JP4772174B2 - Electro-fusion joint - Google Patents

Electro-fusion joint Download PDF

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Publication number
JP4772174B2
JP4772174B2 JP25974999A JP25974999A JP4772174B2 JP 4772174 B2 JP4772174 B2 JP 4772174B2 JP 25974999 A JP25974999 A JP 25974999A JP 25974999 A JP25974999 A JP 25974999A JP 4772174 B2 JP4772174 B2 JP 4772174B2
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Japan
Prior art keywords
resin
embedded
heating element
modified
thermoplastic resin
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JP25974999A
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Japanese (ja)
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JP2001082667A (en
Inventor
一久 井川
裕思 樋口
貞雄 長瀬
実則 遠藤
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Mitsubishi Plastics Inc
Osaka Gas Co Ltd
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Mitsubishi Plastics Inc
Osaka Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/34—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/3404—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the type of heated elements which remain in the joint
    • B29C65/342—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the type of heated elements which remain in the joint comprising at least a single wire, e.g. in the form of a winding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/12—Joint cross-sections combining only two joint-segments; Tongue and groove joints; Tenon and mortise joints; Stepped joint cross-sections
    • B29C66/122—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section
    • B29C66/1222—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section comprising at least a lapped joint-segment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/05—Particular design of joint configurations
    • B29C66/10—Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/12—Joint cross-sections combining only two joint-segments; Tongue and groove joints; Tenon and mortise joints; Stepped joint cross-sections
    • B29C66/122—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section
    • B29C66/1224—Joint cross-sections combining only two joint-segments, i.e. one of the parts to be joined comprising only two joint-segments in the joint cross-section comprising at least a butt joint-segment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/52—Joining tubular articles, bars or profiled elements
    • B29C66/522—Joining tubular articles
    • B29C66/5221—Joining tubular articles for forming coaxial connections, i.e. the tubular articles to be joined forming a zero angle relative to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/50—General aspects of joining tubular articles; General aspects of joining long products, i.e. bars or profiled elements; General aspects of joining single elements to tubular articles, hollow articles or bars; General aspects of joining several hollow-preforms to form hollow or tubular articles
    • B29C66/51—Joining tubular articles, profiled elements or bars; Joining single elements to tubular articles, hollow articles or bars; Joining several hollow-preforms to form hollow or tubular articles
    • B29C66/52—Joining tubular articles, bars or profiled elements
    • B29C66/522—Joining tubular articles
    • B29C66/5229—Joining tubular articles involving the use of a socket
