JPS6333449A - Ethylenic copolymer composition - Google Patents
Ethylenic copolymer compositionInfo
- Publication number
- JPS6333449A JPS6333449A JP17739086A JP17739086A JPS6333449A JP S6333449 A JPS6333449 A JP S6333449A JP 17739086 A JP17739086 A JP 17739086A JP 17739086 A JP17739086 A JP 17739086A JP S6333449 A JPS6333449 A JP S6333449A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- ethylene
- molecular weight
- weight
- average molecular
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 59
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- 238000002844 melting Methods 0.000 claims abstract description 25
- 230000008018 melting Effects 0.000 claims abstract description 25
- -1 polypropylene Polymers 0.000 claims abstract description 25
- 239000004743 Polypropylene Substances 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 230000004927 fusion Effects 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 229920001038 ethylene copolymer Polymers 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 238000000113 differential scanning calorimetry Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 150000003682 vanadium compounds Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910021552 Vanadium(IV) chloride Inorganic materials 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はエチレン系共重合体組成物に関し、さらに詳し
くは高エチレン含量のエチレン・１−ブテン共重合体に
エチレンの長連鎖に基づく結晶性を付与することにより
、透明性、加工性および耐（ｈ撃性に加えて機械的強度
をも向上させたエチレン系共重合体組成物（特にポリプ
ロピレン樹脂組成物）に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an ethylene copolymer composition, and more particularly, to an ethylene-1-butene copolymer with a high ethylene content, crystallinity based on long chains of ethylene is added. This invention relates to an ethylene copolymer composition (particularly a polypropylene resin composition) that has improved transparency, processability, and mechanical strength (in addition to impact resistance) by imparting the following properties.
（従来の技術）
エチレンと１−ブテンとの共重合体は、単体でまたは他
の重合体と混合されてフィルム、テープ、シート、中空
成形品、射出成形品等に成形加工されて使用され、また
樹脂改質剤としても優れており、該共重合体を配合した
樹脂は自動車部品、電線等に広く使用されている。(Prior Art) A copolymer of ethylene and 1-butene is used alone or mixed with other polymers and molded into films, tapes, sheets, blow molded products, injection molded products, etc. It is also excellent as a resin modifier, and resins containing this copolymer are widely used in automobile parts, electric wires, etc.
従来エチレン・ブテン共重合体として種々の共重合体が
提案されてきたが、いずれも透明性および加工性を向上
させると機械的強度等が不足し、これらの性能を要求す
る分野での使用がかなり制限されている。そのため機械
的強度を改良する試みもなされてきたが、機械的強度を
改良すると逆に耐衝撃性、加工性および透明性を悪化さ
せることになり、そこで前記各特性をバランスよく兼ね
備えたエチレン系共重合体の開発が各分野から要望され
てきた。Various copolymers have been proposed as ethylene-butene copolymers, but all of them lack mechanical strength, etc. when improving transparency and processability, making them difficult to use in fields that require these performances. quite limited. Therefore, attempts have been made to improve the mechanical strength, but improving the mechanical strength results in deterioration of impact resistance, processability, and transparency. The development of polymers has been requested from various fields.
またポリオレフィン樹脂改質剤として用ム）る場合には
、樹脂中での共重合体の分散性および樹脂との結合性が
樹脂改質の重要な要因になるが、結晶性の小さいエチレ
ン系共重合体を用いると、樹脂との結合性が弱いため、
充分に耐衝撃性を向上させることができなかった。その
ためポリオレフィン樹脂との結合性がよく、耐衝撃性を
向上せしめる樹脂改質剤の出現が望まれていた。Furthermore, when used as a polyolefin resin modifier, the dispersibility of the copolymer in the resin and its bonding properties with the resin are important factors for resin modification. When using a polymer, the bond with the resin is weak, so
Impact resistance could not be improved sufficiently. Therefore, there has been a desire for a resin modifier that has good bonding properties with polyolefin resins and improves impact resistance.
この要望を実現するため、例えば特開昭６０−８８０１
６号公報には、広い組成分布を持ち、ＤＳＣ（示差走査
型熱量計）で求められる融点を複数個有するエチレン共
重合体が透明性、耐衝撃性、耐熱性および低温ヒートシ
ール性をバランスよ（兼持していることが述べられてい
る。しかしながら、本発明者らの検討によれば、該共重
合体は耐熱性、機械的強度および低温ヒートシール性を
バランスよく兼持させようとして、かえって従来のエチ
レン共重合体よりも透明性および耐衝撃性が悪化してお
り、さらにポリオレフィン樹脂改質剤として使用した場
合にも樹脂との結合性は改良されても耐衝撃性の向上の
点では不満足なものであった。In order to realize this request, for example, JP-A-60-8801
Publication No. 6 states that an ethylene copolymer with a wide compositional distribution and multiple melting points determined by DSC (differential scanning calorimetry) balances transparency, impact resistance, heat resistance, and low-temperature heat sealability. However, according to the studies of the present inventors, the copolymer was designed to have heat resistance, mechanical strength, and low-temperature heat sealability in a well-balanced manner. On the contrary, the transparency and impact resistance are worse than conventional ethylene copolymers, and even when used as a polyolefin resin modifier, even though the bondability with the resin is improved, there is no improvement in impact resistance. It was unsatisfactory.
（発明が解決しようとする問題点）
本発明の目的は、前記従来技術の欠点を除去し、透明性
、加工性、耐衝撃性および機械的強度をバランスよく兼
備したエチレン系共重合体組成物を提供することにある
。(Problems to be Solved by the Invention) An object of the present invention is to eliminate the drawbacks of the prior art and to provide an ethylene copolymer composition that has transparency, processability, impact resistance, and mechanical strength in a well-balanced manner. Our goal is to provide the following.
（問題点を解決するための手段）
本発明者らは鋭意検討した結果、高エチレン含有量の共
重合体中に特定のエチレンの長連鎖を含有させることに
より、透明性、加工性、耐衝撃性および機械的強度をバ
ランスよく兼備できること、さらにこの共重合体を５〜
５０重量％含有する樹脂組成物が、樹脂と共重合体との
結合性を有し、耐衝撃性を向上させることができること
を見出して本発明に到達した。(Means for Solving the Problem) As a result of intensive studies, the present inventors found that by incorporating long chains of specific ethylene into a copolymer with a high ethylene content, transparency, processability, impact resistance, etc. In addition, this copolymer can have a good balance of properties and mechanical strength.
The present invention was achieved by discovering that a resin composition containing 50% by weight has binding properties between the resin and the copolymer and can improve impact resistance.
本発明は、エチレンと１−ブテンを主重合単位とし、下
記（Ａ）〜（Ｅ）の要件を満足する、実質上線状構造を
有するエチレン系共重合体を５重量％以上含有するエチ
レン系共重合体組成物である。The present invention is an ethylene copolymer containing 5% by weight or more of an ethylene copolymer having a substantially linear structure, which has ethylene and 1-butene as main polymer units and satisfies the following requirements (A) to (E). It is a polymer composition.
