JP2006241235A - Molded product and electric wire/cable using crosslinked polyethylene - Google Patents

Molded product and electric wire/cable using crosslinked polyethylene Download PDF

Info

Publication number
JP2006241235A
JP2006241235A JP2005056111A JP2005056111A JP2006241235A JP 2006241235 A JP2006241235 A JP 2006241235A JP 2005056111 A JP2005056111 A JP 2005056111A JP 2005056111 A JP2005056111 A JP 2005056111A JP 2006241235 A JP2006241235 A JP 2006241235A
Authority
JP
Japan
Prior art keywords
polyethylene
weight
antioxidant
added
parts
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
Application number
JP2005056111A
Other languages
Japanese (ja)
Other versions
JP4867178B2 (en
Inventor
Toshiharu Goto
敏晴 後藤
Takanori Yamazaki
孝則 山崎
Shingo Ashihara
新吾 芦原
Junichi Abe
淳一 安部
Kiyoshi Watanabe
清 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Cable Ltd
Original Assignee
Hitachi Cable Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hitachi Cable Ltd filed Critical Hitachi Cable Ltd
Priority to JP2005056111A priority Critical patent/JP4867178B2/en
Publication of JP2006241235A publication Critical patent/JP2006241235A/en
Application granted granted Critical
Publication of JP4867178B2 publication Critical patent/JP4867178B2/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]

Landscapes

  • Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product and an electric wire/cable using a crosslinked polyethylene capable of realizing a closed cycle. <P>SOLUTION: The electric wire/cable is obtained through extrusion coating of a molded product on a conductor, wherein the molded product is obtained by adding an antioxidant, a copper inhibitor and a crosslinking catalyst to a recycled polyethylene obtained by treating the crosslinked polyethylene with a supercritical alcohol etc. and mixing the master batch. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、架橋ポリエチレンを超臨界アルコールで低分子化した再生ポリエチレンを再度成形する架橋ポリエチレンを用いた成形物及び電線・ケーブルに関するものである。   The present invention relates to a molded article and an electric wire / cable using a crosslinked polyethylene obtained by re-molding a recycled polyethylene obtained by reducing the molecular weight of a crosslinked polyethylene with a supercritical alcohol.

シラングラフト・水架橋法は、有機過酸化物を用いて架橋を行う化学架橋方式よりも低コストの架橋ポリオレフィン材料として広く用いられている。   The silane graft / water cross-linking method is widely used as a cross-linked polyolefin material at a lower cost than a chemical cross-linking method in which cross-linking is performed using an organic peroxide.

これは、高温の成形加工機（例えば押出機）中で、少量の有機過酸化物をグラフト反応開始剤として用い、ポリマにビニルアルコキシシランをグラフト共重合した後、高温高湿度雰囲気（または温水中）に電線ケーブルをさらし、ポリマにグラフトしたアルコキシシランの加水分解及び縮合を起こして架橋するものである。   This is because a small amount of organic peroxide is used as a graft reaction initiator in a high-temperature molding machine (for example, an extruder), and after graft copolymerization of vinyl alkoxysilane to the polymer, a high-temperature and high-humidity atmosphere (or warm water) ) Is exposed to an electric cable, and the alkoxysilane grafted on the polymer is hydrolyzed and condensed to cause crosslinking.

このシラン架橋ポリエチレン（ＸＬＰＥ）は、巨大な三次元網目構造をとるため、融点以上に加熱しても形状を保持する耐熱性があり、優れた電気特性を有する材料であるが、反面リサイクルの面からすると、通常の熱可塑性樹脂のように加熱溶融成形ができない問題がある。   Since this silane-crosslinked polyethylene (XLPE) has a huge three-dimensional network structure, it has heat resistance that retains its shape even when heated above its melting point, and has excellent electrical properties. Therefore, there is a problem that it cannot be heat-melt molded like a normal thermoplastic resin.

そこで、架橋ポリマーを超臨界、亜臨界のアルコールを用いて架橋ポリマーのシロキサン結合を切断して低分子化し、これを再生材ペレットとし、この再生ＰＥを用いて絶縁材に再利用することが試みられている。   Therefore, we tried to reduce the molecular weight of the crosslinked polymer by cutting the siloxane bond of the crosslinked polymer using supercritical and subcritical alcohol, making it a recycled material pellet and reusing it as an insulating material using this recycled PE. It has been.