    • B29C66/52291—Joining tubular articles involving the use of a socket said socket comprising a stop
    • B29C66/52292—Joining tubular articles involving the use of a socket said socket comprising a stop said stop being internal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/34—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/3472—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint
    • B29C65/3476—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint being metallic
    • B29C65/348—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint being metallic with a polymer coating

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Branch Pipes, Bends, And The Like (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Description

【０００１】
【発明の属する技術分野】
本発明は、エレクトロヒュ−ジョン継手に関する。さらに詳しくは、都市ガス、水道水、床暖房用床材の熱媒などの流体を通す、架橋熱可塑性樹脂管を接合するためのエレクトロヒュ−ジョン継手に関するものである。
【０００２】
【従来の技術】
従来、都市ガス、水道水、床暖房用熱媒などの流体を通す熱可塑性樹脂管を接合する継手として、接合部分に、通電によって発熱するコイルなどの発熱体が埋設された熱可塑性樹脂からなるエレクトロヒュ−ジョン継手が知られている。このエレクトロヒュ−ジョン継手は、通電すると発熱する発熱体を埋設した熱可塑性樹脂の成形品を射出成形金型にインサ−トし、この成形品の表面に、継手の外殻を構成する熱可塑性樹脂を射出成形し、積層一体化する方法によって製造されている。流体を通す熱可塑性樹脂管の耐熱性、耐久性、耐薬品性などを向上させるために、発熱体を埋設した成形品と積層一体化される外殻を構成する樹脂として、架橋させた熱可塑性樹脂が使用されるようになった。架橋性の未架橋熱可塑性樹脂を射出成形して、発熱体を埋設した成形品と積層一体化した後、この未架橋熱可塑性樹脂を架橋させることによって製造される（例えば、特開平２−２５３０９１号公報参照）。
【０００３】
【発明が解決しようとする課題】
しかし、上記の従来のエレクトロヒュ−ジョン継手によって接合（接続）可能な樹脂管は、その表面が架橋されていない熱可塑性樹脂よりなる管に限定され、架橋性熱可塑性樹脂の樹脂管との接合は不十分であり、この継手によって接合した部分は漏れが生じる等の理由により適用が除外されている。これは、一旦架橋してしまった架橋熱可塑性樹脂管は、発熱体によって溶解させようとしても溶融せず、一体接合できないことによる。
【０００４】
本発明者らは、かかる状況に鑑み、上記欠点を排除したエレクトロヒュ−ジョン継手を提供すべく鋭意検討の結果、本発明を完成するに至ったものである。すなわち、本発明の目的は次の通りである。
(1)架橋熱可塑性樹脂管であっても確実にかつ強固に接合でき、接合部分の漏れが生じないエレクトロヒュ−ジョン継手を提供すること。
(2)耐熱性、耐久性、耐薬品性の優れた架橋熱可塑性樹脂管を接合することができるエレクトロヒュ−ジョン継手を提供すること。
【０００５】
【課題を解決するための手段】
上記課題を解決するため、本発明は、架橋熱可塑性樹脂管を接合する短筒状のエレクトロヒュ−ジョン継手において、エレクトロヒュ−ジョン継手の外殻は架橋熱可塑性樹脂により構成され、短筒内周の架橋熱可塑性樹脂管が接合される箇所に発熱体が樹脂層に埋設されてなり、この発熱体を埋設した樹脂層が接着性を有する改質ポリエチレン共重合体樹脂にエチレン重合体および／またはエチレン共重合体を１０〜９０％配合した樹脂組成物により構成されていることを特徴とする、エレクトロヒュ−ジョン継手を提供する。
【０００６】
【発明の実施の態様】
以下、本発明を詳細に説明する。
本発明に係るエレクトロヒュ−ジョン継手は、外観が短筒状を呈し、両側の開口部から接合されるべき樹脂管を挿入・接合される箇所の内周に発熱体が樹脂層に埋設されてなる（この樹脂層を、「発熱体埋設樹脂層」ということがある）。発熱体は、通電すると発熱するコイルである。
【０００７】
本発明に係るエレクトロヒュ−ジョン継手は、上記の発熱体埋設樹脂層を、接着性を有する改質ポリエチレン共重合体樹脂（以下、「改質ＰＥ樹脂」ということがある）によって構成する。本発明において改質ＰＥ樹脂の基体となる樹脂は、エチレン重合体および／またはエチレン・α−オレフィン共重合体である。エチレン・α−オレフィン共重合体とは、エチレンを主成分としα−オレフィンを共重合したものをいう。α−オレフィンとは、通常、炭素数３〜２０のα−オレフィン、具体的には、プロピレン、１ブテン、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセン、４−メチル−１−ペンテン等であり、単独でも２種類以上の混合物であってもよい。
【０００８】
エチレン重合体の具体例としては、超低密度ポリエチレン（ＶＬＤＰＥ）、直鎖状ポリエチレン樹脂（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）および高密度ポリエチレン（ＨＤＰＥ）とも称され、分子構造は直鎖状を有するものなどが挙げられる。エチレン・α−オレフィン共重合体の具体例としては、エチレン・プロピレン系エラストマ−（ＥＰＲ）、エチレン・ブテン−１系エラストマ−（ＥＢＲ）、プロピレン・ブテン−１系エラストマ−（ＰＢＲ）などが挙げられるが、これら例示したものに限定されるものではない。
【０００９】
上記のエチレン重合体、エチレン・α−オレフィン共重合体は、密度（測定法：ＪＩＳ Ｋ７１１２準拠）が０．８８未満では、改質ＰＥ樹脂の引張強度不足のため、接着体で必要な６０℃での接着強度が低く、０．９５５を超えると接着層での改質ＰＰ樹脂が固いので接着性が劣り、いずれも好ましくない。密度の特に好ましい範囲は、０．８９〜０．９５g/cm3である。
【００１０】
上記のエチレン重合体、エチレン・α−オレフィン共重合体は、そのＭＦＲ（測定法：ＪＩＳ Ｋ７２１０準拠）が０．０５〜５０g/１０minの範囲のものが好ましい。ＭＦＲが上記範囲以外のものは、溶融粘度が低すぎるか高すぎて、成形性に劣るので好ましくない。ＭＦＲの特に好ましい範囲は、０．１〜３０g/１０minである。
【００１１】
本発明において改質ＰＥ樹脂とは、上記のエチレン重合体および／またはエチレン・α−オレフィン共重合体の一部または全部が、不飽和カルボン酸および／またはその誘導体（モノマー）の１種または２種以上の混合物によって、変性されたものをいう。変性するに使用される不飽和カルボン酸および／またはその誘導体としては、アクリル酸、マレイン酸、フマ−ル酸、イタコン酸、シトラコン酸などの不飽和カルボン酸、または、その誘導体、例えば、無水物、アミド、イミド、エステルなどが挙げられる。これらの中では、不飽和ジカルボン酸またはその酸無水物が好適であり、特にマレイン酸またはその無水物が好適である。
