JPH0443364B2 - - Google Patents
Info
- Publication number
- JPH0443364B2 JPH0443364B2 JP59268485A JP26848584A JPH0443364B2 JP H0443364 B2 JPH0443364 B2 JP H0443364B2 JP 59268485 A JP59268485 A JP 59268485A JP 26848584 A JP26848584 A JP 26848584A JP H0443364 B2 JPH0443364 B2 JP H0443364B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- component
- olefins
- ethylene
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 29
- 239000004711 α-olefin Substances 0.000 claims description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 230000007423 decrease Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 238000005187 foaming Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 238000007765 extrusion coating Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/06—Specific viscosities of materials involved
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Processes Specially Adapted For Manufacturing Cables (AREA)
- Manufacturing Of Electric Cables (AREA)
Description
本発明は電線被覆用エチレン重合体組成物に関
し、詳しくは機械的強度、絶縁性、生産性の良好
な電線被覆用、特に発泡被覆用に好適なエチレン
重合体組成物に関する。
従来、通信ケーブル用電線の絶縁被覆には加工
性の良い低密度ポリエチレン（LDPE）が使用さ
れていた。しかし、LDPEは表面硬度が小さいた
め、撚り線時に被覆層が破れ易いという欠点があ
つた。近年、通信形態の変化により、電線被覆も
発泡被覆が主流となつたが、発泡被覆する場合に
は、更に表面硬度の高い材料が望まれている。表
面硬度が高いものとしては、高密度ポリエチレン
（HDPE）が挙げられるが、このHDPEは高速で
押出被覆すると表面が荒れ、撚り線時に破れ易い
という欠点がある。
そこで、これらの欠点を改良するものとして、
種々提案がされている。たとえばHDPEと高密
度エチレン共重合体のブレンド物（特開昭58−
111205号公報）、HDPEとしLDPEのブレンド
物（特開昭58−223210号公報）、HDPEに低分
子量のLDPEおよび高分子量のHDPEをブレンド
した組成物（特開昭52−11235号公報）などがあ
る。しかし、のものは発泡被覆に供した場合、
発泡セルが不均一となり、機械的強度が小さく、
およびのものは高速成形性が不十分で表面荒
れが生じ易いという欠点がある。このように、未
だ十分に満足し得る電線被覆用の素材が提案され
ていない。
そこで、本発明者らは表面硬度が大きく、高速
押出被覆成形性、耐クラツチ性に優れ、また発泡
した場合の発泡セルが微細均一となる機械的強度
の高い電線被覆用ポリエチレン組成物を開発すべ
く鋭意研究した。その結果、特定の物性を有する
エチレン系単独重合体あるいは共重合体を特定の
割合で配合することにより、上記目的を達成しう
る組成物が得られることを見い出し、この知見に
基づいて本発明を完成した。
すなわち本発明は、下記の(A)、(B)および(C)成分
からなると共に、(A)成分の含有量が１〜23重量％
であり、かつ(B)成分：(C)成分＝１：0.5〜1.5（重
量比）であり、組成物の極限粘度〔η〕が1.5〜
2.5dl/ｇ、密度が0.940〜0.965ｇ/cm3である電線被
覆用エチレン重合体組成物を提供するものであ
る。
(A)成分：エチレン単独重合体もしくはエチレン
と他のα−オレフインとの共重合体
（他のα−オレフイン含有量15重量
％以下）であり、極限粘度〔η〕が
４〜10dl/ｇであつて、密度が0.900
〜0.950ｇ/cm3であるもの
(B)成分：エチレン単独重合体もしくはエチレン
と他のα−オレフインとの共重合体
（他のα−オレフイン含有量５重量
％以下）であり、極限粘度〔η〕が
0.3〜1.4dl/ｇであつて、密度が
0.970〜０・980ｇ/cm3であるもの
(C)成分：エチレンと他のα−オレフインとの共
重合体（他のα−オレフイン含有量
３〜20重量％）であり、極限粘度
〔η〕が2.0〜3.8dl/ｇであつて、密
度が0.915〜0.940ｇ/cm3であるもの
本発明の組成物は上記(A)、(B)および(C)成分の三
成分からなるものである。ここで(A)成分は上述し
た如く、エチレン単独重合体またはエチレンと他
のα−オレフインとの共重合体（他のα−オレフ
イン含有量が15重量％以下）であり、極限粘度
〔η〕が４〜10dl/ｇのものである。
共重合体の場合、他のα−オレフイン（即ち、
エチレン以外のα−オレフイン）の含有量が10重
量％以下のものが好ましく、また極限粘度〔η〕
が４〜８dl/ｇのエチレン単独重合体もしくは共
重合体が好ましい。また、(A)成分の密度は0.900
〜0.950ｇ/cm3である。この(A)成分において、共重
合体中の他のα−オレフインの含有量が15重量％
