. The present invention will be explained in detail below. Polyethylenes (A) and (B), which are the constituent components of the present invention, are selected from the group of homopolymers of ethylene and copolymers of ethylene and α-olefins. The α-olefin used for copolymerization has 3 to 14 carbon atoms.
Examples include propylene, butene, pentene, hexene, 4-methylpentene-1, octene, decene, and the like. Polyethylene (A) is a polymer consisting of a low molecular weight part (A-L) and a high molecular weight part (A-H),
The molecular weight (MW AL ) of (A-L) is from 5,000 to 50,000, and the molecular weight (MW AH ) of (A-H) is from 100,000 to 1,500,000. If the MW AL is less than 50,000, the uniform dispersibility and physical properties of each component will deteriorate, while if it exceeds 50,000, it will be difficult to widen the molecular weight distribution within an appropriate molecular weight range of the composition, and processability will decrease. More preferably, it is from 10,000 to 40,000. while MW AH is 10
If it is less than 10,000, the molecular weight of the composition decreases and the impact resistance also decreases. If it exceeds 1,500,000, the balance between processability and physical properties becomes poor, such as the occurrence of hard eyes and a decrease in the uniform dispersibility of each component in the composition. More preferably 150,000 to 1,000,000. Also, the ratio between MW AH and MW AL (MW AH /
MW AL ) is 5 to 200; if it is less than 5, the molecular weight distribution is narrow and processability is low, making it difficult to obtain the excellent physical properties of the present invention. On the other hand, if it exceeds 200, there is no advantage in improving moldability and physical properties, and it is also disadvantageous in terms of manufacturing. More preferably it is 7-150. Also, the density of (A-L) is 0.91 to 0.98 g/cm 3
The density of (A-H) is 0.91 to 0.97 g/cm 3 . In particular, the density of (A-H) is lower than both (A-L) and polyethylene (B), and is 0.91 to
When it is 0.95 g/cm 3 , both processability such as extrudable film formability and physical properties such as impact resistance are improved, which is preferable. Amount of (A-L) in polyethylene (A) versus (A-
The amount of H) ranges from 60:40 to 40:60. A-
When the amount of L or A-H exceeds 60%, the molecular weight distribution becomes narrow, the balance between processability and physical properties becomes poor, and the occurrence of fish eyes increases. The polyethylene (A) can be produced by mixing the low molecular weight part and the high molecular weight part which have been prepared in advance, or by two-stage polymerization of the low molecular weight part and the high molecular weight part. Industrially, a two-stage polymerization method is preferred. Polyethylene (B) has a molecular weight (MW B ) in the range of 30,000 to 80,000. In order to improve the balance between moldability and physical properties of the composition, a particularly desirable embodiment is such that MW B is 40,000 to 70,000 and MW B /MW AL is 40,000 to 70,000.
1.5 or more, and MW AH /MW B is 1.5 or more.
The density of (B) is more than 0.94 g/cm 3 and less than 0.97 g/cm 3 . If the density is low, the rigidity and tensile strength of the composition will decrease, which is not preferable. Further, the amount of polyethylene (B) in the composition is in the range of 2 to 15% by weight, preferably 4% or more13
% or less. When the amount of (B) is less than 2%, workability and impact strength are not improved. On the other hand, if it exceeds 15%, the molecular weight of the composition decreases, film forming processability and physical properties deteriorate, and the characteristics of the polyethylene composition of the present invention are impaired. The polyethylene (A) is polymerized using a transition metal catalyst such as a Ziegler type catalyst or a chromium compound catalyst. Both the low molecular weight part and the high molecular weight part of (A) were polymerized using the same type of transition metal catalyst, or the low molecular weight part and the high molecular weight part were polymerized using different types of transition metal catalysts. Particularly preferred is one in which both the low molecular weight part and the high molecular weight part are produced using a magnesium compound-based Ziegler type catalyst. The polyethylene (B) is produced using a Ziegler-type catalyst, and particularly preferred is one produced using a magnesium compound-based Ziegler-type catalyst that can omit the decatalyst step. Polyethylene (B) produced using a magnesium compound-based Ziegler type catalyst is characterized by a relatively narrow molecular weight distribution, which enhances the effects aimed at in the present application. As the magnesium compound-based Ziegler type catalyst, any system based on inorganic magnesium or organic magnesium can be used. For example, magnesium chloride, hydroxymagnesium chloride, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium alkoxide, organic acid salts of magnesium, or complexes of these with electron-donating compounds such as alcohols and organic acid esters, or mixtures thereof. , carbon-
