TWI429691B - 熱可收縮性聚酯膜 - Google Patents
熱可收縮性聚酯膜 Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
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- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C09D5/26—Thermosensitive paints
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- 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
- B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
- B29C63/38—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor by liberation of internal stresses
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/02—Condition, form or state of moulded material or of the material to be shaped heat shrinkable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0049—Heat shrinkable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
- Y10T428/1331—Single layer [continuous layer]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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Description
本發明係有關於可用於包裹材料、更詳細地說,適於以標籤形式標示容器的熱可收縮性聚酯,因為其在收縮後具有良好成品外觀。
於一預定溫度下加熱時可收縮回到預拉製的形式之熱可收縮性膜業經廣泛用於以標籤形式標示之玻璃或塑膠瓶,因為其具有適於印刷各種物件以吸收消費者之注意並適於完全包裹各種容器以及包裝一捆貨物的性質。
由軟聚氯乙烯(PVC)製成的熱可收縮性膜最近已變得不受歡迎,因為其等具有有限的最大熱收縮比且一旦燃燒時會排放有毒污染物,例如戴奧辛(dioxin)。另一方面,定向性聚苯乙烯(OPS)膜具有均勻的收縮性質及低比重,且其等可輕易地自PET瓶移除以便再生處理,但是其等具有劣抗熱性的問題。因此,此等定向性聚苯乙烯膜不適於高速收縮法或高溫填充法。
具有收縮性質及抗熱性優於PVC及OPS膜之熱可收縮性聚酯膜業經研發以用於包裹玻璃瓶。然而,此等聚酯膜之收縮速率通常不能令人接受地高,當接受使用熱空氣之熱收縮法時,其會導致非均勻收縮現象,因此必需使用蒸汽加熱型收縮機器以防止該膜之非均勻收縮現象。此外,此聚酯膜之收縮應力不能令人接受地高,尤其當接受二次熱收縮方法(例如滅菌或高溫填充方法)時,其通常會導致非均勻收縮現象並因而產生畸變、末端彎曲或破裂。
為了解決上述問題,韓國專利早期公開案第2002-0063158號揭示一含對酞酸、乙二醇、1,4-環己二甲醇、及二乙二醇的共聚物組成物、及一使用該共聚物組成物製成之具有高柔軟度及似PVC之收縮化性質的熱可收縮性膜;且韓國專利早期公開案第2002-0062838號揭示一含5重量%或更多之聚酯彈性體的熱可收縮性聚酯膜。
然而,此等熱可收縮聚酯膜顯示下述裙現象(skirt phenomenon):一以標籤形式標示在具有夾持點(fixing point)之容器(諸如方形容器)上的薄膜會在與收縮方向互成直角的該等夾持點之間的中央處往上皺起;或往上皺起的現象:一以標籤形式標示在圓容器上之薄膜會以和收縮方向互成直角完全往上皺起,因此這些習知薄膜並不能有效用於保護容器或標示市售產物。
而且,亦已知習知聚酯膜具有以下缺點,諸如在高溫收縮化方法進行期間之非均勻熱收縮及起皺現象,其會導致已經過標籤標示之容器的外觀及品質之惡化。
因此,本發明之一目標為提供一具有以下優點的熱可收縮性聚酯膜,該等優點為由於具均勻熱收縮性及對往上皺起或裙現象之抗性,所以具有良好的外觀;以及可印刷性、機械強度、抗熱性、及收縮比特性之改良。