（Ａ）共重合体中のエチレン含量が８５〜９５モル％で
あること、
（Ｂ）重量平均分子量が３万〜２０万であること、（Ｃ
）ＧＰＣ（Ｇｅｌ ＰｅｒｍｅａｔｉｏｎＣｈｒｏｍ
ａｔｏｇｒａｐｈ）で測定した分子量分布が単一のピー
クで、かつ重量平均分子量（Ｍｗ）と数平均分子量（Ｍ
ｎ）との比Ｍ ｗ ／ Ｍ ｎが２〜５であること、
（Ｄ）示差走査型熱量計で求められる融点が高温側と低
温側の２個存在し、高温側融点（Ｔｈ）が１１５〜１２
５℃、低温側融点（Ｔｌ）が４０〜９０℃に存在するこ
と、
（Ｅ）示差走査型熱量計で求められる１１５℃以上の温
度における結晶融解熱量（Ｈｈ）の全結晶融解熱量（Ｈ
ｔ）に対する割合が０．０１５≦Ｈｈ／Ｈｔ≦０．１５
であること。(A) The ethylene content in the copolymer is 85 to 95 mol%, (B) The weight average molecular weight is 30,000 to 200,000, (C
)GPC(Gel PermeationChrom)
The molecular weight distribution measured by atograph has a single peak, and the weight average molecular weight (Mw) and number average molecular weight (M
(D) There are two melting points, a high temperature side and a low temperature side, determined by a differential scanning calorimeter, and the high temperature side melting point (Th) is 115. ~12
5℃, and the low-temperature side melting point (Tl) exists in the range of 40 to 90℃.
t) is 0.015≦Hh/Ht≦0.15
To be.
前記条件（Ａ）〜（Ｅ）を欠（共重合体を用いる樹脂組
成物の場合には、充分な耐衝撃性の向上は得られない。In the case of a resin composition using a copolymer lacking the above conditions (A) to (E), sufficient improvement in impact resistance cannot be obtained.
本発明のエチレン系共重合体は、エチレンと１−ブテン
を主重合単位とするが、エチレンおよび１−ブテンと他
のα−オレフィンとの混合成分であってもよい。他のα
−オレフィンとしては、例えばプロピレン、１−ペンテ
ン、１−ヘキセン、４−メチル−１−ペンテン、１−ペ
ンテン、ｌ−オクテン、１−デセン等が挙げられる。The ethylene copolymer of the present invention has ethylene and 1-butene as main polymerized units, but may be a mixed component of ethylene, 1-butene, and other α-olefins. other α
Examples of the -olefin include propylene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-pentene, 1-octene, and 1-decene.
本発明のエチレン系共重合体中のエチレン含量は８５〜
９５モル％である。９５モル％を越える場合には共重合
体のランダム特性および透明性が著しく損なわれ、樹脂
組成物とした場合の耐衝撃性を得ることができない、一
方、８５モル％未満の場合には本発明の特徴とするＤＳ
Ｃ融点が示すエチレンの長連鎖に基づ（結晶部分が見出
せず、目的とする機械的強度の改良を達成することがで
ない。また樹脂（例えばポリプロピレン）と共重合体と
の結晶同士の相互作用が得られず、組成物の耐衝撃性を
従来以上に向上させることができないことがある。The ethylene content in the ethylene copolymer of the present invention is 85 to
It is 95 mol%. If it exceeds 95 mol%, the random properties and transparency of the copolymer will be significantly impaired, making it impossible to obtain the impact resistance when made into a resin composition. On the other hand, if it is less than 85 mol%, the present invention DS characterized by
Based on the long chains of ethylene indicated by the C melting point (crystalline parts cannot be found and it is not possible to achieve the desired mechanical strength improvement). may not be obtained, and it may not be possible to improve the impact resistance of the composition more than before.
本発明のエチレン系共重合体の重量平均分子量は３〜２
０万であり、ＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ
Ｃｈｒｏｍａｔｏｇｒａｐｈ）で測定した分子量分布
は単一ピークで、重量平均分子量（Ｍｗ）と数平均分子
量（Ｍｎ）とのＭ ｗ ／Ｍｎは２〜５である。Ｍｗ／
Ｍｎが２未満の共重合体は製造が困難であり、また５を
越えると、ポリマ表面のベタ付き等を生じる。The weight average molecular weight of the ethylene copolymer of the present invention is 3 to 2.
00,000, and GPC (Gel Permeation
The molecular weight distribution measured by chromatography has a single peak, and M w /Mn between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 2 to 5. Mw/
Copolymers with Mn less than 2 are difficult to manufacture, and when Mn exceeds 5, the polymer surface becomes sticky.
さらに本発明のエチレン系共重合体の特徴を最も表わす
ものとして、共重合体のエチレン連鎖による部分結晶性
の尺度であるＤＳＣ融点および結晶融解熱量がある。す
なわち本発明のエチレン系共重合体では、示差走査型熱
量計（Ｄ Ｓ Ｃ）で求められる融点（ＤＳＣ融点）が
高温側と低温側の２個存在する。かつ高温側融点（Ｔｈ
）は１１５〜１２５℃に存在し、この融点を示す吸熱ピ
ークはエチレンの長連鎖による結晶部分に基づくもので
ある。また低温側融点（Ｔ１）は４０〜９０℃に存在し
、この融点を示す吸熱ピークはエチレン・α−オレフィ
ン共重合体の微結晶に基づくものである。さらに示差走
査型熱量計で求められる１００℃以上の結晶融解熱Ｉｔ
（Ｈｈ）の全結晶融解熱量（Ｈｔ）に対する割合が０．
０１５≦Ｈｈ／Ｈｔ≦０．１５である。低温側融点（Ｔ
ｊりが存在しなかったり、またＴｌ＞９０℃の場合には
共重合体のランダム性は極めて乏しく、ランダム共重合
体としての特性が失なわれ、結晶性が高く耐衝撃性が著
しく劣化する。Ｔｌ＜４０℃では共重合体の結晶性が低
すぎて、強度が著しく低下してしまう、また高温側融点
（Ｔｈ）が存在しない場合には、本発明の目的のひとつ
である機械的強度の改良は達成されない。Ｔｈ＜ １１
５℃では結晶化しているエチレン連鎖が短いために共重
合体の強度は不満足であり、また共重合体と樹脂成分と
の結合性も弱く、樹脂改質効果も不十分である。またＴ
ｈ＞１２５℃のエチレン・１−ブテンランダム共重合体
は製造困難である。またＨｈ／Ｈｔ＜０゜０１５の場合
にはポリエチレンの部分結晶性が少なすぎて機械的強度
を充分に改良することはできず、一方Ｈｈ／Ｈｔ＞０．
１５の場合には逆に結晶性が高すぎて透明性、耐衝撃性
および加工性を悪化させてしまう、このようにＨｈ／Ｈ
ｔが上記の条件を満足しない共重合体を用いて得られる
ポリプロピレン樹脂組成物では、充分な耐衝撃性は得ら
れない。Further, the most characteristic characteristics of the ethylene copolymer of the present invention are the DSC melting point and the heat of crystal fusion, which are measures of the partial crystallinity of the copolymer due to ethylene chains. That is, the ethylene copolymer of the present invention has two melting points determined by a differential scanning calorimeter (DSC) (DSC melting point): a high temperature side and a low temperature side. and high temperature side melting point (Th
) exists at 115 to 125° C., and the endothermic peak indicating this melting point is based on the crystalline portion of long chains of ethylene. Further, the low temperature side melting point (T1) exists at 40 to 90°C, and the endothermic peak indicating this melting point is based on the microcrystals of the ethylene/α-olefin copolymer. Furthermore, the heat of crystal fusion It, which is determined by a differential scanning calorimeter, is 100°C or more.
The ratio of (Hh) to the total heat of fusion of crystals (Ht) is 0.