Organomagnesium compounds having a magnesium bond, such as dialkylmagnesiums, alkylmagnesium chlorides, alkylmagnesium alkoxides, alkylmagnesium siloxides, or complexes of these organomagnesium compounds with electron donors such as ethers, or with these organomagnesium components. A reaction product with a halide, for example, hydrochloric acid, chlorinated hydrocarbon, silicon tetrachloride, tin tetrachloride is used as the magnesium component, and a component obtained by reacting this with titanium and/or vanadium compound and an organometallic compound. A catalyst consisting of: Among Ziegler type catalysts, particularly preferred magnesium compound catalysts include, for example, the following. (1) General formula MαMgβR 1 p R 2 q X r Y s (where α is 0 or a number larger than 0, p, q,
r, s are 0 or a number larger than 0, p+q+r
+s=mα+2β, M is a metal element belonging to Group 1 or Group 3 of the periodic table, R 1 and R 2 are hydrocarbon groups having the same or different numbers of carbon atoms, X,
Y is the same or different group, halogen,
OR 3 , OSiR 4 R 5 R 6 , NR 7 R 8 , SR 9 represents the groups, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are hydrogen atoms or hydrocarbon groups, and R 9 is (ii) at least one
a titanium or vanadium compound containing halogen atoms; (iii) Al, B, Si, Ge, Sn, Te,
A solid catalyst component [A] obtained by reacting (i) with (ii) or (i) with (ii) and (iii) of Sb halide compounds (i) to (iii) and an organometallic compound [ B]. The organometallic compound [B] is a compound of Groups 1 to 10 of the periodic table, and a complex containing an organoaluminum compound and an organomagnesium is particularly preferable. The reaction between the catalyst component [A] and the organometallic compound [B] component can be carried out under the polymerization conditions by adding both components to the polymerization system and as the polymerization progresses. It's okay.
The reaction ratio of the catalyst components is preferably in the range of 1 to 3000 mmol of component [B] per 1 g of component [A]. Instead of catalyst component [A], inorganic
A Ti compound supported on a Mg compound may also be used. Among these catalyst systems, the ones that are particularly desirable because they can omit the decatalyst step industrially are:
Special Publications Showa 52-36788, 52-36790, 52-36791, 52-
36792, 52−50070, 52−36794, 52−36795, 52−
36796, 52-36915, 52-36917, 53-6019, JP-A-1987-21876, 50-31835, 50-72044, 50-
There are 788619 and 53-40696. The polyethylenes (A) and (B) can be polymerized by suspension polymerization, solution polymerization,
Produced by methods such as gas phase polymerization. It is industrially preferable to produce the polyethylene (A) by two-stage polymerization, but two-stage polymerization methods have already been proposed. Examples of preferred methods used in the present invention are described below. The polymerization is carried out in saturated hydrocarbons having 4 to 10 carbon atoms. The order of polymerization is (A-L)-(A-
H) or (AH)-(AL). For simplicity, the (A-L)-(A-H) pattern will be explained with reference to the drawings. The low molecular weight part (A-L) has a polymerization pressure of 1 to 30 kg/
cm 2 G, preferably 3 to 25 Kg/cm 2 G, and the polymerization temperature is
It is carried out at 60-100°C, preferably 70-90°C. The high molecular weight part (A-H) has a polymerization pressure of 0.5 to 30 Kg/cm 2 G,
Preferably 0.5-20Kg/cm 2 G, polymerization temperature 40-
It is carried out at 110°C, preferably 60-90°C. In the polymerization vessel 1, ethylene, hexane, hydrogen, catalyst components, etc. are supplied from a line 2, and low molecular weight polyethylene (A-L) is polymerized. The slurry in the polymerization vessel 1 is led to a flash drum 3, where unreacted ethylene and hydrogen are removed. The removed ethylene and hydrogen are pressurized by a compressor 4 and returned to the polymerization vessel 1. On the other hand, the slurry in the flash drum 3 is pumped to the second stage polymerizer 6 by the pump 5.