根據本發明之一方面,係提供一熱可收縮性聚酯膜,其在以下溫度範圍內沿著主收縮方向具有一熱收縮變化/℃(%/℃):在60至70℃之範圍內為1.5至3.0,在70℃至80℃之範圍內為2.5至3.5,在80℃至90℃之範圍內為1.0至2.0,而在90℃至100℃之範圍內為0.1至1.0。
可藉使用一共聚酯組成物而製備該熱可收縮性聚酯膜,該共聚酯組成物包含:(i)一二元酸組份,以100莫耳%該二元酸組份計,其含至少90莫耳%對酞酸殘基;及(ii)一二醇組份,以100莫耳%該二醇組份計,其含(a)1至20莫耳%二乙二醇、(b)5至30莫耳%新戊二醇、及(c)50至90莫耳%乙二醇。
此外,可藉以下方法製備該熱可收縮性聚酯膜,該方法包括以下步驟:(a)熔態擠壓一共聚酯組成物以獲得一薄片,然後於自Tg+5℃至Tg+20℃之溫度範圍下,以主收縮方向抽拉該薄片以獲得一定向薄膜;及(b)於一介於Tg+5℃與Tg+50℃間之溫度範圍下熱處理該定向薄膜。
根據本發明該熱可收縮性聚酯膜具有以下之改良效能特徵:可印刷性、機械強度、抗熱性、及適於完全包裹之可收縮性。而且,本發明該膜具往上皺起或裙現象的抗性且在一段時間內具有相當恆定的熱收縮變化。因此,本發明該膜在收縮後並不會顯現皺紋及畸變,因此在收縮後,其可獲得良好外觀品質。
自下文實施方式連同附圖可清楚本發明上述及其它目標及特徵,其中:第1圖:根據溫度之本發明明聚酯膜的熱收縮變化;而第2圖:表示一聚酯膜之裙比(skirt ratio)的闡明性圖解,其中W為收縮前之該膜的寬度,d為收縮後之該膜的寬度,而L為該膜之長度。
本發明該熱可收縮聚酯膜在以下溫度範圍內治著主收縮方向具有一熱收縮變化/℃(%/℃):在60至70℃之範圍內為1.5至3.0,在70℃至80℃之範圍內為2.5至3.5,在80℃至90℃之範圍內為1.0至2.0,而在90℃至100℃之範圍內為0.1至1.0。例如在一段時間內,沿著該主收縮方向的熱收縮變化意指如第1圖內所示,於各溫度區域下之曲線梯度。
如第1圖內所示,本發明該熱可收縮性聚酯膜具有一相當恆定的變化速率(亦即梯度),因此,不同於習知膜,該熱收縮比在整個溫度範圍內並不會激烈改變。詳細地說,已自第1圖發現於範圍自60至80℃之溫度下,本發明該膜顯示實質上恆定的變化速率,亦即似直線曲線,其與PVC膜之熱收縮性質類似。
根據本發明一較佳實例,可藉使用一共聚酯組成物而製成該熱可收縮性聚酯膜,該共聚酯組成物包含(i)一二元酸組份,以100莫耳%該二元酸組份計,其含至少90莫耳%對酞酸殘基、及(ii)一二醇組份,以100莫耳%該二醇組份計,其含(a)1至20莫耳%二乙二醇、(b)5至30莫耳%新戊二醇、及(c)50至90莫耳%乙二醇。
該共聚酯組成物可包含90莫耳%或更多之習知二元酸組份,諸如二亞甲基對苯二甲酸酯(DMT)或對酞酸(TPA)、較佳為含對酞酸(TPA)之二元酸組份。當該數量在上述範圍內時,該膜可具有一在拉製及熱處理方法進行期間藉該膜之定向作用而產生的微晶結構,因此其可得到改良的抗性。
此外,該共聚酯組成物可包今一二醇組份,以100莫耳%該二醇組份計,其含有1至20莫耳%二乙二醇(DEG)、5至30莫耳%新戊醇(NPG)、及50至90莫耳%乙二醇(EG)。
當該二乙二醇之含量為3莫耳%或更高時,可輕易獲得本發明該膜之特性,諸如低裙比(S/R)及恆定收縮速率。當該二乙二醇之含量為16莫耳%或更小時,該熱可收縮膜可具有改良抗熱性。
當該新戊二醇之含量在10至25莫耳%之範圍內時,可獲得令人滿意的收縮比且由於在拉製後之熱處理方法進行期間可防止定向晶體的過量產生或在熱收縮期間在一容器上之二次定向晶體的產生,所以以標籤形式標示在該容器上之所形成膜很難破裂。
該共聚酯組成物可進一步包含一反應催化劑、一聚合物定定劑、反應添加物、及無機材料等。
根據本發明之一較佳實例,該共聚酯組成物可包含0.3至0.5重量%該聚合物安定劑(例如磷酸三甲酯)、0.2至0.4重量該反應催化劑(例如三氧化銻)、及0.05至0.1重量%該無機材料(例如矽石)。
可使用,諸如鎂、錳及鋅金屬之乙酸鹽作為該反應催化劑。
用於本發明之該共聚組成物較佳具有0.6至0.9分升/克(dl/g)之固有黏度。當該固有黏度在上述範圍內時,該膜可獲得令人滿意的機械性質(諸如強度及伸長率),因此在後製程(諸如印刷及以標籤形式標示)期間該膜很難破裂。
當於90℃下在熱水內經處理,費時10秒時,本發明該熱可收縮性聚酯膜沿著主收縮方向之熱收縮比較佳為50%或更高、更佳55%或更高。當該熱收縮比為55%或更高時,在用於各種形狀之容器(甚至容器之頸部)的完全包裹方法中,該膜可獲得令人滿意的收縮現象。
