JP3278913B2 - Method for producing heat-recoverable article - Google Patents
Method for producing heat-recoverable articleInfo
- Publication number
- JP3278913B2 JP3278913B2 JP20853092A JP20853092A JP3278913B2 JP 3278913 B2 JP3278913 B2 JP 3278913B2 JP 20853092 A JP20853092 A JP 20853092A JP 20853092 A JP20853092 A JP 20853092A JP 3278913 B2 JP3278913 B2 JP 3278913B2
- Authority
- JP
- Japan
- Prior art keywords
- molded product
- cylindrical molded
- heat
- article
- cylindrical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電線、ケーブル、パイ
プなどの接続部や端末部をラップラウンド被覆する熱回
復性（熱収縮性）物品の新規な製造方法に関するもので
ある。The present invention relates to a wire, cable, heat-recoverable wrap round covers the connection portion and the terminal portion of such as a pipe (heat shrinkable) is relates to a novel method of manufacturing an article.
【０００２】[0002]
【従来の技術】従来、電線、ケーブル、パイプなどの接
続部又は端末部の防水や絶縁被覆の方法としては、円筒
状の絶縁スリーブを被覆する方法、或いは粘着テープを
接続部にラップする方法や割型の熱回復性物品を被覆、
収縮させる方法が用いられている。2. Description of the Related Art Conventionally, as a method for waterproofing or insulating coating of a connection portion or an end portion of an electric wire, a cable, a pipe or the like, a cylindrical method is used.
Method for coating Jo insulation sleeve, or adhesive tape connection portion covering the heat-recoverable article of the methods and split to wrap a,
A method of contracting is used.
【０００３】割型の熱回復性物品に関しては、特開昭３
９−７６４２号公報、特開昭４７−４４３７号公報、特
開昭４８−６８６７０号公報、特開昭４９−１７４７６
号公報、特開昭５２−１１９６８６号公報などに記載さ
れたものが知られている。しかしながら、これら割型の
熱回復性物品は、いずれも架橋後に延伸した高分子材料
からなるシートを利用したものであり、被着体に巻き付
けた後、図２、３に示されるように連結部品や接着性テ
ープを貼り付けたりして、シートの両端を固定した後、
加熱して使用するものである。[0003] Regarding split-type heat-recoverable articles, Japanese Patent Application Laid-Open
JP-A-9-7742, JP-A-47-4437, JP-A-48-68670, JP-A-49-17476
And Japanese Patent Application Laid-Open No. 52-119686 are known. However, each of these split-type heat-recoverable articles uses a sheet made of a polymer material stretched after crosslinking, and is wound around an adherend and then connected as shown in FIGS. After fixing both ends of the sheet by pasting or adhesive tape,
It is used after heating.
【０００４】上記のうち、図３に示される連結部品を使
用する熱回復性物品は、熱収縮後も連結部品が外部に突
き出した状態となるため美観を損ね、小さな口径のパイ
プや電線には応用しづらい欠点がある。また、図２に示
される粘着テープ（接着テープ）を使用するものでは、
テープに収縮性がないために、加熱収縮中にテープが外
れたり、皺になったりする欠点があり、作業性や美観の
点で必ずしも満足のいくものではなかった。さらには、
高分子材料を断面が螺旋状になるように押出などの成形
方法により異形成形し、該物品を架橋し、この異形成形
品を平坦な構造あるいは断面が「Ｊ」字型や「Ｃ」字型
になるようにヒートセットした熱回復性物品が知られて
いる（特表昭６３−５０３５３０号公報、特表平３−５
０３６１８号公報など）。[0004] Among the above, the heat-recoverable article using the connecting part shown in FIG. 3 impairs aesthetic appearance because the connecting part protrudes to the outside even after the heat shrinkage. There are drawbacks that are difficult to apply. In the case of using the adhesive tape (adhesive tape) shown in FIG. 2,
Since the tape does not have shrinkage, it has a drawback that the tape comes off or wrinkles during heat shrinkage, and it is not always satisfactory in terms of workability and aesthetic appearance. Moreover,
The polymer material is deformed by a forming method such as extrusion so that the cross section becomes helical, the article is crosslinked, and the deformed product is formed into a flat structure or a cross section having a "J" or "C" shape. A heat-recoverable article which has been heat-set so as to obtain a known product is disclosed in JP-T-63-503530, JP-T-Hei 3-5-5.
No. 03618).
【０００５】[0005]
【発明が解決しようとする課題】この熱回復性物品に好
ましく使用される高分子材料は、その熱回復性作用の発
現機構やヒートセット性の観点から、実質的にには中密
度ポリエチレンやポリフッ化ビニリデンのような結晶性
の高い高分子材料に限られてしまう欠点があり、被覆後
に柔軟性の要求される用途では、必ずしも満足の行くも
のではなかった。また、延伸倍率が異なるシート状の高
分子材料を二枚積層すれば、加熱によって、例えば、カ
ール状に熱回復する熱回復性物品が得られることも考え
られる。ところが、延伸倍率が異なるシート状の高分子
材料を二枚貼合わせるには、二枚のシートの両端を固定
しながら熱融着させ、冷却固定する必要があり、この工
程が冷熱サイクルを伴うためバッチ処理とならざるを得
ず、効率良く生産することができない欠点があった。The polymer material preferably used for the heat-recoverable article is substantially a medium-density polyethylene or a poly-fluoropolymer, from the viewpoint of the mechanism of exhibiting the heat-recovery action and the heat setting property. There is a drawback that it is limited to a polymer material having high crystallinity such as vinylidene fluoride, and it is not always satisfactory in applications requiring flexibility after coating. In addition, when two sheet-like polymer materials having different stretching ratios are laminated, a heat-recoverable article that recovers heat in a curl shape, for example, by heating may be obtained. However, in order to attach two sheet-like polymer materials having different draw ratios, it is necessary to heat-bond the two sheets while fixing both ends of the two sheets and fix them by cooling, and this process involves a cooling / heating cycle. There was a drawback that batch processing was inevitable and production could not be performed efficiently.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を種
々検討した結果、 高分子材料からなる円筒状成形物
の架橋体（Ａ）の外周に、高分子材料からなる樹脂組成
物の被覆層（Ｂ）を設けた後、加熱して径方向に膨張せ
しめて冷却固定し、更に外周被覆層（Ｂ）を架橋して円
筒状熱回復性物品を得、該物品の長手方向に任意の１ケ
所を切断し割型とする、熱回復性物品の製造方法であ
る。 高分子材料からなる円筒状成形物の架橋体
（Ａ）を加熱して径方向に膨張せしめながら、該円筒状
成形物の外周に、高分子材料からなる樹脂組成物の被覆
層（Ｂ）を設けた後、外周被覆層（Ｂ）を架橋して円筒
状熱回復性物品を得、該物品の長手方向に任意の１ケ所
を切断し割型とする熱回復性物品の製造方法である。こ
れらの方法により製造された熱回復性物品は、被着体の
周囲に「の」字型等にラップラウンド被覆するのに好適
であり、しかも簡便に製造できることを見出し、本発明
を完成するに至った。更に、本発明によると、上記の方
法で得られた熱回復性物の内面に粘着剤層もしくは接着
剤層（Ｃ）を形成することを特徴とするものである。According to the present invention, as a result of various studies on the above-mentioned problems, the outer periphery of a crosslinked product (A) of a cylindrical molded product made of a polymer material is coated with a resin composition made of a polymer material. after providing the layer (B), cooled and fixed inflated heated to radially form a cylindrical heat-recoverable article by crosslinking further outer peripheral coating layer (B), longitudinally any article This is a method for producing a heat-recoverable article, in which one location is cut to form a split mold . While inflated by thermal crosslinking of the cylindrical molded product made of a polymeric material (A) in the radial direction, the outer periphery of the cylindrical molded article, the coating layer of the resin composition made of a polymer material (B) after providing, by cross-linking the outer peripheral coating layer (B) cylindrical
This is a method for producing a heat-recoverable article in which a shape-like heat-recoverable article is obtained, and an arbitrary point is cut in the longitudinal direction of the article to form a split mold . This
Heat-recoverable articles manufactured by these methods are suitable for wrap-around coating in the shape of an "", etc. around the adherend.