will be introduced in The polymerization vessel 6 is supplied with ethylene, comonomer, hexane, catalyst components, etc. from a line 7, and polymerization of high molecular weight polyethylene (A-H) is carried out, and the polymer in the polymerization vessel 6 is processed as a product through a post-treatment process. Served. The flow explained above is one of the typical examples of the present invention, and in some cases, the high molecular weight part (A-H) is polymerized in the polymerization vessel 1, and the low molecular weight part (A-H) is polymerized in the polymerization vessel 6. L) may be polymerized. When the time comes, it is possible to omit the flash drum 3. Furthermore, the contents of the polymerization vessel may be circulated from the polymerization vessel 6 at the later stage to the polymerization vessel 1 at the front stage. Polyethylene (A) can be continuously polymerized using such a flow sheet. The polyethylene (A) and (B) are mixed and kneaded to form the desired polyethylene composition. The polyethylenes (A) and (B) may be mixed by conventional methods such as powder, slurry, pellet, etc. Kneading is carried out at a temperature of 150 to 300°C using a single-screw or twin-screw extruder, kneader, etc. In this way, the melt index (hereinafter referred to as MI) of the polyethylene composition produced is
It is selected from the range of 0.001g/10min to 10g/10min depending on the application. In particular, as a film composition that has excellent overall processability and physical properties,
The MI is in the range of 0.01 g/10 min to 1 g/10 min, and the density is in the range of 0.935 g/cm 3 to 0.965 g/cm 3 . The polyethylene composition contains substances that can be added or blended with the polyolefin, such as heat stabilizers, antioxidants, ultraviolet absorbers, pigments, antistatic agents, lubricants, fillers, other polyolefins, thermoplastic resins, rubbers, etc. , can be used as needed. It is also possible to mix a foaming agent and perform foam molding. As detailed above, the polyethylene composition obtained by the present invention has the following characteristics. (1) It has a good balance of processing properties such as flow properties when melted, melt extensibility, and melt viscoelasticity, and also has excellent physical properties such as impact resistance, tensile strength, and surface selectivity. (2) In film applications, it has been difficult to produce very thin films of 6 microns or less,
Can process at ultra high speeds of 100m/min or more. (3) The molded product has excellent rigidity, impact resistance, and environmental stress cracking resistance, and all of these properties are well balanced for practical use. In particular, it provides excellent impact resistance for thin-walled molded products. (4) It has excellent physical properties and processability, making it easy to make thin-walled molded products. Therefore, it is suitable for the era of resource saving and energy saving. (5) Easy to manufacture. (6) Can be applied to various molding applications such as hollow, extrusion, injection, rotation and foaming. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Symbols, measurement methods, and measurement conditions shown in Examples and Comparative Examples. (i) MI; represents melt index;
According to ASTMD-1238, temperature 190℃, load 216
Values measured under Kg conditions. (ii) MIR: Means the quotient obtained by dividing the value measured under MI measurement conditions at a load of 21.6 kg by MI, and is one measure of molecular weight distribution, and the larger this value is, the wider the molecular weight distribution is. (iii) Molecular weight (MW); using decalin solution, 135℃
The MW was determined from the intrinsic viscosity (η) measured by the method and the formula described in Journal of Polymer Science, Vol. 36, p. 91 (1957), η=6.8×10 −4 MW 0.67 .
Note that all molecular weights in the present invention are determined by this method. (iv) Density: Measured according to ASTMD-1505. (v) Melt extensibility: Using a melt tension tester manufactured by Toyo Seiki Co., Ltd., stretch a strand melt-extruded with resin at a temperature of 150°C, and check the maximum drawing speed at which the strand can be stretched without breaking. The quotient divided by the linear velocity as it exits the nozzle. (iv) Film moldability; 50mm diameter screw, 75
Inflation film forming machine with mm diameter die, temperature 180℃, blow ratio 3 times, take-up speed 105
The film is molded at m/min and the minimum moldable thickness is measured. (vii) Impact resistance of the film; the above film forming machine,
A film with a thickness of 12 microns obtained by molding under the following conditions is measured using ASTM D1709. (viii) Film fissure eyes: Cut 700 cm of film with a thickness of 12 microns obtained by molding using the above film molding machine and conditions, and visually count all the fissure eyes on it with a diameter of 0.1 mm or more. Example 1-1 (1) Synthesis of catalysts for polyethylene (A) and (B) A hexane solution 2 containing 1 mol of trichlorosilane (HSiCl 3 ) was placed in a No. 8 autoclave and maintained at 50°C. This has the composition AlMg 6.0 (C 2 H 5 )
2.0 (n-C 4 H 9 ) 9.5 (OC 4 H 9 ) 3.5 1 mol/hexane solution 2 of organoaluminium-magnesium complex was added dropwise over 2 hours with stirring, and the mixture was further reacted at this temperature for 2 hours. Ta. The produced solid component was washed twice with hexane by the precipitation method. Titanium tetrachloride 2 was added to the slurry containing this solid component, and after reacting at 130°C for 2 hours, the solid catalyst was isolated and washed with hexane until no free halogen was detected.