特開２００２−１８７９７６号公報JP 2002-187976 A

しかしながら、超臨界メタノール中の反応は、シロキサン結合の分解の他に、酸化防止剤のエステル結合の分解やベンゼン環へのメトキシ基付加、ヒドロキシ基のメトキシ化（−ＯＣＨ3 ）も起こるため、架橋ポリマーを低分子化すると同時に添加した酸化防止剤や銅害防止剤等の添加剤も構造が変わる可能性が大きい。このため、得られたＸＬＰＥ再生材を用いて新たに元の用途である成形物や電線・ケーブルを作製しても使用に耐えうる電線・ケーブルとすることはできず、クローズドサイクルを実現できない問題がある。 However, in the reaction in supercritical methanol, in addition to the decomposition of the siloxane bond, the decomposition of the ester bond of the antioxidant, the addition of a methoxy group to the benzene ring, and the methoxylation of the hydroxy group (-OCH 3 ) also occur. There is a high possibility that the structure of additives such as antioxidants and copper damage inhibitors added at the same time as reducing the molecular weight of the polymer will change. For this reason, it is not possible to make a wire / cable that can withstand use even if a new molded product or wire / cable, which is the original application, is made using the obtained XLPE recycled material, and a closed cycle cannot be realized. There is.

本発明の目的は、クローズドサイクルを実現できる架橋ポリエチレンを用いた成形物及び電線・ケーブルを提供することにある。   An object of the present invention is to provide a molded article and an electric wire / cable using a crosslinked polyethylene capable of realizing a closed cycle.

上記の目的を達成するために、請求項１の発明は、架橋ポリエチレンを超臨界アルコール等によって処理して得られた再生ポリエチレンに、酸化防止剤または／及び銅害防止剤を加え、これに架橋触媒を加えた架橋ポリエチレンを用いた成形物である。   In order to achieve the above object, the invention of claim 1 is directed to adding an antioxidant or / and a copper damage inhibitor to a regenerated polyethylene obtained by treating a crosslinked polyethylene with a supercritical alcohol, etc. It is a molded article using a crosslinked polyethylene to which a catalyst is added.

請求項２の発明は、再生ポリエチレン１００重量部に酸化防止剤と銅害防止剤、架橋触媒をそれぞれ０．０３重量部以上加えた請求項１記載の架橋ポリエチレンを用いた成形物である。   The invention of claim 2 is a molded article using the crosslinked polyethylene of claim 1, wherein 0.03 parts by weight or more of an antioxidant, a copper damage inhibitor and a crosslinking catalyst are added to 100 parts by weight of recycled polyethylene.

請求項３の発明は、バージンのポリエチレン１００重量部に、酸化防止剤、銅害防止剤、架橋触媒をそれぞれ１重量部以上加えてマスタバッチとし、上記再生ポリエチレン８０〜１００重量部に、上記マスタバッチを約２０〜３重量部加えた請求項１記載の架橋ポリエチレンを用いた成形物である。   According to a third aspect of the present invention, a master batch is prepared by adding 1 part by weight or more of an antioxidant, a copper damage inhibitor, and a crosslinking catalyst to 100 parts by weight of virgin polyethylene, and 80 to 100 parts by weight of the recycled polyethylene is added to the master. The molded article using the crosslinked polyethylene according to claim 1, wherein about 20 to 3 parts by weight of a batch is added.

請求項４の発明は、再生ポリエチレン２０〜９５重量部に対し、バージンのポリエチレンを８０〜５重量部加えたものを再生ポリエチレンとし、これに酸化防止剤と銅害防止剤と架橋触媒とを加えたことを特徴とする請求項１〜３いずれかに記載の架橋ポリエチレンを用いた成形物である。   The invention of claim 4 is a regenerated polyethylene obtained by adding 80 to 5 parts by weight of virgin polyethylene to 20 to 95 parts by weight of regenerated polyethylene, to which an antioxidant, a copper damage inhibitor and a crosslinking catalyst are added. A molded article using the crosslinked polyethylene according to any one of claims 1 to 3.

請求項５の発明は、請求項１〜４いずれかに記載の成形物を、導体に押出被覆したことを特徴とする架橋ポリエチレンを用いた電線・ケーブルである。   A fifth aspect of the present invention is an electric wire / cable using cross-linked polyethylene, wherein the molded product according to any one of the first to fourth aspects is extrusion-coated on a conductor.

本発明は、再生ポリエチレンを用い、これに酸化防止剤または／及び銅害防止剤と、架橋触媒とを加えることで、電線・ケーブル用の材料など元の用途に適した良好な特性を持つ材料を得ることができ、架橋ポリエチレン（ＸＬＰＥ）のクローズドサイクルを実現できる。   The present invention uses recycled polyethylene, and by adding an antioxidant or / and copper damage inhibitor and a crosslinking catalyst to this, a material having good characteristics suitable for the original use such as a material for electric wires and cables. And a closed cycle of cross-linked polyethylene (XLPE) can be realized.

