JPH0298425A - Manufacture of heat-shrinkable tubing - Google Patents
Manufacture of heat-shrinkable tubingInfo
- Publication number
- JPH0298425A JPH0298425A JP63250485A JP25048588A JPH0298425A JP H0298425 A JPH0298425 A JP H0298425A JP 63250485 A JP63250485 A JP 63250485A JP 25048588 A JP25048588 A JP 25048588A JP H0298425 A JPH0298425 A JP H0298425A
- Authority
- JP
- Japan
- Prior art keywords
- layer material
- outer layer
- heat
- crosslinking
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 13
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- -1 polyethylene, ethylene-vinyl acetate Polymers 0.000 claims abstract description 5
- 239000012943 hotmelt Substances 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 3
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims abstract description 3
- 239000004840 adhesive resin Substances 0.000 claims description 4
- 229920006223 adhesive resin Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010410 layer Substances 0.000 abstract description 53
- 239000012790 adhesive layer Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001464 adherent effect Effects 0.000 abstract 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 28
- 230000005855 radiation Effects 0.000 description 5
- 238000010382 chemical cross-linking Methods 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、パイプ材等の保護用や電極等の絶縁用等に用
いて有用な熱収縮チューブの製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for manufacturing a heat-shrinkable tube useful for protecting pipe materials, etc., insulating electrodes, etc.
〈従来の技術〉
従来、このような熱収縮チューブは、一般にポリオレフ
ィン系樹脂をチューブ状に押出し、このチューブを放射
線架橋や化学架橋等により架橋させ、次に、連続的に拡
径（膨張）させ、冷却することにより製造している。<Conventional technology> Conventionally, such heat-shrinkable tubes are generally made by extruding polyolefin resin into a tube shape, crosslinking this tube by radiation crosslinking, chemical crosslinking, etc., and then continuously expanding (expanding) the tube. , manufactured by cooling.
そして、一般には１層構造のものが多いが、使用目的に
よっては、収縮させた際、パイプ材や電極等の外表面と
良好に密着するようにチューブの内側に接着層を設けた
ものが提案されている。In general, most tubes have a single-layer structure, but depending on the purpose of use, it is suggested that an adhesive layer be provided on the inside of the tube so that it will adhere well to the outer surface of the pipe material, electrode, etc. when it is shrunk. has been done.
〈発明が解決しようとする課題〉
このような２層構造の熱収縮チューブを製造するには、
従来は、一般に外層の熱収縮チューブを形成した後、塗
布等により接着層を設ける方法によっているため、製造
工程数が増えること、均一な接着層の形成が困難である
こと等の問題があった。<Problem to be solved by the invention> In order to manufacture such a two-layer structure heat shrink tube,
Conventionally, the method of forming an outer layer of heat-shrinkable tube and then applying an adhesive layer by coating, etc. has been used, which has resulted in problems such as an increase in the number of manufacturing steps and difficulty in forming a uniform adhesive layer. .
そこで、外層の熱収縮チューブと内層の接着層とを同時
押出する方法が考えられるが、この同時押出法と放射線
架橋法とを組み合わせる場合には、放射線の透過性から
製造できるチューブの厚さに限界があること、絶縁厚さ
の方向で放射線の吸収量が異なることからチューブの厚
さ方向に均一な架橋度が得られないこと、外層側樹脂の
架橋のための放射線が内層の接着層にも作用し易く、不
要な架橋による接着層の接着性低下が起こり易いこと、
かといって、外層側樹脂だけの架橋を放射線量でコント
ロールすることは甚だ困難であること等、種々の問題が
ある。Therefore, a method of co-extruding the outer layer of heat-shrinkable tube and the inner layer of adhesive layer is considered, but when combining this co-extrusion method and radiation crosslinking method, the thickness of the tube that can be manufactured due to the transparency of radiation The degree of crosslinking is not uniform in the thickness direction of the tube because the amount of radiation absorbed differs in the direction of the insulation thickness. Also, the adhesion of the adhesive layer is likely to decrease due to unnecessary crosslinking.
However, there are various problems, such as the fact that it is extremely difficult to control the crosslinking of only the outer layer resin by the radiation dose.
本発明は、このような従来の実情に鑑みてなされたもの
である。The present invention has been made in view of such conventional circumstances.
〈課題を解決するための手段及びその作用〉か−る本発
明の特徴とする点は、化学架橋方法を採用し、外層材の
ポリオレフィン系樹脂のみに架橋材を含有させ、この外
層材と、接着性を有する内層材とを同時押出し、その後
、外層材のみを架橋させるようにした点にある。<Means for Solving the Problems and Their Effects> The feature of the present invention is that a chemical crosslinking method is adopted, a crosslinking material is contained only in the polyolefin resin of the outer layer material, and this outer layer material and The key point is that the adhesive inner layer material is coextruded, and then only the outer layer material is crosslinked.