This solid catalyst contained 2.1% titanium. (2) Production of polyethylene (A) by two-stage polymerization First, in order to produce polyethylene (A) with a low molecular weight part, the reaction volume
Polymerization was carried out in 300 polymerization vessel 1. Polymerization temperature was 83℃,
The polymerization pressure was 10 kg/cm 2 G. This polymerization vessel 1
Then, the above solid catalyst was added at a rate of 1.3 mmol (based on Ti atoms)/Hr, and triethylaluminum was added at a rate of 20 mmol (based on metal atoms)/Hr.
Polymerization is carried out by supplying purified hexane at a rate of 40/Hr, and supplying ethylene at 7NM 3 /Hr and hydrogen as a molecular weight regulator such that the hydrogen concentration in the gas phase is about 86 mol%. The solution in the polymer slurry in the polymerization vessel 1 was heated to a pressure of 1 Kg/cm 2 G and a temperature of
The slurry is introduced into a flash drum 3 at 75°C to separate unreacted ethylene and hydrogen, and then introduced into a polymerization reactor 6 after being pressurized with a slurry pump 5. In the polymerization vessel 6, polymerization is carried out at a temperature of 80° C. and a pressure of 6 kg/cm 2 G. The polymerization vessel 6 has an internal volume of 250 ml. Triethylaluminum was added to the polymerization vessel 6 at a rate of 7.5 mmol (based on metal atoms)/Hr, and purified hexane was added at a rate of 40/Hr.
Polymerization was carried out by supplying Hr and ethylene at a rate of 7.2 NM 3 /Hr, and introducing hydrogen and butene-1 so that the gas phase concentrations were approximately 1 mol% and 2.5 mol%, respectively. Ta. The MI of the polyethylene (A) powder obtained from the polymerization vessel 6 after performing two-stage polymerization in this way is 0.12 g/10 min.
The density was 0.956 g/cm 3 . In addition, from the results of a separate homopolymerization experiment conducted under similar conditions, the low molecular weight portion (A-L) of polyethylene (A) polymerized in the first stage polymerization vessel 1 has a molecular weight of approximately 15,000 and a density of approximately 0.974. g/cm 3 , the high molecular weight portion (A-H) of polyethylene (A) polymerized in the second stage polymerization vessel 2 has a molecular weight of approximately 620,000 and a density of approximately 0.939 g/cm 3 .
cm3 , respectively. The low molecular weight part (A-L) and the high molecular weight part (A-L)
-H) was calculated from the density of the polyethylene produced in the first stage and the composition density at the outlet of the second stage polymerizer, and was determined to be (AL):(A-H) = 50:50. (3) Production of polyethylene (B) Polyethylene (B) was produced by homopolymerization using a polymerization vessel with a reaction volume of 200. The polymerization temperature was 83° C., the polymerization pressure was 11 Kg/cm 2 G, and the polymerization was controlled so that the production amount was 10.5 Kg/Hr.
The catalyst used was the same as polyethylene (A), hydrogen was used as a molecular weight regulator, and propylene was used as a comonomer, with a molecular weight of 70,000 and a density of 70,000.
Polyethylene (B) of 0.955 g/cm 3 , MI of 6 g/10 min, and MIR of 28 was produced. (4) Production and evaluation of polyethylene composition The powders of polyethylene (A) and polyethylene (B) produced as described above are mixed in a weight ratio of 94:6, and then this mixture is heated and treated with an antioxidant. Then, 1200 ppm of tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, 800 ppm of ditertyabutylphenol, and 2500 ppm of calcium stearate were added. Thoroughly stir and mix in a shell mixer to create a powdery mixture.
The mixture was kneaded using FCM at a temperature of 220°C, and then this kneaded product was extruded using a single screw extruder at a temperature of 230°C and pelletized to produce a polyethylene composition.