, And the yet found that can be easily produced, it has led to the completion of the present invention. Further, according to the present invention , a pressure-sensitive adhesive layer or an adhesive layer (C) is formed on the inner surface of the heat-recoverable material obtained by the above method.
【０００７】即ち、本発明は； 高分子材料からなる
円筒状成形物の架橋体（Ａ）の外周に、高分子材料から
なる樹脂組成物の被覆層（Ｂ）を設けた後、加熱して径
方向に膨張せしめて冷却固定し、更に外周被覆層（Ｂ）
を架橋して円筒状熱回復性物品を得、該物品の長手方向
に任意の１ケ所を切断し割型とする、熱回復性物品の製
造方法を提供する。また、 高分子材料からなる円筒
状成形物の架橋体（Ａ）を加熱して径方向に膨張せしめ
ながら、該円筒状成形物の外周に高分子材料からなる樹
脂組成物の被覆層（Ｂ）を設けた後、外周被覆層（Ｂ）
を架橋して円筒状熱回復性物品を得、該物品の長手方向
に任意の１ケ所を切断し割型とする、熱回復性物品の製
造方法を提供する。また、 高分子材料からなる円筒
状成形物の架橋体（Ａ）の肉厚と外周被覆層（Ｂ）の肉
厚比が１／３〜３／１の範囲にあり、しかもチューブ状
成形物の架橋体（Ａ）の膨張比率が１を越え１．５以下
である点にも特徴を有する。That is, the present invention comprises: a polymer material
After providing a coating layer (B) of a resin composition composed of a polymer material on the outer periphery of the crosslinked body (A) of the cylindrical molded product, the resin composition is heated to expand in the radial direction, fixed by cooling, and further fixed to the outer coating layer. (B)
To obtain a cylindrical heat-recoverable article, and the longitudinal direction of the article is obtained.
The present invention provides a method for producing a heat-recoverable article, which comprises cutting an arbitrary portion into a split mold . Also, a cylinder made of a polymer material
While inflated radially crosslinked product of Jo molded product (A) is heated, after providing the outer periphery of the cylindrical molded product coating layer of a resin composition made of a polymer material (B), the outer peripheral coating layer (B)
To obtain a cylindrical heat-recoverable article, and the longitudinal direction of the article is obtained.
The present invention provides a method for producing a heat-recoverable article, which comprises cutting an arbitrary portion into a split mold . Also, a cylinder made of a polymer material
The ratio of the thickness of the crosslinked body (A) of the tubular molded product to the thickness of the outer peripheral coating layer (B) is in the range of 1/3 to 3/1, and the expansion ratio of the crosslinked product (A) of the tubular molded product. Is also more than 1 and 1.5 or less.
【０００８】以下、図面を用いて本発明をさらに詳細に
説明する。図１は、本発明に従う熱回復性物品を製造す
る手段を示す模式図である。即ち、 高分子材料から
なる円筒状成形物を加速電子線のような電離性放射線を
照射する方法により架橋して架橋体（Ａ）となし、該円
筒状成形物の架橋体（Ａ）の外周に高分子材料からなる
樹脂組成物層（Ｂ）を溶融押出などの既存の方法で被覆
する。この二重構造の円筒状成形物を加熱条件下で、内
部に圧縮空気を送り込むなどの方法により内圧を高め、
径方向に膨張して冷却固定する。次に、この円筒状成形
物の被覆層（Ｂ）を電離性放射線を照射する等の方法に
より架橋した後、長手方向に任意の１ケ所を切断し割型
とすることにより、熱回復性物品を得る。Hereinafter, the present invention will be described in more detail with reference to the drawings. FIG. 1 is a schematic diagram showing a means for producing a heat-recoverable article according to the present invention. That is, a cylindrical molded product made of a polymer material is crosslinked by a method of irradiating ionizing radiation such as an accelerated electron beam to form a crosslinked product (A), and the outer periphery of the crosslinked product (A) of the cylindrical molded product is formed. Is coated with a resin composition layer (B) made of a polymer material by an existing method such as melt extrusion. The internal pressure is increased by a method such as sending compressed air inside the cylindrical molded product of this double structure under heating conditions,
It expands in the radial direction and is fixed by cooling. Next, after cross-linking the coating layer (B) of this cylindrical molded product by a method such as irradiating with ionizing radiation, one arbitrary portion is cut in the longitudinal direction and a split mold is formed.
By doing so , a heat-recoverable article is obtained.
【０００９】 また、予め架橋された円筒状成形物
（Ａ）の外周に、高分子材料からなる樹脂組成物の被覆
層（Ｂ）を被覆してから、径方向に膨張するのではな
く、樹脂組成物の被覆層（Ｂ）の被覆と膨張とを同時に
行う。即ち、円筒状成形物（Ａ）の内部に圧縮空気を送
り込むなどの方法により内圧を高め、径方向に膨張させ
ながら、（Ａ）の外周に被覆層（Ｂ）を形成する方法で
も、熱回復性物品を得ることができる。例えば、溶融押
出機のパスラインに架橋した円筒状成形物（Ａ）を通
し、円筒状成形物（Ａ）の内部に圧縮空気を送り込むな
どの方法により内圧を高め、径方向に膨張させながら、
（Ａ）の外周に被覆層（Ｂ）を形成する方法などを挙げ
ることができる。この熱回復性物品は、さらに、半割り
状に切断後、金型等を使用して断面が「Ｊ」字型や
「Ｕ」字型、或いは「Ｃ」字型になるように加工してお
くと、被着体への装着作業とその後の加熱によるラップ
ラウンド被覆作業をより簡便に行うことができる。In addition, the outer periphery of the preliminarily cross-linked cylindrical molded product (A) is coated with a coating layer (B) of a resin composition made of a polymer material, and the resin is not expanded in the radial direction. The coating and the expansion of the coating layer (B) of the composition are performed simultaneously. That is , heat recovery is also possible by forming the coating layer (B) on the outer periphery of (A) while increasing the internal pressure by, for example, sending compressed air into the inside of the cylindrical molded product (A) so as to expand in the radial direction. Product can be obtained. For example, the internal pressure is increased by, for example, passing a cross-linked cylindrical molded product (A) through a pass line of a melt extruder and sending compressed air into the cylindrical molded product (A), thereby expanding radially,
A method of forming a coating layer (B) on the outer periphery of (A) can be used. This heat-recoverable article is further cut in half and then processed using a mold or the like so that the cross section becomes “J” -shaped, “U” -shaped, or “C” -shaped. By doing so, the work of attaching to the adherend and the subsequent wrap round covering work by heating can be performed more easily.
【００１０】 円筒状成形物（Ａ）の肉厚と外周層
（Ｂ）の肉厚比は、１／３〜３／１の範囲に設定し、膨
張の比率は円筒状成形物（Ａ）の内径比で１を越え１．
５以下に設定することが被着体へのラップラウンド型の
熱回復の点で好ましい結果が得られた。特に、膨張の比
率が１．５を越えると、円筒状成形物の長手方向の切断
部は自己巻きしてうまくラップラウンド被覆しない問題
があった。The thickness ratio of the thickness of the cylindrical molded product (A) to the thickness of the outer peripheral layer (B) is set in the range of 1/3 to 3/1, and the expansion ratio is the same as that of the cylindrical molded product (A). The inner diameter ratio exceeds 1: 1.
Setting it to 5 or less provided a favorable result in terms of wrap round heat recovery to the adherend. In particular, when the expansion ratio exceeds 1.5, there is a problem in that the cut portion in the longitudinal direction of the cylindrical molded product is self-wound and does not cover well the wrap round.