【００１２】
上記のエチレン重合体および／またはエチレン・α−オレフィン共重合体を変性するには、従来から知られている種々の方法によることができる。例えば、(1)オレフィン系共重合体（１種以上の混合物を含む）および上記不飽和カルボン酸および／またはその誘導体（モノマー）を、あらかじめ混合しておき、この混合物を押出機で溶融させてグラフト共重合させる方法、(2)オレフィン系共重合体（１種以上の混合物を含む）を溶媒に溶解させ、この溶液に上記不飽和カルボン酸および／またはその誘導体を添加してグラフト共重合させる方法、などが挙げられる。
【００１３】
上記の(1)、(2)のいずれの方法によって変性するにしても、不飽和カルボン酸および／またはその誘導体を効率よくグラフト共重合させるためには、重合開始剤としてラジカル発生剤を用いるのが好ましい。使用できるラジカル発生剤としては、有機過酸化物が一般的であり、具体的には、２，５−ジメチルヘキサン−２，５ジヒドロパ−オキサイド、２，５−ジメチル−２，５ジ（ｔｅｒｔ−ブチルパ−オキシ）ヘキシン−３、ジ−ｔｅｒｔ−ブチルパ−オキサイド、ｔｅｒｔ−ブチル−クミルパ−オキサイド、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパ−オキシ）ヘキサン、ジ−クミルパ−オキサイド、ｔｅｒｔ−ブチルパ−オキシベンゾエ−ト、ｔｅｒｔ−ブチルパ−オキシアセテ−ト、ｔｅｒｔ−ブチルパ−オキシイソプロピルカ−ボネ−ト、ベンゾイルパ−オキサイド、ｍ−トルオイルパ−オキサイド等が挙げられる。
【００１４】
これらの中では、２，５−ジメチルヘキサン−２，５ジヒドロパ−オキサイド、２，５−ジメチル−２，５ジ（ｔｅｒｔ−ブチルパ−オキシ）ヘキシン−３、ジ−ｔｅｒｔ−ブチルパ−オキサイド、ジ−クミルパ−オキサイド、ベンゾイルパ−オキサイド、ｍ−トルオイルパ−オキサイド等が特に好ましい。
【００１５】
グラフト共重合させる際の反応温度は、エチレン重合体および／またはエチレン・α−オレフィン共重合体の種類、不飽和カルボン酸および／またはその誘導体の種類、ラジカル発生剤の有無および種類、有の場合はその使用量などにより変化するが、通常、８０〜３００℃の温度範囲で選ばれる。ラジカル発生剤の一般的な使用量は、オレフィン系共重合体１００重量部に対して通常０．００１〜８重量部の範囲で選ばれる。
【００１６】
上記方法によって変性して得られた改質ＰＥ樹脂には、変性の条件によっては未反応の不飽和カルボン酸および／またはその誘導体が残存することがあるので、接着性の観点から、出来るだけ残存させない方が好ましい。従って、必要に応じて各種の除去方法、例えば、アセトン等の貧溶媒による抽出、加熱乾燥処理による未反応化合物（モノマ−）の脱気、などの後処理を適用することもできる。
【００１７】
上記方法によって変性された改質ＰＥ樹脂は、グラフト量（測定法：赤外分光光度計による）が０．０１〜１０重量％の範囲が好ましい。グラフト量が０．０１重量％未満では金属との接着性が劣り、１０重量％を超えるとグラフト共重合時に一部架橋を起こし成形性が劣るばかりでなく、ブツ等により製品外観が悪化し、かつ、接着性も低下するので、好ましくない。グラフト量の特に好ましい範囲は、０．１〜５重量％である。
【００１８】
接着性を有する改質ＰＥ樹脂組成物を得るには、改質ＰＥ樹脂にエチレン重合体および／またはエチレン共重合体を１０〜９０重量％配合する。エチレン重合体としては、超低密度ポリエチレン（ＶＬＤＰＥ）、直鎖状ポリエチレン樹脂（ＬＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）およびこれらの混合物が挙げられる。エチレン共重合体としては、エチレン・プロピレン系エラストマ−（ＥＰＲ）、エチレン・ブテン−１系エラストマ−（ＥＢＲ）、プロピレン・ブテン−１系エラストマ−（ＰＢＲ）などが挙げられるが、これら例示したものに限定されるものではない。
【００１９】
上記のエチレン重合体、エチレン・α−オレフィン共重合体は、密度（測定法：ＪＩＳ Ｋ７１１２準拠）が０．８８未満では、改質ＰＥ樹脂の引張強度不足のため、接着体で必要な６０℃での接着強度が低く、０．９５５を超えると接着層での改質ＰＰ樹脂が固いので接着性が劣り、いずれも好ましくない。密度の特に好ましい範囲は、０．８９〜０．９５g/cm3である。
【００２０】
上記のエチレン重合体、エチレン・α−オレフィン共重合体は、密度（測定法：ＪＩＳ Ｋ７１１２準拠）が０．８８未満では、改質ＰＥ樹脂の引張強度不足のため、接着体で必要な６０℃での接着強度が低く、０．９５５を超えると接着層での改質ＰＰ樹脂が固いので接着性が劣り、いずれも好ましくない。密度の特に好ましい範囲は、０．８９〜０．９５g/cm3である。
【００２１】
接着性を有する改質ＰＥ樹脂組成物を得るには、上記の改質ＰＥ樹脂にエチレン重合体および／またはエチレン共重合体を１０〜９０重量％配合する。配合量が１０重量％未満であるとピーリング強度が十分でなく、配合量が９０重量％を超えると、ピーリング強度が著しく低下するので、いずれも好ましくない。
【００２２】
接着性を有する改質ＰＥ樹脂組成物には、前記成分に加えて、耐熱安定剤、耐候安定剤、ブロッキング防止剤、スリップ剤、帯電防止剤、触媒残査の中和剤、顔料、染料、無機および／または有機フィラ−などの各種の樹脂添加剤を、本発明の目的を損なわない範囲で配合することができる。接着性を有する改質ＰＥ樹脂組成物に、前記成分および各種の樹脂添加剤を配合するには、例えば、タンブラ−ブレンダ−、Ｖブレンダ−、リボンブレンダ−、ヘンシェルミキサ−等によって混合し、混合後、単軸押出機、二軸押出機、バンバリ−ミキサ−、ニ−ダ−などで溶融混練し、造粒または粉砕する、従来から知られている方法によることができる。
【００２３】
本発明に係るエレクトロヒュ−ジョン継手は、発熱体が接着性を有する改質ポリエチレン共重合体樹脂（改質ＰＥ樹脂）と、エチレン重合体および／またはエチレン共重合体とよりなる樹脂組成物に埋設されているので、発熱体に通電することによって、発熱体埋設樹脂層を構成する改質ＰＥ樹脂などを容易に溶融させることができ、溶融した発熱体埋設樹脂が架橋熱可塑性樹脂管の表面を隙間なく覆うことになり、冷却後は接合一体化され、各々の特性を十分に発揮する。エレクトロヒュ−ジョン継手によって接合される樹脂管が、溶融し難い架橋熱可塑性樹脂管であっても、優れた相乗接着強度によって優れた接合強度を発揮し、接合部分の漏れがなく確実な接合が可能である。
【００２４】
【実施例】
以下、本発明を図面および実施例に基づいて説明するが、本発明はその趣旨を超えない限り、以下の記載例に限定されるものではない。
【００２５】
図１は、本発明に係るエレクトロヒュ−ジョン継手の一部切り欠き側面図である。図１において、１はエレクトロヒュ−ジョン継手であり短筒状の外観を呈し、長さ方向の中央部を挟んでほぼ対称に、開口部側の内周面の架橋熱可塑性樹脂管を接合する箇所に、通電によって発熱するコイル２が埋設されている。３は、コイル２を埋設した改質ＰＥ共重合体にエチレン重合体とに樹脂組成物よりなる発熱体埋設樹脂層であって、円筒状外観を呈する。４は発熱体２を埋設した改質ＰＥ共重合体樹脂製の層の外表面に形成された架橋熱可塑性樹脂の被覆層である。５、５´はエレクトロヒュ−ジョン継手によって接合される架橋熱可塑性樹脂管である。
【００２６】