As shown in Table 1, this polyethylene resin composition exhibits excellent moldability and physical properties. Example 1-2 Polyethylene powder produced in Example 1-1
A polyethylene composition was prepared using the same additives, mixing, kneading and extrusion conditions as in Example 1-1, except that (A) and (B) were mixed in the amounts shown in Table 1. Table 1 shows the results of manufacturing and evaluating its performance. Comparative Example 1-1 The performance was evaluated in the same manner as in Example 1-1, except that only the polyethylene (A) produced in Example 1-1 was used. Comparative Example 1-2 In Example 1-1, instead of polyethylene (B), molecular weight 150,000, density 0.960 g/cm 3 , MI 0.5
Polyethylene containing propylene as a comonomer and having an MIR of 34 g/10 min was used.
【表】
実施例 ２−１
(1) ポリエチレン(A)の製造
実施例１−１で使用した触媒を用い、実施例
１−１でポリエチレン(B)を重合するのに使用し
た重合器、重合温度および圧力で、ポリエチレ
ン(A)の低分子量部（Ａ−Ｌ）と高分子量部（Ａ
−Ｈ）とを夫々別個に重合した。（Ａ−Ｌ）、
（Ａ−Ｈ）ともにブテン−１をコノマーとして
使用し、分子量調節剤は実施例１−１と同様に
水素を使用した。
製造した（Ａ−Ｌ）は分子量が約３万、密度
が0.965ｇ／cm3、（Ａ−Ｈ）は分子量が約32万、
密度が0.932ｇ／cm3であつた。
(2) ポリエチレン(B)用の触媒の合成
ジ−ｎ−ブチルマグネシウム138ｇとトリエ
チルアルミニウム19ｇとをｎ−ヘプタン２と
ともに容量４の撹拌槽に送入し、80℃で２時
間反応させることにより、組成AlMg6（C2H5）3
（ｎ−C4H9）12の有機アルミニウム−マグネシ
ウム錯体を合成した。この錯体400ｍmol（54
ｇ）を含むｎ−ヘプタン溶液800mlと四塩化チ
タン400ｍmolを含有するｎ−ヘプタン溶液800
mlを、乾燥窒素置換によつて水分と酸素を除去
した後、−20℃で撹拌下４時間反応させた。生
成した炭化水素不溶性固体を単離し、ｎ−ヘプ
タンで洗浄し106ｇの固体を得た。
(3) ポリエチレン(B)の製造
上記の如くしてつくつた固体触媒とトリエチ
ルアルミニウムとを触媒として用い、コモノマ
ーとして、オクテン−１を用い、実施例１−１
のポリエチレン(B)をつくるのに使用した重合
器、重合温度、圧力で水素を分子量調節剤とし
て、下記のようなポリエチレン(B)を重合した。
すなわち、分子量５万、密度0.948ｇ／cm3、
MI16ｇ／10min、MIR30である。
(4) ポリエチレン組成物の製造と評価
上記の如くして製造したポリエチレン(A)の
（Ａ−Ｌ）と（Ａ−Ｈ）およびポリエチレン(B)
とを、第２表に示す配合比で混合し、次いで、
安定剤として、テトラキス〔メチレン−３−
（3′，5′−ジ−ｔ−ブチル−4′−ヒドロキシフエ
ニル）プロピオネート〕メタンを80ppm、およ
びジラウリル−３，3′−チオジプロピオン酸エ
ステルを500ppm、ジターシヤリブチルフエノ
ール700ppm、ステアリン酸カルシウム
2000ppmを添加し、次いで、ヘンシエルミキサ
ー中で十分撹拌混合した。この混合物をフアレ
ル社製FCMで220℃の温度で混練し、次いでこ
の混練物を一軸押出機で200℃の温度で押出し、
ペレタイズをし、ポリエチレン組成物を製造し
た。このポリエチレン組成物の性能は第２表に
示す通り、成形加工性及び物性ともに非常に優
れた性能を示す。
実施例 ２−２
実施例２−１において、（Ａ−Ｌ）、（Ａ−Ｈ）
および(B)の配合比を第２表に示すように変えた以
外は、実施例２−１と同様にした。
比較例 ２−１〜２−２
実施例２−１、２−２における（Ａ−Ｌ）と
（Ａ−Ｈ）を第２表に示すような配合にした以外
は、実施例２−１と同様にして、その性能を評価
した。[Table] Example 2-1 (1) Production of polyethylene (A) Using the catalyst used in Example 1-1, the polymerization vessel and polymerization vessel used to polymerize polyethylene (B) in Example 1-1 At temperature and pressure, the low molecular weight part (A-L) and the high molecular weight part (A
-H) were separately polymerized. (A-L),
In both cases (A-H), butene-1 was used as the conomer, and hydrogen was used as the molecular weight regulator as in Example 1-1. The produced (A-L) has a molecular weight of about 30,000 and a density of 0.965 g/cm 3 , and (A-H) has a molecular weight of about 320,000.