以下本発明の実施形態を説明する。   Embodiments of the present invention will be described below.

本発明は、架橋ポリエチレンを超臨界アルコール等によって処理して得られた再生ポリエチレンに、酸化防止剤または／及び銅害防止剤を加え、これに架橋触媒を加えて成形物とするものである。   In the present invention, an antioxidant or / and a copper damage inhibitor are added to a recycled polyethylene obtained by treating a crosslinked polyethylene with a supercritical alcohol or the like, and a crosslinking catalyst is added thereto to form a molded product.

再生ポリエチレンは、特許文献１に記載されるようにリサイクルする架橋ポリエチレンをペレット状に加工し、これをメチルアルコールやエチルアルコールと共に超臨界，亜臨界状態にして、シロキサン結合を分解して低分子化して得られるもので、二軸押出機に架橋ポリエチレンのペレットを投入し、二軸押出機の途中からアルコールを注入し、これをアルコールの臨界温度と臨界圧力以上（例えばメチルアルコールの臨界温度２３９．６℃と臨界圧力８．０９ＭＰａ、エチルアルコールの臨界温度２４０．９℃と臨界圧力６．１４ＭＰａ、ｎ−プロパノールの臨界温度２６３．７℃と臨界圧力５．１ＭＰａ）、或いはその近傍の亜臨界温度、亜臨界圧力として架橋ポリエチレンを低分子化して再生ポリエチレンとする。   Recycled polyethylene is processed into pellets of cross-linked polyethylene to be recycled as described in Patent Document 1, and this is converted into a supercritical and subcritical state together with methyl alcohol and ethyl alcohol to decompose siloxane bonds and reduce the molecular weight. The pellets of cross-linked polyethylene are put into a twin screw extruder, and alcohol is injected from the middle of the twin screw extruder, which is above the critical temperature and critical pressure of alcohol (for example, the critical temperature of methyl alcohol 239. 6 ° C and a critical pressure of 8.09 MPa, a critical temperature of ethyl alcohol of 240.9 ° C and a critical pressure of 6.14 MPa, a critical temperature of n-propanol of 263.7 ° C and a critical pressure of 5.1 MPa), or a subcritical temperature in the vicinity thereof As a subcritical pressure, the crosslinked polyethylene is reduced in molecular weight to obtain a regenerated polyethylene.

この超臨界、亜臨界処理を行うと、ベンゼン環へのメトキシ基付加、ヒドロキシ基のメトキシ化（−ＯＣＨ3 ）も起こるため、架橋ポリエチレンに加えられていた酸化防止剤と銅害防止剤と架橋触媒の構造が変わってしまい、再生ポリエチレンで押出成形しても諸特性を満たし、かつ外観の良い再生ケーブルを作製することが難しい。 When this supercritical or subcritical treatment is performed, methoxy group addition to the benzene ring and hydroxy group methoxylation (-OCH 3 ) also occur. Therefore, the antioxidant and copper damage inhibitor added to the crosslinked polyethylene are crosslinked. The structure of the catalyst changes, and it is difficult to produce a recycled cable that satisfies various characteristics and has a good appearance even if it is extruded with recycled polyethylene.

そこで、再生ポリエチレンに酸化防止剤と銅害防止剤と架橋触媒とを加えることで、再生ケーブルの絶縁材料に元の架橋ポリエチレンと同等の特性を持たせることができる。   Therefore, by adding an antioxidant, a copper damage inhibitor and a crosslinking catalyst to the recycled polyethylene, the insulating material of the recycled cable can have the same characteristics as the original crosslinked polyethylene.

本発明においては、再生ポリエチレン１００重量部に対して酸化防止剤と銅害防止剤、架橋触媒をそれぞれ０．０３重量部程度添加する。   In the present invention, about 0.03 parts by weight of an antioxidant, a copper damage inhibitor, and a crosslinking catalyst are added to 100 parts by weight of recycled polyethylene.