【００１１】これら図１に示される熱回復性物品の形状
は、円筒状に限定されず、用途などによって使い分けら
れる。本発明で内層を構成する円筒状成形物（Ａ）やそ
の外周の被覆層（Ｂ）に用いる高分子材料の架橋は、加
速電子線、γ線など電離性放射線の照射が好ましく、或
いは有機過酸化物等を配合したものを加熱加硫する方法
や、シラン系架橋型樹脂を使用して水浸漬、加湿により
方法により行うことができる。円筒状成形物（Ａ）やそ
の外周の被覆層（Ｂ）に用いる高分子材料は、同種でも
異種であってもよく、特に結晶性のあまり高くない熱可
塑性エラストマーから選択されるのが好ましい。The shape of the heat-recoverable article shown in FIG. 1 is not limited to a cylindrical shape, and can be properly used depending on the application. Crosslinking of the polymer material used for the cylindrical molded article (A) constituting the inner layer and the outer peripheral coating layer (B) in the present invention is preferably carried out by irradiation with ionizing radiation such as an accelerated electron beam or γ ray, or an organic polymer. It can be carried out by a method of heating and vulcanizing a compound containing an oxide or the like, or a method of immersion in water and humidification using a silane-based cross-linkable resin. The polymer material used for the cylindrical molded product (A) or the outer peripheral coating layer (B) may be the same or different, and is particularly preferably selected from thermoplastic elastomers having not very high crystallinity.
【００１２】その高分子材料の例を挙げると、ポリエチ
レン（低密度、直鎖状低密度、超低密度など）、エチレ
ン−酢酸ビニル共重合体、エチレン−エチルアクリレー
ト共重合体、エチレン−メタクリレート系共重合体など
のオレフィン系樹脂：ポリオレフィン系熱可塑性エラス
トマー、エチレン−プロピレン系共重合体ゴム、エチレ
ン−プロピレン−共役ジエン三元共重合体ゴムなどの熱
可塑性エラストマーなど：ポリエステル系、ポリウレタ
ン系、ポリアミド系などの熱可塑性エラストマー：フッ
素ゴム、フッ素系熱可塑性エラストマーなどまたはこれ
らの混合物を使用できる。Examples of the polymer material include polyethylene (low density, linear low density, ultra low density, etc.), ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate type. Olefin-based resins such as copolymers: thermoplastic elastomers such as polyolefin-based thermoplastic elastomers, ethylene-propylene-based copolymer rubber, ethylene-propylene-conjugated diene terpolymer rubber, etc .: polyester-based, polyurethane-based, polyamide Thermoplastic elastomer such as a fluoroelastomer, a fluoroplastic thermoplastic elastomer, or a mixture thereof can be used.
【００１３】さらに、上記高分子材料に、必要に応じて
種々の添加剤、例えば、難燃剤、酸化防止剤、紫外線安
定剤、滑剤、架橋促進剤、加工助剤、充填剤、着色剤な
どを配合できる。 特に、１）電離性放射線の照射による架橋の場合、トリ
アリル（イソ）シアヌレートなどの多官能性アリル化合
物などからなる架橋促進剤を好適には予め添加するとよ
く、或いは ２）化学架橋の場合、有機過酸化物（ジクミルパーオキ
シドなど）、又はシラン系架橋型樹脂を、必要に応じて
上記架橋促進剤と共に添加して、加熱架橋又は加湿架橋
するとよい。Further, various additives such as a flame retardant, an antioxidant, an ultraviolet stabilizer, a lubricant, a crosslinking accelerator, a processing aid, a filler, a coloring agent, and the like may be added to the polymer material as required. Can be blended. In particular, 1) in the case of crosslinking by irradiation with ionizing radiation, a crosslinking accelerator comprising a polyfunctional allyl compound such as triallyl (iso) cyanurate is preferably added in advance, or 2) In the case of chemical crosslinking, A peroxide (such as dicumyl peroxide) or a silane-based cross-linkable resin may be added together with the above-mentioned cross-linking accelerator, if necessary, to perform heat cross-linking or wet cross-linking.
【００１４】本発明の場合、熱回復性物品の長さ方向を
１ケ所のみに半割り状に切断し、割型とするので、被着
体に該熱回復性物品を覆うのに都合がよい。このように
割型としたので、特に接続部に後から嵌め込み加熱収縮
する場合に、内層側が収縮し、ラセン状に接続部分を覆
うことができる。In the case of the present invention, since the longitudinal direction of the heat-recoverable article is cut in half at only one place to form a split mold, it is convenient to cover the heat-recoverable article on the adherend. . Since the split mold is used in this manner, the inner layer side shrinks, and the connection portion can be spirally covered, particularly when the connection portion is later fitted and heated and contracted.
【００１５】本発明の方法により製造された熱回復性物
品は、被着体の絶縁保護としてのみでなく、最内層に接
着剤層または粘着剤層（Ｃ）を設けることができる。こ
れにより、熱回復後のラップラウンド被覆物を固定し易
くなり、また、被着体の防水や防食機能を持たせること
ができると共に、電気絶縁上より好ましい結果が得られ
る。該接着剤としては、エチレン−酢酸ビニル共重合
体、エチレン−エチルアクリレート共重合体、エチルア
クリレート−一酸化炭素共重合体などのポリオレフィン
系ホットメルト接着剤；飽和ポリエステル系共重合体、
又はポリアミド系などのホットメルト接着剤等の１種又
は２種以上が使用できる。The heat-recoverable article manufactured by the method of the present invention can be provided with an adhesive layer or a pressure-sensitive adhesive layer (C) as an innermost layer, as well as for insulation protection of an adherend. This makes it easier to fix the wrap round covering after the heat recovery, and also allows the adherend to have a waterproof and anticorrosive function, as well as more favorable results in terms of electrical insulation. Examples of the adhesive include polyolefin-based hot melt adhesives such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethyl acrylate-carbon monoxide copolymer; saturated polyester-based copolymer,
Alternatively, one or more kinds of hot melt adhesives such as polyamides can be used.
【００１６】該粘着剤としては、例えば、天然ゴム、ブ
チルゴムなどのゴム系粘着剤：アクリル酸エステル系共
重合体のようなアクリル系粘着剤：アルキルビニルエー
ル共重合体のようなビニル系粘着剤：シリコーン系粘着
剤等の１種又は２種以上が使用できる。また、これら
に、テルペン樹脂、芳香族炭化水素樹脂等の粘着付与剤
を配合できる。該接着剤や粘着剤には、必要に応じて酸
化防止剤、滑剤、難燃剤等の各種の添加剤を配合しても
よい。該接着剤や粘着剤層（Ｃ）は、その用途により
０．２〜２．０ｍｍ程度の厚みになるように通常塗布又
は噴霧又はシート状に積層などの手段により形成され
る。該接着剤や粘着剤層の熱回復性物品への適用は、円
筒状成形物（Ａ）と被覆層（Ｂ）との一体化と同時に或
いはその後に適宜実施できる。Examples of the pressure-sensitive adhesive include: rubber-based pressure-sensitive adhesives such as natural rubber and butyl rubber; acrylic-based pressure-sensitive adhesives such as acrylate-based copolymers; and vinyl-based pressure-sensitive adhesives such as alkyl vinyl ale copolymers. : One or more silicone-based pressure-sensitive adhesives can be used. In addition, a tackifier such as a terpene resin or an aromatic hydrocarbon resin can be added to these. Various additives such as an antioxidant, a lubricant, and a flame retardant may be added to the adhesive or the pressure-sensitive adhesive as needed. The adhesive or pressure-sensitive adhesive layer (C) is usually formed by coating, spraying, or laminating in a sheet form so as to have a thickness of about 0.2 to 2.0 mm depending on the use. Application to heat-recoverable articles of the adhesive or pressure-sensitive adhesive layer, circular
It can be carried out at the same time as or after the integration of the tubular molded product (A) and the coating layer (B).