The density was 0.932 g/cm 3 . (2) Synthesis of catalyst for polyethylene (B) By feeding 138 g of di-n-butylmagnesium and 19 g of triethylaluminum into a stirring tank with a capacity of 4 with 2 n-heptane and reacting at 80°C for 2 hours, Composition AlMg 6 (C 2 H 5 ) 3
An organoaluminum-magnesium complex of (n- C4H9 ) 12 was synthesized. 400 mmol (54
800 ml of n-heptane solution containing g) and 800 ml of n-heptane solution containing 400 mmol of titanium tetrachloride.
ml was subjected to dry nitrogen purging to remove moisture and oxygen, and then reacted at -20°C for 4 hours with stirring. The resulting hydrocarbon-insoluble solid was isolated and washed with n-heptane to yield 106 g of solid. (3) Production of polyethylene (B) Using the solid catalyst prepared as described above and triethylaluminum as catalysts, and using octene-1 as a comonomer, Example 1-1
The following polyethylene (B) was polymerized using the polymerization vessel, polymerization temperature, and pressure used to produce polyethylene (B) using hydrogen as a molecular weight regulator.
That is, molecular weight 50,000, density 0.948g/cm 3 ,
MI16g/10min, MIR30. (4) Production and evaluation of polyethylene compositions (A-L) and (A-H) of polyethylene (A) produced as described above and polyethylene (B)
were mixed at the blending ratio shown in Table 2, and then
As a stabilizer, tetrakis [methylene-3-
(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate] 80 ppm of methane, 500 ppm of dilauryl-3,3'-thiodipropionic acid ester, 700 ppm of ditertiarybutylphenol, stearyl calcium phosphate
2000 ppm was added, and then thoroughly stirred and mixed in a Henschel mixer. This mixture was kneaded at a temperature of 220°C using FCM manufactured by Farel, and then this kneaded product was extruded using a single screw extruder at a temperature of 200°C.
It was pelletized to produce a polyethylene composition. As shown in Table 2, this polyethylene composition exhibits excellent moldability and physical properties. Example 2-2 In Example 2-1, (A-L), (A-H)
The procedure was the same as in Example 2-1 except that the blending ratios of (B) and (B) were changed as shown in Table 2. Comparative Examples 2-1 to 2-2 Example 2-1 and 2-2 except that (A-L) and (A-H) in Examples 2-1 and 2-2 were mixed as shown in Table 2. The performance was evaluated in the same manner.
【表】
実施例 ３−１〜３−２
(1) ポリエチレン(A)の製造
実施例２−１と同様の触媒、同様の方法でＡ
−Ｌ、Ａ−H1をそれぞれ別々に重合した。
製造したＡ−Ｌは分子量が約1.4万、密度が
0.969ｇ／cm3、Ａ−H1は分子量が約89万、密度
が0.928ｇ／cm3であつた。
(2) ポリエチレン(B)
実施例２−１(B)と同じポリマーを使用した。
(3) ポリエチレン組成物の製造と評価
実施例２−１と同様にして第３表に示す割合
いの組成物を製造した。このポリエチレンの性
能は第３表に示す通り、成形加工性、物性、フ
イツシユアイレベル共に非常に優れた性能を示
した。
比較例 ３−１〜３−３
ポリエチレン(A)の製造
実施例３−１のポリエチレン(A)のＡ−Ｌ、Ａ−
H1及び実施例３−１のポリエチレン(A)と同じ触
媒、同じ方法で重合したＡ−H2（分子量が約185
万、密度が0.924）を用いた。
他は全て、実施例３−１と同じ方法によつた。
ポリエチレンＡとＢの割合い等を第３表に示し
た。第３表に示す通り、成形加工性、物性、フイ
ツシユアイ等のレベルにおいて劣ることが判る。[Table] Examples 3-1 to 3-2 (1) Production of polyethylene (A) A using the same catalyst and the same method as in Example 2-1.