酸化防止剤としては、２，２−チオ−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリチル−テトラエキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，４−ビス−（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、ビス［２−メチル−４−｛３−ｎ−アルキル（Ｃ12またはＣ14）チオプロピオニルオキシ｝−５−ｔ−ブチルフェニル］スルフィド、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）あるいは、ジラウリルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ジトリデシルチオジプロピオネート、テトラキス（メチレンドデシルチオプロピオネート）メタンなどから選ばれる１種類または２種類以上を混合して用いるが、これに限るものではなく、フェノール系、イオウ系、アミン系、りん系の酸化防止剤を単独または併用して用いることができる。 Antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetra extract [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- ( 4-hydroxy-3,5-di -t- butylanilino) -1,3,5-triazine, bis [2-methyl-4-{3-n-alkyl (C 12 or C 14) thio propionyloxy} -5 -T-butylphenyl] sulfide, 4,4'-thiobis (3-methyl-6-t-butylphenol) or dilaurylthiodipropionate, dimyristylthiodip One or two or more kinds selected from pionate, distearyl thiodipropionate, ditridecyl thiodipropionate, tetrakis (methylene dodecyl thiopropionate) methane, etc. are used, but not limited thereto, Phenol, sulfur, amine and phosphorus antioxidants can be used alone or in combination.

銅害防止剤としては、２，６-Di-tert-butyl-p-cresol（２，６−ジ−ターシャル−ブチル−ｐ−クレゾール）、２，６-Di-tert-butyl-４-methylphenol（２，６−ジ−ターシャル−ブチル−４−メチルフェノール）、３，５-Di-tert-butyl-４-hydroxytoluene（３，５−ジ−ターシャル−ブチル−４−ヒドロキシトルエン）、２，６−Di-tert-butyl-p-cresol（２，６−ジ−ターシャル−ブチル−ｐ−クレゾール）などのフェノール系化合物や、Ｎ，Ｎ’−ジ−２−ナフチル−ｐ−フェニレンジアミン、N-Phenyl-N'-１（Ｎ−フェニル−Ｎ’−１）、３−dimethylbutyl-p-phenylenediamine（３−ジメチルブチル−ｐ−ｐフェニレンジアミン）、N-Isopropyl-N'-phenyl-p-phenylenediamine（Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン）などのアミン系化合物、イソフタル酸ビス（２フェノキシプロピオニル ヒドラジン）などのヒドラジド、アルコールカルボン酸エステルなどが挙げられる。   Examples of copper damage inhibitors include 2,6-Di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol), 2,6-Di-tert-butyl-4-methylphenol ( 2,6-di-tert-butyl-4-methylphenol), 3,5-Di-tert-butyl-4-hydroxytoluene (3,5-di-tert-butyl-4-hydroxytoluene), 2,6- Phenolic compounds such as Di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol), N, N′-di-2-naphthyl-p-phenylenediamine, N-Phenyl -N'-1 (N-phenyl-N'-1), 3-dimethylbutyl-p-phenylenediamine (3-dimethylbutyl-p-phenylenediamine), N-Isopropyl-N'-phenyl-p-phenylenediamine (N Amine compounds such as -isopropyl-N'-phenyl-p-phenylenediamine), bis (2-phenol) isophthalate And hydrazides such as xylpropionyl hydrazine) and alcohol carboxylic acid esters.

架橋触媒としては、マグネシウムやカルシウムなどのII族、コバルト、鉄などのVIII族の元素、もしくは亜鉛、Ｔｉ等の金属化合物、オクチル酸またはアジピン酸の金属塩、アミン系化合物、酸などが挙げられる。より具体的には、ジブチル錫ジラウリレート、ジブチル錫ジアセテート、ジブチル錫ジオクタエート、酢酸第一錫、カブリル酸第一錫、ナフテン酸鉛、カブリル酸亜鉛、ナフテン酸コバルト、エチルアミン、ジブチルアミン、ヘキシルアミン、ピリジン、硫酸、塩酸などの無機酸、トルエンスルホン酸、酢酸、ステアリン酸、マレイン酸などの有機酸が使用される。   Examples of the crosslinking catalyst include Group II elements such as magnesium and calcium, Group VIII elements such as cobalt and iron, or metal compounds such as zinc and Ti, metal salts of octylic acid or adipic acid, amine compounds, acids, and the like. . More specifically, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctaate, stannous acetate, stannous cablate, lead naphthenate, zinc cablate, cobalt naphthenate, ethylamine, dibutylamine, hexylamine, Inorganic acids such as pyridine, sulfuric acid and hydrochloric acid, and organic acids such as toluenesulfonic acid, acetic acid, stearic acid and maleic acid are used.

具体的な製造法としては、再生ポリエチレンに、酸化防止剤と銅害防止剤と架橋触媒をそれぞれ０．０３重量部以上加える代わりに、バージンポリエチレンにあらかじめ酸化防止剤と銅害防止剤と架橋触媒を加えてマスタバッチを作製し、再生ポリエチレンに、酸化防止剤と銅害防止剤と架橋触媒が、それぞれ０．０３重量部以上となるようにマスタバッチを加える。また、再生ポリエチレンには適宜バージンＰＥを混ぜて用いてもよい。   As a specific manufacturing method, instead of adding 0.03 parts by weight or more of an antioxidant, a copper damage inhibitor, and a crosslinking catalyst to recycled polyethylene, an antioxidant, a copper damage inhibitor, and a crosslinking catalyst are added to virgin polyethylene in advance. Is added to the recycled polyethylene, and the master batch is added to the recycled polyethylene so that the antioxidant, the copper damage inhibitor and the crosslinking catalyst are each 0.03 parts by weight or more. Further, virgin PE may be appropriately mixed with recycled polyethylene.

マスタバッチを用いて、酸化防止剤と銅害防止剤と架橋触媒を再生ポリエチレンに混合する方法を用いれば分散性が良好となり、再生ポリエチレンで押出成形しても諸特性を満たし、かつ外観の良い再生ケーブルを作製することができる。   Using a masterbatch, a method of mixing an antioxidant, a copper damage inhibitor and a cross-linking catalyst into the regenerated polyethylene will improve the dispersibility. A reproduction cable can be produced.

次に本発明の実施例を比較例と共に説明する。   Next, examples of the present invention will be described together with comparative examples.

Figure 2006241235
Figure 2006241235

表１の実施例１〜６及び比較例１〜５に示す絶縁組成物を、３８ｍｍ2 の軟銅撚線上にそれぞれ１．２ｍｍ厚さに押し出した。この時の詳細は次の通りである。 The insulating compositions shown in Examples 1 to 6 and Comparative Examples 1 to 5 in Table 1 were each extruded to a thickness of 1.2 mm on 38 mm 2 annealed copper stranded wire. The details at this time are as follows.

始めに、ロール混練によって表１に示す配合剤のマスタバッチを作製した。   First, a master batch of the compounding agent shown in Table 1 was prepared by roll kneading.

すなわち、ベースＰＥとしてＬＬＤＰＥ（低密度ポリエチレン）１００重量部に酸化防止剤（ペンタエリスリチル−テトラエキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］）、銅害防止剤（イソフタル酸ビス（２フェノキシプロピオニル ヒドラジン））、架橋触媒（ジブチル錫ラウリレート）を混合し、ロール混練にてマスタバッチ（実施例２〜６）とした。但し、実施例１は、マスタバッチを作らず、再生ポリエチレンに酸化防止剤、銅害防止剤、架橋触媒を直接添加し、実施例６は、マスタバッチを作らず、さらに銅害防止剤を添加しない例を示している。   That is, 100 parts by weight of LLDPE (low density polyethylene) as a base PE was added with an antioxidant (pentaerythrityl-tetra extract [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]), copper damage An inhibitor (bis (2-phenoxypropionyl hydrazine) isophthalate) and a crosslinking catalyst (dibutyltin laurate) were mixed, and a master batch (Examples 2 to 6) was prepared by roll kneading. However, Example 1 does not make a masterbatch, and directly adds an antioxidant, a copper damage inhibitor, and a crosslinking catalyst to recycled polyethylene. Example 6 does not make a masterbatch and adds a copper damage inhibitor. An example that does not.

また、比較例１〜５として、マスタバッチを作らず再生ＰＥのみ（比較例１）、ＬＬＤＰＥに架橋触媒のみを添加してマスタバッチとしたもの（比較例２、４）、ＬＬＤＰＥに架橋触媒を添加しないでマスタバッチとしたもの（比較例３、５）を用意した。   Further, as Comparative Examples 1 to 5, only a regenerated PE without producing a master batch (Comparative Example 1), a master batch obtained by adding only a crosslinking catalyst to LLDPE (Comparative Examples 2 and 4), and a crosslinking catalyst for LLDPE A master batch (Comparative Examples 3 and 5) was prepared without addition.

次に、再生ＰＥ、または再生ＰＥとベースＰＥを所定の割合でブレンドして再生ＰＥとしたものに対して、実施例１〜６，比較例１〜５に示すようにマスタバッチを、０，５，２０重量部の割合で混合し、これを２００℃の１３０ｍｍ押出機に投入した。   Next, as shown in Examples 1 to 6 and Comparative Examples 1 to 5, the master batch is set to 0, 0 for the regenerated PE or the regenerated PE by blending the regenerated PE and the base PE at a predetermined ratio. The mixture was mixed at a ratio of 5, 20 parts by weight, and this was put into a 130 mm extruder at 200 ° C.

これをストランド状に押し出してペレタイズした後に、１５０℃のロール混練機でシート状にし、１８０℃で５分間のプレス成形を行って材料評価用のシートを作製した。その後、８０℃、９５％水蒸気の雰囲気に２４時間放置して架橋させて試料とした。   This was extruded into a strand shape and pelletized, and then formed into a sheet shape with a roll kneader at 150 ° C., and subjected to press molding at 180 ° C. for 5 minutes to produce a sheet for material evaluation. Thereafter, the sample was allowed to crosslink for 24 hours in an atmosphere of 80 ° C. and 95% steam to prepare a sample.

これらの各試料について、酸化劣化の指標である酸素指数（ＯＩＴ；酸化誘導期）測定と劣化試験（老化試験）を行った。またゲル分率を測定し、再生配合が架橋ポリエチレンになっているかどうかを確認した。   Each of these samples was subjected to an oxygen index (OIT; oxidation induction period) measurement, which is an index of oxidative degradation, and a degradation test (aging test). Moreover, the gel fraction was measured and it was confirmed whether the reproduction | regeneration mixing | blending became cross-linked polyethylene.

ＯＩＴ測定は、ＤＳＣ（示差走査型熱量計）を用い、材料が１８０℃の酸素雰囲気下で酸化による発熱が始まるまでの時間を測定した。   The OIT measurement was performed using a DSC (Differential Scanning Calorimeter), and the time until the material started to generate heat due to oxidation in an oxygen atmosphere at 180 ° C. was measured.

また、老化試験用のサンプルは、プレス成形の際に、１ｍｍシートに成形してＪＩＳ Ｃ３６０５の引張試験方法に記載のダンベル３号で打ち抜いて引張試験を行った。   A sample for aging test was formed into a 1 mm sheet at the time of press molding and punched with dumbbell No. 3 described in the tensile test method of JIS C3605, and a tensile test was performed.

老化試験のＴＳ残率（引張強度残率）およびＴＥ残率の合格基準は電線用の絶縁材料として使用することを考慮に入れて設定した。老化試験の残率Ｒとは老化試験前の特性Ｓｂと老化試験後の特性値Ｓａから以下の式で与えられる。   The acceptance criteria for the TS remaining ratio (tensile strength remaining ratio) and TE remaining ratio in the aging test were set in consideration of use as an insulating material for electric wires. The residual rate R of the aging test is given by the following equation from the characteristic Sb before the aging test and the characteristic value Sa after the aging test.

Ｒ＝Ｓａ／Ｓｂ × １００
１２０℃老化試験後のＴＳ算後のＴＳ残率、ＴＥ残率がそれぞれ８０％以上、６５％以上のものを○、未満のものを×とした。また、１３５℃老化試験後のＴＳ算後のＴＳ残率、ＴＥ残率ともに７５〜１２５％のものを○、それ以外のものを×とした。 R = Sa / Sb × 100
TS residual ratio and TE residual ratio after TS calculation after 120 ° C. aging test were 80% or more and 65% or more, respectively. In addition, the TS residual ratio and the TE residual ratio after TS calculation after the 135 ° C. aging test were evaluated as “◯” for 75 to 125%, and “X” for the rest.

ゲル分率は１１０℃キシレン中で２４時間抽出した後、８０℃で４時間真空乾燥し、抽出乾燥後の重量と抽出前の重量から次式を用いてゲル分率を計算した。   The gel fraction was extracted in xylene at 110 ° C. for 24 hours and then vacuum-dried at 80 ° C. for 4 hours, and the gel fraction was calculated from the weight after extraction and the weight before extraction using the following formula.

ゲル分率（％）＝（乾燥後重量／抽出前重量）×１００
この結果、ゲル分率２０％以上を○、それ以下を×とした。 Gel fraction (%) = (weight after drying / weight before extraction) × 100
As a result, the gel fraction of 20% or more was marked with ◯, and the lower percentage was marked with ×.

実施例１〜６では全ての特性において合格したが、比較例１〜５では、いずれかの特性において不合格となった。
In Examples 1-6, it passed in all the characteristics, but in Comparative Examples 1-5, it failed in any of the characteristics.

