JPH09227708A - Foamable resin composition for coating foamed insulating polyethylene and foamed insulating polyethylene-coated electric wire produced by coating with the same - Google Patents
Foamable resin composition for coating foamed insulating polyethylene and foamed insulating polyethylene-coated electric wire produced by coating with the sameInfo
- Publication number
- JPH09227708A JPH09227708A JP11301696A JP11301696A JPH09227708A JP H09227708 A JPH09227708 A JP H09227708A JP 11301696 A JP11301696 A JP 11301696A JP 11301696 A JP11301696 A JP 11301696A JP H09227708 A JPH09227708 A JP H09227708A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- polyethylene
- coating
- foamed insulating
- foamable resin
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、発泡絶縁ポリエチ
レン被覆用の発泡性樹脂組成物及びこれを被覆して製造
された発泡絶縁ポリエチレン被覆電線に関する。本発明
で製造された電線は、同軸ケーブル、通信ケーブルとし
て利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamable resin composition for covering foamed insulated polyethylene, and a foamed insulated polyethylene-coated wire manufactured by coating the same. The electric wire manufactured by the present invention is used as a coaxial cable and a communication cable.
【0002】[0002]
【従来の技術】近年、絶縁電線、特に高周波信号伝送に
用いられる同軸ケーブル等においては、絶縁被膜の発泡
率を上げることによって誘電率やtanδの低下を図
り、これによりケーブル等の漏洩減衰率を低減させ、画
像や音声の鮮明化及び中継器の数の減少を図っている。
このような高発泡率の絶縁電線を製造するには、化学発
泡法やガス発泡法が一般的に行われている。2. Description of the Related Art In recent years, in the case of insulated wires, particularly coaxial cables used for high-frequency signal transmission, the dielectric constant and tan δ are reduced by increasing the foaming rate of an insulating film, thereby reducing the leakage attenuation rate of the cable and the like. In order to reduce the number of repeaters, sharpening of images and sounds is attempted.
In order to manufacture such an insulated wire having a high foaming rate, a chemical foaming method or a gas foaming method is generally performed.
【0003】化学発泡法は、樹脂成分に化学発泡剤をそ
の分解温度以下で配合し、それを押出機に供給し、前記
化学発泡剤の分解温度以上の温度で金属導体上に押出被
覆し、次いでこれを大気中で発泡させた後、水等により
冷却固化する方法である。この化学発泡法は、ガス発泡
法に比べて設備コストが低く、操作も簡単であるので、
ガス発泡法による場合より発泡率が低く、発泡体の機械
的強度が低いにもかかわらず、一定のシェアを獲得して
きた。しかしながら、化学発泡法による発泡体の発泡度
は、最も進んだ技術でもってしても、7C−HFB及び
7C−HFLにおいて70%が限界であり、又、使用で
きる樹脂は、高圧法低密度ポリエチレンであるので機械
的強度が劣り、高品位の同軸ケーブルの製造には不十分
であった。[0003] In the chemical foaming method, a chemical foaming agent is mixed with a resin component at a temperature not higher than its decomposition temperature, and the resulting mixture is supplied to an extruder, and extruded on a metal conductor at a temperature higher than the decomposition temperature of the chemical foaming agent. Next, this is foamed in the air, and then cooled and solidified with water or the like. This chemical foaming method has lower equipment costs and is easier to operate than the gas foaming method.
Despite having a lower foaming rate than the gas foaming method and a lower mechanical strength of the foam, it has gained a certain share. However, the foaming degree of the foam by the chemical foaming method is limited to 70% in 7C-HFB and 7C-HFL even with the most advanced technology, and the resin that can be used is a high-pressure low-density polyethylene. Therefore, the mechanical strength was inferior, and it was insufficient for producing a high-quality coaxial cable.
【0004】一方、ガス発泡法は、化学発泡剤の代り
に、モノフルオロトリクロロメタン、ジフルオロジクロ
ロメタン、トリフルオロトリクロロエタン、テトラフル
オロジクロロエタン等のフロンガスを発泡剤として用い
るので、発泡度80%前後の高発泡体が容易に得られ、
また、使用できる樹脂も機械的強度の強い高密度ポリエ
チレンが使用でき、従って高品位の同軸ケーブルを作る
ことができる。しかしながら、フロンガスは、オゾン層
の破壊を引き起こす物質とされ、モントリオール議定書
に基づくスケジュールにより、順次全廃されることとな
り、1997年以降はこれに代わるガス発泡剤として窒
素ガス、アルゴンガス、炭酸ガス等が提案されている。On the other hand, in the gas foaming method, a freon gas such as monofluorotrichloromethane, difluorodichloromethane, trifluorotrichloroethane or tetrafluorodichloroethane is used as a foaming agent instead of a chemical foaming agent. The body is easily obtained,
In addition, high-density polyethylene having high mechanical strength can be used as a resin that can be used, so that a high-quality coaxial cable can be manufactured. However, Freon gas is considered to be a substance that causes the destruction of the ozone layer, and will be completely abolished in sequence according to the schedule based on the Montreal Protocol. Proposed.