【００１７】本発明では、熱回復性物品として長尺品を
作製した後に、必要に応じて数センチ〜数十センチに切
断しても良い。本発明の方法で製造された熱回復性物品
は、従来にない電気絶縁性、防水・防食性、割型による
接続作業性に優れた熱回復性物品を提供する。In the present invention , after a long product is prepared as a heat-recoverable article, it may be cut into several centimeters to several tens of centimeters as needed. The heat-recoverable article manufactured by the method of the present invention provides a heat-recoverable article having unprecedented electrical insulation properties, waterproof / corrosion-proof properties, and excellent workability in connection with a split mold.
【００１８】[0018]
【実施例】本発明を下記の実施例により具体的に説明す
るが、これらは本発明の範囲を制限しない。 （実施例１） ＥＶＡ樹脂（酢酸ビニル含量２５重量％、ＭＩ＝３）を
使用し、溶融押出機で内径が８．４ｍｍφ、肉厚０．３
ｍｍの円筒状成形物を作製した。この円筒状成形物に加
速電圧が１ＭＶの電子線を２００ｋＧｙ照射して、架橋
させた。円筒状成形物のキシレン抽出のゲル分率は５８
％であった。溶融押出機を使用して、この円筒状成形物
の外周にＥＥＡ樹脂（エチルアクリレート含量１９重量
％、ＭＩ＝５）を肉厚０．５ｍｍで押出被覆し、外径１
０．０ｍｍφの二層構造のチューブ状成形物を作製し
た。The present invention will be illustrated by the following examples, which do not limit the scope of the present invention. (Example 1) Using an EVA resin (vinyl acetate content 25% by weight, MI = 3), an inner diameter of 8.4 mmφ and a wall thickness of 0.3 by a melt extruder.
It was produced mm cylindrical molded product. The cylindrical molded product was irradiated with an electron beam having an acceleration voltage of 1 MV at 200 kGy to crosslink. The gel fraction of xylene extraction of the cylindrical molded product was 58.
%Met. An EEA resin (ethyl acrylate content 19% by weight, MI = 5) was extrusion-coated to a thickness of 0.5 mm on the outer periphery of the cylindrical molded product using a melt extruder.
A two-layer tubular molded product having a diameter of 0.0 mm was produced.
【００１９】この二層構造の円筒状成形物を１４０℃の
恒温槽内に投入して３分間予熱後、圧縮空気を用いて円
筒状成形物に内圧をかけ、外径が１１．５ｍｍφになる
ように膨張させ、冷却して膨張径を保持させた。この膨
張した二層構造の円筒状成形物に加速電圧１ＭＶの電子
線を１００ｋＧｙ照射して架橋させた。円筒状成形物外
層のキシレン抽出のゲル分率は４５％であった。この円
筒状成形物を長さ５０ｍｍに切断し、長手方向に平行な
任意の一辺を切断して半割状の円筒状成形物を得た。こ
の半割状の円筒状成形物を金型を用いて、断面が「Ｊ」
字型になるように１３０℃で熱成型した。この断面が
「Ｊ」字型の熱回復性成形品を外径６．０ｍｍφのアル
ミニウムパイプに被せ、１４０℃の恒温槽内に水平に設
置して３分間放置した。その結果、半割状の円筒状成形
物がアルミニウムパイプの周囲に「の」の字型にラップ
ラウンド被覆することが分かった。The cylindrical molded product having the two-layer structure is placed in a thermostat at 140 ° C., preheated for 3 minutes, and then circularly compressed air.
An internal pressure was applied to the cylindrical molded product to expand the outer diameter to 11.5 mmφ, and then cooled to maintain the expanded diameter. The expanded cylindrical molded product having a two-layer structure was irradiated with 100 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. The gel fraction of xylene extraction of the outer layer of the cylindrical molded product was 45%. This circle
The cylindrical molded product was cut into a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . Using a mold, this half-shaped cylindrical molded product has a cross section of “J”.
It was thermoformed at 130 ° C. to form a letter shape. This heat-recoverable molded product having a “J” cross section was placed on an aluminum pipe having an outer diameter of 6.0 mmφ, placed horizontally in a thermostat at 140 ° C., and left for 3 minutes. As a result, half- cylindrical cylindrical molding
Things it was found that the wraparound cover to shape the "no" around the aluminum pipe.
【００２０】（実施例２） ＥＶＡ樹脂（酢酸ビニル含量１０重量％、ＭＩ＝２）を
使用し、溶融押出機で内径が８．０ｍｍφ、肉厚０．５
ｍｍの円筒状成形物を作製した。この円筒状成形物に加
速電圧が１ＭＶの電子線を１５０ｋＧｙ照射して架橋さ
せた。円筒状成形物のキシレン抽出のゲル分率は５３％
であった。溶融押出機を使用して、この円筒状成形物の
外周にシラン架橋型ＥＶＡ樹脂（比重＝０．９３５、Ｍ
Ｉ＝０．３：三菱油化（株）製、架橋剤マスターバッチ
５％混合）を肉厚０．２５ｍｍで押出被覆し、外径９．
５ｍｍφの二層構造の円筒状成形物を作製した。Example 2 Using an EVA resin (vinyl acetate content: 10% by weight, MI = 2), the inner diameter was 8.0 mmφ and the wall thickness was 0.5 by a melt extruder.
It was produced mm cylindrical molded product. The cylindrical molded product was irradiated with an electron beam having an acceleration voltage of 1 MV at 150 kGy to crosslink. Gel fraction of xylene extraction of cylindrical molded product is 53%
Met. Using a melt extruder, the silane cross-linked EVA resin on the outer periphery of the cylindrical molded product (specific gravity = 0.935, M
I = 0.3: 5% of a cross-linking agent master batch manufactured by Mitsubishi Yuka Co., Ltd.) was extrusion-coated with a wall thickness of 0.25 mm, and the outer diameter was 9.
A cylindrical molded product having a two-layer structure of 5 mmφ was produced.
【００２１】この二層構造の円筒状成形物を１５０℃の
恒温槽内に投入して３分間予熱後、圧縮空気を用いて円
筒状成形物に内圧をかけ、外径が１２．５ｍｍφになる
ように膨張させ、冷却して膨張径を保持させた。この膨
張した二層構造の円筒状成形物を６０℃の水に８時間浸
漬して、円筒状成形物外層を架橋させた。円筒状成形物
外層のキシレン抽出のゲル分率は６０％であった。この
円筒状成形物を長さ５０ｍｍに切断し、長手方向に平行
な任意の一辺を切断して半割状の円筒状成形物を得た。
この半割状の円筒状成形物を金型を用いて、断面が
「Ｊ」字型になるように１３０℃で熱成型した。この断
面が「Ｊ」字型の熱回復性成形品を外径８．０ｍｍφの
アルミニウムパイプに被せ、１５０℃の恒温槽内に水平
に設置して３分間放置した。その結果、半割状の円筒状
成形物がアルミニウムパイプの外周に「の」の字型にラ
ップラウンド被覆することが分かった。[0021] After turned to preheat for 3 minutes in this two-layer cylindrical molded product of a thermostatic chamber at 0.99 ° C. structures, circles using compressed air
An internal pressure was applied to the cylindrical molded product to expand the outer diameter to 12.5 mmφ, and then cooled to maintain the expanded diameter. This expanded cylindrical molded product having a two-layer structure was immersed in water at 60 ° C. for 8 hours to crosslink the outer layer of the cylindrical molded product . Cylindrical molded product The gel fraction of xylene extraction of the outer layer was 60%. this
The cylindrical molded product was cut to a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product .
This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. This heat-recoverable molded product having a “J” cross section was placed on an aluminum pipe having an outer diameter of 8.0 mmφ, placed horizontally in a thermostat at 150 ° C., and left for 3 minutes. As a result, the half cylindrical shape
It was found that the molded product was wrapped around the outer circumference of the aluminum pipe in the shape of a "-".