Claims (5)

架橋ポリエチレンを超臨界アルコール等によって処理して得られた再生ポリエチレンに、酸化防止剤または／及び銅害防止剤を加え、これに架橋触媒を加えたことを特徴とする架橋ポリエチレンを用いた成形物。   A molded article using crosslinked polyethylene, characterized by adding an antioxidant or / and a copper damage inhibitor to a recycled polyethylene obtained by treating the crosslinked polyethylene with a supercritical alcohol or the like, and adding a crosslinking catalyst thereto. . 再生ポリエチレン１００重量部に酸化防止剤と銅害防止剤、架橋触媒をそれぞれ０．０３重量部以上加えた請求項１記載の架橋ポリエチレンを用いた成形物。   The molded article using the crosslinked polyethylene according to claim 1, wherein 0.03 parts by weight or more of an antioxidant, a copper damage inhibitor and a crosslinking catalyst are added to 100 parts by weight of recycled polyethylene. バージンのポリエチレン１００重量部に、酸化防止剤、銅害防止剤、架橋触媒をそれぞれ１重量部以上加えてマスタバッチとし、上記再生ポリエチレン８０〜１００重量部に、上記マスタバッチを約２０〜３重量部加えた請求項１記載の架橋ポリエチレンを用いた成形物。   1 part by weight or more of an antioxidant, a copper damage inhibitor and a crosslinking catalyst are added to 100 parts by weight of virgin polyethylene to form a master batch, and about 20 to 3 weights of the master batch is added to 80 to 100 parts by weight of the recycled polyethylene. A molded article using the cross-linked polyethylene according to claim 1 to which part is added. 再生ポリエチレン２０〜９５重量部に対し、バージンのポリエチレンを８０〜５重量部加えたものを再生ポリエチレンとし、これに酸化防止剤と銅害防止剤と架橋触媒とを加えた請求項１〜３いずれかに記載の架橋ポリエチレンを用いた成形物。   Any one of claims 1 to 3, wherein 80 to 5 parts by weight of virgin polyethylene is added to 20 to 95 parts by weight of recycled polyethylene to make recycled polyethylene, and an antioxidant, a copper damage inhibitor and a crosslinking catalyst are added thereto. A molded article using the crosslinked polyethylene according to any one of the above. 請求項１〜４いずれかに記載の成形物を、導体に押出被覆したことを特徴とする架橋ポリエチレンを用いた電線・ケーブル。
An electric wire / cable using cross-linked polyethylene, wherein the molded product according to any one of claims 1 to 4 is extrusion-coated on a conductor.
JP2005056111A 2005-03-01 2005-03-01 Manufacturing method of molded product using recycled polyethylene and manufacturing method of electric wire and cable using recycled polyethylene Expired - Fee Related JP4867178B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005056111A JP4867178B2 (en) 2005-03-01 2005-03-01 Manufacturing method of molded product using recycled polyethylene and manufacturing method of electric wire and cable using recycled polyethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005056111A JP4867178B2 (en) 2005-03-01 2005-03-01 Manufacturing method of molded product using recycled polyethylene and manufacturing method of electric wire and cable using recycled polyethylene

Publications (2)

Publication Number Publication Date
JP2006241235A true JP2006241235A (en) 2006-09-14
JP4867178B2 JP4867178B2 (en) 2012-02-01

Family

ID=37047965

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2005056111A Expired - Fee Related JP4867178B2 (en) 2005-03-01 2005-03-01 Manufacturing method of molded product using recycled polyethylene and manufacturing method of electric wire and cable using recycled polyethylene

Country Status (1)

Country Link
JP (1) JP4867178B2 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235367A (en) * 2008-03-07 2009-10-15 Furukawa Electric Co Ltd:The Polyethylene resin composition and telecommunication cable comprising the resin composition
JP2011080019A (en) * 2009-10-09 2011-04-21 Hitachi Cable Ltd Cross-linked resin material containing regenerated resin, method for producing the same, and electric wire/cable
JP2012007097A (en) * 2010-06-25 2012-01-12 Sekisui Chem Co Ltd Recycled resin-containing polyolefin-based resin composition and method for recycling polyolefin-based resin

