JP4243797B2 - Heat shrinkable polyester tube - Google Patents
Heat shrinkable polyester tube Download PDFInfo
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- JP4243797B2 JP4243797B2 JP2003069648A JP2003069648A JP4243797B2 JP 4243797 B2 JP4243797 B2 JP 4243797B2 JP 2003069648 A JP2003069648 A JP 2003069648A JP 2003069648 A JP2003069648 A JP 2003069648A JP 4243797 B2 JP4243797 B2 JP 4243797B2
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- tube
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- shrinkable polyester
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- polyethylene terephthalate
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Description
【0001】
【発明の属する技術分野】
本発明は熱収縮性を付与したシームレスのポリエステルチューブに係り、特に収縮特性に優れ、熱収縮後の耐久性に優れたチューブであって、例えばアルミ固体コンデンサ、アルミ非固体コンデンサ、1次電池、2次電池等の電子部品への被覆材料や、蛍光灯、OA複合機器の光源、鋼管等への被覆材料、更にキャップシール、雑貨用途としての利用価値が大きい熱収縮性ポリエステルチューブに関する。
【0002】
【従来の技術及びその課題】
コンデンサ、電池等の電子部品を被覆するための熱収縮性チューブ状電気絶縁材料としては、通常、ポリ塩化ビニル樹脂(PVC)やポリエチレンテレフタレート樹脂(PET)からなる熱収縮性チューブが使用されている。
しかしながら、ポリ塩化ビニル樹脂製チューブは安価であるが耐熱性に問題があり、また廃棄物処理に伴う環境問題が起こりやすいという問題が有る。
ポリエチレンテレフタレート樹脂製チューブは耐熱性に優れるが、コンデンサ、電池等の円筒状物の胴体部から端面にかけて1ピースで被覆した場合、その端面において収縮したチューブがカール状になったり、局所的に収縮して塊状となる等被覆仕上がり外観を大きく損ね、被覆対象物の最終寸法精度を満足しないという問題がある。
【0003】
そこで、被覆仕上がり外観を改良する手段としてチューブの長さ方向の収縮率を径方向収縮率より小さくする方法が知られている。この方法では、被覆対象物への被覆仕上がり外観は改良されるが、例えばコンデンサ等の実装工程等の高温下に曝された場合、一度収縮したチューブが弛緩し、外観を損ねるばかりでなく、印字の判読を困難にし、被覆対象物の最終寸法精度を満足しないという問題がある。
【0004】
さらに、ポリエチレンテレフタレート樹脂製チューブはポリ塩化ビニル樹脂製チューブに比べて、被覆対象物に被覆する場合に多くの熱量を必要としエネルギーコストが割高になるという問題がある。そこで、従来のポリエチレンテレフタレート樹脂製チューブより、収縮開始温度が低い熱収縮性ポリエステルフィルムを使用し、端部を背貼り加工してチューブ状とし使用する場合がある(例えば特許文献1参照)が、加工可能なサイズが限定され、また、被覆対象物への被覆仕上がり外観を損ね易く、さらに貼り合わせた部分に印刷した場合、欠字するという問題がある。
【0005】
【特許文献1】
特開平6−345878号公報
【0006】
【課題を解決するための手段】
本発明は上記問題点を解消できる熱収縮性ポリエステルチューブを見出したものであって、その要旨とするところは、ポリエチレンテレフタレートを主成分とし、該ポリエチレンテレフタレートとポリトリメチレンテレフタレート又は該ポリエチレンテレフタレートとポリトリメチレンテレフタレートとポリブチレンテレフタレートとのブレンド樹脂より製膜されてなり、動的粘弾性測定により周波数1または10Hz、昇温速度1℃/分で測定された20〜70℃における貯蔵弾性率E’が1010〜1013[Pa]、100℃における貯蔵弾性率E’が108〜1010[Pa]であり、沸騰水中、5秒浸漬時の長さ方向の収縮率が0〜30%、径方向の収縮率が20〜70%であることを特徴とするシームレスの熱収縮性ポリエステルチューブにある。