エレクトロヒュ−ジョン継手１の双方の開口部側の内周面に、架橋熱可塑性樹脂管５、５´を嵌合し、コイル２に通電すると、改質ＰＥ共重合体で構成されている発熱体埋設樹脂層３が溶融し、架橋熱可塑性樹脂管５、５´の表面を隙間なく覆い、冷却後は接合一体化され、発熱体埋設樹脂層３と架橋熱可塑性樹脂管５、５´との間に隙間や、接着不良部分ができることがなく、確実にかつ強固に融着接合されることとなる。
【００２７】
短筒状の外観を呈するエレクトロヒュ−ジョン継手１は、被覆層４が架橋熱可塑性樹脂によって構成され、この架橋熱可塑性樹脂被覆層は耐熱性、耐薬品性に優れているので、水道水用、温水用、都市ガス用の熱可塑性樹脂管５、５´などの接続継手として好適に用いることができる。
【００２８】
［実施例１〜実施例３、比較例１〜比較例３］
以下の実施例および比較例で使用した原料樹脂は、次のとおりである。
発熱体埋設樹脂層は、接着性を有する改質ポリエチレン樹脂とエチレン重合体の混合物であり、接着性を有する改質ポリエチレン樹脂は、三菱化学社製、商品名：モデック−ＡＰ、グレードＭ１０３（ＭＦＲは２．０g/１０min、密度は０．９２３）であり、エチレン重合体は、日本ポリケム社製、商品名：ノバテックＬＬ、グレードＵＦ２４０（ＭＦＲは２．１g/１０min、密度は０．９２０）であり、被覆層を形成する架橋熱可塑性樹脂は、シラン架橋性ポリエチレン（三菱化学社製、商品名：リンクロンＸ、グレ−ドＣＨ−７５０Ｔ、ＭＦＲは２．５g/１０min、密度は０．９２５）である。改質ポリエチレン樹脂とエチレン重合体との混合比率は、表−１に示した。
【００２９】
上記の図面で説明したような構成で、パイプ呼称１０Ａのエレクトロヒュ−ジョン継手を射出成形法によって製造した。発熱体埋設層３に埋設したコイル２は、太さ０．３mmのニッケル線製、ピッチは３mmで、発熱体埋設層３の肉厚の中心部に埋設した。発熱体埋設層３の内径は１３．１mmφ、外径は１５．７mmφで、円筒体のコイル部の長さは１３mmであり、被覆層４の厚さは３mmとした。
【００３０】
このエレクトロヒュ−ジョン継手の双方の開口部に、架橋ポリエチレン管（三菱化学産資社製、商品名エクセルパイプ、呼称ＸＬＦＨ−１０）を嵌合し、コイル２に１５Ｖ平均の電圧を３４秒間通電した。接合してから２４時間経過した後、かかる継手をから竹割りに巾１０mmで切断し、ピ−ル試験（ＩＳＯ１３９５４）を行った（ｎ＝８）。ピ−ル試験での剥離率（％）を表−１に示す。
【００３１】
【表１】

Figure 0004772174
【００３２】
表−１より、次のことが明らかである。
(1)発熱体を埋設した樹脂層が、接着性を有する改質ポリエチレン共重合体樹脂にエチレン重合体を１０〜９０重量％配合した樹脂組成物より構成されていると、ピ−ル試験での剥離率（％）が２０％未満と低く、発熱体埋設層３と架橋ポリエチレン管５の界面は破壊し難くく、優れた接合強度を発揮している（実施例１〜実施例３参照）。
(2)これに対して、発熱体を埋設した樹脂層がエチレン重合体のみで構成されていると、ピ−ル試験での剥離率（％）が約７０％と高く、破壊し易い（比較例３参照）。
(3)また、発熱体を埋設した樹脂層のエチレン重合体の含有量が１０〜９０重量％の範囲外であると、比較例３のものに比べるとピ−ル試験での剥離率（％）は若干低く、接合強度が優れているとは言えない。
【００３３】
【発明の効果】
本発明は、以上詳細に説明した通りであり、以下のような特別に有利な効果を奏し、その産業上の利用価値は極めて大である。
１．本発明に係るエレクトロヒュージョン継手は、発熱体が接着性を有する改質ポリエチレン共重合体樹脂（改質ＰＥ樹脂）に埋設されているので、発熱体に通電することによって改質ＰＥ樹脂が容易に溶融し、この部分と接合される樹脂管が溶融し難くい架橋熱可塑性樹脂管であっても、接着性を有する発熱体埋設樹脂は優れた接着強度を発揮し、接合部分で漏れがなく、確実な接合が可能である。
２．本発明に係るエレクトロヒュージョン継手は、外殻が架橋熱可塑性樹脂より構成され、架橋熱可塑性樹脂管を接合することができるので、接合部分は耐熱性、耐久性、耐薬品性の優れたものとすることができる。
【図面の簡単な説明】
【図１】 本発明に係るエレクトロヒュ−ジョン継手の一部切り欠き側面図である。
【符号の説明】
１：エレクトロヒュ−ジョン継手
２：通電によって発熱する発熱体（コイル）
３：改質ポリオレフィン共重合体樹脂性の発熱体埋設樹脂層
４：架橋熱可塑性樹脂の被覆層（外殻）
５、５´：架橋熱可塑性樹脂管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrofusion joint. More specifically, the present invention relates to an electrofusion joint for joining a cross-linked thermoplastic resin pipe through which a fluid such as city gas, tap water, or a heating medium for floor heating is passed.
[0002]
[Prior art]
Conventionally, as a joint for joining a thermoplastic resin pipe through which a fluid such as city gas, tap water, or a heating medium for floor heating passes, a joining body is made of a thermoplastic resin in which a heating element such as a coil that generates heat when energized is embedded. Electrofusion joints are known. In this electrofusion joint, a thermoplastic resin molded product in which a heating element that generates heat when energized is embedded is inserted into an injection mold, and the thermoplastic that forms the outer shell of the joint is formed on the surface of the molded product. It is manufactured by a method in which resin is injection molded and laminated and integrated. In order to improve the heat resistance, durability, chemical resistance, etc. of thermoplastic resin pipes that allow fluids to pass through, crosslinked thermoplastic as a resin that constitutes the outer shell that is laminated and integrated with the molded product in which the heating element is embedded Resin came to be used. A crosslinkable uncrosslinked thermoplastic resin is injection-molded and laminated and integrated with a molded product in which a heating element is embedded, and then this uncrosslinked thermoplastic resin is crosslinked (for example, Japanese Patent Laid-Open No. 2-253091). No. publication).