【００２２】（実施例３） ＥＥＡ樹脂（エチルアクリレート含量２５重量％、ＭＩ
＝１）をチューブ層の材料とし、エチルアクリレート−
一酸化炭素共重合体（エチルアクリレート含量２０重量
％、一酸化炭素含量５重量％、ＭＩ＝５０）１００重量
部に対して、ハイドロキノンモノメチルエーテルを３重
量部添加した材料を接着剤層の材料として溶融押出機で
共押出し、円筒状成形物層の内径が８．０ｍｍφで肉厚
０．５ｍｍ、接着剤層の内径が７．０ｍｍφの接着剤層
付きの円筒状成形物を作製した。この円筒状成形物に加
速電圧が１ＭＶの電子線を１００ｋＧｙ照射して架橋さ
せた。円筒状成形物のキシレン抽出のゲル分率は４１％
であった。溶融押出機を使用して、この円筒状成形物の
外周にＥＥＡ樹脂（エチルアクリレート含量２５重量
％、ＭＩ＝１）１００重量部に対し、トリメチロールプ
ロパントリメタクリレートを２重量部添加した材料を肉
厚０．２５ｍｍで押出被覆し、外径が９．５ｍｍφの三
層構造の円筒状成形物を作製した。Example 3 EEA resin (ethyl acrylate content 25% by weight, MI
= 1) as the material of the tube layer,
A material obtained by adding 3 parts by weight of hydroquinone monomethyl ether to 100 parts by weight of a carbon monoxide copolymer (ethyl acrylate content 20% by weight, carbon monoxide content 5% by weight, MI = 50) was used as a material for the adhesive layer. coextruded melt extruder, the inner diameter of the cylindrical molded product layer thickness of 0.5mm in 8.0Mmfai, the inner diameter of the adhesive layer to prepare a cylindrical molded product with the adhesive layer of 7.0 mm. The cylindrical molded product was irradiated with 100 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. Gel fraction of xylene extraction of cylindrical molded product is 41%
Met. Using a melt extruder, a material obtained by adding 2 parts by weight of trimethylolpropane trimethacrylate to 100 parts by weight of an EEA resin (ethyl acrylate content: 25% by weight, MI = 1) was added to the outer periphery of the cylindrical molded product. It was extrusion-coated with a thickness of 0.25 mm to produce a cylindrical molded product having a three-layer structure with an outer diameter of 9.5 mmφ.
【００２３】この三層構造の円筒状成形物を１４０℃の
恒温槽内に投入して３分間予熱後、圧縮空気を用いて円
筒状成形物に内圧をかけ、外径が１２．０ｍｍφになる
ように膨張させ、冷却して膨張径を保持させた。この膨
張した三層構造の円筒状成形物に加速電圧１ＭＶの電子
線を５０ｋＧｙ照射して架橋させた。円筒状成形物外層
のキシレン抽出のゲル分率は５４％であった。この円筒
状成形物を長さ５０ｍｍに切断し、長手方向に平行な任
意の一辺を切断して半割状の円筒状成形物を得た。この
半割状の円筒状成形物を金型を用いて、断面が「Ｊ」字
型になるように１３０℃で熱成型した。この断面が
「Ｊ」字型の熱回復性成形品を外径５．０ｍｍφの軟質
架橋ＰＶＣ被覆電線に被せ、１４０℃の恒温槽内に水平
に設置して３分間放置した。その結果、熱回復性成形品
が軟質架橋ＰＶＣ被覆電線の周囲に「の」の字型にラッ
プラウンド被覆して、軟質架橋ＰＶＣ被覆電線に固定さ
れ、手で剥がすことはできなかった。The three-layered cylindrical molded product is put into a thermostat at 140 ° C., preheated for 3 minutes, and then circularly compressed air.
An internal pressure was applied to the cylindrical molded product, and the cylindrical molded product was expanded so as to have an outer diameter of 12.0 mmφ, and cooled to maintain the expanded diameter. The expanded cylindrical molded product having a three-layer structure was irradiated with 50 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. The gel fraction of xylene extraction of the outer layer of the cylindrical molded product was 54%. This cylinder
The shaped article was cut to a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical article . This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. This heat-recoverable molded product having a cross section of “J” shape was covered on a soft crosslinked PVC-coated electric wire having an outer diameter of 5.0 mmφ, placed horizontally in a thermostat at 140 ° C., and left for 3 minutes. As a result, the heat-recoverable molded article was wrapped around the soft cross-linked PVC-coated electric wire in the shape of a "-" and fixed to the soft cross-linked PVC-coated electric wire, and could not be peeled off by hand.
【００２４】（実施例４） 実施例１で用いた内径８．４ｍｍφ、肉厚０．３ｍｍの
架橋ＥＶＡ樹脂円筒状成形物をクロスヘッド温度を１５
０℃に設定した溶融押出機のパスラインに５ｍ／分の線
速で通し、円筒状成形物に圧縮空気を送り込んで内圧を
かけながら、円筒状成形物の外周にＥＶＡ樹脂（酢酸ビ
ニル含量２５重量％、ＭＩ＝３）を被覆し、円筒状成形
物内径が１０．５ｍｍφ、外径が１１．５ｍｍφになる
ように膨張させながら、外皮のＥＶＡ樹脂を被覆した。
この円筒状成形物に加速電圧が１ＭＶの電子線を１００
ｋＧｙ照射して架橋し、長さ５０ｍｍに切断し、長手方
向に平行な任意の一辺を切断して半割状の円筒状成形物
を得た。この半割状の円筒状成形物を金型を用いて、断
面が「Ｊ」字型になるように１３０℃で熱成型した。こ
の断面が「Ｊ」字型の熱回復性成形品を外径６．０ｍｍ
φのアルミニウムパイプに被せ、１５０℃の恒温槽内に
水平に設置して３分間放置した。その結果、半割状の円
筒状成形物がアルミニウムパイプの周囲に「の」の字型
にラップラウンド被覆することが分かった。Example 4 The crosslinked EVA resin cylindrical molded product having an inner diameter of 8.4 mmφ and a thickness of 0.3 mm used in Example 1 was heated at a crosshead temperature of 15 ° C.
0 pass line of ℃ Set melt extruder through at a linear velocity of 5 m / min, while applying a pressure by feeding compressed air into a cylindrical molded product, the outer circumference EVA resin cylindrical molded product (vinyl content acetate 25 Weight%, MI = 3), cylindrical molding
While expanding so that the inner diameter of the object was 10.5 mmφ and the outer diameter of 11.5 mmφ, the outer skin was covered with EVA resin.
An electron beam having an acceleration voltage of 1 MV was applied to this cylindrical molded product for 100 minutes.
It was cross-linked by irradiation with kGy, cut to a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. The cross section of the heat recovery molded article having a “J” shape is 6.0 mm in outer diameter.
It was placed on a φ aluminum pipe, placed horizontally in a thermostat at 150 ° C., and left for 3 minutes. As a result, a half-split circle
It was found that the tubular molding wrapped around the aluminum pipe in a "-" shape.