を超えると、耐環境応力亀裂性（ESCR）が低下
するという問題がある。また、極限粘度〔η〕が
４dl/ｇ未満では、溶融張力が低下して発泡セル
径が不均一で粗大となり、引張強度が低下する。
一方10dl/ｇを超えると、表面荒れが生じて好ま
しくない。
次に、エチレン重合体組成物の(B)成分は上述し
たように、エチレン単独重合体もしくはエチレン
と他のα−オレフインとの共重合体（他のα−オ
レフインの含有量が５重量％以下）であり、極限
粘度〔η〕が0.3〜1.4dl/ｇのものである。共重
合体の場合、他のα−オレフインの含有量が３重
量％以下のものが好ましく、また極限粘度〔η〕
が0.4〜1.0dl/ｇのエチレン単独重合体もしくは
共重合体が好ましい。また、(B)成分の密度は
0.970〜0.980ｇ/cm3である。この(B)成分において、
共重合体中の他のα−オレフインの含有量が５重
量％を超えると、ESCRが低下する。また、極限
粘度〔η〕が0.3dl/ｇ未満では、表面にブツや荒
れが発生し、1.4dl/ｇを超えると、流動性が低下
してメルトフラクチヤーが発生し、表面外観が悪
化して好ましくない。
さらに、本発明のエチレン重合体組成物の(C)成
分は、上述したように、エチレンと他のα−オレ
フインとの共重合体（他のα−オレフインの含有
量が３〜20重量％）であり、極限粘度〔η〕が
2.0〜3.8dl/ｇであつて、密度が0.915〜０・940
ｇ／cm3のものであるが、さらに好ましくは、他の
α−オレフインの含有量が３〜15重量％のもので
ある。この(C)成分において、他のα−オレフイン
の含有量が３重量％未満であると、ESCRが低下
し、また20重量％を超えると、耐摩耗性が低下す
るという問題がある。また、極限粘度〔η〕が
2.0dl/ｇ未満では、溶融張力が低下し、発泡被覆
した場合に発泡セル径が不均一で粗大となる。一
方、極限粘度〔η〕が4.0dl/ｇを超えると、流動
性が低下してメルトフラクチヤーが発生し、表面
外観が悪化し、好ましくない。
本発明のエチレン重合体組成物は、上述の(A)、
(B)および(C)の三成分よりなるものであり、同時に
(A)成分の含有量が組成物全体の１〜23重量％、好
ましくは２〜20重量％であり、また(B)成分と(C)成
分の重量比が１：0.5〜1.5、好ましくは１：0.6〜
1.0である。しかも、組成物全体の極限粘度〔η〕
は1.5〜2.5dl/ｇ、好ましくは1.6〜2.3dl/ｇであ
り、密度は0.940〜0.965ｇ/cm3、好ましくは0.945
〜0.960ｇ/cm3である。ここで、組成物全体におけ
る(A)成分の含有量が１重量％未満では、溶融張力
が低下し、発泡セル径が不均一で、粗大となり、
23重量％を超えると、ブツが発生する。また、(B)
成分と、(C)成分の重量比において、(C)成分が1.5
を超えると、流動性が低下し、メルトフラクチヤ
ーが発生して外観不良となる。また、0.5未満で
は、相溶性が低下し、ゲル、フイシユアイが発生
し、外観不良となる。さらに、組成物の極限粘度
〔η〕が1.5dl/ｇ未満であると、溶融張力が低下
し、発泡セルが不均一で粗大となり、2.5dl/ｇを
超えると、流動性が低下し、外観不良となる。組
成物の密度が0.940ｇ/cm3未満では、引張抗張力が
低下し、また0.965ｇ/cm3を超えると、ESCRが低
下する。
なお、(A)、(B)、(C)成分中の他のα−オレフイ
ン、つまりエチレン以外のオレフインとしては
様々のものがあるが、通常は炭素数３〜12、好ま
しくは４〜８のα−オレフイン、具体的にはプロ
ピレン、ブテン−１、ヘキセン−１、オクテン−
１などが挙げられる。
本発明の組成物は原則的には上記三成分よりな
るが、必要により亜リン酸エステル系、リン酸エ
ステル系などの酸化防止剤；ベンゾトリアゾール
系、ベンゾフエノン系などの紫外線吸収剤；帯電
防止剤；高級脂肪酸金属塩、ハイドロタルサイト
などの滑剤；着色剤等を添加することができる。
本発明の組成物は以上のような構成よりなるも
のであり、高速押出被覆成形性、ESCR等に優
れ、表面外観が良好で、電線被覆用として極めて
好適である。
このような組成物の製造方法としては、各成分
をあらかじめ製造し、その所定量を配合して加熱
混練する方法のほか多段重合法、これらの併用法
等種々の方法が適用できる。特に好適な方法は特
開昭54−161691号公報、特開昭55−40724号公報、
特開昭55−149307号公報等に記載されたチーグラ
ー型触媒を用いた３段重合法であり、この場合の
重合方式としては懸濁重合、溶液重合、気相重合
など種々の方法が選択でき、また連続式、回分式
等いずれでもよい。
このようにして得られる本発明の組成物は機械
的強度、絶縁性が良好で、電線被覆用として極め
て好適である。電線の被覆方法としては組成物を
シート状に成形して電線に巻き付ける方法なども
あるが、本発明の組成物は発泡被覆に特に好適で
あり、高速押出被覆成形性に優れ、生産性が高
い。また、表面外観が良好であるため、撚り線時
に破れることがない。
発泡被覆は通常行なわれている方法によれば良
く、ガス発泡、化学発泡など特に制限なく適用で
きる。ガス発泡を適用する場合の発泡剤としては
窒素ガス、二酸化炭素などが用いられ、化学発泡
の場合の発泡剤としてはアゾジカルボンアミドな
どが用いられる。また、発泡核剤としてはクレ
イ、炭酸カルシウム、タルクなどが使用できる。
本発明の組成物を発泡した場合、発泡セルが微
細均一であり、機械的強度や絶縁性に優れてい
る。
したがつて本発明の組成物は通信ケーブル等の
電線の被覆素材として極めて有用である。
次に本発明を実施例により、詳しく説明する。
実施例１〜７および比較例１〜11
第１表に示す(A)、(B)、(C)成分よりなる組成物と
アゾジカルボンアミド2.0重量％、ペンタエリス
リチル−テトラキス〔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〕（商品名：イルガノツクス1010）0.2重量％、