【0007】
本発明では、上記チューブにおいて、チューブの固有粘度(測定方法:ASTM D2857に準拠)が0.5〜0.9[dl/g]であること、チューブ厚みが0.02〜0.6mm、チューブを折り畳んだ状態の幅が4〜300mmであるものを含んでいる。
【0008】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明のチューブに使用する原料樹脂としては、ポリエチレンテレフタレート(PET)とポリトリメチレンテレフタレート(PTT)又はPETとPTTとポリブチレンテレフタレート(PBT)を使用する。上記樹脂はPET成分を主成分とするものであり少量のコポリマー成分(PTT又はPTT+PBT)を適宜ブレンドして使用することができる。
【0009】
本発明のチューブでは、上記樹脂から製膜されてなるとともに、特定の粘弾性を有する必要がある。粘弾性特性としては、動的粘弾性測定により周波数1Hzまたは10Hz、昇温速度1℃/分で測定された20℃〜70℃における貯蔵弾性率E'が1010〜1013[Pa]、100℃における貯蔵弾性率E'が108〜1010[Pa]の範囲の動的粘弾性の挙動を示す必要がある。
上記範囲以外、つまり20℃〜70℃における貯蔵弾性率E'が1010[Pa]未満ではチューブに腰がなく、被覆対象物に被覆する場合に被覆し難い等、作業性に劣るという問題があり、1013[Pa]を超えるものでは硬すぎるという問題が生じる。
また、100℃における貯蔵弾性率E'が108[Pa]未満では軟らかく加工性が悪いという問題があり、1013[Pa]を超えるものでは硬すぎて製膜(延伸)できないという問題が生じる。
【0010】
上記貯蔵弾性率E'は、製膜されたチューブを用い、アイティー計測制御(株)製動的粘弾性測定装置(型式:DVA−200)を用いて、チューブの長さ方向で測定した数値である。測定周波数、1Hz又は、10Hz、測定温度域−50℃〜200℃、昇温速度1℃/分で測定した。
上記貯蔵弾性率の範囲内にするには、樹脂の組み合せ等を適宜行うことにより可能である。
【0011】
上記樹脂組成物から得られるチューブは、その固有粘度が0.5〜0.9[dl/g]の範囲のものが好ましい。固有粘度の測定は、ASTM D2857に準拠して行えばよく、0.5[dl/g]未満では機械的強度に劣り易く、0.9[dl/g]を超えるものでは、例えばコンデンサ等の実装工程等の高温下に曝された場合、一度収縮したチューブが弛緩し外観を損ねるばかりでなく、印字の判読を困難にし、被覆対象物の最終寸法精度を満足しないという問題があり、チューブの製膜性も劣り易い。
上記の範囲に固有粘度を調整する方法としては、製膜時の固有粘度低下を考慮して、使用する原料として適当な固有粘度のPET等を混合することにより、容易に得ることが出来る。
【0012】
本発明のチューブでは、上記樹脂組成からなり、特定の熱収縮を有するものが特にコンデンサや電池の被覆材としての性能が優れているものであり、
(1)沸騰水中、5秒浸漬時の長さ方向の収縮率が0〜30%、径方向の収縮率が20〜70%、好ましくは、30〜60%の範囲となるように調整することにより達成できる。
更に好ましくは(1)と同様に次の特性を満足するものが好ましい。
(2)70℃温水中、5秒浸漬時の長さ方向の収縮率が0〜10%、好ましくは、0〜8%の範囲、径方向の収縮率が15〜50%、好ましくは、20〜50%となるように調整する。
【0013】
上記(1)の熱収縮特性、好ましくは(1)及び(2)の熱収縮特性を満足しないチューブは、被覆外観が悪くなり、被覆対象物に被覆する場合に多くの熱量を必要とし、エネルギーコストが割高になる傾向がある。(1)、(2)の特性を満たせば、既存の被覆機を用い、PVCチューブとほぼ同じ条件で被覆することが可能となる。なお、上記収縮率は、沸騰水や温水中に5秒間浸漬した際に得られる収縮率であるが、これまでに同様の評価において温水中に30秒間浸漬した際の収縮率を用いる場合があるが、近年、生産性の向上を目的としてコンデンサなどにチューブを被覆する工程の速度が早くなり、被覆に要する加熱が高温で時間が短くなる傾向があり、従来の測定時間では現実の生産工程と合致し難いため上記条件としている。
【0014】
本発明のチューブの製造方法は通常のチューブラ法により製膜することができ、上記記載のポリエステル原料を溶融後チューブ状に環状ダイで円筒状に押出して成形加工することにより達成される。