-L and A-H 1 were polymerized separately. The produced A-L has a molecular weight of approximately 14,000 and a density of
A-H 1 had a molecular weight of about 890,000 and a density of 0.928 g/cm 3 . (2) Polyethylene (B) The same polymer as in Example 2-1 (B) was used. (3) Production and evaluation of polyethylene composition Compositions having the proportions shown in Table 3 were produced in the same manner as in Example 2-1. As shown in Table 3, this polyethylene exhibited very excellent performance in terms of moldability, physical properties, and firm eye level. Comparative Examples 3-1 to 3-3 Production of polyethylene (A) A-L and A- of polyethylene (A) of Example 3-1
H 1 and A-H 2 (with a molecular weight of about 185
10,000, density is 0.924). All other procedures were the same as in Example 3-1.
Table 3 shows the proportions of polyethylene A and B. As shown in Table 3, it can be seen that the moldability, physical properties, firm eye, etc. are inferior.
【表】
注１：ストランドに激しいメルトフラクチヤーが発生
し不安定であつた。
注２：フイルムがサメ肌(シヤークスキン)状となり、
正常な外観のフイルムが得られなかつた。
注３：12μのフイルムが得られなかつたので測定でき
なかつた。
[Table] Note 1: Severe melt fracture occurred in the strand, making it unstable.
Note 2: The film becomes shark skin-like,
A film with normal appearance could not be obtained.
Note 3: Measurement could not be performed because a 12μ film could not be obtained.
図面は本発明の実施態様の２段重合の一例を示
すフローシートである。
The drawing is a flow sheet showing an example of two-stage polymerization according to an embodiment of the present invention.
Claims (1)
オレフインの共重合体の群から選ばれるポリエチ
レン(A)及び(B)から成り、 (i) ポリエチレン(A)は分子量が0.5万から５万の
低分子量部（Ａ−Ｌ）と分子量が10万から150
万の高分子量部（Ａ−Ｈ）とから成り、（Ａ−
Ｈ）の分子量／（Ａ−Ｌ）の分子量が５〜200
であり、且つ、（Ａ−Ｌ）の量対（Ａ−Ｈ）の
量が重量比で、60対40から40対60の範囲であ
り、組成物中のポリエチレン(A)の量は98重量％
から85重量％の範囲であり、 (ii) ポリエチレン(B)はチーグラー型触媒により重
合されたものであり、かつその分子量は３万か
ら８万であり、密度が0.94を越え0.97ｇ／cm3以
下であり、組成物中のポリエチレン(B)の量は２
重量％から15重量％の範囲であり、 (iii) 組成物のメルトインデツクスが0.001ｇ／
10min.以上10ｇ／10min.以下である ことを特徴とするポリエチレン組成物。 ２ ポリエチレン(A)が２段重合によつてつくられ
た特許請求の範囲第１項記載のポリエチレン組成
物。 ３ ポリエチレン(A)および(B)が、マグネシウム化
合物系チーグラー型触媒によつてつくられた特許
請求の範囲第１又は２項記載のポリエチレン組成
物。 ４ ポリエチレン(B)の分子量が４万から７万であ
り、ポリエチレン(B)の分子量／（Ａ−Ｌ）の分子
量が1.5以上で、（Ａ−Ｈ）の分子量／ポリエチレ
ン(B)の分子量が1.5以上である特許請求の範囲第
１、２又は３項記載のポリエチレン組成物。[Claims] 1. Ethylene homopolymer and ethylene and α-
Consisting of polyethylene (A) and (B) selected from the group of olefin copolymers, (i) polyethylene (A) has a low molecular weight part (A-L) with a molecular weight of 50,000 to 50,000, and a low molecular weight part (A-L) with a molecular weight of 100,000. from 150
It consists of 10,000 high molecular weight parts (A-H), (A-
Molecular weight of H)/molecular weight of (A-L) is 5 to 200
and the weight ratio of the amount of (A-L) to the amount of (A-H) is in the range of 60:40 to 40:60, and the amount of polyethylene (A) in the composition is 98% by weight %
(ii) Polyethylene (B) is polymerized using a Ziegler type catalyst, has a molecular weight of 30,000 to 80,000, and has a density of more than 0.94 and 0.97 g/cm 3 and the amount of polyethylene (B) in the composition is 2
(iii) the composition has a melt index of 0.001 g/wt.