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0668714A (en) * 1992-03-31 1994-03-11 Furukawa Electric Co Ltd:The Crosslinked polyolefin insulated electric cable
JPH07320548A (en) * 1994-05-19 1995-12-08 Hitachi Cable Ltd Polyolefine insulated wire
JPH08142153A (en) * 1994-11-16 1996-06-04 Nippon Unicar Co Ltd Prevention of generation of die refuse
JPH11172057A (en) * 1997-12-15 1999-06-29 Nippon Unicar Co Ltd Semiconducting resin composition having good water-crosslinkability and power cable made by using it
JP2002187976A (en) * 2000-10-12 2002-07-05 National Institute Of Advanced Industrial & Technology Method for recycling polymer
JP2002216541A (en) * 2001-01-15 2002-08-02 Fujikura Ltd Polyethylene composition and insulated electrical wire using the same
JP2004010864A (en) * 2002-06-11 2004-01-15 Nippon Unicar Co Ltd Tracking-resistant resin composition crosslinkable with water and power cable having insulating coated layer formed out of the composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0668714A (en) * 1992-03-31 1994-03-11 Furukawa Electric Co Ltd:The Crosslinked polyolefin insulated electric cable
JPH07320548A (en) * 1994-05-19 1995-12-08 Hitachi Cable Ltd Polyolefine insulated wire
JPH08142153A (en) * 1994-11-16 1996-06-04 Nippon Unicar Co Ltd Prevention of generation of die refuse
JPH11172057A (en) * 1997-12-15 1999-06-29 Nippon Unicar Co Ltd Semiconducting resin composition having good water-crosslinkability and power cable made by using it
JP2002187976A (en) * 2000-10-12 2002-07-05 National Institute Of Advanced Industrial & Technology Method for recycling polymer
JP2002216541A (en) * 2001-01-15 2002-08-02 Fujikura Ltd Polyethylene composition and insulated electrical wire using the same
JP2004010864A (en) * 2002-06-11 2004-01-15 Nippon Unicar Co Ltd Tracking-resistant resin composition crosslinkable with water and power cable having insulating coated layer formed out of the composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009235367A (en) * 2008-03-07 2009-10-15 Furukawa Electric Co Ltd:The Polyethylene resin composition and telecommunication cable comprising the resin composition
JP2011080019A (en) * 2009-10-09 2011-04-21 Hitachi Cable Ltd Cross-linked resin material containing regenerated resin, method for producing the same, and electric wire/cable
JP2012007097A (en) * 2010-06-25 2012-01-12 Sekisui Chem Co Ltd Recycled resin-containing polyolefin-based resin composition and method for recycling polyolefin-based resin

Also Published As

Publication number Publication date
JP4867178B2 (en) 2012-02-01

Similar Documents

Publication Publication Date Title
JP5640889B2 (en) Electric wire / cable
JP3551755B2 (en) Easily peelable semiconductive resin composition and electric wire / cable
JP5343327B2 (en) Method for producing flame retardant silane-crosslinked olefin resin, insulated wire and method for producing insulated wire
JP6582002B2 (en) Stabilized moisture curable polymer composition
JP2017521514A (en) Stabilized moisture curable polymer composition
JP2019014794A (en) Resin composition, resin coating material, wire harness for automobile and method for manufacturing wire harness for automobile
JP4867178B2 (en) Manufacturing method of molded product using recycled polyethylene and manufacturing method of electric wire and cable using recycled polyethylene
KR20170134720A (en) Crosslinking method of polypropylene
JP2013155269A (en) Flame-retardant composition and insulated wire
RU2440633C1 (en) Electrically insulating cross-linking composition
JP5614376B2 (en) Silane cross-linked polyolefin insulated wire
JP7060582B2 (en) Heat-resistant chlorine-containing crosslinked resin molded article and its manufacturing method, silane masterbatch and masterbatch mixture, and heat-resistant products
JP3187048B2 (en) Crosslinkable polymer composition
KR102593181B1 (en) polyethylene compound composition
JP5609780B2 (en) Electric wires and cables using silane-crosslinked polyolefin compositions
JP2000319464A (en) Semi-conductive resin composition and crosslinked polyethylene-insulated electric power cable
JP2016037563A (en) Silane graft composition and method for producing the same, and wire and cable prepared therewith
JP5776389B2 (en) Flame retardant composition having peelability and heat resistance, method for producing flame retardant resin, and insulated wire
JP3988308B2 (en) Electric wire / cable
JP3858511B2 (en) Electric wire / cable
JP4016533B2 (en) Electric wire / cable
JP2010116465A (en) Resin material for electric wire/cable or connector
CN115838509B (en) POE elastomer composite material modified based on dual-dynamic cross-linked network and preparation method thereof
JP5598408B2 (en) Electric wire / cable manufacturing method using recycled resin
KR101704026B1 (en) Composition for producing of silane crosslinked insulating material with flame retardant

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20070413

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20100222

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20100302

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20100406

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110125

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110210

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20111018

A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20111031

R150 Certificate of patent or registration of utility model

Ref document number: 4867178

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20141125

Year of fee payment: 3

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313111

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

LAPS Cancellation because of no payment of annual fees