本発明の収縮率を得るために、上記のように押出した未延伸チューブの長さ方向に1.0〜2.0倍、径方向に1.2〜4.5倍延伸する製膜法がある。得られるチューブの厚みが0.02〜0.6mmで、チューブを折り畳んだ状態の幅(以下「折径」という)が4〜300mmの範囲のものは汎用コンデンサや電池の被覆、汎用の電池のパッケージング全般に対応できる点で好ましい。
本発明の熱収縮性ポリエステルチューブでは、チューブに易滑性を向上させるため有機滑剤、無機滑剤、無機充填剤を添加したり、また必要に応じて可塑剤、安定剤、着色剤、酸化防止剤、紫外線吸収剤等の助剤を配合することができる。
【0015】
以下、本発明を実施例により更に具体的に説明するが、本発明は実施上の内容に限定されるものではない。
【実施例】
【0016】
収縮率:
沸騰水又は70℃の温水中に5秒間浸漬した前後の長さ及び折径を測定して、算出した。
長さ方向収縮率[%]=[(浸漬前の長さ−浸漬後の長さ)/浸漬前の長さ]×100
径方向収縮率[%]=[(浸漬前の折径−浸漬後の折径)/浸漬前の折径]×100
【0017】
コンデンサの耐熱性:
コンデンサ(φ8)に熱収縮性チューブを被覆した後、160℃の熱風循環式オーブンに5分間入れて加熱して、加熱後のチューブの外観を目視で評価した。
(○) チューブに膨れ、緩みなどなく生地の変化もなく外観が良好
(△) チューブに膨れ、緩みなどが若干発生して、生地も若干変化するが、使用可能
(×) チューブに膨れ、緩みなどが顕著に発生して、生地も変化して外観不良のため
使用できない。
【0018】
被覆外観:
コンデンサに被覆した際の仕上がり外観を目視にて評価した。
(○) 胴体部の皺、端面の立ちあがり等が無く外観が極めて良好。
(△) 胴体部の皺、端面の立ちあがり等が発生し外観が悪い。
(×) 胴体部の皺、端面の立ちあがり等が発生し外観が極めて悪い。
【0019】
[実施例1〜3及び比較例1]
表1に記載した内容の樹脂組成物(重量%)をシリンダー温度270℃に設定した押出機で溶融させ丸ダイを通してチューブラ成形加工し、外径8.8mm、厚み75μmのシームレスの熱収縮性ポリエステルチューブを得た。得られたチューブに付いて特性を評価した結果を表1に示した。
【0020】
なお、表1に示した各略称は下記内容を意味している。
樹脂組成物A:ポリエチレンテレフタレート樹脂
(固有粘度0.7〜0.8[dl/g]:日本ユニペット社:ユニペットRT553)
樹脂組成物B:ポリトリメチレンテレフタレート樹脂
(固有粘度0.7[dl/g] :シェルケミカルズジャパン社:コルテラ)
樹脂組成物C:ポリブチレンテレフタレート樹脂
(固有粘度0.9[dl/g] 三菱エンジニアリングプラスチック社:ノバデュラン5505)
【0021】
【0022】
【0023】
表1、表2より本発明の熱収縮性ポリエステルチューブは熱収縮性、被覆外観に優れていることがわかる。
【発明の効果】
本発明の熱収縮性ポリエステルチューブは熱収縮性、耐熱性及び被覆外観に優れている。したがって、従来の塩化ビニル系熱収縮チューブやポリエステル系熱収縮シームレスチューブで用いられているコンデンサ、1次電池、2次電池等の電子部品への被覆以外にも蛍光灯、OA機器、鋼管への被覆、さらにはキャップシール、雑貨用途への有用性も大である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a seamless polyester tube provided with heat shrinkage, and is a tube particularly excellent in shrinkage characteristics and excellent in durability after heat shrinkage, such as an aluminum solid capacitor, an aluminum non-solid capacitor, a primary battery, The present invention relates to a heat-shrinkable polyester tube having a large utility value as a coating material for electronic parts such as a secondary battery, a fluorescent lamp, a light source for OA composite equipment, a coating material for steel pipes, a cap seal, and miscellaneous goods.