本発明をより具体的に示すと、架橋剤含有のポリオレフ
ィン系樹脂を外層材とし、接着性を有する樹脂を内層材
としてチューブ状に同時押出し、次に、当該チューブを
加熱により架橋させ、引き続き、連続的に拡径（膨張）
させ、冷却する熱収縮チューブの製造方法にある。To explain the present invention more specifically, a polyolefin resin containing a crosslinking agent is used as an outer layer material, and a resin having adhesive properties is used as an inner layer material, which is coextruded into a tube shape, and then the tube is crosslinked by heating, and then, Continuous diameter expansion (expansion)
A method of manufacturing a heat shrinkable tube is provided.
この本発明製造方法によれば、外層材が架橋され、内側
の内層材が接着剤として機能する熱収縮チューブが簡単
に得られる。According to the manufacturing method of the present invention, a heat-shrinkable tube in which the outer layer material is crosslinked and the inner layer material inside functions as an adhesive can be easily obtained.
本発明で用いるポリオレフィン系樹脂としては、特に限
定されないが、例えばポリエチレン、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−プロピレン共重合体等が挙げられる。The polyolefin resin used in the present invention is not particularly limited, and examples thereof include polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer, and the like.
また、上記ポリオレフィン系樹脂に添加される架橋剤と
しては、ジクミルパーオキサイド、２゜２′−ビスベン
ゼン、ｔ−ブチルクミルパーオキサイド等が挙げられ、
その添加量は、ポリオレフィン系樹脂１００重量部に対
して、０．１〜１０重量部が好ましい、なぜなら、０．
１重量部未満では必要な架橋度が得られず、１０重量部
を越えるとスコーチ（早期架橋）が発生する恐れがある
からである。Further, examples of the crosslinking agent added to the polyolefin resin include dicumyl peroxide, 2゜2'-bisbenzene, t-butylcumyl peroxide, etc.
The amount added is preferably 0.1 to 10 parts by weight per 100 parts by weight of the polyolefin resin.
This is because if it is less than 1 part by weight, the required degree of crosslinking cannot be obtained, and if it exceeds 10 parts by weight, scorch (early crosslinking) may occur.
本発明で用いる内層材の接着性を有する樹脂としては、
特に限定されないが、例えばホットメルト系樹脂の使用
が好ましい。The adhesive resin for the inner layer material used in the present invention includes:
Although not particularly limited, it is preferable to use, for example, a hot melt resin.
また、上記外層材のポリオレフィン系樹脂および内層材
の接着性を有する樹脂には、必要により、その他の添加
剤を添加することが可能である。例えば、４．４゛−チ
オビス（３−メチル−６−タージヤリーープチルフエノ
ール）等の老化防止剤、カーボン、着色用顔料等の充填
剤等が挙げられる。Further, other additives may be added to the polyolefin resin of the outer layer material and the adhesive resin of the inner layer material, if necessary. Examples include anti-aging agents such as 4.4'-thiobis(3-methyl-6-tertiarybutylphenol), fillers such as carbon, and coloring pigments.
上記老化防止剤の場合、外層材への添加にあってはポリ
オレフィン系樹脂１００重量部に対して０゜１〜１重量
部、内層材への添加にあっては接着性を有する樹脂に対
して０．０５〜１重量部程度が好ましい。In the case of the above anti-aging agent, when added to the outer layer material, it is 0.1 to 1 part by weight per 100 parts by weight of polyolefin resin, and when added to the inner layer material, it is added to the adhesive resin. About 0.05 to 1 part by weight is preferable.
上記本発明での架橋温度は、１６０〜３００℃程度とす
るのがよい。The crosslinking temperature in the present invention is preferably about 160 to 300°C.
〈実施例〉
第１図は本発明方法により製造した熱収縮チューブの一
例を示したものである。<Example> FIG. 1 shows an example of a heat-shrinkable tube manufactured by the method of the present invention.
図中、１は外層材、２は内層材であり、いずれも膨張工
程により、拡径されている。In the figure, 1 is an outer layer material, and 2 is an inner layer material, both of which have been expanded in diameter by the expansion process.
本実施例では、外層材１として、ポリエチレン１００重
量部に対し、架橋剤のジクミルパーオキサイドを０．４
重量部、熱老化防止剤の４．４′−チオビス（３−メチ
ル−６−タージヤリーープチルフエノール）を０．０８
重量部含有した材料、また内層材２として、ホットメル
ト系樹脂の酸変性ポリオレフィンを用い、これらの両者
を同時押出機によりチューブ状に同時押出し、これに続
して、加熱部、拡径部、冷却部が連続的に構成されたパ
イプ内に導入し、冷却部用口の引取り機により引き取り
、本熱収縮チューブを得た。なお、パイプと押出チュー
ブ間には、走行性を向上させるため、潤滑油を使用した
。In this example, as the outer layer material 1, 0.4 parts of dicumyl peroxide as a crosslinking agent was added to 100 parts by weight of polyethylene.