[0003]
[Problems to be solved by the invention]
However, the resin pipes that can be joined (connected) by the above-described conventional electro-fusion joint are limited to pipes made of a thermoplastic resin whose surface is not crosslinked, and are joined to a resin pipe of a crosslinkable thermoplastic resin. Therefore, the application is excluded for the reason that leakage occurs in the part joined by this joint. This is because the crosslinked thermoplastic resin tube once crosslinked is not melted and cannot be integrally joined even if it is dissolved by the heating element.
[0004]
In view of this situation, the present inventors have completed the present invention as a result of intensive studies to provide an electro-fusion joint that eliminates the above-mentioned drawbacks. That is, the object of the present invention is as follows.
(1) To provide an electro-fusion joint that can be securely and firmly bonded even if it is a crosslinked thermoplastic resin tube and does not cause leakage of the bonded portion.
(2) To provide an electro-fusion joint capable of joining a crosslinked thermoplastic resin tube having excellent heat resistance, durability and chemical resistance.
[0005]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention provides a short cylindrical electro-fusion joint for joining cross-linked thermoplastic resin pipes, wherein the outer shell of the electro-fusion joint is made of a cross-linked thermoplastic resin, A heating element is embedded in the resin layer at a location where the circumferential cross-linked thermoplastic resin tube is joined, and the resin layer in which the heating element is embedded has an ethylene polymer and / or a modified polyethylene copolymer resin having adhesiveness. Alternatively, the present invention provides an electro-fusion joint characterized by being composed of a resin composition containing 10 to 90% of an ethylene copolymer.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The electro-fusion joint according to the present invention has a short cylindrical appearance, and a heating element is embedded in the resin layer on the inner periphery of the place where the resin pipe to be joined is inserted and joined from the openings on both sides. (This resin layer may be referred to as a “heating element embedded resin layer”). The heating element is a coil that generates heat when energized.
[0007]
In the electrofusion joint according to the present invention, the heating element-embedded resin layer is formed of a modified polyethylene copolymer resin having adhesiveness (hereinafter, also referred to as “modified PE resin”). In the present invention, the resin that is the base of the modified PE resin is an ethylene polymer and / or an ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer is a copolymer of ethylene as a main component and α-olefin. The α-olefin is usually an α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1 butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, 4- Methyl-1-pentene and the like may be used alone or in combination of two or more.