[0002]
[Prior art and problems]
As a heat-shrinkable tubular electrical insulating material for covering electronic parts such as capacitors and batteries, a heat-shrinkable tube made of polyvinyl chloride resin (PVC) or polyethylene terephthalate resin (PET) is usually used. .
However, the tube made of polyvinyl chloride resin is inexpensive but has a problem in heat resistance, and there is a problem that environmental problems associated with waste disposal are likely to occur.
Polyethylene terephthalate resin tubes are excellent in heat resistance, but when they are covered with one piece from the body to the end surface of a cylindrical object such as a capacitor or battery, the tube contracted at the end surface becomes curled or locally contracted. As a result, there is a problem in that the appearance of the finished coating is greatly impaired and the final dimensional accuracy of the object to be coated is not satisfied.
[0003]
Therefore, as a means for improving the finished appearance of the coating, a method of making the contraction rate in the length direction of the tube smaller than the contraction rate in the radial direction is known. In this method, the appearance of the finished coating on the object to be coated is improved. However, when exposed to a high temperature such as a mounting process of a capacitor or the like, the tube once shrunk loosens, not only deteriorating the appearance, but also printing. This makes it difficult to read the data and does not satisfy the final dimensional accuracy of the coated object.
[0004]
Furthermore, the polyethylene terephthalate resin tube has a problem that it requires a larger amount of heat when the object to be coated is coated, and the energy cost is higher than that of the polyvinyl chloride resin tube. Therefore, from the conventional polyethylene terephthalate resin tube, using a heat-shrinkable polyester film having a low shrinkage start temperature, there is a case where the end portion is back-pasted and used as a tube shape (see, for example, Patent Document 1). There is a problem that the size that can be processed is limited, the coating finish appearance on the coating object is easily damaged, and the characters are missing when printed on the bonded portion.
[0005]
[Patent Document 1]
JP-A-6-345878
[Means for Solving the Problems]
The present invention has found a heat-shrinkable polyester tube capable of solving the above-mentioned problems, the gist of which is polyethylene terephthalate as a main component, the polyethylene terephthalate and polytrimethylene terephthalate or the polyethylene terephthalate and poly Storage elastic modulus E ′ at 20 to 70 ° C. formed from a blend resin of trimethylene terephthalate and polybutylene terephthalate and measured at a frequency of 1 or 10 Hz and a heating rate of 1 ° C./min by dynamic viscoelasticity measurement. Is 10 10 to 10 13 [Pa], the storage elastic modulus E ′ at 100 ° C. is 10 8 to 10 10 [Pa], and the shrinkage in the length direction when immersed in boiling water for 5 seconds is 0 to 30%. Seamless heat-shrinkable polyester having a shrinkage ratio in the radial direction of 20 to 70% It is in Tertub .
[0007]
In the present invention, the tube has an intrinsic viscosity (measurement method: conforming to ASTM D2857) of 0.5 to 0.9 [dl / g], a tube thickness of 0.02 to 0.6 mm, The width of the folded state is 4 to 300 mm.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
Polyethylene terephthalate (PET) and polytrimethylene terephthalate (PTT) or PET and PTT and polybutylene terephthalate (PBT) are used as the raw material resin used in the tube of the present invention. The above resin contains a PET component as a main component and can be used by appropriately blending a small amount of a copolymer component (PTT or PTT + PBT) .
[0009]
In the tube of this invention, while forming into a film from the said resin, it is necessary to have specific viscoelasticity. As the viscoelastic characteristics, the storage elastic modulus E ′ at 20 ° C. to 70 ° C. measured at a frequency of 1 Hz or 10 Hz and a temperature rising rate of 1 ° C./min by dynamic viscoelasticity measurement is 10 10 to 10 13 [Pa], 100. It is necessary to exhibit dynamic viscoelastic behavior in the range of storage elastic modulus E ′ at 10 ° C. in the range of 10 8 to 10 10 [Pa].