ステアリン酸カルシウム0.2重量％を配合した後、
押出被覆成形機で押出温度200℃で線速1500m／
分の押出条件で直径0.4mmの銅線上に0.15mmの厚
みで発泡被覆した。この被覆電線についての物性
測定結果を第１表に示す。
The present invention relates to an ethylene polymer composition for coating electric wires, and more particularly to an ethylene polymer composition suitable for coating electric wires, particularly foam coatings, that has good mechanical strength, insulation properties, and productivity. Conventionally, low-density polyethylene (LDPE), which has good workability, has been used for the insulation coating of communication cable wires. However, since LDPE has a low surface hardness, it has the disadvantage that the coating layer is easily torn when the wire is twisted. In recent years, due to changes in communication formats, foamed coatings have become the mainstream for wire coatings, but when foaming is used, materials with even higher surface hardness are desired. An example of a material with high surface hardness is high-density polyethylene (HDPE), but this HDPE has the disadvantage that the surface becomes rough when extruded at high speed and is easily torn when wire is twisted. Therefore, in order to improve these shortcomings,
Various proposals have been made. For example, a blend of HDPE and high-density ethylene copolymer
111205), a blend of HDPE and LDPE (Japanese Unexamined Patent Publication No. 58-223210), a blend of HDPE with low molecular weight LDPE and high molecular weight HDPE (Japanese Unexamined Patent Publication No. 11235/1982), etc. be. However, when subjected to foam coating,
Foam cells become uneven, mechanical strength is low,
The disadvantage of these is that they have insufficient high-speed moldability and are prone to surface roughness. As described above, a material for covering electric wires that is fully satisfactory has not yet been proposed. Therefore, the present inventors have developed a polyethylene composition for wire coating that has high surface hardness, excellent high-speed extrusion coating formability, clutch resistance, and high mechanical strength that produces fine and uniform foamed cells when foamed. I researched as much as possible. As a result, it was discovered that by blending ethylene homopolymers or copolymers having specific physical properties in a specific ratio, a composition capable of achieving the above object can be obtained.Based on this knowledge, the present invention was developed. completed. That is, the present invention consists of the following components (A), (B), and (C), and the content of component (A) is 1 to 23% by weight.