【0005】フロンガスに代えて、窒素ガスを用い、ガ
ス発泡法で従来の素材である高密度ポリエチレンを用い
て同軸ケーブルを作ったところ、均一でかつ微細なセル
構造の発泡体は得られなかった。この原因は、窒素ガス
がフロンガスほどにはポリエチレンに対して親和性がな
く、沸点が低く、比熱も小さいので、上記のような不十
分な結果となったと推定される。従って、窒素ガスを使
用するガス発泡法において、通常、ガス発泡法において
使用される高密度ポリエチレンに代えて、新しい樹脂組
成物を採用することによって、均一でかつ微細なセル構
造を有し、しかも80%に近い高発泡度で且つ機械的強
度に優れた高発泡体を作ることができる高発泡絶縁ポリ
エチレン被覆用の発泡性樹脂組成物及びこれを用いて高
発泡絶縁ポリエチレン被覆電線を製造する方法を本発明
者等は提案し、特願平7−226118号として特許出
願した。この発明においては、窒素ガス単独では高発泡
体が得られないので、化学発泡剤を併用することによっ
て解決している。Nitrogen gas was used in place of Freon gas, and when a coaxial cable was made by the gas foaming method using high density polyethylene which is a conventional material, a foam having a uniform and fine cell structure could not be obtained. . It is presumed that this is because the nitrogen gas does not have an affinity for polyethylene as much as the chlorofluorocarbon gas, the boiling point is low, and the specific heat is small, so that the above-mentioned insufficient results are obtained. Therefore, in the gas foaming method using nitrogen gas, by adopting a new resin composition in place of the high-density polyethylene that is usually used in the gas foaming method, a uniform and fine cell structure is obtained, and A foamable resin composition for coating a high-foaming insulating polyethylene capable of producing a high-foaming body having a high foaming degree close to 80% and excellent mechanical strength, and a method for producing a high-foaming insulating polyethylene-coated electric wire using the same The present inventors have proposed and filed a patent application as Japanese Patent Application No. 7-226118. In this invention, since a high foam cannot be obtained by nitrogen gas alone, the problem is solved by using a chemical foaming agent together.
【0006】[0006]
【発明が解決しようとする課題】上述したように、最近
は発泡絶縁ポリエチレン被覆電線は、化学発泡法によっ
ても、また窒素ガスを用いたガス発泡法によっても製造
されるようになってきたが、いずれの方法においても化
学発泡剤が使用されており、その代表的なものとして
は、p,p’−オキシ−ビス−ベンゼンスルホニルヒド
ラジド(以下、OBSHと略すこともある)が用いられ
ている。その理由は、OBSHの分解温度が130〜1
60℃の範囲であり、ポリエチレン系樹脂を用いた発泡
性樹脂組成物を製造するときの温度範囲である120〜
130℃では分解せず、電線にこの樹脂組成物を発泡被
覆する適性温度である130〜160℃において分解す
るからである。しかしながら、OBSHを用いて製造し
た発泡絶縁ポリエチレン被覆電線は、発泡絶縁ポリエチ
レンと接触している導体金属を腐蝕させ、画像や音声の
質を劣化させる問題が起きている。従って、本発明は、
OBSHによる導体金属の腐蝕を発生させないこと、す
なわち、OBSHを含有しておりながら導体金属に被覆
した場合に、腐蝕を発生させない発泡絶縁ポリエチレン
被覆用の発泡性樹脂組成物を提案することを課題とす
る。As described above, recently, the foam-insulated polyethylene-coated electric wire has been manufactured by the chemical foaming method or the gas foaming method using nitrogen gas. In either method, a chemical foaming agent is used, and as a typical one, p, p'-oxy-bis-benzenesulfonyl hydrazide (hereinafter sometimes abbreviated as OBSH) is used. The reason is that the decomposition temperature of OBSH is 130 to 1
The temperature is in the range of 60 ° C., which is the temperature range for producing a foamable resin composition using a polyethylene-based resin.
This is because it does not decompose at 130 ° C., but decomposes at 130 to 160 ° C., which is an appropriate temperature for foam-coating the electric wire with the resin composition. However, the foam-insulated polyethylene-coated electric wire produced by using OBSH has a problem of corroding the conductor metal in contact with the foam-insulated polyethylene and deteriorating the quality of images and sounds. Therefore, the present invention
It is an object of the present invention to prevent corrosion of a conductor metal due to OBSH, that is, to propose a foamable resin composition for coating a foamed insulating polyethylene that does not cause corrosion when the conductor metal is coated while containing OBSH. To do.
【0007】[0007]
【課題を解決するための手段】本発明者等は、OBSH
による金属腐蝕の原因について、種々の実験を行ったと
ころ、OBSH自体の製造において、OBSHに混入
し、除去されないある種の化合物が原因であることを実
証し、この化合物の発錆作用をなくす化合物を樹脂組成
物に配合すれば解決できると想定し、数多くの化合物に
ついて配合実験を行ったところ、特定の化合物を配合し
た場合に解決できることを見出し、本発明を完成させ
た。The inventors of the present invention have found that OBSH
As a result of various experiments on the cause of metal corrosion caused by the above, it was proved that in the production of OBSH itself, a certain compound that was mixed with OBSH and was not removed was the cause, and a compound that eliminates the rusting action of this compound. Assuming that the problem can be solved by blending with the resin composition, a compounding experiment was conducted on many compounds, and it was found that the problem can be solved when a specific compound was compounded, and the present invention was completed.