Part by weight, heat aging inhibitor 4.4'-thiobis(3-methyl-6-tertiarybutylphenol): 0.08
Using an acid-modified polyolefin hot-melt resin as the material containing parts by weight and as the inner layer material 2, both are co-extruded into a tube shape using a co-extruder, followed by a heating section, an expanded diameter section, The tube was introduced into a pipe having a continuous cooling section and taken out by a take-up machine at the opening of the cooling section to obtain a heat-shrinkable tube. Note that lubricating oil was used between the pipe and the extruded tube to improve running performance.
この場合、外層材１の均一な架橋にあたっては、架橋時
間の設定が重要であり、一般には架橋は外層材の外表面
から内部に向かって進行するため、内表面部分の架橋が
完了する時間（架橋剤が全量消費される時間）を架橋時
間とすれば、外層材１の内外に渡って均一な架橋が得ら
れる。In this case, setting the crosslinking time is important for uniform crosslinking of the outer layer material 1. Generally, crosslinking progresses from the outer surface of the outer layer material toward the inside, so the time required to complete crosslinking of the inner surface portion ( If the crosslinking time is the time during which the entire amount of the crosslinking agent is consumed, uniform crosslinking can be obtained both inside and outside the outer layer material 1.
因みに、本発明者等が、第１図の外層材１において、そ
の外表面、内部中央、内表面の各部位Ａ〜Ｃにおける架
橋進行状態を調べたところ、第２図の如くで、内表面Ｃ
での架橋完了時間が最も遅く、この結果、内表面Ｃの架
橋が完了する時間を架橋時間とすればよいことが確認さ
れた。Incidentally, when the present inventors investigated the progress of crosslinking in the outer surface, the inner center, and each part A to C of the inner surface of the outer layer material 1 shown in FIG. 1, it was found that the inner surface C
The completion time of crosslinking was the slowest, and as a result, it was confirmed that the time when crosslinking of inner surface C was completed should be taken as the crosslinking time.
本実施例の場合、架橋部でのチューブ本来が１ｍｍ
ｋ場合、加熱温度を２４０°Ｃ１加熱時間を４０秒程度
としたところ、ゲル分率が６０％の架橋度で、内外に渡
って均一な架橋度の外層材１が得られた。In the case of this example, the original length of the tube at the bridge section is 1 mm.
In case k, when the heating temperature was set to 240° C. and the heating time was set to about 40 seconds, an outer layer material 1 with a gel fraction of 60% and a crosslinking degree uniform inside and outside was obtained.
また、外層材１の架橋度は、添加する架橋剤の量により
任意に調整することが可能である。Further, the degree of crosslinking of the outer layer material 1 can be arbitrarily adjusted by adjusting the amount of crosslinking agent added.
また、接着層の内層材２側では、上記外層材ｌ側からの
架橋剤の拡散が懸念されるが、実際の製造では、架橋剤
は外層材１中で消費されるため、内層材２を架橋させる
ことは殆どなかった。すなわち、内層材２側での架橋に
よる接着性の低下は殆ど見られなかった。In addition, on the inner layer material 2 side of the adhesive layer, there is a concern that the crosslinking agent may diffuse from the outer layer material I side, but in actual manufacturing, the crosslinking agent is consumed in the outer layer material 1, so the inner layer material 2 There was almost no crosslinking. That is, almost no decrease in adhesiveness due to crosslinking on the inner layer material 2 side was observed.
従って、この熱収縮チューブを被々覆物に被せ、加熱し
て収縮させたところ、内層材２の接着層が被々覆物の表
面と強固に接着し、極めて良好な密着状態が得られた。Therefore, when this heat-shrinkable tube was placed over the covering and heated to shrink it, the adhesive layer of the inner layer material 2 firmly adhered to the surface of the covering, resulting in extremely good adhesion. .
なお、使用する架橋剤の種類によって、より内層材２側
への拡散が懸念される場合には、この内層材２中に架橋
抑止剤、例えば４．４′−チオビス（３−メチル−６−
タージヤリーーブチルフエノール）等を添加するとよい
。Depending on the type of crosslinking agent used, if there is a concern that it will diffuse further toward the inner layer material 2, a crosslinking inhibitor such as 4,4'-thiobis(3-methyl-6-
It is recommended to add tertiary butylphenol).