【００２５】（比較例１） ＥＥＡ樹脂（エチルアクリレート含量２５重量％、ＭＩ
＝１）を使用し、溶融押出機で外径８．０ｍｍφ、肉厚
０．３ｍｍの円筒状成形物を作製した。この円筒状成形
物に加速電圧が１ＭＶの電子線を２００ｋＧｙ照射して
架橋させた。この円筒状成形物を１４０℃の恒温槽内に
投入して３分間予熱後、圧縮空気を用いて円筒状成形物
に内圧をかけ、外径が１１．０ｍｍφになるように膨張
させ、冷却して膨張径を保持させた。この円筒状成形物
を長さ５０ｍｍに切断し、長手方向に平行な任意の一辺
を切断して半割状の円筒状成形物を得た。この半割状の
円筒状成形物を外径９．０ｍｍφのアルミニウムパイプ
に被せ、１２０℃の恒温槽内に水平に設置して、半割状
の円筒状成形物がアルミニウムパイプの周囲にラップラ
ウンド被覆するかどうか調べた。その結果、半割状の円
筒状成形物がアルミニウムパイプの周囲にはラップラウ
ンド被覆しなかった。Comparative Example 1 EEA resin (ethyl acrylate content 25% by weight, MI
= 1), a cylindrical extruded product having an outer diameter of 8.0 mmφ and a wall thickness of 0.3 mm was produced with a melt extruder. This cylindrical molding
The object was irradiated with an electron beam having an acceleration voltage of 1 MV at 200 kGy to crosslink. This cylindrical molded product is put into a 140 ° C. constant temperature bath, preheated for 3 minutes, and then the internal pressure is applied to the cylindrical molded product using compressed air to expand the outer diameter to 11.0 mmφ. After cooling, the expanded diameter was maintained. This cylindrical molded product was cut to a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . This half-shaped
The cylindrical molded product is placed on an aluminum pipe with an outer diameter of 9.0 mmφ, placed horizontally in a thermostat at 120 ° C, and examined to determine whether the half- cylindrical cylindrical molded product is wrapped around the aluminum pipe. Was. As a result, a half-split circle
The tubular molding did not wrap around the aluminum pipe.
【００２６】（比較例２） 比較例１で使用した架橋円筒状成形物を１４０℃恒温槽
内に投入して３分間予熱後、圧縮空気を用いて円筒状成
形物に内圧をかけ、外径が２０．０ｍｍφになるように
膨張させ、冷却して膨張径を保持させた。この円筒状成
形物を長さ５０ｍｍに切断し、長手方向に平行な任意の
一辺を切断して半割状の円筒状成形物を得た。この半割
状の円筒状成形物を外径９．０ｍｍφのアルミニウムパ
イプに被せ、１２０℃の恒温槽内に水平に設置して、半
割状の円筒状成形物がアルミニウムパイプの周囲にラッ
プラウンド被覆するかどうか調べた。その結果、半割状
の円筒状成形物がアルミニウムパイプの周囲にはラップ
ラウンド被覆しなかった。[0026] (Comparative Example 2) after 3 minutes preheat was charged crosslinked cylindrical forming product used for 140 ° C. constant temperature bath in Comparative Example 1, cylindrical with compressed air JoNaru
An internal pressure was applied to the shaped article to expand the outer diameter to 20.0 mmφ, and then cooled to maintain the expanded diameter. This cylindrical component
The shaped article was cut to a length of 50 mm, and an arbitrary side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded article . This half-shaped cylindrical molded product is placed on an aluminum pipe having an outer diameter of 9.0 mmφ and placed horizontally in a thermostat at 120 ° C., and the half-shaped cylindrical molded product is wrapped around the aluminum pipe. It was checked whether to coat. As a result, the half-shaped cylindrical molded product did not cover the aluminum pipe around the wrap round.
【００２７】（比較例３） 実施例３で使用した三層構造の円筒状成形物を１４０℃
の恒温槽内に投入して３分間予熱後、圧縮空気を用いて
円筒状成形物に内圧をかけ、外径が１８．０ｍｍφにな
るように膨張させ、冷却して膨張径を保持させた。この
膨張した三層構造の円筒状成形物に加速電圧が１ＭＶの
電子線を１００ｋＧｙ照射して架橋させた。円筒状成形
物外層のキシレン抽出のゲル分率は４５％であった。こ
の円筒状成形物を長さ５０ｍｍに切断し、長手方向に平
行な任意の一辺を切断して半割状の円筒状成形物を得
た。この半割状の円筒状成形物を金型を用いて、断面が
「Ｊ」字型になるように１３０℃に熱成型した。この断
面が「Ｊ」字型の熱回復性成形品を外径が５．０ｍｍφ
の軟質架橋ＰＶＣ被覆電線に被せ、１３０℃の恒温槽内
に水平に設置して、軟質架橋ＰＶＣ被覆電線にラップラ
ウンド被覆するかどうか調べた。その結果、円筒状成形
物の長手方向の切断部が自己巻きする現象が見られ、軟
質架橋ＰＶＣ被覆電線の周囲にうまくラップラウンド被
覆しなかった。Comparative Example 3 The three-layered cylindrical molded product used in Example 3 was heated to 140 ° C.
Into a constant temperature bath, preheat for 3 minutes and use compressed air
An internal pressure was applied to the cylindrical molded product to expand the outer diameter to 18.0 mmφ, and then cooled to maintain the expanded diameter. The expanded cylindrical molded product having a three-layer structure was irradiated with 100 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. Cylindrical molding
The gel fraction of the xylene extraction of the object the outer layer was 45%. This cylindrical molded product was cut into a length of 50 mm, and any one side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. This cross-section is a J-shaped heat-recoverable molded product having an outer diameter of 5.0 mmφ.
Was placed horizontally in a thermostat at 130 ° C., and it was examined whether or not the soft crosslinked PVC-coated wire was wrapped round. As a result, cylindrical molding
The phenomenon that the cut portion in the longitudinal direction of the product self-wound was observed, and the wrap round coating was not well performed around the soft crosslinked PVC-coated electric wire.
【００２８】（比較例４） 溶融押出機を使用して、実施例１で用いた内径が８．４
ｍｍφ、肉厚０．３ｍｍの円筒状成形物の外周にＥＥＡ
樹脂（エチルアクリレート含量１９重量％、ＭＩ＝５）
を肉厚１．０ｍｍで押出被覆し、外径１１．０ｍｍφの
二層構造の円筒状成形物を作製した。この二層構造の円
筒状成形物を１４０℃の恒温槽内に投入して３分間予熱
後、圧縮空気を用いて円筒状成形物に内圧をかけ、外径
が１４．０ｍｍφになるように膨張させ、冷却して膨張
径を保持させた。この膨張した二層構造の円筒状成形物
に加速電圧が１ＭＶの電子線を１００ｋＧｙ照射して架
橋させた。円筒状成形物外層のキシレン抽出のゲル分率
は４４％であった。この円筒状成形物を長さ５０ｍｍに
切断し、長手方向に平行な任意の一辺を切断して半割状
の円筒状成形物を得た。この半割状の円筒状成形物を金
型を用いて、断面が「Ｊ」字型になるように１３０℃に
熱成型した。この断面が「Ｊ」字型の熱回復性成形品を
外径が６．０ｍｍφのアルミニウムパイプに被せ、１４
０℃の恒温槽内に水平に設置して３分間放置したが、口
開きした状態となって、アルミニウムパイプの周囲に
「の」の字型にラップラウンド被覆しなかった。(Comparative Example 4) Using a melt extruder, the inner diameter used in Example 1 was 8.4.
mmφ, EEA on the outer periphery of a cylindrical molded product with a wall thickness of 0.3 mm
Resin (ethyl acrylate content 19% by weight, MI = 5)
Was extruded to a thickness of 1.0 mm to produce a cylindrical molded product having a two-layer structure with an outer diameter of 11.0 mmφ. This two-layered circle
The cylindrical molded product is put into a constant temperature bath at 140 ° C. and preheated for 3 minutes . Then , an internal pressure is applied to the cylindrical molded product using compressed air, expanded to an outer diameter of 14.0 mmφ, and cooled. The expanded diameter was maintained. The expanded cylindrical molded product having a two-layer structure was irradiated with 100 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. The gel fraction of xylene extraction of the outer layer of the cylindrical molded product was 44%. This cylindrical molded product was cut into a length of 50 mm, and any one side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. This heat-recoverable molded product having a J-shaped cross section is covered on an aluminum pipe having an outer diameter of 6.0 mmφ,
Although placed horizontally in a thermostat at 0 ° C. and allowed to stand for 3 minutes, the mouth was in an open state, and the wrap round was not covered around the aluminum pipe in the shape of “”.