此外,當在以該膜之主收縮方向固定兩端後,於90℃在熱水中經處理,費時10秒時,藉下式(I)而代表之本發明該熱可收縮性聚酯膜的裙比(S/R)較佳為14%或更小:
裙比(%)=(W-d)/L×100 (I)
其中,L為與該主收縮方向成一直線的該膜之長度,W為收縮前之該膜的寬度,d為收縮後之該厚的寬度。
當該裙比為14%或更小時,該膜顯示對以下裙現象及往上皺起現象之改良抗性,該裙現象為一以標籤形式標示在具有夾持點之容器(諸如方形容器)上的薄膜會在與收縮方向互成直角的該等夾持點之間的中央處往上皺起;而往上皺起現象為一以標籤形式標示在圓形容器上之薄膜會以和其收縮方向互成直角完全往上皺起,由於該改良之抗性,所以可獲得良好的成品外觀及該經印刷標籤之標示。
此外,當於90℃下在熱水中處理,費時10秒時,本發明該熱可收縮聚酯膜具有6N或更小的最大收縮應力、較佳3.0N至5.5N。較佳使用一具有40微米厚度之薄膜測定該最大收縮應力。當該最大收縮應力為6N或更小時,該薄膜可顯示對破裂、往上皺起或裙現象具高抗性且可避免該容器在以標籤標示期間發生畸變。
可藉一方法而製備本發明該聚酯膜,該方法包括以下步驟:(a)熔態擠壓該共聚酯組成物以獲得一薄片,然後較佳藉調整軋輥之沿周速度或使用一拉幅器而於Tg+5℃至Tg+20℃之溫度下,沿著該主收縮方向抽拉該薄片以獲得一定向薄膜;及(b)於一介於Tg+5℃與Tg+50℃間之溫度範圍下熱處理該定向薄膜。
較佳藉沿著該定向薄膜之主收縮方向固定兩端,然後使該固定薄膜通過一熱處理區(其溫度範圍介於Tg+5℃與Tg+5℃之間)而進行步驟(b)該熱處理方法。
就恆定收縮速率、該定向薄膜之熱收縮比、低收縮應力、及低裙比而言,該熱處理法較佳。當該熱處理之溫度為自Tg+5℃至Tg+50℃時,該薄膜可經充份地熱處理且可防止結晶過份成長以維持良好的機械性質。
以下實例係計劃用以進一步闡明本發明但無意限制其範圍
根據表1內所示的組成物及含量製備共聚酯樹脂,其係藉使用習用且在本發明之技術領域中已為吾人所熟知的共聚酯之標準製法(例如韓國專利第10-0987065號之實例1至7)而製成。
藉使用表2內所示的樹脂11至14而製成聚酯膜。熔態擠壓各樹脂以獲得薄片,於80℃下以4.0之比率,沿著主收縮方向抽拉該薄片以獲得一定向薄膜。固定沿著該定向薄膜之主收縮方向的兩端,然後藉快速通過一其中之溫度範圍介於85℃與105℃間的熱處理區而使該固定薄膜經熱定形以獲得具有40微米厚度之熱可收縮性聚酯膜。
藉下述方法而評估經由實例1至4、及比較例1至5所製成的該等薄膜之性質,且結果示於表3內。
沿著該主收縮方向將一薄膜試樣切成13.0厘米(長)×6.0厘米(寬)之片段。去除該試樣表面上之雜質,將該試樣之沿著主收縮方向的兩端固定,然後放入90℃之熱水中,費時10秒。如第1圖所示,測定收縮後該試樣之寬度,並使用以下方程式計算該試樣之裙比:
裙比(%)=[(收縮前試樣之寬度-收縮後試樣之寬度)/試樣之長度]×100
藉使用DSC(差示掃描式量熱法)而測定薄膜試樣的玻璃轉化溫度(Tg)。60℃或更高之Tg被分級為“O”,而小於65℃之Tg被分級為“X”。
將薄膜試樣包裹在重為22克且一側為6厘米之立方形容器上,然後使其通過蒸氣加熱型收縮隧道。其後,觀測該薄膜收縮後之外觀品質。各薄膜經測試20次。若收縮缺陷,諸如該薄膜之皺紋或往上皺起、或該容器之畸變被發現兩次或較少次,則該薄膜被分級為“O”,若被發現3次或更多次,則該薄膜被分級為“X”。
以和該主收縮方向成一直線,將薄膜試樣切成300毫米(長度)×15毫米(寬度)之片段並放入維持於60℃、70℃、80℃、90℃或100℃下之水浴內,費時10秒,且測定經該熱處理後之薄膜長度的變化。使用以下方程式計算收縮程度。
熱收縮比(%)=[(300-經熱處理後之試樣的長度)/300]×100。
將薄膜試樣切成120毫米(長度)×15毫米(寬度)之片段並於遠離該長度方向之兩側的5毫米部位標示。將此獲得之該110毫米長之薄膜試樣施加至一在夾盤之間具有95毫米之距離且配備一用於感測連接至其夾持器(grip)中之一者的收縮應力之測力器的裝置。其後,將配置該薄膜試樣之裝置放入已維持於90℃下之水浴內。當已發現收縮度為13.6%時,使該薄膜試樣經熱處理,費時1分鐘以獲得最大收縮應力。
測定在實例1至3、及比較例1與2中所獲得之薄膜、以及PVC與OPS膜的收縮圖案且結果示於表4及第1圖內。
使用表4內該等熱收縮比計算在各溫度範圍內沿著該主收縮方向之熱收縮變化/℃(%/℃)。