015≦Hh/Ht≦0.15. Low-temperature melting point (T
If the copolymer does not exist or Tl>90°C, the randomness of the copolymer is extremely poor, the properties as a random copolymer are lost, the crystallinity is high, and the impact resistance is significantly deteriorated. . If Tl < 40°C, the crystallinity of the copolymer will be too low and the strength will drop significantly, and if there is no high-temperature melting point (Th), the mechanical strength, which is one of the objectives of the present invention, will deteriorate. No improvement is achieved. Th< 11
At 5°C, the strength of the copolymer is unsatisfactory because the crystallized ethylene chains are short, and the bond between the copolymer and the resin component is also weak, resulting in insufficient resin modification effect. Also T
It is difficult to produce an ethylene/1-butene random copolymer with h>125°C. Further, when Hh/Ht<0°015, the partial crystallinity of polyethylene is too low to sufficiently improve mechanical strength, while on the other hand, when Hh/Ht>0.
Conversely, in the case of Hh/H
A polypropylene resin composition obtained using a copolymer in which t does not satisfy the above conditions will not have sufficient impact resistance.
このように前記（Ａ）〜（Ｅ）の要件を満足する本発明
のエチレン系共重合体は従来知られていない新規な共重
合体であり、従来公知のエチレン系共重合体とは異なる
０例えば特開昭６０−８８０１６号公報に記載されたエ
チレン共重合体は、低温融点の値が高く、非常に結晶性
の高い共重合体である点で本発明の共重合体とは異なる
。このため、本発明の共重合体は、透明性、加工性、耐
衝撃性および機械的強度をバランスよく兼備したものと
なる。さらに本発明は、この共重合体を結合性のポリオ
レフィンに含有させることにより、後述の耐衝撃性に優
れた樹脂組成物が得られる。As described above, the ethylene copolymer of the present invention that satisfies the requirements (A) to (E) above is a novel copolymer that has not been previously known, and is different from conventionally known ethylene copolymers. For example, the ethylene copolymer described in JP-A-60-88016 differs from the copolymer of the present invention in that it has a high low-temperature melting point and is a very highly crystalline copolymer. Therefore, the copolymer of the present invention has a good balance of transparency, processability, impact resistance, and mechanical strength. Furthermore, in the present invention, by incorporating this copolymer into a binding polyolefin, a resin composition having excellent impact resistance, which will be described later, can be obtained.
本発明のエチレン系共重合体は、例えば重合触媒として
、可溶性バナジウム化合物および有機アルミニウム化合
物の、組成比（モル比）１０／１〜２００／１の割合か
らなる触媒を用い、エチレンと１−ブテン（他のα−オ
レフィンとの混合成分でもよい）とを、重合温度−２０
〜８０℃で共重合させることにより製造される。The ethylene copolymer of the present invention can be produced by using, for example, a catalyst consisting of a soluble vanadium compound and an organoaluminum compound in a composition ratio (mole ratio) of 10/1 to 200/1 as a polymerization catalyst, and ethylene and 1-butene. (may be a mixed component with other α-olefins) at a polymerization temperature of -20
Manufactured by copolymerization at ~80°C.
上記可溶性バナジウム化合物としては、例えばオキシ三
塩化バナジウム、四塩化バナジウム、アルキルバナデー
ト、オキシ三塩化バナジウムとアルコールとの反応混合
物、オキシ塩化バナジウムとアルコール以外の電子供与
体（アミン類、ケトン類、エーテル類等）との反応混合
物等が挙げられ、好ましくはオキシ三塩化バナジウム、
四塩化バナジウム、アルキルバナデート（例えばエチル
アルコール、ｎ−プロビルバナデート、イソプロビルバ
ナデート、ｎ−プチルバナデート、５ｅｃ−ブチルアル
コール、２−エチルへキシルバナデート等）、オキシ三
塩化バナジウムとアルコール（例えばエチルアルコール
、ｎ−プロピルアルコール、イソプロピルアルコール、
ｎ ７”チルアルコール、５ｅＣ−ブチルアルコール
、ｔ−ブチルアルコール、２−エチルヘキシルアルコー
ル等）とのＲＯＭ／Ｖ＝１／１〜３／１ （モル比）の
反応混合物が用いられる。Examples of the above-mentioned soluble vanadium compounds include vanadium oxytrichloride, vanadium tetrachloride, alkylvanadates, reaction mixtures of vanadium oxytrichloride and alcohols, vanadium oxychloride and electron donors other than alcohols (amines, ketones, ethers, etc.). etc.), preferably vanadium oxytrichloride,
Vanadium tetrachloride, alkylvanadate (e.g. ethyl alcohol, n-probylvanadate, isoprobylvanadate, n-butylvanadate, 5ec-butyl alcohol, 2-ethylhexylvanadate, etc.), vanadium oxytrichloride and Alcohol (e.g. ethyl alcohol, n-propyl alcohol, isopropyl alcohol,
A reaction mixture of ROM/V=1/1 to 3/1 (molar ratio) with n7'' methyl alcohol, 5eC-butyl alcohol, t-butyl alcohol, 2-ethylhexyl alcohol, etc. is used.
有機アルミニウム化合物としては、例えば一般式ＲｎＡ
ｆＸ３−ｎ（式中Ｒはアルキル基、Ｘはハロゲン原子、
ｎは１≦ｎ≦３の整数を意味する）で表わされるハロゲ
ン化有機アルミニウム化合物、例えばエチルアルミニウ
ムジクロリド、ジエチルアルミニウムクロリド、エチル
セスキアルミニウムクロリド、イソブチルセスキアルミ
ニウムクロリド等、好ましくはエチルセスキアルミニウ
ムクロリドが用いられる。またこれらの２種以上を組合
わせた混合物を用いることもできる。As the organoaluminum compound, for example, the general formula RnA
fX3-n (in the formula, R is an alkyl group, X is a halogen atom,
n means an integer of 1≦n≦3), such as ethylaluminum dichloride, diethylaluminum chloride, ethylsesquialuminum chloride, isobutylsesquialuminum chloride, etc., preferably ethylsesquialuminum chloride is used. It will be done. Moreover, a mixture of two or more of these can also be used.
バナジウム化合物と有機アルミニウム化合物との組成比
（モル比）は、Ａｌ／Ｖ＝１０／１〜２００／１、好ま
しくは１０／１〜１５０／１である。本発明のエチレン
系共重合体は、幅広いＡＮ／■の範囲で製造可能である
が、Ａｌ／Ｖが１０／１より小さい場合には分子量分布
（ＧＰＣ測定におけるＭ ｗ ／ Ｍ ｎで示される）
がブロードになり、成形物の表面ベタ付き性が悪化し、
また触媒活性の低下のために多量のバナジウム化合物を
使用する必要があり、共重合体中にバナジウム金属の酸
化物が多く残り、最終製品の色相を悪化させる。一方Ａ
ｌｌ／■が２００／１より大きい場合には、バナジウム
化合物の還元が進みすぎるため重合活性が低下し、さら
にα−オレフィンの共重合性も低下してしまい、目的と
する共重合体が得られない。The composition ratio (molar ratio) of the vanadium compound and the organic aluminum compound is Al/V=10/1 to 200/1, preferably 10/1 to 150/1. The ethylene copolymer of the present invention can be produced in a wide range of AN/■, but when Al/V is smaller than 10/1, the molecular weight distribution (indicated by M w / M n in GPC measurement)
becomes broad, the surface stickiness of the molded product worsens,
Furthermore, it is necessary to use a large amount of vanadium compound to reduce the catalyst activity, and a large amount of vanadium metal oxide remains in the copolymer, which deteriorates the hue of the final product. On the other hand, A
If ll/■ is larger than 200/1, the reduction of the vanadium compound will proceed too much, resulting in a decrease in polymerization activity, and in addition, copolymerizability of α-olefin will also decrease, making it impossible to obtain the desired copolymer. do not have.