【００２９】（比較例５） 溶融押出機を使用して、ＥＶＡ樹脂（酢酸ビニル含量２
５重量％、ＭＩ＝３）からなる内径が８．０ｍｍφ、肉
厚０．５ｍｍの円筒状成形物の架橋体（加速電圧１ＭＶ
の電子線を１５０ｋＧｙ照射して架橋）の外周にＥＥＡ
樹脂（エチルアクリレート含量１９重量％、ＭＩ＝５）
を肉厚０．１５ｍｍで押出被覆し、外径９．３ｍｍφの
二層構造の円筒状成形物を作製した。この二層構造の円
筒状成形物を１４０℃の恒温槽内に投入して３分間予熱
後、圧縮空気を用いて円筒状成形物に内圧をかけ、外径
が１１．５ｍｍφになるように膨張させ、冷却して膨張
径を保持させた。この膨張した二層構造の円筒状成形物
に加速電圧が１ＭＶの電子線を１００ｋＧｙ照射して架
橋させた。円筒状成形物外層のキシレン抽出のゲル分率
は３９％であった。この円筒状成形物を長さ５０ｍｍに
切断し、長手方向に平行な任意の一辺を切断して半割状
の円筒状成形物を得た。この半割状の円筒状成形物を金
型を用いて、断面が「Ｊ」字型になるように１３０℃に
熱成型した。この断面が「Ｊ」字型の熱回復性成形品を
外径が６．０ｍｍφのアルミニウムパイプに被せ、１４
０℃の恒温槽内に水平に設置して３分間放置したが、ア
ルミニウムパイプの周囲に「の」の字型にラップラウン
ド被覆しなかった。Comparative Example 5 Using a melt extruder, EVA resin (vinyl acetate content 2
5% by weight, MI = 3), a cross-linked body (acceleration voltage 1MV) of a cylindrical molded product having an inner diameter of 8.0mmφ and a wall thickness of 0.5mm
Cross-link by irradiation with 150 kGy of electron beam
Resin (ethyl acrylate content 19% by weight, MI = 5)
Was extruded to a thickness of 0.15 mm to produce a cylindrical molded product having a two-layer structure with an outer diameter of 9.3 mmφ. This two-layered circle
The cylindrical molded product is put into a constant temperature bath at 140 ° C., preheated for 3 minutes , and then the internal pressure is applied to the cylindrical molded product using compressed air, expanded to an outer diameter of 11.5 mmφ, and cooled. The expanded diameter was maintained. The expanded cylindrical molded product having a two-layer structure was irradiated with 100 kGy of an electron beam having an acceleration voltage of 1 MV to crosslink. The gel fraction of xylene extraction of the outer layer of the cylindrical molded product was 39%. This cylindrical molded product was cut into a length of 50 mm, and any one side parallel to the longitudinal direction was cut to obtain a half-shaped cylindrical molded product . This half-shaped cylindrical molded product was thermoformed at 130 ° C. using a mold so that the cross section became a “J” shape. This heat-recoverable molded product having a J-shaped cross section is covered on an aluminum pipe having an outer diameter of 6.0 mmφ,
It was placed horizontally in a thermostat at 0 ° C. and allowed to stand for 3 minutes, but was not wrapped around the aluminum pipe in the shape of “”.
【００３０】[0030]
【発明の効果】本発明によれば、被着体の周囲にラップ
ラウンド被覆する熱回復性物品を簡便な方法で製造する
ことができる。また、本発明の方法で製造された熱回復
性物品は、電線ハーネスや金属パイプなどの保護、防
水、防食の分野での利用価値は非常に大きいものがあ
る。また、最内層に接着剤層を設けた熱回復性物品は、
特に被覆後の防水テストにおいて水の浸水もなく、絶
縁、防水、防食効果が発揮される。According to the present invention, it is possible to manufacture a heat-recoverable article having a wrap round coating around an adherend by a simple method. Further, the heat-recoverable articles manufactured by the method of the present invention have a very large value in the fields of protection, waterproofing, and anticorrosion of electric wire harnesses and metal pipes. In addition, the heat-recoverable article provided with an adhesive layer on the innermost layer is
In particular, in a waterproof test after coating, there is no water infiltration, and the insulating, waterproof, and anticorrosive effects are exhibited.
【図１】本発明の方法により製造された熱回復性物品を
示す模式図である。FIG. 1 is a schematic view showing a heat-recoverable article manufactured by the method of the present invention.
【図２】従来法の接着テープによる熱回復性物品を示す
模式図である。FIG. 2 is a schematic view showing a heat-recoverable article using a conventional adhesive tape.
【図３】従来法の連結部品により熱回復性物品を示す模
式図である。FIG. 3 is a schematic diagram showing a heat-recoverable article using a conventional connecting component.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ６５Ｄ 59/04 Ｂ６５Ｄ 59/04 // Ｂ２９Ｋ 105:02 Ｂ２９Ｋ 105:02 Ｂ２９Ｌ 9:00 Ｂ２９Ｌ 9:00 (56)参考文献 特開 昭63−15729（ＪＰ，Ａ) 特開 昭60−2337（ＪＰ，Ａ) 特開 昭60−229744（ＪＰ，Ａ) 特開 昭57−61527（ＪＰ，Ａ) 特開 昭57−63243（ＪＰ，Ａ) 特開 昭52−119686（ＪＰ，Ａ) 特開 昭49−17476（ＪＰ，Ａ) 特開 昭48−68670（ＪＰ，Ａ) 特開 昭47−4437（ＪＰ，Ａ) 特開 平５−154912（ＪＰ，Ａ) 特開 平３−26542（ＪＰ，Ａ) 特開 平２−98425（ＪＰ，Ａ) 特開 平２−63829（ＪＰ，Ａ) 特開 平２−63828（ＪＰ，Ａ) 特開 平２−175242（ＪＰ，Ａ) 特開 平２−139236（ＪＰ，Ａ) 特開 平２−139235（ＪＰ，Ａ) 特開 平１−241439（ＪＰ，Ａ) 実開 昭63−184573（ＪＰ，Ｕ) 実開 昭62−48524（ＪＰ，Ｕ) 実開 昭62−180527（ＪＰ，Ｕ) 実開 昭61−8128（ＪＰ，Ｕ) 実開 昭61−173335（ＪＰ，Ｕ) 実開 昭61−152429（ＪＰ，Ｕ) 実開 昭61−152428（ＪＰ，Ｕ) 実開 昭58−74526（ＪＰ，Ｕ) 実開 昭55−177411（ＪＰ，Ｕ) 特公 昭39−7642（ＪＰ，Ｂ１) 特表 昭63−503530（ＪＰ，Ａ) 特表 平４−502341（ＪＰ，Ａ) 特表 平３−503618（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B29C 61/00 - 61/10 B29C 63/00 - 63/48 B32B 1/00 - 35/00 B65B 53/00 - 53/06 B65D 59/00 - 59/08 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI B65D 59/04 B65D 59/04 // B29K 105: 02 B29K 105: 02 B29L 9:00 B29L 9:00 (56) References Special JP-A-63-15729 (JP, A) JP-A-60-2337 (JP, A) JP-A-60-229744 (JP, A) JP-A-57-61527 (JP, A) JP-A-57-63243 (JP, A) JP, A) JP-A-52-119686 (JP, A) JP-A-49-17476 (JP, A) JP-A-48-68670 (JP, A) JP-A-47-4437 (JP, A) JP-A-5-154912 (JP, A) JP-A-3-26542 (JP, A) JP-A-2-98425 (JP, A) JP-A-2-63829 (JP, A) JP-A-2-63828 (JP) JP-A-2-175242 (JP, A) JP-A-2-139236 (JP, A) JP-A-2-139235 (JP, A) 1-241439 (JP, A) Full-opened 63-184573 (JP, U) Full-opened 62-52424 (JP, U) Full-opened 62-180527 (JP, U) Full-opened 61-8128 ( JP, U) Actually open 1986-173335 (JP, U) Actually open 1986-152429 (JP, U) Actually open 1986-152428 (JP, U) Actually open 1983-74526 (JP, U) Actually open Showa 55-177411 (JP, U) Special publication 39-7642 (JP, B1) Special table 63-503530 (JP, A) Special table 4-502341 (JP, A) Special table 3-503618 (JP , A) (58) Fields investigated (Int. Cl. 7 , DB name) B29C 61/00-61/10 B29C 63/00-63/48 B32B 1/00-35/00 B65B 53/00-53 / 06 B65D 59/00-59/08
Claims (3)
体（Ａ）の外周に、高分子材料からなる樹脂組成物の被
覆層（Ｂ）を設けた後、加熱して径方向に膨張せしめて
冷却固定し、更に外周被覆層（Ｂ）を架橋して円筒状熱
回復性物品を得、該物品の長手方向に任意の１ケ所を切
断し割型とすることを特徴とする、熱回復性物品の製造
方法。1. A coating layer (B) of a resin composition made of a polymer material is provided on the outer periphery of a cross-linked body (A) of a cylindrical molded product made of a polymer material, and then heated to expand radially. allowed to cool and fixed, to give an additional cylindrical heat-recoverable article crosslinked outer peripheral coating layer (B), characterized by a split mold to cleave any one location in the longitudinal direction of the article, the heat A method for manufacturing a recoverable article.
体（Ａ）を加熱して径方向に膨張せしめながら、該円筒
状成形物の外周に高分子材料からなる樹脂組成物の被覆
層（Ｂ）を設けた後、外周被覆層（Ｂ）を架橋して円筒
状熱回復性物品を得、該物品の長手方向に任意の１ケ所
を切断し割型とすることする、熱回復性物品の製造方
法。2. A coating layer of a resin composition composed of a polymer material on the outer periphery of the cylindrical molded product while heating and expanding the crosslinked body (A) of the cylindrical molded product composed of a polymer material in the radial direction. After providing (B), the outer peripheral coating layer (B) is cross-linked to form a cylinder.
Give Jo heat recoverable article, and this to split to cleave any one location in the longitudinal direction of the article, the manufacturing method of the heat recoverable article.
体（Ａ）の肉厚と外周被覆層（Ｂ）の肉厚比が１／３〜
３／１の範囲にあり、しかもチューブ状成形物の架橋体
（Ａ）の膨張比率が１を越え１．５以下であることを特
徴とする、請求項１又は２記載の熱回復性物品の製造方
法。3. The ratio of the thickness of the crosslinked body (A) of the cylindrical molded product made of a polymer material to the thickness of the outer peripheral coating layer (B) is from 1/3 to 3
In the range of 3/1, moreover, wherein the expansion ratio of the crosslinked product of the tubular molded article (A) is 1.5 or less than 1, the heat-recoverable article according to claim 1 or 2, wherein Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853092A JP3278913B2 (en) | 1992-07-14 | 1992-07-14 | Method for producing heat-recoverable article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20853092A JP3278913B2 (en) | 1992-07-14 | 1992-07-14 | Method for producing heat-recoverable article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0631807A JPH0631807A (en) | 1994-02-08 |
| JP3278913B2 true JP3278913B2 (en) | 2002-04-30 |
Family
ID=16557716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20853092A Expired - Fee Related JP3278913B2 (en) | 1992-07-14 | 1992-07-14 | Method for producing heat-recoverable article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3278913B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3050699A4 (en) * | 2013-09-26 | 2017-05-17 | Sumitomo Electric Industries, Ltd. | Multilayer heat recovery article, wire splice and wire harness |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU227213B1 (en) * | 2007-01-25 | 2010-11-29 | Origo Plan Kft | Procedure for making matching forms of air-handling systems, matching form and air-handling system |
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| JPS4868670A (en) * | 1971-12-20 | 1973-09-19 | ||
| JPS4917476A (en) * | 1972-06-05 | 1974-02-15 | ||
| JPS5912919B2 (en) * | 1976-04-02 | 1984-03-26 | 日本ユニカ−株式会社 | Heat-shrinkable composite sleeve |
| JPS5852095Y2 (en) * | 1979-06-07 | 1983-11-28 | 住友電気工業株式会社 | heat shrink tube |
| JPS5761527A (en) * | 1980-09-30 | 1982-04-14 | Mitsubishi Plastics Ind Ltd | Manufacture of heat-shirinkable composite tube or film |
| JPS5763243A (en) * | 1980-10-02 | 1982-04-16 | Mitsubishi Plastics Ind | Heat-shrinkable composite tube and shrinking coating method by said tube |
| JPS5941088Y2 (en) * | 1981-11-16 | 1984-11-26 | 古河電気工業株式会社 | Waterproof heat shrink tube |
| JPH0717007B2 (en) * | 1983-06-21 | 1995-03-01 | 住友電気工業株式会社 | Method for producing heat-shrinkable tube |
| IL74682A (en) * | 1984-04-06 | 1991-01-31 | Raychem Corp | Heat-recoverable tubular composite articles and their production |
| JPS618128U (en) * | 1984-06-22 | 1986-01-18 | 三菱樹脂株式会社 | Laminated shrink tube |
| JPS61152428U (en) * | 1985-03-13 | 1986-09-20 | ||
| JPH0636915Y2 (en) * | 1985-03-14 | 1994-09-28 | 古河電気工業株式会社 | Heat-shrinkable tube |
| JPS61173335U (en) * | 1985-04-17 | 1986-10-28 | ||
| JPS6248524U (en) * | 1985-09-13 | 1987-03-25 | ||
| JPH056122Y2 (en) * | 1986-05-09 | 1993-02-17 | ||
| WO1987007869A1 (en) * | 1986-06-23 | 1987-12-30 | Raychem Corporation | Wrap-around heat-recoverable article and method therefor |
| JPS6315729A (en) * | 1986-07-07 | 1988-01-22 | Fujikura Ltd | Manufacture of heat-shrinkable tubing |
| JPH028380Y2 (en) * | 1987-05-21 | 1990-02-28 | ||
| JPH01241439A (en) * | 1988-03-23 | 1989-09-26 | Showa Electric Wire & Cable Co Ltd | Heat-shrinkable tube |
| IL89671A0 (en) * | 1988-03-29 | 1989-09-28 | Raychem Corp | Heat-recoverable article and method for enclosing and sealing a substrate |
| JPH0263828A (en) * | 1988-08-31 | 1990-03-05 | Showa Electric Wire & Cable Co Ltd | Watertight heat-shrinkable tube |
| JPH0263829A (en) * | 1988-08-31 | 1990-03-05 | Showa Electric Wire & Cable Co Ltd | Watertight heat-shrinkable tube |
| JP2639511B2 (en) * | 1988-10-04 | 1997-08-13 | 株式会社フジクラ | Heat shrink tube manufacturing method |
| JPH02139236A (en) * | 1988-11-21 | 1990-05-29 | Sumitomo Electric Ind Ltd | Heat shrinkable object |
| JPH02139235A (en) * | 1988-11-21 | 1990-05-29 | Sumitomo Electric Ind Ltd | Heat shrinkable object |
| EP0489004B1 (en) * | 1988-12-21 | 1995-10-25 | Raychem Corporation | Thermoplastic fluoropolymer adhesive composition |
| JP2650996B2 (en) * | 1988-12-28 | 1997-09-10 | 古河電気工業株式会社 | Heat shrinkable articles |
| US5055328A (en) * | 1989-06-16 | 1991-10-08 | Viskase Corporation | Differentially cross-linked multilayer film |
| JP3042105B2 (en) * | 1991-11-07 | 2000-05-15 | 住友電気工業株式会社 | Method for producing heat-recoverable article |
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- 1992-07-14 JP JP20853092A patent/JP3278913B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3050699A4 (en) * | 2013-09-26 | 2017-05-17 | Sumitomo Electric Industries, Ltd. | Multilayer heat recovery article, wire splice and wire harness |
| US9985425B2 (en) | 2013-09-26 | 2018-05-29 | Sumitomo Electric Industries, Ltd. | Multilayered heat-recoverable article, wire splice, and wire harness |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0631807A (en) | 1994-02-08 |
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