如表3至5、及第1圖內所示,實例1至3之本發明薄膜的機械強度、抗熱性及熱收縮效能特性優於習知薄膜,且本發明該等薄膜顯示完全包裹所需的均勻熱收縮。
雖然本發明業經參考上述具體實施例加以描述,但是應瞭解可藉熟悉本項技藝者而進行亦屬於藉附加申請專利範圍而定義的本發明範圍之各種修飾及變異。
第1圖:根據溫度之本發明明聚酯膜的熱收縮變化;而
第2圖:表示一聚酯膜之裙比(skirt ratio)的闡明性圖解,其中W為收縮前之該膜的寬度,d為收縮後之該膜的寬度,而L為該膜之長度。
Claims (5)
- 一種熱可收縮性聚酯膜,其在以下溫度範圍內沿著主收縮方向具有一熱收縮變化/℃(%/℃):在60至70℃之範圍內為1.5至3.0,在70℃至80℃之範圍內為2.5至3.5,在80℃至90℃之範圍內為1.0至2.0,且在90℃至100℃之範圍內為0.1至1.0,其中該熱可收縮性聚酯膜係藉使用一共聚酯組成物而製成,該共聚酯組成物包含(i)一二元酸組份,以100莫耳%該二元酸組份計,其含至少90莫耳%對酞酸殘基;及(ii)一二醇組份,其係由共聚合下列而製成:以100莫耳%該二醇組份計,(a)5至16莫耳%二乙二醇、(b)5至30莫耳%新戊二醇、及(c)50至90莫耳%乙二醇。
- 如申請專利範圍第1項之熱可收縮性聚酯膜,當其於熱水中在90℃下處理10秒時,沿著該主收縮方向具有58%或更高之熱收縮比、14%或較小之以式(I)表示的裙比(S/R)、及6N或較小之最大收縮應力:裙比(%)=(W-d)/L×100 (I)其中,L為沿著主收縮方向之該薄膜的長度,W為收縮前之該薄膜之寬度,d為收縮後該薄膜之寬度。
- 如申請專利範圍第1項之熱可收縮性聚酯膜,其中該共聚酯組成物進一步包含選自由下列所構成之群組中至少一者:一反應催化劑、一聚合物安定劑、一反應添加物、及一無機材料。
- 如申請專利範圍第1項之熱可收縮性聚酯膜,其中該共聚酯組成物具有一0.6至0.9分升/克之固有黏度。
- 一種用於製備如申請專利範圍第1項之熱可收縮性聚酯膜的方法,其包括以下步驟:(a)熔態擠壓一共聚酯組成物以獲得一薄片,然後於範圍自Tg+5℃至Tg+20℃之溫度下沿著主收縮方向抽拉該薄片以獲得一定向薄膜;及(b)於一範圍介於Tg+5℃與Tg+50℃間之溫度下,熱處理該定向薄膜。
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- 2011-03-07 US US13/041,831 patent/US8632865B2/en active Active
- 2011-03-08 TW TW100107714A patent/TWI429691B/zh active
- 2011-03-08 CN CN201110057308.6A patent/CN102190867B/zh active Active
- 2011-03-09 JP JP2011051400A patent/JP5971897B2/ja active Active
-
2012
- 2012-02-08 HK HK12101224.2A patent/HK1160878A1/zh unknown
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI727163B (zh) * | 2017-04-27 | 2021-05-11 | 日商東洋紡股份有限公司 | 熱收縮性膜用聚酯樹脂、熱收縮性膜、熱收縮性標籤以及包裝體 |
Also Published As
Publication number | Publication date |
---|---|
JP2011184690A (ja) | 2011-09-22 |
KR100981129B1 (ko) | 2010-09-10 |
TW201139531A (en) | 2011-11-16 |
CN102190867B (zh) | 2015-10-21 |
HK1160878A1 (zh) | 2012-08-17 |
EP2365025A1 (en) | 2011-09-14 |
US8632865B2 (en) | 2014-01-21 |
JP5971897B2 (ja) | 2016-08-17 |
US20110224369A1 (en) | 2011-09-15 |
CN102190867A (zh) | 2011-09-21 |
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