and (B) component: (C) component = 1:0.5 to 1.5 (weight ratio), and the intrinsic viscosity [η] of the composition is 1.5 to
The present invention provides an ethylene polymer composition for coating electric wires having a density of 2.5 dl/g and a density of 0.940 to 0.965 g/cm 3 . Component (A): Ethylene homopolymer or copolymer of ethylene and other α-olefins (content of other α-olefins 15% by weight or less), with an intrinsic viscosity [η] of 4 to 10 dl/g. and the density is 0.900
~0.950g/cm 3 Component (B): Ethylene homopolymer or copolymer of ethylene and other α-olefins (content of other α-olefins 5% by weight or less), with intrinsic viscosity [ η] is
0.3 to 1.4 dl/g, and the density is
0.970 to 0.980 g/cm 3 Component (C): A copolymer of ethylene and other α-olefins (content of other α-olefins: 3 to 20% by weight), with intrinsic viscosity [η] is 2.0 to 3.8 dl/g and has a density of 0.915 to 0.940 g/cm 3 The composition of the present invention consists of the above three components (A), (B) and (C). . As mentioned above, component (A) is an ethylene homopolymer or a copolymer of ethylene and other α-olefins (the content of other α-olefins is 15% by weight or less), and has an intrinsic viscosity [η] is 4 to 10 dl/g. In the case of copolymers, other α-olefins (i.e.
The content of α-olefin other than ethylene is preferably 10% by weight or less, and the intrinsic viscosity [η]
An ethylene homopolymer or copolymer having a particle diameter of 4 to 8 dl/g is preferred. Also, the density of component (A) is 0.900
~0.950g/ cm3 . In this component (A), the content of other α-olefins in the copolymer is 15% by weight.
If it exceeds , there is a problem that environmental stress cracking resistance (ESCR) decreases. Furthermore, if the intrinsic viscosity [η] is less than 4 dl/g, the melt tension decreases, the foam cell diameter becomes uneven and coarse, and the tensile strength decreases.
On the other hand, if it exceeds 10 dl/g, surface roughness will occur, which is not preferable. Next, as mentioned above, component (B) of the ethylene polymer composition is an ethylene homopolymer or a copolymer of ethylene and other α-olefins (the content of other α-olefins is 5% by weight or less). ) and has an intrinsic viscosity [η] of 0.3 to 1.4 dl/g. In the case of a copolymer, the content of other α-olefins is preferably 3% by weight or less, and the intrinsic viscosity [η]
An ethylene homopolymer or copolymer having a particle diameter of 0.4 to 1.0 dl/g is preferred. Also, the density of component (B) is
It is 0.970-0.980g/cm <3> . In this (B) component,
When the content of other α-olefins in the copolymer exceeds 5% by weight, the ESCR decreases. In addition, if the intrinsic viscosity [η] is less than 0.3 dl/g, bumps and roughness will occur on the surface, and if it exceeds 1.4 dl/g, fluidity will decrease and melt fracture will occur, deteriorating the surface appearance. I don't like it. Furthermore, as mentioned above, component (C) of the ethylene polymer composition of the present invention is a copolymer of ethylene and other α-olefins (the content of other α-olefins is 3 to 20% by weight). and the limiting viscosity [η] is
2.0 to 3.8 dl/g and density 0.915 to 0.940
g/cm 3 , more preferably the content of other α-olefins is 3 to 15% by weight. In this component (C), if the content of other α-olefins is less than 3% by weight, the ESCR decreases, and if it exceeds 20% by weight, there is a problem that the wear resistance decreases. Also, the intrinsic viscosity [η] is
If it is less than 2.0 dl/g, the melt tension decreases, and when foamed coating is applied, the foamed cell diameter becomes uneven and coarse. On the other hand, when the intrinsic viscosity [η] exceeds 4.0 dl/g, the fluidity decreases, melt fracture occurs, and the surface appearance deteriorates, which is not preferable. The ethylene polymer composition of the present invention comprises the above-mentioned (A),
It consists of three components (B) and (C), and at the same time
The content of component (A) is 1 to 23% by weight, preferably 2 to 20% by weight of the entire composition, and the weight ratio of component (B) to component (C) is 1:0.5 to 1.5, preferably 1:0.6～
It is 1.0. Furthermore, the intrinsic viscosity of the entire composition [η]
is 1.5 to 2.5 dl/g, preferably 1.6 to 2.3 dl/g, and the density is 0.940 to 0.965 g/cm 3 , preferably 0.945
~0.960g/ cm3 . Here, if the content of component (A) in the entire composition is less than 1% by weight, the melt tension will decrease and the foamed cell diameter will become uneven and coarse.
If it exceeds 23% by weight, lumps will occur. Also, (B)
The weight ratio of component (C) to component (C) is 1.5.
If it exceeds this value, fluidity decreases and melt fracture occurs, resulting in poor appearance. Moreover, if it is less than 0.5, the compatibility decreases, gels and flakes occur, and the appearance becomes poor. Furthermore, if the intrinsic viscosity [η] of the composition is less than 1.5 dl/g, the melt tension will decrease and the foam cells will become uneven and coarse; if it exceeds 2.5 dl/g, the fluidity will decrease and the appearance It becomes defective. When the density of the composition is less than 0.940 g/cm 3 , the tensile strength decreases, and when it exceeds 0.965 g/cm 3 , the ESCR decreases. There are various other α-olefins in components (A), (B), and (C), that is, olefins other than ethylene, but they usually have 3 to 12 carbon atoms, preferably 4 to 8 carbon atoms. α-olefins, specifically propylene, butene-1, hexene-1, octene-1
1 etc. The composition of the present invention basically consists of the above three components, but if necessary, an antioxidant such as a phosphite ester or a phosphate ester; an ultraviolet absorber such as a benzotriazole or benzophenone; and an antistatic agent. ; A lubricant such as a higher fatty acid metal salt or hydrotalcite; a coloring agent, etc. can be added. The composition of the present invention has the above-mentioned structure, has excellent high-speed extrusion coating moldability, ESCR, etc., has a good surface appearance, and is extremely suitable for coating electric wires. As a method for manufacturing such a composition, various methods can be applied, such as a method in which each component is prepared in advance, a predetermined amount thereof is blended, and kneaded by heating, a multistage polymerization method, and a combination method thereof. Particularly suitable methods are those disclosed in JP-A-54-161691, JP-A-55-40724,
This is a three-stage polymerization method using a Ziegler type catalyst described in JP-A-55-149307, etc., and various methods can be selected as the polymerization method in this case, such as suspension polymerization, solution polymerization, and gas phase polymerization. , continuous type, batch type, etc. may be used. The composition of the present invention thus obtained has good mechanical strength and insulation properties, and is extremely suitable for coating electric wires. As a method for coating electric wires, there are methods such as forming the composition into a sheet shape and wrapping it around the electric wire, but the composition of the present invention is particularly suitable for foam coating, has excellent high-speed extrusion coating formability, and has high productivity. . Furthermore, since the surface appearance is good, the wire will not be torn during twisting. The foam coating may be formed by any commonly used method, such as gas foaming or chemical foaming, without any particular limitation. Nitrogen gas, carbon dioxide, or the like is used as a blowing agent when gas foaming is applied, and azodicarbonamide or the like is used as a blowing agent when chemical foaming is applied. Further, as the foaming nucleating agent, clay, calcium carbonate, talc, etc. can be used. When the composition of the present invention is foamed, the foamed cells are fine and uniform, and have excellent mechanical strength and insulation properties. Therefore, the composition of the present invention is extremely useful as a coating material for electric wires such as communication cables. Next, the present invention will be explained in detail with reference to Examples. Examples 1 to 7 and Comparative Examples 1 to 11 A composition consisting of components (A), (B), and (C) shown in Table 1, 2.0% by weight of azodicarbonamide, and pentaerythrityl-tetrakis [3-(3 , 5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010) 0.2% by weight,
After adding 0.2% by weight of calcium stearate,
Extrusion coating machine with extrusion temperature of 200℃ and linear speed of 1500m/
The foam coating was applied to a copper wire with a diameter of 0.4 mm to a thickness of 0.15 mm under extrusion conditions of 10 minutes. Table 1 shows the physical property measurement results for this coated wire.
【表】【table】
【表】【table】
Claims (1)
(A)成分の含有量が１〜23重量％であり、かつ(B)成
分：(C)成分＝１：0.5〜1.5（重量比）であり、組
成物の極限粘度〔η〕が1.5〜2.5dl/ｇ、密度が
0.940〜0.965ｇ/cm3である電線被覆用エチレン重
合体組成物。 (A)成分：エチレン単独重合体もしくはエチレン
と他のα−オレフインとの共重合体
（他のα−オレフイン含有量15重量
％以下）であり、極限粘度〔η〕が
４〜10dl/ｇであつて、密度が0.900
〜0.950ｇ/cm3であるもの (B)成分：エチレン単独重合体もしくはエチレン
と他のα−オレフインとの共重合体
（他のα−オレフイン含有量５重量
％以下）であり、極限粘度〔η〕
が、0.3〜1.4dl/ｇであつて、密度
が0.970〜0.980ｇ/cm3であるもの (C)成分：エチレンと他のα−オレフインとの共
重合体（他のα−オレフイン含有量
３〜20重量％）であり、極限粘度
〔η〕が2.0〜3.8dl/ｇであつて、密
度が0.915〜0.940ｇ/cm3であるもの。[Claims] 1 Consists of the following components (A), (B) and (C), and
The content of component (A) is 1 to 23% by weight, and the ratio of component (B) to component (C) is 1:0.5 to 1.5 (weight ratio), and the intrinsic viscosity [η] of the composition is 1.5 to 23% by weight. 2.5dl/g, density is
An ethylene polymer composition for coating electric wires having a weight of 0.940 to 0.965 g/cm 3 . Component (A): Ethylene homopolymer or copolymer of ethylene and other α-olefins (content of other α-olefins 15% by weight or less), with an intrinsic viscosity [η] of 4 to 10 dl/g. and the density is 0.900
~0.950g/ cm3 Component (B): Ethylene homopolymer or copolymer of ethylene and other α-olefins (content of other α-olefins 5% by weight or less), with intrinsic viscosity [ η〕
is 0.3 to 1.4 dl/g and has a density of 0.970 to 0.980 g/cm 3 Component (C): Copolymer of ethylene and other α-olefins (other α-olefin content 3 ~20% by weight), an intrinsic viscosity [η] of 2.0 to 3.8 dl/g, and a density of 0.915 to 0.940 g/cm 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59268485A JPS61148703A (en) | 1984-12-21 | 1984-12-21 | Ethylene polymer composition for wire covering |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59268485A JPS61148703A (en) | 1984-12-21 | 1984-12-21 | Ethylene polymer composition for wire covering |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61148703A JPS61148703A (en) | 1986-07-07 |
| JPH0443364B2 true JPH0443364B2 (en) | 1992-07-16 |
Family
ID=17459147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59268485A Granted JPS61148703A (en) | 1984-12-21 | 1984-12-21 | Ethylene polymer composition for wire covering |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61148703A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2535898B2 (en) * | 1987-04-07 | 1996-09-18 | 日立電線株式会社 | Method for manufacturing foamed fluororesin insulated wire |
| JPH01173512A (en) * | 1987-12-25 | 1989-07-10 | Hitachi Cable Ltd | Formation of high-foaming ethylene resin insulating cover |
| JPH0637585B2 (en) * | 1988-12-17 | 1994-05-18 | 日産丸善ポリエチレン株式会社 | Ethylene copolymer composition for wire coating |
| JP2792234B2 (en) * | 1990-12-25 | 1998-09-03 | 大日本インキ化学工業株式会社 | Polyethylene resin composition and extrusion coating material |
| JP5922571B2 (en) * | 2010-03-25 | 2016-05-24 | 古河電気工業株式会社 | Foamed wire and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58111205A (en) * | 1981-12-25 | 1983-07-02 | 三井化学株式会社 | Wire coating ethylene copolymer composition |
-
1984
- 1984-12-21 JP JP59268485A patent/JPS61148703A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58111205A (en) * | 1981-12-25 | 1983-07-02 | 三井化学株式会社 | Wire coating ethylene copolymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61148703A (en) | 1986-07-07 |
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