【0008】[0008]
【発明の概要】すなわち、本発明は、 (1) ポリエチレン系樹脂100重量部に、不純物を含有
するp,p’−オキシ−ビス−ベンゼンスルホニルヒド
ラジド0.5〜5重量部及び不純物捕集剤0.005〜
0.5重量部を配合させてなる発泡絶縁ポリエチレン被
覆用の発泡性樹脂組成物、及び (2) 上記の発泡性樹脂組成物を用いて製造された発泡絶
縁ポリエチレン被覆電線 (3) 不純物捕集剤がハイドロタルサイト、高級脂肪酸金
属塩、酸化マグネシウム、酸化カルシウム、水酸化マグ
ネシウム、水酸化カルシウム、ゼオライト、有機スズ化
合物、リン酸カルシウムからなる群から選択されたこと
を特徴とする発泡性樹脂組成物に関する。SUMMARY OF THE INVENTION That is, the present invention is: (1) 0.5 to 5 parts by weight of p, p'-oxy-bis-benzenesulfonyl hydrazide containing impurities in 100 parts by weight of a polyethylene resin and an impurity scavenger 0.005-
A foamable resin composition for coating foam insulating polyethylene, which is prepared by blending 0.5 part by weight, and (2) a foam insulating polyethylene coated electric wire produced by using the above foam resin composition (3) Impurity collection Relates to a foamable resin composition, wherein the agent is selected from the group consisting of hydrotalcite, higher fatty acid metal salt, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, zeolite, organotin compound, calcium phosphate .
【0009】[0009]
【発明の実施の形態】本発明においてポリエチレン系樹
脂とは、高圧法低密度ポリエチレン、高密度ポリエチレ
ン、中密度ポリエチレン、低圧法エチレン−α−オレフ
ィン共重合体等であり、これらの組合せ又はこれらを主
体として少量の他のオレフィン系樹脂を配合してもよ
い。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the polyethylene resin is a high-pressure low-density polyethylene, a high-density polyethylene, a medium-density polyethylene, a low-pressure ethylene-α-olefin copolymer, or the like. A small amount of another olefin-based resin may be blended as a main component.
【0010】本発明において化学発泡剤として使用され
るp,p’−オキシ−ビス−ベンゼンスルホニルヒドラ
ジド(OBSH)は、通常、前述のように、ある種の化
合物を不純物として含有するので、これを使用して高発
泡絶縁ポリエチレン被覆電線を作ると導体金属を腐蝕さ
せ、発錆させることがあるが、本発明ではハイドロタル
サイトを併用することによりこれらの不純物による腐蝕
・発錆作用を防止することができる。例えば、同軸ケー
ブルの絶縁層として本発明の高発泡絶縁ポリエチレン被
覆を適用すると、同軸ケーブルの内部導体や外部導体に
発錆は認められず、良好な品質の同軸ケーブルが得られ
た。従って、本発明によれば、通常市販されている不純
物を含むOBSHをそのまま使用することができる。本
発明においては、OBSHの他に、アゾジカルボンアミ
ド等の化学発泡剤、アルゴン、キセノン等の不活性ガス
を併用してもよい。OBSHの使用量は、ポリエチレン
系樹脂100重量部に対して0.5〜5重量部である。
0.5重量部未満では、同軸ケーブルの性質を満たす高
発泡体が、ガスを併用しても得られず、5重量部を越え
ると過発泡が起き、均一な発泡体が得られず、発泡体表
面も不均一となり、画像や音声が鮮明に送信できなくな
るので望ましくない。The p, p'-oxy-bis-benzenesulfonyl hydrazide (OBSH) used as a chemical foaming agent in the present invention usually contains a certain compound as an impurity as described above. When a high-foam insulation polyethylene-coated electric wire is made by using it, the conductor metal may be corroded and rusted, but in the present invention, by using hydrotalcite in combination, it is possible to prevent corrosion and rusting action by these impurities. You can For example, when the highly foamed insulating polyethylene coating of the present invention was applied as an insulating layer of a coaxial cable, no rust was observed on the inner conductor and the outer conductor of the coaxial cable, and a good quality coaxial cable was obtained. Therefore, according to the present invention, normally commercially available OBSH containing impurities can be used as it is. In the present invention, in addition to OBSH, a chemical foaming agent such as azodicarbonamide or an inert gas such as argon or xenon may be used together. The amount of OBSH used is 0.5 to 5 parts by weight based on 100 parts by weight of the polyethylene resin.
If it is less than 0.5 part by weight, a high foam satisfying the properties of the coaxial cable cannot be obtained even if gas is used together, and if it exceeds 5 parts by weight, overfoaming occurs and a uniform foam cannot be obtained. The surface of the body is also non-uniform, and it is not desirable because images and sounds cannot be transmitted clearly.