本発明に用いられる触媒系にはさらに必要に応じて活性
向上剤を添加することもできる。活性向上剤としては、
例えばトリクロロ酢酸エステル、２．３，４．４−テト
ラクロルブテン酸エステル等の多ハロゲン化合物が用い
られる。その他必要に応じてアルコール類、ケトン類、
アミン類等の電子供与体を、前記バナジウム化合物また
は前記アルミニウム化合物と予め混合してまたは同時に
添加して使用することもできる。If necessary, an activity enhancer may be added to the catalyst system used in the present invention. As an activity enhancer,
For example, polyhalogen compounds such as trichloroacetic acid ester and 2,3,4,4-tetrachlorobutenoic acid ester are used. Other alcohols, ketones, etc. as necessary.
An electron donor such as amines can also be used by being mixed in advance with the vanadium compound or the aluminum compound or by being added at the same time.
本発明において重合に際し用いられる重合溶媒としては
、炭素数３〜１ｏの脂肪族炭化水素化合物、炭素数１〜
５のハロゲン化脂肪族炭化水素化合物が挙げられ、例え
ばプロパン、ブタン、ペンタン、ヘキサン、ヘプタン、
オクタン、デカン、プロピレン、１−ブテン、ヘキセン
、塩化メチル、塩化エチル、塩化メチレン、塩化エチレ
ン等、好ましくはｎ−ヘキサン、ｎ−へブタンが用いら
れる。The polymerization solvent used in the polymerization in the present invention includes aliphatic hydrocarbon compounds having 3 to 1 carbon atoms, and 1 to 1 carbon atoms.
5 halogenated aliphatic hydrocarbon compounds, such as propane, butane, pentane, hexane, heptane,
Octane, decane, propylene, 1-butene, hexene, methyl chloride, ethyl chloride, methylene chloride, ethylene chloride, etc., preferably n-hexane and n-hebutane are used.
重合温度は一２０〜８０℃、好ましくは１０〜６０℃で
ある。−２０℃より低い場合には冷却に多量のエネルギ
ーが必要となる等経済的な面で不利益となる。一方、８
０℃より高い場合には重合活性が低下し、さらにα−オ
レフィンの共重合性が低下してしまい、目的とする共重
合体が得られない。The polymerization temperature is -20 to 80°C, preferably 10 to 60°C. If the temperature is lower than -20° C., a large amount of energy is required for cooling, which is disadvantageous from an economic point of view. On the other hand, 8
If the temperature is higher than 0°C, the polymerization activity decreases, and the copolymerizability of α-olefin also decreases, making it impossible to obtain the desired copolymer.
重合の際の単位バナジウム触媒光たり、ブテン−ｌモノ
マー量は１５００〜２００００ （モル比）の範囲であ
ることが好ましい。１５００未満ではブテン−１濃度が
低すぎ、組成コントロールが困難であり、また２０００
０をこえると液相中のブテン−１濃度が高く目的とする
エチレン長連鎖を得ることはできない。The amount of butene-1 monomer and vanadium catalyst unit during polymerization is preferably in the range of 1,500 to 20,000 (molar ratio). If it is less than 1500, the butene-1 concentration is too low and composition control is difficult;
If it exceeds 0, the concentration of butene-1 in the liquid phase will be high, making it impossible to obtain the desired long ethylene chain.
本発明の共重合体製造において重合形態は、スラリ重合
、均一溶液重合のいずれでもよいが、好ましくはスラリ
重合が行なわれる。均一溶液重合では該共重合体がポリ
エチレンの結晶を持つことから重合温度をかなり上昇さ
せなければならない。In producing the copolymer of the present invention, the polymerization form may be either slurry polymerization or homogeneous solution polymerization, but slurry polymerization is preferably carried out. In homogeneous solution polymerization, since the copolymer has polyethylene crystals, the polymerization temperature must be raised considerably.
また重合は回分式または連続式のいずれでもよい。Moreover, the polymerization may be carried out either batchwise or continuously.
反応器は単一または複数個を直列または並列に連結し、
原料オレフィンを別にまたは予め混合して導入する。反
応温度の維持は外部冷却法、溶媒・七ツマ−の蒸発潜熱
の利用等により行なわれる。A single reactor or multiple reactors connected in series or parallel,
The raw olefins are introduced separately or premixed. The reaction temperature is maintained by an external cooling method, by utilizing the latent heat of vaporization of the solvent, or the like.
圧力は減圧下（１００ｍｍＨｇ）ないし加圧下（５０気
圧程度）に保持される。分子量の制御は先に述べた触媒
組成比、触媒量、触媒種、重合温度等によってもある程
度可能であるが、さらに水素等の分子量制御剤を用いて
行なうこともできる。生成した共重合体の反応媒体およ
び未反応モノマーからの分離、使用触媒の活性停止、触
媒残渣の除去、共重合体の乾燥、造粒等の成形などは、
公知方法により行なわれる。The pressure is maintained at reduced pressure (100 mmHg) or increased pressure (about 50 atm). The molecular weight can be controlled to some extent by the above-mentioned catalyst composition ratio, catalyst amount, catalyst type, polymerization temperature, etc., but it can also be controlled by using a molecular weight controlling agent such as hydrogen. Separation of the produced copolymer from the reaction medium and unreacted monomers, termination of the activity of the catalyst used, removal of catalyst residue, drying of the copolymer, and shaping such as granulation, etc.
This is done by a known method.
このようにして得られる本発明のエチレン系共重合体は
、単独でまたは他の樹脂に５重量％以上混合して本発明
のエチレン系共重合体組成物とされる。前記エチレン系
共重合体が５重量％未満では本願の効果が得られない。The ethylene copolymer of the present invention thus obtained is used alone or mixed with 5% by weight or more of another resin to form the ethylene copolymer composition of the present invention. If the amount of the ethylene copolymer is less than 5% by weight, the effects of the present application cannot be obtained.
さらに目的に応じて他のオレフィン（共）重合体ゴム、
カルボン酸類のグラフト等で変性された変性オレフィン
（共）重合体類等と、さらに場合により有機系、無機系
のフィラー、繊維等の補強剤と混合し、積石等の手段を
施してフィルム、テープ、シート、中空成形品、射出成
形品等として使用される。Furthermore, depending on the purpose, other olefin (co)polymer rubbers,
Modified olefin (co)polymers modified with grafts of carboxylic acids, etc. are mixed with reinforcing agents such as organic or inorganic fillers and fibers, and then processed by means such as stacking stones to form a film. Used as tapes, sheets, hollow molded products, injection molded products, etc.
特に本発明の好適な組成物は、前記の新規エチレン系共
重合体（イ）と、結晶性ポリプロピレン（ロ）とを含み
、（イ）と（ロ）との重量比（（イ）／（ロ））が５０
１５０〜５／９５であるエチレン系共重合体樹脂組成物
が好ましい。In particular, a preferred composition of the present invention comprises the above-mentioned novel ethylene copolymer (a) and crystalline polypropylene (b), and the weight ratio of (a) and (b) is ((i)/( b)) is 50
Preferably, the ethylene copolymer resin composition has a molecular weight of 150 to 5/95.
本発明に用いる結晶性ポリプロピレン（ロ）には結晶性
のポリプロピレンホモポリマーのほか、エチレンおよび
／またはプロピレン以外のα−オレフィン２０重量％以
下を含有する結晶性プロピレン共重合体も含まれる。The crystalline polypropylene (b) used in the present invention includes not only crystalline polypropylene homopolymers but also crystalline propylene copolymers containing 20% by weight or less of α-olefin other than ethylene and/or propylene.
このエチレン系共重合体樹脂組成物中のエチレン系共重
合体（イ）の含有割合は、５重量％以上、特に５〜５０
Ｍ量％、好ましくは１０〜４０重量％である。エチレン
系共重合体（イ）の含有割合が５重量％より少ない場合
には、低温での耐衝撃性が低く、一方５０重量％を越え
る場合には、剛性および機械的強度が低下する。The content of the ethylene copolymer (a) in this ethylene copolymer resin composition is 5% by weight or more, particularly 5 to 50% by weight.
The amount of M is %, preferably 10 to 40% by weight. If the content of the ethylene copolymer (a) is less than 5% by weight, the impact resistance at low temperatures will be low, while if it exceeds 50% by weight, the rigidity and mechanical strength will decrease.
本発明のエチレン系共重合体組成物は、例えばポリプロ
ピレン樹脂と共重合体とを混合することにより製造され
る。例えば本発明の新規エチレン系共重合体とポリプロ
ピレンとを押出機、ニーダープレンダー、バンバリーミ
キサ−等を用いて混合するか、または前記エチレン系共
重合体に任意量のポリプロピレンをバンバリーミキサ−
、ニーダーブレンダーを用いて混合し、常法によりペレ
ット状とし、最終的に共重合体とポリプロピレンとの割
合が目的とする値となるように該ベレットとポリプロピ
レンとを投入し、成形物を得るなどの方法がある。また
特願昭５８−１８１３７７号に開示された方法によって
も目的とする本発明の樹脂組成物を得ることができる。The ethylene copolymer composition of the present invention is produced, for example, by mixing a polypropylene resin and a copolymer. For example, the novel ethylene copolymer of the present invention and polypropylene are mixed using an extruder, kneader blender, Banbury mixer, etc., or an arbitrary amount of polypropylene is added to the ethylene copolymer using a Banbury mixer.
, mixed using a kneader blender, made into pellets by a conventional method, and finally added the pellets and polypropylene so that the ratio of copolymer and polypropylene becomes the desired value to obtain a molded product. There is a method. The desired resin composition of the present invention can also be obtained by the method disclosed in Japanese Patent Application No. 58-181377.
本発明の樹脂組成物には、さらに必要に応じて酸化止剤
、熱安定剤、紫外線吸収剤、着色剤等の補助添加成分を
添加することもできる。また本発明の樹脂組成物には、
例えば炭酸カルシウム、カオリン、タルク、アスベスト
、ガラス繊維等の充填剤、本発明で用いられている共重
合体以外のオし・フィン系共重合体（例えばＥＰＲ等）
、ポリエチレン樹脂、ポリスチレン樹脂、アクリロニト
リル・ブタジェン・スチレン共重合樹脂、エチレン−酢
酸ビニル共重合樹脂、ポリブタジェン樹脂等のゴム、樹
脂などを配合することもでき、その添加量は本発明の樹
脂組成物１００重量部に対して０〜３０重量部が好まし
い。The resin composition of the present invention may further contain auxiliary additive components such as antioxidants, heat stabilizers, ultraviolet absorbers, and colorants, if necessary. Further, the resin composition of the present invention includes:
For example, fillers such as calcium carbonate, kaolin, talc, asbestos, glass fiber, etc., oxide-fin type copolymers other than the copolymers used in the present invention (e.g., EPR, etc.)
Rubbers and resins such as polyethylene resin, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, ethylene-vinyl acetate copolymer resin, polybutadiene resin, etc. can also be blended, and the amount added is 100% of the resin composition of the present invention. It is preferably 0 to 30 parts by weight.
（発明の効果）
本発明によるエチレン系共重合体は、従来のエチレン共
重合体と異なり、透明性、耐衝撃性および機械的強度を
バランスよく兼備しており、このためフィルム、シート
等の用途に好適である。また本発明のエチレン系共重合
体は加工性も良好であるため各種成形加工品材料等とし
ても使用することができる。(Effects of the Invention) Unlike conventional ethylene copolymers, the ethylene copolymer of the present invention has transparency, impact resistance, and mechanical strength in a well-balanced manner, and is therefore used for films, sheets, etc. suitable for Furthermore, since the ethylene copolymer of the present invention has good processability, it can be used as a material for various molded products.
また本発明のエチレン系共重合体を含有する本発明の樹
脂組成物、例えばポリプロピレン樹脂組成物は耐衝撃性
に優れたものであり、自動車バンパー、各種自動車部品
、電線、電気機器等に使用することができる。Furthermore, the resin composition of the present invention containing the ethylene copolymer of the present invention, such as a polypropylene resin composition, has excellent impact resistance and can be used for automobile bumpers, various automobile parts, electric wires, electrical equipment, etc. be able to.
（実施例） 以下、実施例により本発明を詳説する。(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.
なお本発明のエチレン系共重合体を特定するために次に
示す分析手段および物性評価方法が用いられた。In order to specify the ethylene copolymer of the present invention, the following analysis means and physical property evaluation method were used.
（エチレン含量）
エチレン・α−オレフィン共重合体をＩ Ｈ−ＮＭＲお
よび１３ Ｃ−Ｎ Ｍ Ｒを用いてエチレン／α−オレ
フィン組成比を求め、赤外分析で検量線を作成した。こ
の検量線をもとにして各実施例で得られる共重合体の組
成を求めた。(Ethylene Content) The ethylene/α-olefin composition ratio of the ethylene/α-olefin copolymer was determined using I H-NMR and 13 C-NMR, and a calibration curve was created using infrared analysis. Based on this calibration curve, the composition of the copolymer obtained in each example was determined.
（Ｍｗ／Ｍｎ）
行内＝ｖ ｒゲルパーミェーションクロマトグラフＪ
（丸蓋（株）刊）に準じて次のようにして測定した。(Mw/Mn) In the row = v r gel permeation chromatograph J
(published by Marugata Co., Ltd.), and was measured as follows.
（１）分子量既知の標準ポリスチレン（東洋ソーダ（株
）製、単分散ポリスチレン）を使用し、分子量Ｍとその
ＧＰＣ（Ｇｅｆｆｉ Ｐｅｒｍｅａｔ ｉｏｎ ｑ
ｈｒｏｍａｔｏｇｒａｐｈ）カウントを測定し、分子量
ＭとＥＶ（Ｅｊｔｕｔｉｏｎ Ｖ。(1) Using standard polystyrene with a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodisperse polystyrene), the molecular weight M and its GPC (Geffi Permeation Q
chromatography) counts, molecular weight M and EV (Ejtition V).
ｆｕｍｅ）との相関図更正曲線を作図する。このときの
濃度は０．０２ｆｉ量％とする。標準ポリスチレンによ
る更正曲線をユニバーサル法によりＥＢＭの更正曲線に
補正する。Plot a correlation diagram correction curve with fume). The concentration at this time is 0.02 fi amount %. The standard polystyrene calibration curve is corrected to the EBM calibration curve using the universal method.
（２）ＧＰＣ測定法により試料のＧＰＣパターンをとり
、前記（１）によりＭを求める。その際のサンプル調製
条件およびＧＰＣ測定条件は以下のとおりである。(2) Obtain a GPC pattern of the sample using the GPC measurement method, and obtain M using the above (1). The sample preparation conditions and GPC measurement conditions at that time are as follows.
（サンプル調製条件）
（ａ）０−ジクロルベンゼン溶媒に老化防止剤として２
，６−ジーｔ−ブチル−クレゾールを０．０８％添加し
、溶解する。(Sample preparation conditions) (a) 2 as an anti-aging agent in 0-dichlorobenzene solvent
, 0.08% of 6-di-t-butyl-cresol is added and dissolved.
（ｂ）試料を０．１％になるように０−ジクロルベンゼ
ンとともに三角フラスコに分取する。(b) Separate the sample into an Erlenmeyer flask together with 0-dichlorobenzene to a concentration of 0.1%.
（Ｃ）三角フラスコを１２０℃に加温し、約６０分間攪
拌して溶解させる。(C) Heat the Erlenmeyer flask to 120°C and stir for about 60 minutes to dissolve.
（ｄ）（Ｃ）で得られた溶媒をＧＰＣにかける。(d) The solvent obtained in (C) is subjected to GPC.
なおＧＰＣ装置内で自動的に０．５ミクロンの焼結フィ
ルタで濾過させる。Note that the sample is automatically filtered using a 0.5 micron sintered filter within the GPC device.
（ＧＰＣ測定条件）
（ａ）装置 ：Ｗａｔｅｒｓ社製１５０Ｃ型（ｂ）
カラム ：東洋ソーダ（株）製Ｈタイプ（ｃ）サンプ
ル量二５００マイクロ２
（ｄ）温度 ：１２０℃
（ｅ）流速 ：１ｍｊ！／分
（ｆ）カラム総理論段数：１＊１０ ２＊１０（アセト
ンによる測定値）
（示差走査型熱量計による融点および結晶融解熱量の測
定方法）
示差走査型熱量計はＤｕｐｏｎｔ社製 ９１０型Ｄｅｆ
ｅｒｅｎｔｉａｊ！ ＳｃａｎｎｉｎｇＣａｎ！ｏｆｆ
ｉｉｍｅｔｅｒ （以下、ＤＳＣと略称する）を用い、
記録針はＤｕｐＯｎｔ社製 ９９０型 Ｔｈｅｒｍａｌ
Ａｎａｊ！ｙｚｅｒを用いた。サンプル量は１０±
０．１■、Ｒｅｆｅｒｅｎｃｅとしてはα−アルミナを
用いた。測定はサンプルおよびＲｅｆｅｒｅｎｃｅをＤ
ＳＣに装置し、１８０℃まで加温し、その後１分間に１
０℃の一定速度で一１００℃まで冷却する。次いで１分
間に２０℃の一定昇温速度で分析する。得られる代表的
なりＳＣパターンを第１図に示す。(GPC measurement conditions) (a) Apparatus: Waters 150C type (b)
Column: H type manufactured by Toyo Soda Co., Ltd. (c) Sample amount: 2500 microns (d) Temperature: 120°C (e) Flow rate: 1mj! /min (f) Column total theoretical plate number: 1 * 10 2 * 10 (measured value with acetone) (Method of measuring melting point and heat of crystal fusion using differential scanning calorimeter) Differential scanning calorimeter is Dupont 910 type Def.
erentiaj! Scanning Can! off
Using iimeter (hereinafter abbreviated as DSC),
The recording needle is DupOnt 990 type Thermal.
Anaj! yzer was used. Sample amount is 10±
0.1■, α-alumina was used as the reference. Measurements are made using the sample and Reference
Place the device in an SC, heat it to 180℃, and then heat it at 1 minute per minute.
Cool to -100°C at a constant rate of 0°C. The analysis is then performed at a constant heating rate of 20° C. per minute. A typical SC pattern obtained is shown in FIG.
第１図においてＴｊｌおよびＴｈをＤＳＣ融点と称し、
本発明のエチレン系共重合体の有する高温側融点はＴｈ
を、また低温側融点はＴｆを指し、これらのＤＳＣ融点
は各々の点における温度座標軸より読み取られる。In FIG. 1, Tjl and Th are referred to as DSC melting points,
The high temperature side melting point of the ethylene copolymer of the present invention is Th
, and the melting point on the low temperature side refers to Tf, and these DSC melting points are read from the temperature coordinate axis at each point.
（結晶の吸熱量の計算）
第１図における低温側ベースラインＡ−Ｂの接線（ａ）
を求める。次いでＴｇ部分と考えられる吸熱ピークＢ−
Ｃの接線（ｂ）を求める。接線（ａ）と（ｂ）の交点を
（ア）とし、（ア）より垂線（ｃ）を描く０次いで次式
（１）に従ってｈを求める。(Calculation of endothermic amount of crystal) Tangent line (a) of low temperature side baseline A-B in Fig. 1
seek. Next, there is an endothermic peak B- which is considered to be the Tg portion.
Find the tangent line (b) of C. Let the intersection of tangents (a) and (b) be (a), draw a perpendicular line (c) from (a), then calculate h according to the following equation (1).
ｈ（鶴）＝２．２５ｘｓ（■） （１）（ただ
し、ｈはＤＳＣチャート原寸における（ア）からの距離
（鶴）、Ｓはサンプル量（■））（ア）からの垂線（Ｃ
）に沿って距離りの位置に水平線（ｄ）を描く。水平線
（ｄ）と吸熱カーブとの交点（イ）を求める。h (crane) = 2.25xs (■) (1) (where h is the distance from (a) in the original size of the DSC chart (crane), S is the sample amount (■)) the perpendicular line from (a) (C
), draw a horizontal line (d) at a distance. Find the intersection point (a) between the horizontal line (d) and the endothermic curve.
交点（イ）より高温側ベースラインＤ−Ｅ部との接線（
ｅ）を描く。接線（ｅ）とベースラインとの接点（つ）
を求める。接線（ｅ）と吸熱カーブで囲まれた斜線部分
が全結晶融解熱量に相当する。続いて１１０℃の位置で
吸熱部分を分割し、１１０℃以上の吸熱部分を高温側吸
熱量として取扱った。全結晶融解熱量および高温側結晶
融解熱量は各々の面積（第１図の斜線部分）を求め、イ
ンジウム（Ｄｕｐｏｎｔ社ＤＳＣ用標準試料）を基準に
して算出した。Tangent line (
Draw e). Point of contact between tangent line (e) and baseline
seek. The shaded area surrounded by the tangent line (e) and the endothermic curve corresponds to the total heat of fusion of the crystals. Subsequently, the endothermic portion was divided at the 110° C. position, and the endothermic portion above 110° C. was treated as the endothermic amount on the high temperature side. The total crystal fusion heat amount and the high temperature side crystal fusion heat amount were calculated by determining the area (shaded area in FIG. 1) of each crystal and using indium (Dupont DSC standard sample) as a reference.
（その他の物性の測定方法） （１）メルトフローインデックス ＪＩＳ Ｋ ６７５８に従った。(Methods for measuring other physical properties) (1) Melt flow index According to JIS K 6758.
（２）破断点強度および伸び
ＪＩＳ Ｋ ６３０１の引張り試験法に基づき、温
度２５℃、引張り速度５００ｍｍＺ分で測定された。(2) Strength at break and elongation Measured based on the tensile test method of JIS K 6301 at a temperature of 25° C. and a tensile speed of 500 mmZ.
（３）アイゾツト衝撃強度 ＪＩＳ Ｋ ７１１０に従った。(3) Izotsu impact strength In accordance with JIS K 7110.
（４）成形物の表面ベタ付き性
前記（２）で用いた引張り試験用成形シートの表面肌の
感触より下記基準で示した。(4) Surface stickiness of molded product The texture of the surface of the molded sheet for tensile test used in (2) above was evaluated based on the following criteria.
ベタ付きが全く感じられない試料：◎
ベタ付きがほとんど感じられない試料二〇ベタ付きがや
や感じられる試料：Δ
ベタ付きが明らかに感じられる試料：×（５）透明性
本発明のエチレン系共重合体およびそのポリプロピレン
樹脂組成物をそれぞれ０．５ｍｌのシートに成形した後
、各実施例および比較例の試料間で比較して下記基準で
示した。Sample with no stickiness: ◎ Sample with almost no stickiness: 20 Sample with slight stickiness: Δ Sample with obvious stickiness: ×(5) Transparency The ethylene-based copolymer of the present invention After molding the polymer and its polypropylene resin composition into sheets of 0.5 ml each, the samples of each Example and Comparative Example were compared and shown according to the following criteria.
非常に透明性に優れている試料：◎
透明性がよい試料 ：○
透明性が劣る試料 ：×
実施例１
内容量４８Ｎの連続重合装置をＮ２ガスで充分に置換し
た後、エチルセスキアルミニウムクロリド１２．９ｇ／
Ｈｒ、オキシ三塩化バナジウム０．３ｇ／Ｈｒ、ｎ−ヘ
キサン１８１／Ｈｒおよび１−ブテン１５４０ｇ／Ｈｒ
を連続供給し、水素を６Ｎｌ／Ｈの流量で吹込み、２０
℃に維持し、圧力が３．０ｋｇ／ｃｄＧになるようにエ
チレンを連続供給して共重合を行なった。なお滞留時間
は１時間とした。重合の結果、本発明のエチレン系共重
合体９００ｇ／Ｈｒが得られ、得られた共重合体の分析
および物性評価の結果を第１表に示した。Sample with very good transparency: ◎ Sample with good transparency: ○ Sample with poor transparency: × Example 1 After sufficiently replacing a continuous polymerization device with an internal capacity of 48N with N2 gas, ethylsesquialuminum chloride 12 .9g/
Hr, vanadium oxytrichloride 0.3g/Hr, n-hexane 181/Hr and 1-butene 1540g/Hr
was continuously supplied, hydrogen was blown in at a flow rate of 6Nl/H, and 20
The copolymerization was carried out by maintaining the temperature at 0.degree. C. and continuously supplying ethylene at a pressure of 3.0 kg/cdG. Note that the residence time was 1 hour. As a result of the polymerization, 900 g/Hr of the ethylene copolymer of the present invention was obtained, and the results of analysis and physical property evaluation of the obtained copolymer are shown in Table 1.
実施例２
実施例１と同様の装置を用い、エチルセスキアルミニウ
ムクロリドを４．３ｇ／Ｈｒ、１−ブテンを７００ ｇ
／Ｈｒで連続供給し、圧力を３．５ｋｇ／−Ｇになるよ
うにエチレンを連続供給し、その他は実施例１と同様に
処理して得られた共重合体の分析および物性評価の結果
を第１表に示した。一実施例３
実施例１と同様の装置を用い、圧力を２．８ｋｇ／ｃｊ
Ｇになるようにエチレンを連続供給し、その他は実施例
１と同様に処理して得られた共重合体の分析および物性
評価の結果を第１表に示した。Example 2 Using the same equipment as in Example 1, 4.3 g/Hr of ethylsesquialuminum chloride and 700 g of 1-butene
/Hr, ethylene was continuously supplied at a pressure of 3.5 kg/-G, and the other conditions were the same as in Example 1. The results of analysis and physical property evaluation of the copolymer obtained were as follows. It is shown in Table 1. Example 3 Using the same device as Example 1, the pressure was 2.8 kg/cj
Table 1 shows the results of the analysis and physical property evaluation of the copolymer obtained by continuously supplying ethylene so as to obtain G and otherwise treating the same as in Example 1.
比較例１および２
実施例１と同様の装置を用い、それぞれ圧力を２．０ｋ
ｇ／Ｃｌ１ｉＧ（比較例１）および５．０ ｋｇ／ｃＩ
ａＧ （比較例２）になるようにエチレンを連続供給し
、その他は実施例１と同様に処理して得られた共重合体
の分析および物性評価の結果を第１表に示した。Comparative Examples 1 and 2 Using the same equipment as in Example 1, the pressure was 2.0 k, respectively.
g/Cl1iG (Comparative Example 1) and 5.0 kg/cI
Table 1 shows the results of analysis and physical property evaluation of a copolymer obtained by continuously supplying ethylene so as to obtain aG (Comparative Example 2) and otherwise treating the copolymer in the same manner as in Example 1.
エチレン含量が７０重量％未満の比較例１の場合には実
施例の場合に比べて破断点強度が劣り、またＭ ｗ ／
Ｍ ｎが大きくなり、表面のベタ付きが感じられた。In the case of Comparative Example 1 in which the ethylene content was less than 70% by weight, the strength at break was inferior to that in the Examples, and M w /
Mn increased and the surface felt sticky.
また９５重量％を越える比較例２の場合には透明性が低
下した。Moreover, in the case of Comparative Example 2 where the content exceeded 95% by weight, the transparency decreased.
比較例３
実施例１と同様の装置を用い、ｎ−ヘキサンを２Ｑ１／
Ｈｒ、１−ブテンを１０００ｋｇ／Ｈｒで連続供給し、
圧力を２．０ｋｇ／ｃｄＧになるようにエチレンを連続
供給し、その他は実施例１と同様に処理して得られた共
重合体の分析および物性評価の結果を第１表に示した。Comparative Example 3 Using the same apparatus as in Example 1, n-hexane was converted into 2Q1/
Hr, 1-butene is continuously supplied at 1000 kg/Hr,
Table 1 shows the results of the analysis and physical property evaluation of the copolymer obtained by continuously supplying ethylene at a pressure of 2.0 kg/cdG and otherwise treating the copolymer in the same manner as in Example 1.
得られた共重合体は、ＤＳＣ測定で１２０℃に見られる
ポリエチレンの部分結晶が見られず、破断点強度が劣っ
ていた。In the obtained copolymer, no partial polyethylene crystals observed at 120° C. were observed by DSC measurement, and the strength at break was poor.
比較例４
実施例１と同様の装置を用い、ｎ−ヘキサンを１８、ｇ
／Ｈｒ、１−ブテンを２１６０ｇ／Ｈｒで連続供給し、
圧力を８．８ ｋｇ／ ｃｒＡ Ｇになるようにエチレ
ンを連続供給し、その他は実施例１と同様に処理して得
られた共重合体の分析および物性評価の結果を第１表に
示した。Comparative Example 4 Using the same apparatus as in Example 1, 18 g of n-hexane was
/Hr, 1-butene was continuously supplied at 2160g/Hr,
Table 1 shows the results of the analysis and physical property evaluation of the copolymer obtained by continuously supplying ethylene so that the pressure was 8.8 kg/crA G, and otherwise treating the same as in Example 1. .
得られた共重合体はポリエチレンの結晶が多く、透明性
が悪く、また柔軟性にも劣っていた。The obtained copolymer contained many polyethylene crystals, had poor transparency, and was also poor in flexibility.
比較例５
実施例１と同様の装置を用い、エチルセスキアルミニウ
ムクロリドを１．１ｇ／Ｈｒで連続供給し、その他は実
施例１と同様に処理して得られた共重合体の分析および
物性評価の結果を第１表に示した。Comparative Example 5 Analysis and physical property evaluation of a copolymer obtained by using the same apparatus as in Example 1, continuously supplying ethylsesquialuminum chloride at 1.1 g/Hr, and otherwise treating in the same manner as in Example 1. The results are shown in Table 1.
得られた共重合体はＧＰＣ測定でＭ ｗ ／ Ｍ ｎが
６．１と大きく、表面のベタ付きが感じられた。The obtained copolymer had a large M w / M n of 6.1 as measured by GPC, and the surface appeared sticky.