[0008]
Specific examples of the ethylene polymer are also called very low density polyethylene (VLDPE), linear polyethylene resin (LLDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE), and the molecular structure is linear. And the like. Specific examples of the ethylene / α-olefin copolymer include ethylene / propylene elastomer (EPR), ethylene butene-1 elastomer (EBR), propylene / butene-1 elastomer (PBR), and the like. However, it is not limited to those exemplified.
[0009]
When the density (measurement method: JIS K7112 compliant) is less than 0.88, the above-mentioned ethylene polymer and ethylene / α-olefin copolymer have a tensile strength of the modified PE resin that is insufficient. When the adhesive strength is low and exceeds 0.955, the modified PP resin in the adhesive layer is hard, so the adhesiveness is inferior. A particularly preferred range of density is 0.89 to 0.95 g / cm 3 .
[0010]
The ethylene polymer and ethylene / α-olefin copolymer preferably have an MFR (measurement method: JIS K7210 compliant) in the range of 0.05 to 50 g / 10 min. Those having an MFR outside the above range are not preferred because the melt viscosity is too low or too high and the moldability is poor. A particularly preferable range of MFR is 0.1 to 30 g / 10 min.
[0011]
In the present invention, the modified PE resin means that one or two of the above-mentioned ethylene polymer and / or ethylene / α-olefin copolymer is an unsaturated carboxylic acid and / or a derivative (monomer) thereof. The one modified by a mixture of seeds or more. Examples of the unsaturated carboxylic acid and / or its derivative used for modification include an unsaturated carboxylic acid such as acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or a derivative thereof such as an anhydride. , Amide, imide, ester and the like. Of these, unsaturated dicarboxylic acids or their anhydrides are preferred, and maleic acid or its anhydride is particularly preferred.
[0012]
In order to modify the ethylene polymer and / or ethylene / α-olefin copolymer, various conventionally known methods can be used. For example, (1) an olefin copolymer (including one or more mixtures) and the unsaturated carboxylic acid and / or derivative (monomer) are mixed in advance, and the mixture is melted with an extruder. A method of graft copolymerization, (2) an olefin copolymer (including one or more mixtures) is dissolved in a solvent, and the above unsaturated carboxylic acid and / or derivative thereof is added to the solution for graft copolymerization. Method, etc.
[0013]
In order to efficiently graft copolymerize the unsaturated carboxylic acid and / or its derivative, regardless of the method (1) or (2) above, a radical generator is used as a polymerization initiator. Is preferred. As the radical generator that can be used, an organic peroxide is generally used. Specifically, 2,5-dimethylhexane-2,5 dihydroperoxide, 2,5-dimethyl-2,5 di (tert- Butyl peroxy) hexyne-3, di-tert-butyl peroxide, tert-butyl-cumyl peroxide, 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane, di-cumyl peroxide, Examples thereof include tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxyisopropyl carbonate, benzoyl peroxide, and m-toluoyl peroxide.
[0014]
Among these, 2,5-dimethylhexane-2,5 dihydroperoxide, 2,5-dimethyl-2,5 di (tert-butylperoxy) hexyne-3, di-tert-butylperoxide, di- Cumyl peroxide, benzoyl peroxide, m-toluoyl peroxide and the like are particularly preferable.
[0015]
The reaction temperature during graft copolymerization is the type of ethylene polymer and / or ethylene / α-olefin copolymer, the type of unsaturated carboxylic acid and / or its derivative, the presence or absence and type of radical generator, Varies depending on the amount used, but is usually selected in the temperature range of 80 to 300 ° C. The general use amount of the radical generator is usually selected in the range of 0.001 to 8 parts by weight with respect to 100 parts by weight of the olefin copolymer.
[0016]
In the modified PE resin obtained by modification by the above method, an unreacted unsaturated carboxylic acid and / or its derivative may remain depending on the modification conditions, so that it remains as much as possible from the viewpoint of adhesiveness. It is preferable not to do so. Therefore, various removal methods, for example, post-treatment such as extraction with a poor solvent such as acetone, degassing of an unreacted compound (monomer) by heat drying treatment, and the like can be applied.
[0017]
The modified PE resin modified by the above method preferably has a graft amount (measurement method: by infrared spectrophotometer) in the range of 0.01 to 10% by weight. If the graft amount is less than 0.01% by weight, the adhesion to the metal is inferior, and if it exceeds 10% by weight, not only the cross-linking is caused at the time of graft copolymerization, but the moldability is inferior. And since adhesiveness also falls, it is not preferable. A particularly preferable range of the graft amount is 0.1 to 5% by weight.
[0018]
In order to obtain a modified PE resin composition having adhesiveness, an ethylene polymer and / or an ethylene copolymer is blended in an amount of 10 to 90% by weight in the modified PE resin. Examples of the ethylene polymer include very low density polyethylene (VLDPE), linear polyethylene resin (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and mixtures thereof. Examples of the ethylene copolymer include ethylene / propylene elastomer (EPR), ethylene butene-1 elastomer (EBR), propylene / butene-1 elastomer (PBR), and the like. It is not limited to.
[0019]
When the density (measurement method: JIS K7112 compliant) is less than 0.88, the above-mentioned ethylene polymer and ethylene / α-olefin copolymer have a tensile strength of the modified PE resin that is insufficient. When the adhesive strength is low and exceeds 0.955, the modified PP resin in the adhesive layer is hard, so the adhesiveness is inferior. A particularly preferred range of density is 0.89 to 0.95 g / cm 3 .
[0020]
When the density (measurement method: JIS K7112 compliant) is less than 0.88, the above-mentioned ethylene polymer and ethylene / α-olefin copolymer have a tensile strength of the modified PE resin that is insufficient. When the adhesive strength is low and exceeds 0.955, the modified PP resin in the adhesive layer is hard, so the adhesiveness is inferior. A particularly preferred range of density is 0.89 to 0.95 g / cm 3 .
[0021]
In order to obtain a modified PE resin composition having adhesiveness, 10 to 90% by weight of an ethylene polymer and / or an ethylene copolymer is blended with the modified PE resin. When the blending amount is less than 10% by weight, the peeling strength is not sufficient, and when the blending amount exceeds 90% by weight, the peeling strength is remarkably lowered.
[0022]
In addition to the above components, the modified PE resin composition having adhesiveness includes a heat stabilizer, a weather stabilizer, an anti-blocking agent, a slip agent, an antistatic agent, a neutralizer for a catalyst residue, a pigment, a dye, Various resin additives such as inorganic and / or organic fillers can be blended within a range not impairing the object of the present invention. In order to blend the above-mentioned components and various resin additives into the modified PE resin composition having adhesiveness, for example, mixing with a tumbler blender, V blender, ribbon blender, Henschel mixer, etc., and mixing Thereafter, it can be performed by a conventionally known method of melt-kneading with a single screw extruder, twin screw extruder, Banbury mixer, kneader or the like, and granulating or pulverizing.
[0023]
The electrofusion joint according to the present invention is a resin composition comprising a modified polyethylene copolymer resin (modified PE resin) having a heat-generating body having adhesiveness, and an ethylene polymer and / or an ethylene copolymer. Because it is embedded, the modified PE resin that constitutes the heating element embedded resin layer can be easily melted by energizing the heating element, and the molten heating element embedded resin is the surface of the crosslinked thermoplastic resin tube. Without cooling, and after cooling, they are joined and integrated to fully exhibit their respective characteristics. Even if the resin pipe to be joined by the electro-fusion joint is a cross-linked thermoplastic resin pipe that is difficult to melt, it exhibits excellent joint strength due to its excellent synergistic adhesive strength, and there is no leakage of the joint part and reliable joining is possible. Is possible.
[0024]
【Example】
Hereinafter, the present invention will be described based on the drawings and examples, but the present invention is not limited to the following description examples unless it exceeds the gist thereof.
[0025]
FIG. 1 is a partially cutaway side view of an electrofusion joint according to the present invention. In FIG. 1, reference numeral 1 denotes an electrofusion joint, which has a short cylindrical appearance, and joins a cross-linked thermoplastic resin tube on the inner peripheral surface on the opening side substantially symmetrically with respect to the central portion in the length direction. A coil 2 that generates heat when energized is embedded in the place. Reference numeral 3 denotes a heating element-embedded resin layer made of a resin composition and a modified PE copolymer having the coil 2 embedded therein and an ethylene polymer, and has a cylindrical appearance. Reference numeral 4 denotes a coating layer of a crosslinked thermoplastic resin formed on the outer surface of a layer made of a modified PE copolymer resin in which the heating element 2 is embedded. Reference numerals 5 and 5 'denote cross-linked thermoplastic resin pipes joined by an electro-fusion joint.
[0026]
When the crosslinked thermoplastic resin pipes 5 and 5 'are fitted to the inner peripheral surfaces of the opening portions of the electro-fusion joint 1 and the coil 2 is energized, the heat generated by the modified PE copolymer is generated. The body-embedded resin layer 3 is melted, covers the surface of the crosslinked thermoplastic resin pipes 5 and 5 'without any gaps, and is joined and integrated after cooling, and the heating element-embedded resin layer 3 and the crosslinked thermoplastic resin tubes 5 and 5' No gaps or poorly bonded parts are formed between the two, and the fusion bonding is surely and firmly performed.
[0027]
In the electrofusion joint 1 having a short cylindrical appearance, the coating layer 4 is made of a crosslinked thermoplastic resin, and this crosslinked thermoplastic resin coating layer is excellent in heat resistance and chemical resistance. It can be suitably used as a connection joint for thermoplastic resin pipes 5 and 5 'for hot water and city gas.
[0028]
[Example 1 to Example 3, Comparative Example 1 to Comparative Example 3]
The raw material resins used in the following examples and comparative examples are as follows.
The heating element-embedded resin layer is a mixture of an adhesive modified polyethylene resin and an ethylene polymer. The adhesive modified polyethylene resin is manufactured by Mitsubishi Chemical Corporation, trade name: MODEC-AP, grade M103 (MFR). Is 2.0 g / 10 min, density is 0.923), and ethylene polymer is manufactured by Nippon Polychem Co., Ltd., trade name: Novatec LL, grade UF240 (MFR is 2.1 g / 10 min, density is 0.920). Yes, the crosslinked thermoplastic resin forming the coating layer is a silane crosslinkable polyethylene (Mitsubishi Chemical Co., Ltd., trade name: Linkron X, Grade CH-750T, MFR 2.5 g / 10 min, density 0.925) ). The mixing ratio of the modified polyethylene resin and the ethylene polymer is shown in Table-1.