When the storage elastic modulus E ′ at 20 ° C. to 70 ° C. is less than 10 10 [Pa] except the above range, there is a problem that the tube has no waist and is inferior in workability. Yes, if it exceeds 10 13 [Pa], there is a problem that it is too hard.
Further, when the storage elastic modulus E ′ at 100 ° C. is less than 10 8 [Pa], there is a problem that it is soft and the workability is poor, and when it exceeds 10 13 [Pa], the film is too hard to be formed (stretched). .
[0010]
The storage elastic modulus E ′ is a numerical value measured in the length direction of a tube using a film-formed tube and a dynamic viscoelasticity measuring device (model: DVA-200) manufactured by IT Measurement Control Co., Ltd. It is. Measurement was performed at a measurement frequency of 1 Hz or 10 Hz, a measurement temperature range of −50 ° C. to 200 ° C., and a heating rate of 1 ° C./min.
In order to make it in the range of the said storage elastic modulus, it is possible by performing combining of resin etc. suitably.
[0011]
The tube obtained from the resin composition preferably has an intrinsic viscosity in the range of 0.5 to 0.9 [dl / g]. The intrinsic viscosity may be measured in accordance with ASTM D2857. If it is less than 0.5 [dl / g], the mechanical strength tends to be inferior. If it exceeds 0.9 [dl / g], for example, a capacitor or the like When exposed to high temperatures such as in the mounting process, the tube once shrunk loosens and deteriorates the appearance, making it difficult to interpret the print and not satisfying the final dimensional accuracy of the coated object. The film forming property is also inferior.
As a method for adjusting the intrinsic viscosity within the above-mentioned range, it can be easily obtained by mixing PET having an appropriate intrinsic viscosity as a raw material to be used in consideration of a decrease in intrinsic viscosity during film formation.
[0012]
In the tube of the present invention, the one having the above resin composition and having a specific heat shrinkage is particularly excellent in performance as a capacitor or battery coating material,
(1) Adjust so that the contraction rate in the length direction when immersed in boiling water for 5 seconds is 0 to 30%, the contraction rate in the radial direction is 20 to 70%, preferably 30 to 60%. Can be achieved.
More preferably, those satisfying the following characteristics as in (1) are preferred.
(2) The shrinkage in the length direction when immersed in 70 ° C. warm water for 5 seconds is 0 to 10%, preferably in the range of 0 to 8%, and the shrinkage in the radial direction is 15 to 50%, preferably 20 Adjust to -50%.
[0013]
A tube that does not satisfy the heat shrinkage characteristics of (1) above, preferably (1) and (2), has a poor coating appearance, and requires a large amount of heat when coated on the object to be coated. Cost tends to be high. If the characteristics of (1) and (2) are satisfied, it is possible to coat under the same conditions as the PVC tube using an existing coating machine. In addition, although the said shrinkage rate is a shrinkage rate obtained when immersed in boiling water or warm water for 5 seconds, the shrinkage rate when immersed in warm water for 30 seconds in the same evaluation so far may be used. However, in recent years, the speed of the process of coating a tube on a capacitor or the like has been increased for the purpose of improving productivity, and the heating required for coating tends to be short at a high temperature. The above conditions are used because it is difficult to match.
[0014]
The tube production method of the present invention can be formed by a normal tubular method, and is achieved by melting the above-described polyester raw material into a tube shape and then extruding it into a cylindrical shape with an annular die.
In order to obtain the shrinkage rate of the present invention, a film forming method of stretching 1.0 to 2.0 times in the length direction of the unstretched tube extruded as described above and 1.2 to 4.5 times in the radial direction is performed. is there. A tube having a thickness of 0.02 to 0.6 mm and a width in which the tube is folded (hereinafter referred to as “folded diameter”) in the range of 4 to 300 mm is a general-purpose capacitor or battery cover, This is preferable in that it can be applied to packaging in general.