以下余白
実施例４〜６
実施例１で得られた共重合体（イ）と結晶性ポリプロピ
レン樹脂（三菱油化（株）製、ノープレンＢＣ−４）
（ロ）との（イ）／（ロ）−２０／８０．５／９５．
５０１５０の重量比の混合物６５０ｇを、内容量１ｉの
ニーグーを用いて予熱温度１５０℃、混練時間５分間で
混練りしてポリプロピレン樹脂組成物を得た。次いで直
ちに５０℃のロールを用いてシートにした後、カッター
を用いて角ベレットを得、この角ペレットのメルトイン
デックスを測定した。残った角ペレットを日本製鋼所（
株）１６．５オンス インラインスクリュータイプの射
出成形機を用いてテストピースを作成した。Below are blank spaces Examples 4 to 6 Copolymer (A) obtained in Example 1 and crystalline polypropylene resin (Noprene BC-4, manufactured by Mitsubishi Yuka Co., Ltd.)
(b) with (a)/(b)-20/80.5/95.
A polypropylene resin composition was obtained by kneading 650 g of a mixture having a weight ratio of 50150 using a Ni-Goo with an internal capacity of 1i at a preheating temperature of 150° C. for a kneading time of 5 minutes. Next, it was immediately formed into a sheet using a roll at 50° C., a square pellet was obtained using a cutter, and the melt index of this square pellet was measured. The remaining square pellets are sent to Japan Steel Works (
A test piece was prepared using a 16.5 oz. inline screw type injection molding machine.
射出成形条件は第２表のとおりである。The injection molding conditions are shown in Table 2.
第 ２ 表
得られた樹脂組成物の物性評価の結果を第３表に示した
。Table 2 Table 3 shows the results of evaluating the physical properties of the resin compositions obtained.
比較例６〜８
それぞれ比較例３〜５で得られたエチレン系共重合体を
用い、その他は実施例４と同様に処理してポリプロピレ
ン樹脂組成物を得た。得られた樹脂組成物の物性評価の
結果を第３表に示した。Comparative Examples 6 to 8 Polypropylene resin compositions were obtained by using the ethylene copolymers obtained in Comparative Examples 3 to 5, respectively, and otherwise treating in the same manner as in Example 4. The results of physical property evaluation of the obtained resin composition are shown in Table 3.
比較例７の場合には実施例４の場合に比べて耐衝撃性が
劣り、また比較例６および８の場合には破断点強度が低
下していた。In the case of Comparative Example 7, the impact resistance was inferior to that in Example 4, and in the cases of Comparative Examples 6 and 8, the strength at break was decreased.
以下余白Margin below
Claims (2)
Ａ）〜（Ｅ）の要件を満足する実質上線状構造を有する
エチレン系共重合体（イ）を少なくとも５重量％含有す
るエチレン系共重合体組成物。 （Ａ）共重合体中のエチレン含量が８５〜９５モル％で
あること、 （Ｂ）重量平均分子量が３万〜２０万であること、（Ｃ
）ＧＰＣで測定した分子量分布が単一のピークで、かつ
重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比
Ｍｗ／Ｍｎが２〜５であること、（Ｄ）示差走査型熱量
計で求められる融点が高温側と低温側の２個存在し、高
温側融点（Ｔｈ）が１１５〜１２５℃、低温側融点（Ｔ
ｌ）が４０〜９０℃に存在すること、 （Ｅ）示差走査型熱量計で求められる１１５℃以上の温
度における結晶融解熱量（Ｈｈ）の全結晶融解熱量（Ｈ
ｔ）に対する割合が０．０１５≦Ｈｈ／Ｈｔ≦０．１５
であること。(1) The main polymerization units are ethylene and 1-butene, and the following (
An ethylene copolymer composition containing at least 5% by weight of an ethylene copolymer (a) having a substantially linear structure that satisfies the requirements of A) to (E). (A) The ethylene content in the copolymer is 85 to 95 mol%, (B) The weight average molecular weight is 30,000 to 200,000, (C
) The molecular weight distribution measured by GPC is a single peak, and the ratio Mw/Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) is 2 to 5, (D) Differential scanning calorimeter There are two melting points, one on the high temperature side and one on the low temperature side.
(E) The total heat of crystal fusion (Hh) at a temperature of 115°C or higher determined by a differential scanning calorimeter
t) is 0.015≦Hh/Ht≦0.15
To be.
ロピレン（ロ）とを含み、（イ）と（ロ）の混合比率（
（イ）／（ロ））が５０／５０〜５／９５（重量比）で
あることを特徴とする、特許請求の範囲第１項に記載の
エチレン系共重合体組成物。(2) Contains the above ethylene copolymer (a) and crystalline polypropylene (b), and the mixing ratio of (a) and (b) (
The ethylene copolymer composition according to claim 1, wherein (a)/(b)) is 50/50 to 5/95 (weight ratio).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61177390A JPH0645731B2 (en) | 1986-07-28 | 1986-07-28 | Ethylene copolymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61177390A JPH0645731B2 (en) | 1986-07-28 | 1986-07-28 | Ethylene copolymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6333449A true JPS6333449A (en) | 1988-02-13 |
| JPH0645731B2 JPH0645731B2 (en) | 1994-06-15 |
Family
ID=16030101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61177390A Expired - Fee Related JPH0645731B2 (en) | 1986-07-28 | 1986-07-28 | Ethylene copolymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645731B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268220A (en) * | 1989-05-11 | 1993-12-07 | Nippon Petrochemicals Company, Limited | Polypropylene film |
| US5389448A (en) * | 1990-08-13 | 1995-02-14 | W.R. Grace & Co.-Conn. | Blends of polypropylene and ethylene copolymer and films made from the blend |
| JP2002256027A (en) * | 1992-03-20 | 2002-09-11 | Dow Chem Co:The | Ethylenic copolymer |
| JP2022541941A (en) * | 2019-09-30 | 2022-09-28 | エルジー・ケム・リミテッド | Polypropylene composite material |
| JP2022541943A (en) * | 2019-09-30 | 2022-09-28 | エルジー・ケム・リミテッド | Polypropylene composite material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5295759A (en) * | 1976-02-06 | 1977-08-11 | Mitsui Petrochem Ind Ltd | Polypropylene compositions with good transparency and shock resistance |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| JPS6320309A (en) * | 1986-07-11 | 1988-01-28 | Japan Synthetic Rubber Co Ltd | Ethylene copolymer and its production |
-
1986
- 1986-07-28 JP JP61177390A patent/JPH0645731B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5295759A (en) * | 1976-02-06 | 1977-08-11 | Mitsui Petrochem Ind Ltd | Polypropylene compositions with good transparency and shock resistance |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| JPS6320309A (en) * | 1986-07-11 | 1988-01-28 | Japan Synthetic Rubber Co Ltd | Ethylene copolymer and its production |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5268220A (en) * | 1989-05-11 | 1993-12-07 | Nippon Petrochemicals Company, Limited | Polypropylene film |
| US5389448A (en) * | 1990-08-13 | 1995-02-14 | W.R. Grace & Co.-Conn. | Blends of polypropylene and ethylene copolymer and films made from the blend |
| JP2002256027A (en) * | 1992-03-20 | 2002-09-11 | Dow Chem Co:The | Ethylenic copolymer |
| JP2002284904A (en) * | 1992-03-20 | 2002-10-03 | Dow Chem Co:The | Film |
| JP2022541941A (en) * | 2019-09-30 | 2022-09-28 | エルジー・ケム・リミテッド | Polypropylene composite material |
| JP2022541943A (en) * | 2019-09-30 | 2022-09-28 | エルジー・ケム・リミテッド | Polypropylene composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0645731B2 (en) | 1994-06-15 |
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