【0011】本発明において、不純物捕集剤とは、OB
SH中に存在する不純物を物理的及び/又は化学的に吸
着及び/又は反応により捕集し、不純物によって発現す
る発錆を抑制し、又、不純物によるポリエチレン系樹脂
の発泡阻害をなくする効果を発現する化合物であり、ハ
イドロタルサイト、高級脂肪酸金属塩、酸化マグネシウ
ム、酸化カルシウム、水酸化マグネシウム、水酸化カル
シウム、ゼオライト、有機スズ化合物、リン酸カルシウ
ム等が挙げられ、特にハイドロタルサイトが望ましい。
高級脂肪酸金属塩としては、ステアリン酸カルシウム、
ステアリン酸亜鉛、ステアリン酸リチウム、ステアリン
酸マグネシウム、ステアリン酸アルミニウム、ステアリ
ン酸鉛、ステアリン酸バリウム、ステアリン酸カドミウ
ム、ラウリン酸カルシウム、ラウリン酸亜鉛、ラウリン
酸カドミウム、リシノール酸バリウム、2−エチルヘキ
ソイン酸亜鉛、2−エチルヘキソイン酸鉛、パラ−第三
ブチル安息香酸亜鉛、12−ヒドロキシステアリン酸カ
ルシウム、12−ヒドロキシステアリン酸亜鉛、12−
ヒドロキシステアリン酸マグネシウム、12−ヒドロキ
システアリン酸バリウム、12−ヒドロキシステアリン
酸鉛等が挙げられる。これらのうち、ステアリン酸カル
シウム、ステアリン酸亜鉛が特に望ましい。本発明にお
いて、ハイドロタルサイトとは、マグネシウム、アルミ
ニウムの含水塩基性炭酸塩であり、天然物、合成物いず
れでもよい。天然物は、Mg6 Al2 (OH)16CO3
・4H2 Oの構造を有し、合成物はMgとAlとの比が
異なったもの、例えば、Mg4 Al2 (OH)12CO3
・3H2 O、Mg5 Al2 (OH)14CO3 ・4H2
O、Mg10Al2 (OH)22CO3 ・4H2 O、Mg8
Al2 (OH)20CO3 ・5H2 O等があげられる。不
純物捕集剤の使用量は、OBSHの1〜10%の範囲、
すなわち0.005〜0.5重量部である。0.005
重量部未満では、金属腐蝕防止効果(防錆効果)が発現
しなく、0.5重量部を越えると、押出ダイ付近に目や
にが発生し、生産性が悪くなり、また均一な発泡体が得
られず、望ましくない。In the present invention, the impurity scavenger means OB
Impurities existing in SH are physically and / or chemically adsorbed and / or collected by a reaction to suppress rusting caused by the impurities, and also to prevent the foaming inhibition of the polyethylene resin due to the impurities. Compounds that are expressed include hydrotalcite, higher fatty acid metal salts, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, zeolite, organotin compounds, calcium phosphate, and the like, with hydrotalcite being particularly preferable.
As the higher fatty acid metal salt, calcium stearate,
Zinc stearate, lithium stearate, magnesium stearate, aluminum stearate, lead stearate, barium stearate, cadmium stearate, calcium laurate, zinc laurate, cadmium laurate, barium ricinoleate, zinc 2-ethylhexoate, 2 -Lead ethylhexoate, zinc para-tertiary butyl benzoate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, 12-
Examples thereof include magnesium hydroxystearate, barium 12-hydroxystearate, and lead 12-hydroxystearate. Of these, calcium stearate and zinc stearate are particularly desirable. In the present invention, hydrotalcite is a water-containing basic carbonate of magnesium or aluminum, which may be a natural product or a synthetic product. The natural product is Mg 6 Al 2 (OH) 16 CO 3
-Having a structure of 4H 2 O, and the compound having a different ratio of Mg and Al, for example, Mg 4 Al 2 (OH) 12 CO 3
· 3H 2 O, Mg 5 Al 2 (OH) 14 CO 3 · 4H 2
O, Mg 10 Al 2 (OH) 22 CO 3 .4H 2 O, Mg 8
Al 2 (OH) 20 CO 3 · 5H 2 O , and the like. The amount of the impurity scavenger used is in the range of 1 to 10% of OBSH,
That is, 0.005 to 0.5 part by weight. 0.005
If it is less than 0.5 parts by weight, the effect of preventing metal corrosion (anticorrosion effect) will not be exhibited, and if it exceeds 0.5 parts by weight, eye bleeding will occur in the vicinity of the extrusion die, resulting in poor productivity and uniform foam. Not be desirable.
【0012】本発明の樹脂組成物には、発泡助剤、発泡
均一剤、着色剤、酸化防止剤、成核剤、銅害防止剤、加
工助剤、目やに発生防止剤等を配合してもよい。The resin composition of the present invention may contain a foaming aid, a foaming uniformizing agent, a coloring agent, an antioxidant, a nucleating agent, a copper damage inhibitor, a processing aid, an eyelash generation inhibitor and the like. Good.