また、本発明の熱収縮チューブは、チューブ本来の形の
他に、当該チューブを切断し一端を閉塞させたキャップ
等として使用することも可能で、このような応用物にも
その技術的範囲が及ぶことは勿論である。In addition, the heat-shrinkable tube of the present invention can be used not only in its original form, but also as a cap, etc., which is obtained by cutting the tube and closing one end. Of course, this will extend.
〈発明の効果〉
以上の説明から明らかなように本発明によれば、■内外
の２層を同時押出で形成するため、従来のように接着層
を後から別工程で製造する必要がなく・■また・化学架
橋により、外層材の厚さにあまり影響されることなく、
内外均一で、かつその架橋度を任意にコントロールして
架橋することができ、■さらに、内層材の接着性を何ら
低下させることなく、この結果、収縮性が均一な優れた
熱収縮チューブを製造することができる。<Effects of the Invention> As is clear from the above description, according to the present invention, (1) the inner and outer layers are formed by simultaneous extrusion, so there is no need to manufacture the adhesive layer later in a separate process as in the past; ■Also, due to chemical crosslinking, it is not affected by the thickness of the outer layer material,
Cross-linking can be done uniformly inside and out, and the degree of cross-linking can be controlled arbitrarily. ■Furthermore, without any reduction in the adhesion of the inner layer material, an excellent heat-shrinkable tube with uniform shrinkability can be produced. can do.
第１図は本発明方法により製造された熱収縮チューブの
一例を示した縦断面図、第２図は外層材部分における架
橋の進行状態を示したグラフである。
図中、
１・・・・・外層材、
２・・・・・内層材、
第１図
第２図
特許出願人 藤倉電線株式会社
□時間FIG. 1 is a longitudinal sectional view showing an example of a heat-shrinkable tube manufactured by the method of the present invention, and FIG. 2 is a graph showing the progress of crosslinking in the outer layer material portion. In the figure, 1... Outer layer material, 2... Inner layer material, Figure 1 Figure 2 Patent applicant Fujikura Electric Cable Co., Ltd. □ Time
Claims (3)
、接着性を有する樹脂を内層材としてチューブ状に同時
押出し、次に、当該チューブを加熱により架橋させ、さ
らに引き続き、連続的に拡径させ、冷却することを特徴
とする熱収縮チューブの製造方法。(1) A polyolefin resin containing a crosslinking agent is used as an outer layer material, and a resin with adhesive properties is used as an inner layer material, which is co-extruded into a tube shape. Next, the tube is crosslinked by heating, and then continuously expanded in diameter. , a method for manufacturing a heat shrinkable tube characterized by cooling.
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−プロピレン共重合体である
請求項１記載の熱収縮チューブの製造方法。(2) The method for producing a heat-shrinkable tube according to claim 1, wherein the polyolefin resin is polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, or ethylene-propylene copolymer.
である請求項１または２記載の熱収縮チューブの製造方
法。(3) The method for manufacturing a heat-shrinkable tube according to claim 1 or 2, wherein the adhesive resin is a hot melt resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63250485A JP2639511B2 (en) | 1988-10-04 | 1988-10-04 | Heat shrink tube manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63250485A JP2639511B2 (en) | 1988-10-04 | 1988-10-04 | Heat shrink tube manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0298425A true JPH0298425A (en) | 1990-04-10 |
| JP2639511B2 JP2639511B2 (en) | 1997-08-13 |
Family
ID=17208560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63250485A Expired - Fee Related JP2639511B2 (en) | 1988-10-04 | 1988-10-04 | Heat shrink tube manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2639511B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631807A (en) * | 1992-07-14 | 1994-02-08 | Sumitomo Electric Ind Ltd | Preparation of thermally recovering article |
| WO2007090265A1 (en) * | 2006-02-07 | 2007-08-16 | Shawcor | Heat shrinkable laminated covering |
| JP2021081016A (en) * | 2019-11-20 | 2021-05-27 | Ｍｃｐｐイノベーション合同会社 | Cylindrical molded body and its manufacturing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152429U (en) * | 1985-03-14 | 1986-09-20 |
-
1988
- 1988-10-04 JP JP63250485A patent/JP2639511B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152429U (en) * | 1985-03-14 | 1986-09-20 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631807A (en) * | 1992-07-14 | 1994-02-08 | Sumitomo Electric Ind Ltd | Preparation of thermally recovering article |
| WO2007090265A1 (en) * | 2006-02-07 | 2007-08-16 | Shawcor | Heat shrinkable laminated covering |
| JP2021081016A (en) * | 2019-11-20 | 2021-05-27 | Ｍｃｐｐイノベーション合同会社 | Cylindrical molded body and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2639511B2 (en) | 1997-08-13 |
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| LAPS | Cancellation because of no payment of annual fees |