A polyethylene composition characterized in that it has a yield of 10 min. or more and 10 g/10 min. or less. 2. The polyethylene composition according to claim 1, wherein the polyethylene (A) is produced by two-stage polymerization. 3. The polyethylene composition according to claim 1 or 2, wherein the polyethylene (A) and (B) are produced using a magnesium compound-based Ziegler type catalyst. 4 The molecular weight of polyethylene (B) is 40,000 to 70,000, the molecular weight of polyethylene (B)/(A-L) is 1.5 or more, and the molecular weight of (A-H)/molecular weight of polyethylene (B) is 1.5 or more. 1.5 or more, the polyethylene composition according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13295483A JPS6026050A (en) | 1983-07-22 | 1983-07-22 | Polyethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13295483A JPS6026050A (en) | 1983-07-22 | 1983-07-22 | Polyethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6026050A JPS6026050A (en) | 1985-02-08 |
| JPH0112780B2 true JPH0112780B2 (en) | 1989-03-02 |
Family
ID=15093378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13295483A Granted JPS6026050A (en) | 1983-07-22 | 1983-07-22 | Polyethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6026050A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63154753A (en) * | 1986-12-18 | 1988-06-28 | Nippon Oil Co Ltd | Polyethylene composition |
| JPH0826181B2 (en) * | 1987-12-15 | 1996-03-13 | 三井石油化学工業株式会社 | Polyolefin composition |
| JPH0826183B2 (en) * | 1987-12-15 | 1996-03-13 | 三井石油化学工業株式会社 | Polyolefin composition |
| JPH01156346A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JPH0826182B2 (en) * | 1987-12-15 | 1996-03-13 | 三井石油化学工業株式会社 | Polyolefin composition |
| JPH0819283B2 (en) * | 1987-12-15 | 1996-02-28 | 三井石油化学工業株式会社 | Polyolefin composition |
| JPH01156349A (en) * | 1987-12-15 | 1989-06-19 | Mitsui Petrochem Ind Ltd | Polyolefin composition |
| JP2583790Y2 (en) * | 1992-10-27 | 1998-10-27 | 日本電気硝子株式会社 | Bubbling nozzle |
| US5371145A (en) * | 1993-06-08 | 1994-12-06 | Union Carbide Chemicals & Plastics Technology Corporation | High density, high molecular weight polyethylene |
| WO2019162760A1 (en) | 2018-02-05 | 2019-08-29 | Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54100445A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition for injection molding |
| JPS54100444A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition |
| JPS55152735A (en) * | 1979-05-18 | 1980-11-28 | Asahi Chem Ind Co Ltd | Polyethylene composition |
| JPS56841A (en) * | 1979-06-19 | 1981-01-07 | Mitsubishi Chem Ind Ltd | Polyethylene composition |
| JPS5626940A (en) * | 1979-08-08 | 1981-03-16 | Mitsubishi Chem Ind Ltd | Polyolefin composition and production thereof |
| JPS5731945A (en) * | 1980-08-04 | 1982-02-20 | Asahi Chem Ind Co Ltd | Polyethylene composition and preparation of the same |
| JPS57159834A (en) * | 1981-03-30 | 1982-10-02 | Idemitsu Petrochem Co Ltd | Ethylene polymer composition |
| JPS58132953A (en) * | 1982-02-03 | 1983-08-08 | Matsushita Electronics Corp | Semiconductor integrated circuit |
| JPS58132955A (en) * | 1982-02-03 | 1983-08-08 | Nec Corp | Semiconductor device and manufacture thereof |
-
1983
- 1983-07-22 JP JP13295483A patent/JPS6026050A/en active Granted
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54100445A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition for injection molding |
| JPS54100444A (en) * | 1978-01-26 | 1979-08-08 | Showa Denko Kk | Polyethylene resin composition |
| JPS55152735A (en) * | 1979-05-18 | 1980-11-28 | Asahi Chem Ind Co Ltd | Polyethylene composition |
| JPS56841A (en) * | 1979-06-19 | 1981-01-07 | Mitsubishi Chem Ind Ltd | Polyethylene composition |
| JPS5626940A (en) * | 1979-08-08 | 1981-03-16 | Mitsubishi Chem Ind Ltd | Polyolefin composition and production thereof |
| JPS5731945A (en) * | 1980-08-04 | 1982-02-20 | Asahi Chem Ind Co Ltd | Polyethylene composition and preparation of the same |
| JPS57159834A (en) * | 1981-03-30 | 1982-10-02 | Idemitsu Petrochem Co Ltd | Ethylene polymer composition |
| JPS58132953A (en) * | 1982-02-03 | 1983-08-08 | Matsushita Electronics Corp | Semiconductor integrated circuit |
| JPS58132955A (en) * | 1982-02-03 | 1983-08-08 | Nec Corp | Semiconductor device and manufacture thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6026050A (en) | 1985-02-08 |
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