【0013】本発明の発泡性樹脂組成物は、一般に、ポ
リエチレン系樹脂、OBSH、ハイドロタルサイト、そ
の他の添加剤を好適な混練手段、例えばバンバリーミキ
サーによって混練することによって製造される。特に好
ましい混練法によれば、ポリエチレン系樹脂、所定量の
不純物捕集剤、その他の添加剤(酸化防止剤など)をバ
ンバリーミキサーにおいて、ポリエチレン系樹脂の融点
以上の温度に加熱して混練し、次いでこの混練物に所定
量のOBSHを添加し、OBSHの分解温度(130〜
160℃)よりも低い温度で混練し、冷却してシート状
物にされる。この場合に、このシート状物は予備発泡さ
れている場合がある。このシート状物は次いで切断して
ペレットにすることができる。The expandable resin composition of the present invention is generally produced by kneading a polyethylene resin, OBSH, hydrotalcite and other additives with a suitable kneading means such as a Banbury mixer. According to a particularly preferable kneading method, a polyethylene resin, a predetermined amount of an impurity scavenger, and other additives (such as an antioxidant) are kneaded in a Banbury mixer by heating to a temperature equal to or higher than the melting point of the polyethylene resin, Next, a predetermined amount of OBSH is added to this kneaded product, and the OBSH decomposition temperature (130-
It is kneaded at a temperature lower than 160 ° C.) and cooled into a sheet. In this case, this sheet material may be pre-foamed. The sheet can then be cut into pellets.
【0014】本発明の発泡性ポリエチレン系樹脂組成物
は、斯界で周知の電線被覆法により銅やアルミニウムの
ような金属導体上に絶縁被覆として被覆することができ
る。特に好ましい方法によれば、上記のように作ったペ
レットを押出機に供給し、所定の温度にもたらし、溶融
樹脂組成物を予熱された金属導体上に同軸押出すること
によって高発泡絶縁ポリエチレン被覆を形成させること
ができる。電線被覆法における種々のパラメーターは、
当業者により容易に決定することができる。The foamable polyethylene resin composition of the present invention can be coated as an insulating coating on a metal conductor such as copper or aluminum by a wire coating method well known in the art. According to a particularly preferred method, a pellet made as described above is fed to an extruder, brought to a predetermined temperature, and a highly foamed insulating polyethylene coating is formed by coaxial extrusion of the molten resin composition onto a preheated metal conductor. Can be formed. Various parameters in the wire coating method are:
It can be easily determined by those skilled in the art.
【0015】[0015]
【実施例】次に実施例によって本発明をさらに詳細に説
明する。Next, the present invention will be described in more detail by way of examples.
【0016】実施例1 メルトインデックス2.0g/10分、密度0.917
g/cm3 、スウェリング比60%の高圧法低密度ポリ
エチレン70重量部に対して、メルトインデックス3.
0g/10分、密度0.960g/cm3 、スウェリン
グ比45%、融点135℃の高密度ポリエチレン30重
量部、酸化防止剤(ブチル化ヒドロキシトルエン)0.
2重量部及びハイドロタルサイト(Mg4 Al2 (O
H)12CO3 ・3H2 O)0.3重量部をバンバリーミ
キサーで10分間、140℃で混練して融点124℃の
混練物を得た。この混練物100重量部に、不純物5%
を含むp,p’−オキシ−ビス−ベンゼンスルホニルヒ
ドラジド1.3重量部を添加し、127℃でバンバリー
ミキサーを使って10分間混練し、予備発泡度4%のシ
ートを得た。これをシートカッターで切断し、厚さ3m
m、長さ5mm、幅4mmのペレットを得た。次いで、
50mmφの押出機(L/D=24)に前記ペレットを
供給し、供給領域のシリンダー温度を130℃、圧縮領
域のシリンダー温度を140℃、計量領域のシリンダー
温度を147℃とし、1.05mmφの70℃に予熱し
た銅芯線上に線巻取り速度20m/minで押出被覆
し、外径5.1mmの発泡絶縁同軸ケーブルコアを得
た。得られた発泡体は、発泡度50%、気泡径5〜15
0μを有し、長さ20mmの同軸ケーブルコアの円柱状
の試験片を10mm/分の速度で径方向に圧縮し、圧縮
量(歪)と力から算出したヤング率をもって圧縮強さを
測定したところ0.87kg/mm2 であり、機械的強
度が十分であることが判明した。この同軸ケーブルの周
囲に外部導管(銅製)を被覆し、温度50℃、湿度10
0%RHの条件で300日間加湿処理した後、目視した
ところ発錆は認められなかった。また、この同軸ケーブ
ルで画像や音声を送信したが、異常は認められなかっ
た。 Example 1 Melt index 2.0 g / 10 minutes, density 0.917
Melt index of 3. with respect to 70 parts by weight of high-pressure low-density polyethylene having g / cm 3 and swelling ratio of 60%.
0 g / 10 min, density 0.960 g / cm 3 , swelling ratio 45%, melting point 135 ° C., 30 parts by weight of high-density polyethylene, antioxidant (butylated hydroxytoluene) 0.