[0029]
With the configuration as described in the above drawings, an electrofusion joint having a pipe designation of 10A was manufactured by an injection molding method. The coil 2 embedded in the heating element embedded layer 3 was made of nickel wire having a thickness of 0.3 mm, the pitch was 3 mm, and embedded in the central part of the thickness of the heating element embedded layer 3. The inner diameter of the heating element embedded layer 3 was 13.1 mmφ, the outer diameter was 15.7 mmφ, the length of the coil portion of the cylindrical body was 13 mm, and the thickness of the coating layer 4 was 3 mm.
[0030]
A cross-linked polyethylene pipe (Mitsubishi Chemical Industrial Co., Ltd., trade name: Excel pipe, XLFH-10) is fitted into both openings of this electro-fusion joint, and a 15 V average voltage is applied to coil 2 for 34 seconds. did. After 24 hours from joining, the joint was cut into bamboo pieces with a width of 10 mm, and a peel test (ISO13954) was performed (n = 8). Table 1 shows the peel rate (%) in the peel test.
[0031]
[Table 1]
Figure 0004772174
[0032]
From Table 1, the following is clear.
(1) When the resin layer in which the heating element is embedded is composed of a resin composition in which 10 to 90% by weight of an ethylene polymer is blended with a modified polyethylene copolymer resin having adhesiveness, The peel rate (%) is as low as less than 20%, the interface between the heating element buried layer 3 and the crosslinked polyethylene pipe 5 is not easily broken, and exhibits excellent bonding strength (see Examples 1 to 3). .
(2) On the other hand, if the resin layer in which the heating element is embedded is composed only of ethylene polymer, the peel rate (%) in the peel test is as high as about 70%, and it is easy to break (comparison) See Example 3).
(3) If the content of the ethylene polymer in the resin layer in which the heating element is embedded is outside the range of 10 to 90% by weight, the peel rate (% ) Is slightly low and it cannot be said that the bonding strength is excellent.
[0033]
【The invention's effect】
The present invention is as described in detail above, and has the following particularly advantageous effects, and its industrial utility value is extremely great.
1. In the electrofusion joint according to the present invention, since the heating element is embedded in a modified polyethylene copolymer resin (modified PE resin) having adhesiveness, the modified PE resin can be easily formed by energizing the heating element. Even if the resin pipe that is melted and joined to this part is hard to melt, the heat-dissipating element embedded resin has excellent adhesive strength, and there is no leakage at the joined part. Reliable joining is possible.
2. In the electrofusion joint according to the present invention, the outer shell is composed of a cross-linked thermoplastic resin , and a cross-linked thermoplastic resin pipe can be joined. Therefore, the joint portion has excellent heat resistance, durability, and chemical resistance. can do.
[Brief description of the drawings]
FIG. 1 is a partially cutaway side view of an electrofusion joint according to the present invention.
[Explanation of symbols]
1: Electro-fusion joint 2: Heating element (coil) that generates heat when energized
3: Modified polyolefin copolymer resinous heating element embedded resin layer 4: Cross-linked thermoplastic resin coating layer (outer shell)
5, 5 ': Crosslinked thermoplastic resin tube

Claims (1)

架橋熱可塑性樹脂管を接合する短筒状のエレクトロヒュ−ジョン継手において、エレクトロヒュ−ジョン継手の外殻は架橋熱可塑性樹脂により構成され、短筒内周の架橋熱可塑性樹脂管が接合される箇所に発熱体が樹脂層に埋設されてなり、この発熱体を埋設した樹脂層が接着性を有する改質ポリエチレン共重合体樹脂にエチレン重合体および／またはエチレン共重合体を１０〜９０重量％配合した樹脂組成物により構成されていることを特徴とする、エレクトロヒュ−ジョン継手。In a short cylindrical electrofusion joint for joining crosslinked thermoplastic resin pipes, the outer shell of the electrofusion joint is made of a crosslinked thermoplastic resin, and the crosslinked thermoplastic resin pipe on the inner periphery of the short cylinder is joined. A heating element is embedded in a resin layer at a location, and the resin layer in which the heating element is embedded has 10 to 90% by weight of an ethylene polymer and / or an ethylene copolymer in a modified polyethylene copolymer resin having adhesiveness. An electro-fusion joint comprising a blended resin composition.
JP25974999A 1999-09-14 1999-09-14 Electro-fusion joint Expired - Lifetime JP4772174B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016033391A (en) * 2014-07-31 2016-03-10 三菱樹脂インフラテック株式会社 Connection method of resin pipe and resin joint, and piping unit

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Publication number Priority date Publication date Assignee Title
JP2007040385A (en) * 2005-08-02 2007-02-15 Mitsubishi Kagaku Sanshi Corp Electrofusion joint for connecting blade hose
JP5173571B2 (en) * 2008-05-09 2013-04-03 大阪瓦斯株式会社 Electrofusion fitting

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016033391A (en) * 2014-07-31 2016-03-10 三菱樹脂インフラテック株式会社 Connection method of resin pipe and resin joint, and piping unit

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