In the heat-shrinkable polyester tube of the present invention, an organic lubricant, an inorganic lubricant, and an inorganic filler are added to the tube to improve lubricity, and a plasticizer, a stabilizer, a colorant, and an antioxidant are added as necessary. An auxiliary agent such as an ultraviolet absorber can be blended.
[0015]
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the contents of the embodiments.
【Example】
[0016]
Shrinkage factor:
The length and folding diameter before and after being immersed in boiling water or warm water at 70 ° C. for 5 seconds were measured and calculated.
Lengthwise shrinkage [%] = [(length before immersion−length after immersion) / length before immersion] × 100
Radial shrinkage [%] = [(folded diameter before immersion−folded diameter after immersion) / folded diameter before immersion] × 100
[0017]
Capacitor heat resistance:
After the heat-shrinkable tube was coated on the capacitor (φ8), it was heated in a 160 ° C. hot air circulation oven for 5 minutes, and the appearance of the heated tube was visually evaluated.
(○) Appearance is good with no swelling or looseness in the tube and no change in the fabric (△) Swelling or loosening of the tube occurs slightly, and the fabric changes slightly, but it can be used (×) The tube expands and loosens Etc. occur remarkably, the fabric changes and cannot be used due to poor appearance.
[0018]
Cover appearance:
The finished appearance when the capacitor was coated was visually evaluated.
(○) The appearance of the body is extremely good with no wrinkles on the fuselage or rising of the end face.
(△) The appearance of the fuselage is poor due to wrinkles on the body and rising edges.
(×) Wrinkles of the body part, rising of the end face, etc. occur and the appearance is extremely bad.
[0019]
[Examples 1 to 3 and Comparative Example 1]
The resin composition (% by weight) described in Table 1 is melted with an extruder set at a cylinder temperature of 270 ° C., and tubular molded through a round die. A seamless heat-shrinkable polyester having an outer diameter of 8.8 mm and a thickness of 75 μm. A tube was obtained. Table 1 shows the results of evaluating the characteristics of the obtained tube.
[0020]
In addition, each abbreviation shown in Table 1 means the following contents.
Resin composition A: Polyethylene terephthalate resin (intrinsic viscosity 0.7 to 0.8 [dl / g]: Nihon Unipet Corporation: Unipet RT553)
Resin composition B: Polytrimethylene terephthalate resin (inherent viscosity 0.7 [dl / g]: Shell Chemicals Japan, Inc .: Cortera)
Resin composition C: Polybutylene terephthalate resin (inherent viscosity 0.9 [dl / g] Mitsubishi Engineering Plastics: Nova Duran 5505)
[0021]
[0022]
[0023]
Tables 1 and 2 show that the heat-shrinkable polyester tube of the present invention is excellent in heat-shrinkability and coating appearance.
【The invention's effect】
The heat shrinkable polyester tube of the present invention is excellent in heat shrinkability, heat resistance and coating appearance. Therefore, in addition to coating capacitors, primary batteries, secondary batteries and other electronic parts used in conventional vinyl chloride heat shrinkable tubes and polyester heat shrinkable seamless tubes, fluorescent lamps, OA equipment, and steel pipes It is also very useful for coating, cap seals, and miscellaneous goods.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069648A JP4243797B2 (en) | 2003-03-14 | 2003-03-14 | Heat shrinkable polyester tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003069648A JP4243797B2 (en) | 2003-03-14 | 2003-03-14 | Heat shrinkable polyester tube |
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| Publication Number | Publication Date |
|---|---|
| JP2004276364A JP2004276364A (en) | 2004-10-07 |
| JP4243797B2 true JP4243797B2 (en) | 2009-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2003069648A Expired - Fee Related JP4243797B2 (en) | 2003-03-14 | 2003-03-14 | Heat shrinkable polyester tube |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100814290B1 (en) | 2006-10-31 | 2008-03-18 | 한국생산기술연구원 | Polyester Heat Shrinkable Tube for Capacitor Covering |
| CN100543061C (en) * | 2007-03-22 | 2009-09-23 | 南亚塑胶工业股份有限公司 | Mixed thermoplastic polyester and heat shrinkable sleeve made of same |
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| JP2004276364A (en) | 2004-10-07 |
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