2 parts by weight and hydrotalcite (Mg 4 Al 2 (O
0.3 parts by weight of H) 12 CO 3 .3H 2 O) was kneaded with a Banbury mixer for 10 minutes at 140 ° C. to obtain a kneaded product having a melting point of 124 ° C. 5 parts by weight of impurities in 100 parts by weight of this kneaded material
1.3 parts by weight of p, p′-oxy-bis-benzenesulfonyl hydrazide containing was added and kneaded at 127 ° C. for 10 minutes using a Banbury mixer to obtain a sheet having a prefoaming degree of 4%. Cut this with a sheet cutter, thickness 3m
m, length 5 mm, width 4 mm pellets were obtained. Then
The pellets were fed to a 50 mmφ extruder (L / D = 24), the cylinder temperature in the feed zone was 130 ° C., the cylinder temperature in the compression zone was 140 ° C., the cylinder temperature in the metering zone was 147 ° C. A copper core wire preheated to 70 ° C. was extrusion-coated at a wire winding speed of 20 m / min to obtain a foam insulated coaxial cable core having an outer diameter of 5.1 mm. The obtained foam has a degree of foaming of 50% and a cell diameter of 5 to 15
A cylindrical test piece of a coaxial cable core having a length of 0 μm and a length of 20 mm was radially compressed at a speed of 10 mm / min, and the compressive strength was measured by Young's modulus calculated from the amount of compression (strain) and the force. However, it was 0.87 kg / mm 2 , and it was found that the mechanical strength was sufficient. An external conduit (made of copper) is coated around this coaxial cable, and the temperature is 50 ° C and the humidity is 10
After moisturizing for 300 days under the condition of 0% RH, visual observation showed no rusting. Images and sounds were transmitted using this coaxial cable, but no abnormality was found.
【0017】比較例1 ハイドロタルサイトの配合量を0とした以外は、実施例
1と同様な実験を行ったところ、銅表面に発錆が認めら
れた。また、この同軸ケーブルで画像や音声を送信した
ところ、鮮明性において劣った。 Comparative Example 1 The same experiment as in Example 1 was carried out except that the amount of hydrotalcite was changed to 0, and rust was observed on the copper surface. When images and sounds were transmitted using this coaxial cable, the sharpness was poor.
【0018】実施例2 メルトインデックス2.3g/10分、密度0.918
g/cm3 、スウェリング比54%の高圧法で製造した
長鎖分岐を有する低密度ポリエチレン100重量部に対
して、融点133℃、密度0.958g/cm3 、スウ
ェリング比48%、メルトインデックス3.5g/10
分の高密度ポリエチレン80重量部、融点155℃、密
度0.90g/cm3 、メルトフローレイト3g/10
分のポリプロピレン5重量部、ビニルトリエトキシシラ
ン0.2重量部及び酸化防止剤(ブチル化ヒドロキシト
ルエン)0.3重量部及びハイドロタルサイト(Mg10
Al2 (OH)22CO3 ・4H2 O)0.05重量部を
配合し、バンバリーミキサーで140℃、10分間加熱
混練して融点124℃の混練物を得た。この混練物10
0重量部にOBSH1.5重量部を添加し、バンバリー
ミキサーで127℃、10分間混練し、予備発泡度4%
のシートを製造し、これをシートカッターで切断し、厚
さ3mm、長さ5mm、幅4mmのペレットとした。次
に、50mmφの押出機(L/D=28)に前記ペレッ
トを供給し、供給領域のシリンダー温度を132℃、圧
縮領域のシリンダー温度を142℃、計量領域のシリン
ダー温度を148℃とし、供給領域において発泡性樹脂
組成物(ペレット)100重量部に対して0.8重量部
の窒素を圧入し、ペレットを十分加熱混練し、存在する
窒素を樹脂成分中に均一に分散させ、70℃に予熱した
2.0mmφの銅芯線上に線巻取り速度20m/分で押
出被覆し、外径9.4mmの発泡絶縁同軸ケーブルコア
を得た。このようにして得られた発泡体は、発泡度50
%、気泡径5〜130μを有し、長さ20mmの同軸ケ
ーブルコアの円柱状試験片を作り、10mm/分の速度
で径方向に圧縮し、圧縮量(歪)と力から算出したヤン
グ率をもって圧縮強さを測定したところ0.75kg/
mm2 であり、機械的強度が十分であることが判明し
た。また、静電容量を測定すると54F/kmであり、
電気特性が良好であることが判明した。この同軸ケーブ
ルの周囲に外部導管(銅製)を被覆し、温度50℃、湿
度100%RHの条件で300日間加湿処理した後、目
視したところ発錆は認められなかった。また、この同軸
ケーブルで画像や音声を送信したが、異常は認められな
かった。 Example 2 Melt index 2.3 g / 10 minutes, density 0.918
100 parts by weight of low-density polyethylene having a long chain branch produced by a high-pressure method with g / cm 3 and a swelling ratio of 54%, melting point 133 ° C., density 0.958 g / cm 3 , swelling ratio 48%, melt Index 3.5g / 10
80 parts by weight of high density polyethylene, melting point 155 ° C., density 0.90 g / cm 3 , melt flow rate 3 g / 10
5 parts by weight polypropylene, 0.2 parts by weight vinyltriethoxysilane, 0.3 parts by weight of antioxidant (butylated hydroxytoluene) and hydrotalcite (Mg 10
0.05 part by weight of Al 2 (OH) 22 CO 3 .4H 2 O) was mixed and heated and kneaded at 140 ° C. for 10 minutes with a Banbury mixer to obtain a kneaded product having a melting point of 124 ° C. This kneaded product 10
OBSH (1.5 parts by weight) was added to 0 parts by weight, and the mixture was kneaded with a Banbury mixer at 127 ° C. for 10 minutes to obtain a pre-expansion degree of 4%.
Was manufactured and cut with a sheet cutter to obtain pellets having a thickness of 3 mm, a length of 5 mm and a width of 4 mm. Next, the pellets were supplied to a 50 mmφ extruder (L / D = 28), the cylinder temperature in the supply area was 132 ° C., the cylinder temperature in the compression area was 142 ° C., the cylinder temperature in the metering area was 148 ° C. In the region, 0.8 parts by weight of nitrogen was pressed into 100 parts by weight of the expandable resin composition (pellets), the pellets were sufficiently heated and kneaded, and the existing nitrogen was uniformly dispersed in the resin component, and the temperature was raised to 70 ° C. A preheated 2.0 mmφ copper core wire was extrusion coated at a wire winding speed of 20 m / min to obtain a foam insulated coaxial cable core having an outer diameter of 9.4 mm. The foam thus obtained has a foaming degree of 50.
%, A cylindrical test piece of a coaxial cable core having a cell diameter of 5 to 130 μ and a length of 20 mm was prepared, and was radially compressed at a speed of 10 mm / min, and the Young's modulus calculated from the compression amount (strain) and the force. The compressive strength was measured with 0.75kg /
mm 2 and it was found that the mechanical strength was sufficient. Also, when the capacitance is measured, it is 54 F / km,
It was found that the electrical characteristics were good. An outer conduit (made of copper) was coated around the coaxial cable, humidified at a temperature of 50 ° C. and a humidity of 100% RH for 300 days, and rusting was not visually observed. Images and sounds were transmitted using this coaxial cable, but no abnormality was found.
【0019】比較例2 ハイドロタルサイトの配合量を0とした以外は、実施例
2と同様な実験を行ったところ、銅表面に発錆が認めら
れた。また、この同軸ケーブルで画像や音声を送信した
ところ、鮮明性において劣った。 Comparative Example 2 The same experiment as in Example 2 was carried out except that the blending amount of hydrotalcite was set to 0. As a result, rusting was recognized on the copper surface. When images and sounds were transmitted using this coaxial cable, the sharpness was poor.
【0020】実施例3 実施例1において、ハイドロタルサイトに代えて、ステ
アリン酸カルシウム、ステアリン酸亜鉛、酸化マグネシ
ウム、酸化カルシウム、水酸化マグネシウム、水酸化カ
ルシウム、ゼオライト、ジブチル錫ジラウレート、ジオ
クチル錫ジラウレート、リン酸カルシウムをそれぞれ使
用した以外は、実施例1と同様な実験を行った。発泡も
実施例1と同様正常に行われ、銅線表面に発錆は認めら
れなく、これらの同軸ケーブルで画像や音声を送信した
が鮮明であり、ハイドロタルサイト以外の不純物捕集剤
の効果が確認された。 Example 3 In Example 1, instead of hydrotalcite, calcium stearate, zinc stearate, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, zeolite, dibutyltin dilaurate, dioctyltin dilaurate, calcium phosphate. The same experiment as in Example 1 was performed except that each of the above was used. Foaming was also performed normally as in Example 1, no rusting was observed on the copper wire surface, and images and sounds were transmitted using these coaxial cables, but they were clear, and the effect of an impurity scavenger other than hydrotalcite was observed. Was confirmed.
【0021】[0021]
【発明の効果】本発明においては、通常市販されている
不純物を含む化学発泡剤であるOBSHを使用しても、
作られた同軸ケーブルの内部導体や外部導体に発錆は認
められず、良好な品質の同軸ケーブルが得られるという
効果があった。INDUSTRIAL APPLICABILITY In the present invention, even if OBSH which is a commercially available chemical blowing agent containing impurities is used,
No rust was observed on the inner conductor and the outer conductor of the manufactured coaxial cable, and there was an effect that a good quality coaxial cable could be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 H01B 7/02 H01B 7/02 G ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H01B 7/02 H01B 7/02 G
Claims (3)
純物を含むp,p’−オキシ−ビス−ベンゼンスルホニ
ルヒドラジド0.5〜5重量部及び不純物捕集剤0.0
05〜0.5重量部を配合させてなる発泡絶縁ポリエチ
レン被覆用の発泡性樹脂組成物。1. 0.5 to 5 parts by weight of p, p'-oxy-bis-benzenesulfonyl hydrazide containing impurities and 100 parts by weight of a polyethylene-based resin, and 0.0 as an impurity scavenger.
A foamable resin composition for coating foamed insulating polyethylene, which comprises 0.5 to 0.5 parts by weight.
いて製造された発泡絶縁ポリエチレン被覆電線。2. A foam-insulated polyethylene-coated electric wire manufactured using the foamable resin composition according to claim 1.
級脂肪酸金属塩、酸化マグネシウム、酸化カルシウム、
水酸化マグネシウム、水酸化カルシウム、ゼオライト、
有機スズ化合物、リン酸カルシウムからなる群から選択
されたことを特徴とする請求項1の発泡性樹脂組成物。3. The method according to claim 1, wherein the impurity trapping agent is hydrotalcite, a metal salt of a higher fatty acid, magnesium oxide, calcium oxide,
Magnesium hydroxide, calcium hydroxide, zeolite,
The foamable resin composition according to claim 1, wherein the foamable resin composition is selected from the group consisting of an organotin compound and calcium phosphate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8113016A JP3026755B2 (en) | 1995-12-22 | 1996-04-11 | Foamable resin composition for covering foamed insulated polyethylene and foamed insulated polyethylene covered wire manufactured by covering the same |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7-349535 | 1995-12-22 | ||
JP34953595 | 1995-12-22 | ||
JP8113016A JP3026755B2 (en) | 1995-12-22 | 1996-04-11 | Foamable resin composition for covering foamed insulated polyethylene and foamed insulated polyethylene covered wire manufactured by covering the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09227708A true JPH09227708A (en) | 1997-09-02 |
JP3026755B2 JP3026755B2 (en) | 2000-03-27 |
Family
ID=26452044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8113016A Expired - Fee Related JP3026755B2 (en) | 1995-12-22 | 1996-04-11 | Foamable resin composition for covering foamed insulated polyethylene and foamed insulated polyethylene covered wire manufactured by covering the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3026755B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008031353A (en) * | 2006-07-31 | 2008-02-14 | Hitachi Cable Ltd | Non-halogen flame-retardant resin composition |
JP2008163128A (en) * | 2006-12-27 | 2008-07-17 | Inoac Corp | Polyolefin-based resin foamed body |
-
1996
- 1996-04-11 JP JP8113016A patent/JP3026755B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008031353A (en) * | 2006-07-31 | 2008-02-14 | Hitachi Cable Ltd | Non-halogen flame-retardant resin composition |
JP2008163128A (en) * | 2006-12-27 | 2008-07-17 | Inoac Corp | Polyolefin-based resin foamed body |
Also Published As
Publication number | Publication date |
---|---|
JP3026755B2 (en) | 2000-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1440119B1 (en) | Insulating foam composition | |
US5346926A (en) | Small diameter electric wire insulated with highly expanded cellular polyethylene and production thereof | |
JP3523943B2 (en) | Foamable resin composition for highly foamed insulated polyethylene and high foamed insulated polyethylene coated wire made by coating the same | |
JP2008019379A (en) | Masterbatch for foaming resin composition, foamed coaxial cable and method for producing the same | |
JP3049218B2 (en) | Foamable resin composition for covering foamed insulated polyethylene and foamed insulated polyethylene covered wire manufactured by covering the same | |
JP2008021585A (en) | Foamed coaxial cable | |
JP3026755B2 (en) | Foamable resin composition for covering foamed insulated polyethylene and foamed insulated polyethylene covered wire manufactured by covering the same | |
JP3962421B1 (en) | Foam molding method, foamed coaxial cable, and foamed coaxial cable manufacturing method | |
JP3532816B2 (en) | Foaming composition, method for producing the same, and foamed coaxial insulated cable | |
JP3241126B2 (en) | Small diameter high foam polyethylene insulated cable and method of manufacturing the same | |
JP2007090787A (en) | Foaming method, foamed coaxial cable and manufacturing method of the foamed coaxial cable | |
JP2002042555A (en) | Ethylene resin composition and electric wire/cable coated with it | |
KR101418565B1 (en) | Foam composition, foamed insulator thereof and coaxial cable | |
JP3926827B1 (en) | Foaming resin composition, foam molding method, foamed coaxial cable and foamed coaxial cable manufacturing method | |
JP2939565B2 (en) | Foamable resin composition for highly foamed insulating polyethylene and method for producing the same | |
JP2007051190A (en) | Resin composition for foaming, foamed coaxial cable, and method for foamed coaxial cable | |
JP3761606B2 (en) | Manufacturing method of insulation composition for electric wire | |
JP2007100961A (en) | Foaming polyethylene coated metallic pipe | |
JP3193209B2 (en) | Method for producing high-expansion foam | |
JP2007242589A (en) | Foamed coaxial cable | |
JP2668198B2 (en) | Polymer composition for foam extrusion | |
JPH10279722A (en) | Foaming polyethylene resin composition for metallic pipe covering and metallic pipe covered with foamed polyethylene using the same | |
JPH0440379B2 (en) | ||
JPH0755990B2 (en) | Expandable polyolefin resin composition for coating electric wires | |
JP2003096225A (en) | Production method of open-cell crosslinked polyolefin foam |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090128 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100128 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110128 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110128 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120128 Year of fee payment: 12 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120128 Year of fee payment: 12 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130128 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130128 Year of fee payment: 13 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140128 Year of fee payment: 14 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |