TWI292409B - Biaxially oriented polyester films and processing method thereof - Google Patents
Biaxially oriented polyester films and processing method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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Description
I2924Q§58pifdoc 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種具有良好扭轉特質的雙軸向聚酯 薄膜，且特別是有關於一種用於包裝糖果、巧克力、焦糖 荨的雙軸向聚酯薄膜以及製造雙軸向聚酯的方法，此雙軸 向聚酯薄膜被賦予扭轉特性，且雙軸向聚酯薄膜本身具有I2924Q§58pifdoc IX. Description of the Invention: [Technical Field] The present invention relates to a biaxial polyester film having good torsion characteristics, and more particularly to a package for confectionery, chocolate, caramel Biaxial polyester film and method for producing biaxial polyester, the biaxial polyester film is imparted with torsional characteristics, and the biaxial polyester film itself has
良好機械性質、可列印性、透明性、厚度均一性、裁切性、 無毒害性等。 【先前技術】 禾工i的冰a日塑成品已廣泛的使用在纖維、 薄膜與其他塑成品，特別是聚氧化乙烯對二為 (polyethyleneterephthalate，PET)塑成品。特別是，從芳名 二羧酸（aromatic dicarboxylic ad(J)與乙烯乙二 g (ethyleneglycol)^^^ ^ pET ， 其包括抗高溫、延展力、延伸比、揚氏係數、彈性回復力 财撞擊性、尺寸穩定性、轉電特料，所以其可作為』 業材料，農業材料，例如磁帶、相機底片 、絕緣材料、_ ^尤積㈣（域相沈積而成的薄膜)等。此外，由於聚館 j之化¥性質’包括抗化學性、耐久性、防水性以及这 二胺：ί香味特性、防水、阻礙氣體特性，因此使得影 專=為包裝材料的實用性大為增加。 PET取tf^’PET薄膜的工業製造方法包括融化喷庄 薄片Π ίί且在冷卻财冷卻融化喷出物則彡成非結盖 非結晶薄片進行回火以形成雙軸向薄臈。名Good mechanical properties, printability, transparency, thickness uniformity, cutability, non-toxicity, etc. [Prior Art] Wogong i's ice-a-plastic products have been widely used in fibers, films and other plastic products, especially polyethylene terephthalate (PET) plastic products. In particular, from the aromatic dicarboxylic ad (J) and ethylene ethylene (ethyleneglycol) ^ ^ ^ ^ pET, which includes high temperature resistance, ductility, elongation ratio, Young's coefficient, elastic recovery force impact , dimensional stability, special materials for turning, so it can be used as a material, agricultural materials, such as magnetic tape, camera film, insulating materials, _ ^ special product (four) (film deposited by domain phase), etc. The nature of the museum's use includes chemical resistance, durability, water repellency, and the diamine: scent characteristics, water resistance, and gas barrier properties, thus greatly increasing the practicality of packaging materials for PET. ^'Industrial manufacturing methods for PET film include melting the sprayed sheet and drying the melted material to form a non-junched amorphous sheet for tempering to form a biaxial thin crucible.
有相當大的工業價值。然而，PET薄膜的實用性卻僅限於 一些應用上。特別是，由於使用在包裝糖果、巧克力、焦 糖等的薄膜必須具有良好的扭轉特性、高剛挺度、可列印 1292409 17258pif.doc 则朗PET聚合物的工業製造方法中，服 氏細至28G度且在周遭環境勤或有壓力 =件下製備’其係將二羧酸作為主要成分，例如是雜 ，(therephthalic acid)舆乙稀乙二醇(ethylen物⑽，並將 其直接進行酯化反應而製得。或者是在攝氏140至240度 且於催化劑存在之條件下，將二甲基碳酸酯作為主要成 伤’其例如疋—甲基對細旨以及乙烯乙二醇進行反醋化反 應’以製得以雙(β·羥基乙基）對酞酯及其低分子量縮合物 為主之成份，然後在攝氏260至3〇〇度將其與聚縮合催化 物一起成功的加熱以進行聚縮合反應。 由於PET薄膜具有良好機械性質，使得pet薄膜具 性、對人體無毒害性、裁切性等。但是，pET薄膜卻由於 其高回復性而具有非常微弱的扭轉性質。 此外，由於玻璃紙、OPS、PVC薄膜等具有良好的扭 轉特性，因而已廣泛用來包括糖果、巧克力、焦糖等。 然而，以PVC薄膜來說，由於其塑化劑會產生環境贺 爾蒙以及燃燒後產生戴奥辛等問題，所以PVC薄膜的使用 在許多國、家與區域是受到管制的。而且在一些食物的包裝 應用上，PVC薄膜的使用也是受到管制。 而以OPS來說，由於其具有較差的厚度均一性、熱穩 定度（尺寸穩定度）、機械粗糙度以及可處理性，所以也限 7 12924098pitd〇c 其實用性。再者，以玻軌來說，由於其沒有國内製 二：：因此必須仰賴進口。而且製造玻璃紙薄膜的過程被 j疋具有污㈣4。_是，玻魏聚合物的價格非 吊咼，所以也限制了其實用性。 近來，共擠壓的非向聚丙稀薄膜已逐漸開發並使用， 但由於其列印性及熱贼餘差，所財場财率相當低。 =，倘若PET薄膜缝具有可轉雜，此薄膜將 可滿足各働理性質，包括其他機_性、 =材Γ:均一性、裁切性、無毒害性等，因而侧^ A J而目别為止，由於pET薄膜的高回復性（彈 吏得具有扭轉特性的PET薄膜還未開發出來。 並二==要解決習知技術所產生的問題 及無環境污 ^及甘、狄方法，其储蛾予雙㈣聚酯薄膜扭轉特 性’且二具有良好機械性質、可列印性、透明性、厚产均 :性：ί切性、無毒害性等，因而可用作為包裝糖果，隹 糖、巧克力的材料。 不焦 為達此目的，本發明提供一種雙軸向聚 有70度或更小的可摺疊性⑻，其中可摺纽是夢由 度機(Heat Gradient)且在〇.2MPa壓力、J种#曰s二呆 度條件下，將一薄膜對半摺疊，並於3 ^彳兄溫 1來計算摺疊部分的角度而獲得。77鐘後猎由方程式There is considerable industrial value. However, the practicality of PET films is limited to some applications. In particular, since the film used for packaging candy, chocolate, caramel, etc. must have good torsional characteristics, high stiffness, and printable 1292409 17258pif.doc, the industrial method of manufacturing the PET polymer is as fine as 28G degree and prepared under the environment or under pressure = 'the main component of the dicarboxylic acid, such as the (therephthalic acid) ethylene glycol (ethylen (10), and directly ester Manufactured by a reaction, or at a temperature of 140 to 240 degrees Celsius and in the presence of a catalyst, dimethyl carbonate is used as a major injury, which is, for example, a quinone-methyl group and a vinyl acetate. The reaction is based on the preparation of bis(β·hydroxyethyl)-p- oxime ester and its low molecular weight condensate, and then it is successfully heated together with the polycondensation catalyst at 260 to 3 degrees Celsius. Polycondensation reaction. Due to the good mechanical properties of PET film, pet film is toxic, non-toxic to human body, cutting property, etc. However, pET film has very weak torsional properties due to its high recovery. In addition, because of the good torsional properties of cellophane, OPS, PVC film, etc., it has been widely used to include candy, chocolate, caramel, etc. However, in the case of PVC film, due to its plasticizer, it produces environmental hormones and After burning, it causes problems such as dioxin, so the use of PVC film is regulated in many countries, homes and regions. Moreover, in some food packaging applications, the use of PVC film is also regulated. For OPS, because of its Poor thickness uniformity, thermal stability (dimensional stability), mechanical roughness and handleability, so it is limited to 7 12924098pitd〇c. Its practicality. In addition, for the glass rail, because it has no domestic system :: Therefore, it must rely on imports. Moreover, the process of making cellophane film is contaminated by (4) 4. _ Yes, the price of BAO Wei polymer is not condolence, so it also limits its practicability. Recently, co-extruded non-directional polypropylene Thin film has been gradually developed and used, but due to its printability and hot thief surplus, the financial margin is quite low. = If the PET film seam has a turntable, the film Can meet the various physicochemical properties, including other machine _ sex, = material Γ: uniformity, cutting, non-toxic, etc., so the side ^ AJ and eyesight, due to the high recovery of pET film The PET film with torsional properties has not been developed. And the second == to solve the problems caused by the prior art and the environmental pollution and the method of Gan and Di, the moth to the double (four) polyester film torsion characteristics 'and two have good Mechanical properties, printability, transparency, and thick product are all: sex: cleavability, non-toxicity, etc., and thus can be used as a material for packaging candy, sucrose, and chocolate. For the purpose of the present invention, the present invention provides a The biaxial gather has a foldability of 70 degrees or less (8), wherein the foldable button is a Heat Gradient and a film is obtained under the conditions of MPa. 2 MPa pressure and J type 曰 s s. It is obtained by half folding and calculating the angle of the folded portion at 3 ^ 彳 温 1 . After 77 hours of hunting by the equation
1292409 17258pif.doc 方程式1 0-2sin-l(F/2L) 其中，F是連接對半摺疊薄膜的兩端點之虛線的距 離’且2L是摺疊薄膜的總距離。 此外，本發明亦提供一種製造雙軸向聚酯薄膜的程 序，此薄膜具有70度或更小的可摺疊性（0 )，其中可摺疊 性是藉由熱梯度機(Heat Gradient)且在〇.2MPa壓力、1秒 鐘以及環境溫度條件下，將一薄膜對半摺疊，並於3〇分鐘 後藉由方程式1來計算摺疊部分的角度而獲， 方程式1 0=2sin-l(F/2L) 其中’ F是連接對半摺疊薄膜兩端點的虛線的距離， 且2L是摺疊薄膜的總距離，此程序包括： 在融點或更高的溫度下融化一聚合物，其是從單獨的 ♦氧化乙烯對二苯(p〇lyethyleneterephthalate)或是結合至 少一共聚合成份而成的混合物而獲得，之後在玻璃轉換溫 度或更低的溫度下快速冷卻此融化的聚合物，以製出非結 晶薄片； 以大於橫向方向（TD)定位比例的機械方向(MD)定位 比例之方式對此非結晶薄片進行雙軸向處理，其係在機械 方向定位溫度滿足方程式2以及橫向方向定位溫度滿足方 程式3的條件下進行； 方程式21292409 17258pif.doc Equation 1 0-2sin-l(F/2L) where F is the distance of the dashed line connecting the ends of the half-folded film and 2L is the total distance of the folded film. Further, the present invention also provides a process for producing a biaxial polyester film having a foldability (0) of 70 degrees or less, wherein the foldability is by a heat gradient machine (Heat Gradient) and Under a pressure of 2 MPa, 1 second and ambient temperature, a film is folded in half, and after 3 minutes, the angle of the folded portion is calculated by Equation 1, and Equation 10 = 2 sin-l (F/2L) Where 'F is the distance connecting the dashed lines to the ends of the semi-folded film, and 2L is the total distance of the folded film. This procedure includes: Melting a polymer at a melting point or higher, which is from a separate ♦ Ethylene oxide p-p-ethylene terephthalate or a mixture of at least one copolymerized component, and then rapidly cooling the melted polymer at a glass transition temperature or lower to produce an amorphous flake. Biaxial processing of the amorphous sheet in a mechanical direction (MD) positioning ratio greater than the transverse direction (TD) positioning ratio, which is in the mechanical direction positioning temperature satisfying Equation 2 and the lateral direction positioning temperature Degree is satisfied under the condition of Equation 3; Equation 2
Tg $機械方向定位溫度(Tsm) $ Tg+3 0 °C 9 1292409 17258pif.doc 其中’ Tg是玻璃轉換溫度， 方程式3Tg $ mechanical orientation temperature (Tsm) $ Tg+3 0 °C 9 1292409 17258pif.doc where ' Tg is the glass transition temperature, Equation 3
Tsm S橫向方向定位溫度(Tst) $ Tsm+3 0 °C 其中，Tsm是機械方向定位溫度， 在溫度滿足方程式4的情況下，對此雙軸向薄膜進行回火;Tsm S transverse direction positioning temperature (Tst) $ Tsm+3 0 °C where Tsm is the mechanical orientation temperature, and the biaxial film is tempered when the temperature satisfies Equation 4.
方程式4Equation 4
Tg$回火溫度$Tst+30°C 其中’ Tg是玻璃轉換溫度，且Tst是橫向方向定位溫 度， 在滿足方程式5的條件下，鬆弛此回火的薄膜。 方程式5 -3%$鬆弛率$3% 【實施方式】 為讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉一較佳實施例，並配合所附圖式，作詳 細說明如下。 ，據本發明之聚酯薄膜，其具有70度或少於70度的 可摺宜性（如下所定義）以增加其扭轉特性。 在此，本發明的，，可摺疊性，，表示一角度，其是藉由熱 1292409 17258pif.doc =2ireat Gmdi!nt)且在G.2MPa壓力、1秒鐘以及環境 I _膜對半摺疊，並於3G分鐘後藉由方程 式1來计异摺®部分的角度。 方程式1 e=2sin- 1(F/2L) 其^ ’ F是連接對伟㈣膜兩端點的虛線的距離， 且2L疋摺疊薄膜的總距離。Tg$ tempering temperature $Tst + 30 °C where 'Tg is the glass transition temperature, and Tst is the lateral direction positioning temperature, and the tempered film is relaxed under the condition that Equation 5 is satisfied. The above-mentioned and other objects, features, and advantages of the present invention will become more apparent and understood. A detailed description is as follows. According to the polyester film of the present invention, it has a compromiseability of 70 degrees or less (as defined below) to increase its torsional characteristics. Here, the present invention, foldability, represents an angle which is by heat 1292409 17258 pif.doc = 2 ireat Gmdi! nt) and at G. 2 MPa pressure, 1 second and ambient I _ film half folding And after 3G minutes, the angle of the different-folding part is calculated by Equation 1. Equation 1 e = 2 sin - 1 (F / 2 L) where ^ ′ F is the distance connecting the dotted lines of the ends of the film of the wei (4) film, and the total distance of the 2 L 疋 folded film.
田田因為本發明的聚酯薄膜具有7〇度或少於70度的可摺 且I*生所以g將其作為包裝材料的聚醋薄膜以包裝糖果等 時:即使在一段長時間過後包裝也不會瓦解。倘若可摺疊 性是70度或更大時，在短時間後包裝就可能會瓦解，且内 容物就會暴露出來。因此，具有7 〇度摺疊性的聚乙稀薄膜 就不適合用於包裝材料。 再者，本發明的聚酯薄膜可由單獨的聚氧化乙烯對二 本(polyethyleneterephthalate)或結合至少一共聚合成份而 成之混合而獲得。 再者，上述之至少一共聚合成份最好是選自酸類、酯 類或醇類，更佳的是，酸類包括間苯二曱酸(isophthalic acid) 以及已二酸（adpic acid);酯類包括萘羧基甲基酯 (naphtalenecarboxylicmethylester);醇類包括二乙烯乙二醇 (diethyleneglycol)、聚乙稀乙二醇(polyethyleneglycol)、聚〜 丙烯乙二醇（polypropyleneglycol)以及聚四亞甲乙二醇 (polytetramethyleneglycol)。 接著，以下將描述製造聚酯薄膜的程序。 11 1292409 17258pif.doc 聚醋薄膜的扭轉特性可藉由最佳化聚酯薄臈的製造條 件來改善。 ” 如上所述，本發明的聚酯薄膜可由單獨的聚氧化乙烯 對二苯(polyethyleneterephthalate)或結合至少一共聚入成Tian Tian, because the polyester film of the present invention has a thickness of 7 degrees or less and is less than 70 degrees, so when it is used as a packaging material, the polyester film is used to package candy, etc., even after a long period of time. Will not collapse. If the foldability is 70 degrees or more, the package may collapse after a short time and the contents will be exposed. Therefore, a polyethylene film having a 7-fold folding property is not suitable for use in packaging materials. Further, the polyester film of the present invention can be obtained by mixing polyethylene oxide with polyethylene terephthalate alone or in combination with at least one copolymerization component. Further, the at least one copolymerization component is preferably selected from the group consisting of an acid, an ester or an alcohol, and more preferably, the acid includes isophthalic acid and adipic acid; the ester includes Naphtalenecarboxylicmethylester; alcohols include diethyleneglycol, polyethyleneglycol, polypropyleneglycol, and polytetramethyleneglycol . Next, a procedure for producing a polyester film will be described below. 11 1292409 17258pif.doc The torsional properties of polyester film can be improved by optimizing the manufacturing conditions of polyester tanning. As described above, the polyester film of the present invention may be copolymerized into polyethylene terephthalate alone or in combination with at least one copolymerized polyethylene oxide.
份而成得一混合物而獲得。而此共聚合成份的加入可透過 任何方法包括聚合方法或混合方法來完成。 U « 聚酯薄膜的製造條件可依據個別成分的熱行為來設 定。 ，口 一本發明之製造聚自旨薄膜的程序，第一步驟是在融點或 更高+的溫度下融化-聚合物，其是從單獨的聚氧化乙稀對 二苯(polyethyleneterephthalate)或結合至少一共聚合成份 而成的-混合物而獲得，之後在玻璃轉換溫度或更^的^ 度下快速冷卻此融化的聚合物，以製出非結晶薄片。/皿 接著’第二步驟是以大於橫向方向定位比例的機械方 向疋位比例，在機械方向定位溫度滿足方程式2以及棒向 =位Ϊ度滿足方程式3的條件下，對此非結晶薄片進 订雙軸向處理。 也就是’對於定位步驟來說，機械方自（職心 ir=MD)定位溫度可以是在組成物的玻璃轉換溫度 鐘:Ϊ 溫度3G度的_。較佳的是，在接近破璃 轉換溫度的溫度下完成定位。 肖 成了疋位姐度至同於域方向定位溫度3〇度的範圍内完The mixture is obtained as a mixture. The addition of the copolymerization component can be carried out by any method including a polymerization method or a mixing method. U « The manufacturing conditions of the polyester film can be set according to the thermal behavior of the individual components. The procedure of the invention for producing a film from a film, the first step is to melt the polymer at a melting point or higher + temperature, which is from polyethylene terephthalate or a combination of polyethylene oxide alone. It is obtained by mixing at least a mixture of the components, and then rapidly cooling the melted polymer at a glass transition temperature or higher to produce an amorphous sheet. /The next step of the 'second step is the mechanical direction clamping ratio which is larger than the lateral direction positioning ratio, and the amorphous sheet is ordered under the condition that the mechanical direction positioning temperature satisfies the equation 2 and the rod direction = position twist satisfies the equation 3. Biaxial treatment. That is, for the positioning step, the mechanical position (employment ir = MD) positioning temperature can be the glass transition temperature of the composition: Ϊ temperature 3G degree _. Preferably, the positioning is completed at a temperature close to the glass transition temperature. Xiao became the sister-in-law to the range of 3 degrees in the same direction as the domain direction.
1292409 17258pif.doc 疋1立疋在機械方向谁 進行3-5:欠。較佳的是 :人’且在橫向方向 定位比例。 ㈣方向定位_大於横向方向 後在滿足方程式4的溫度 火，之後在滿足方程式5 姓士于又轴向賴進行回 >外β 、条件日守鬆他已回火的薄膜。 也就疋，在回火步驟中火、w 、 至高於橫向方向定位溫度3Q /；：度^介於玻轉換溫度 度或低—點。在後續的程序t 备要對雜加熱時’加祕理應 高溫度下完成以使耗損最錢。辣玻_換酿度或更 在^區中’鬆弛率（％)可以是3%或更少，最好是 〇更確切的說，是在加熱固定區（鬆弛率（％): =位。然而’在定位的情況下，可能會發生出現敵 /以下將配合幾個實_更詳細描述本發明，以下實例 疋用於解釋本發明，本發明的範圍不限於此。 實例1、2以及比較例1至4 非結晶薄片是藉由擠壓聚氧化乙烯對二苯 (polyethyleneterephthalate)，且之後快速冷卻擠壓的聚氧化 乙烯對—笨而製造出。而薄膜則是在表丨所列示的條件下 對此非結晶溥片進行雙轴向而製得。 根據不同掃猫比色（differential scanning calorimetry， DSC)的分析結果，快速冷卻的非向聚氧化乙烯對二苯的 玻璃轉換溫度是攝氏68度。 13 12924盤p_ 表1 非結晶 薄片的 Tg 定位溫度 (°C) 定位比例 鬆地率 (%) 回火溫 度（°c) MD TD MD TD 實例1 68〇C 90 100 4.5 3.8 —— 0 70 實例2 68〇C 90 100 4.0 3.8 0 80 比較例1 68〇C 100 130 4.5 3.8 7 230 比較例2 68〇C 90 100 4.5 3.8 7 230 比較例3 68〇C 95 130 4.5 3.8 0 230 比較例4 68〇C 95 140 4.0 3.5 0 150 在下列實例中，薄膜的可摺疊性的量測如下。1292409 17258pif.doc 疋 1 standing in the mechanical direction who carried out 3-5: owed. Preferably: the person's and the ratio is positioned in the lateral direction. (4) Directional orientation _ greater than the lateral direction After the temperature of the equation 4 is satisfied, after the flame is satisfied, the film surpasses the equation 5 and the axis is retracted > outside β, and the conditional day keeps the film that has been tempered. In other words, in the tempering step, the fire, w, and the positioning temperature higher than the lateral direction 3Q /;: degrees ^ between the glass transition temperature or low - point. In the subsequent procedure t, when it is necessary to heat the impurities, the addition of the secret should be done at a high temperature to make the most cost. Spicy glass _ change brewing degree or more in the ^ zone 'relaxation rate (%) can be 3% or less, preferably 〇 more precisely, is in the heating fixed zone (relaxation rate (%): = bit. However, in the case of positioning, it may occur that the enemies/belows will be described in more detail. The following examples are intended to explain the present invention, and the scope of the present invention is not limited thereto. Examples 1, 2, and comparison Examples 1 to 4 Non-crystalline flakes were produced by extruding polyethylene oxide polyethylene terephthalate, and then rapidly cooling the extruded polyethylene oxide pair, while the film was listed in Table 丨. Under the condition, the amorphous ruthenium is biaxially prepared. According to different analysis results of differential scanning calorimetry (DSC), the glass transition temperature of the rapidly cooled non-oriented polyethylene oxide to diphenyl is Celsius. 68 degrees. 13 12924 disk p_ Table 1 Tg positioning temperature of amorphous sheet (°C) Positioning ratio loosening rate (%) Tempering temperature (°c) MD TD MD TD Example 1 68〇C 90 100 4.5 3.8 —— 0 70 Example 2 68〇C 90 100 4.0 3.8 0 80 ratio Example 1 68〇C 100 130 4.5 3.8 7 230 Comparative Example 2 68〇C 90 100 4.5 3.8 7 230 Comparative Example 3 68〇C 95 130 4.5 3.8 0 230 Comparative Example 4 68〇C 95 140 4.0 3.5 0 150 In the following examples The measurement of the foldability of the film is as follows.
所謂可摺疊性，是當以越多的外力來改變仍無法回復 原始狀態的形體時，表示其扭轉特質就越好。因此，可以 以相同的壓力摺疊一薄膜相同的時間、鬆開壓力，之後再 比較薄膜的擅疊角度來評估可摺疊性。 ⑴瓜置·熱梯度機(Heat Gradient)(由Toy〇seiki製造） (2) 測量條件：壓力_(x2MPa、時間]秒、溫度_環境溫 度 (3) 樣本：尺寸（寬*長）-1〇毫米*15毫米 (4) 可摺疊性的評估方法 —如上所述，以相同壓力加壓於薄膜上，並於3〇分鐘後 计异摺疊部分的角度，再將所有實例進行比較。計算方法 可參考圖1以及依據方程式丨。圖丨中冒是8毫米且^是 8毫米。 ^可摺璺性可以計算出的Θ來作比較。在上述條件下， 倘右可摺$性是在〇度至7〇度的範圍，則表示扭轉特性是 良好的。 1292409 17258pif.doc 評估的結果如表2所示。 可摺疊性(Θ)。 _實例1 58 _實例2 62 比較例1 107 比較例2 81 比較例3 89 比較例4 78The so-called foldability is that when the more external force is used to change the shape that still cannot return to the original state, the better the twisting characteristic is. Therefore, it is possible to fold a film at the same pressure for the same time, release the pressure, and then compare the angle of the film to evaluate the foldability. (1) Heat Gradient (manufactured by Toy 〇 Seiki) (2) Measurement conditions: pressure _ (x2 MPa, time) seconds, temperature _ ambient temperature (3) Sample: size (width * length) -1 〇 mm * 15 mm (4) Evaluation method of foldability - as described above, pressurize the film at the same pressure, and measure the angle of the folded portion after 3 minutes, and then compare all the examples. Refer to Figure 1 and according to the equation 丨. The figure is 8 mm and the figure is 8 mm. ^ The creasability can be calculated by comparing the Θ. Under the above conditions, if the right is $ $ is in 〇 The range of degrees to 7 degrees indicates that the torsional characteristics are good. 1292409 17258pif.doc The results of the evaluation are shown in Table 2. Foldability (Θ). _Example 1 58 _Example 2 62 Comparative Example 1 107 Comparative Example 2 81 Comparative Example 3 89 Comparative Example 4 78
如表2的結果所示，根據本發明之方法所製造的心細 薄膜其可摺疊性是70度或更低，因此聚酯薄膜顯系具有良 好的摺疊特性。 實例3至7以及比較例5 此些實例是關於結合共聚合成份所製造出的雙軸向聚 酯薄膜。非結晶薄片是藉由結合共聚合成份（如表3所示） ϋ以擠壓共聚合聚酯來製造，再快速冷卻。非結晶聚酯共 聚合物薄片的玻璃轉換溫度是藉由DSC來測量，此結 示於表3。製造此薄膜的條件如下，其係包括在實例 圍中。 、、乾 -機械方向定位比例：4.0倍 -橫向方向定位比例：3·5倍 -機械方向定位溫度：Tg+25t： -松向方向定位溫度：機械方向定位溫度+ l〇°C -鬆弛率（％) : 0% -回火溫度：橫向方向定位溫度+ 10。〇 1292409 17258pif.docAs shown in the results of Table 2, the core film produced by the method of the present invention has a foldability of 70 degrees or less, so that the polyester film has a good folding property. Examples 3 to 7 and Comparative Example 5 These examples are about biaxial polyester films produced by combining copolymerized components. The amorphous sheet was produced by combining a copolymerized component (as shown in Table 3) to extrude a copolymerized polyester, and then rapidly cooled. The glass transition temperature of the amorphous polyester copolymer sheet was measured by DSC, which is shown in Table 3. The conditions for producing this film are as follows, which are included in the examples. , dry-mechanical direction positioning ratio: 4.0 times - lateral direction positioning ratio: 3 · 5 times - mechanical direction positioning temperature: Tg + 25t: - loose direction positioning temperature: mechanical direction positioning temperature + l 〇 ° C - relaxation rate (%) : 0% - Tempering temperature: Positioning temperature + 10 in the lateral direction. 〇 1292409 17258pif.doc
5〇。。imw除了加熱溫度是橫向方向定位溫度+ ==製r共聚合物薄片是以與實例3至7相 表35〇. . Imw except the heating temperature is the transverse direction positioning temperature + == r-composite sheet is in phase with examples 3 to 7
—如表3的結果所示，根據本發明之方法所製造的 ==性是70度或更低，因此聚㈣膜顯示具“ 工業可用性- As shown by the results of Table 3, the == property produced according to the method of the present invention is 70 degrees or less, so the poly(tetra) film display has "industrial availability"
如上所述，倘若聚酯薄膜滿足以本發明所測量 圍的可摺疊性時，由於聚自旨薄膜具有良好機械性質、、 列印性、透明性、厚度均一性、裁切性、無毒害性等，所 以此聚酯薄膜可用作為包裝糖果、焦糖、巧克力的材料。As described above, if the polyester film satisfies the foldability measured by the present invention, the film has good mechanical properties, printability, transparency, thickness uniformity, cutability, and non-toxicity. Etc., so this polyester film can be used as a material for packaging candy, caramel, and chocolate.
雖然本發明已以較佳實施例揭露如上，然其並非用以 限^本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保諜 範圍當視後附之申請專利範圍所界定者為準。 X 【圖式簡單說明】 圖1是繪示可摺疊性的計算方法的示意圖。 16 1292409 17258pif.doc 【主要元件符號說明】 W:薄膜的寬度 L:對半摺疊薄膜的距離 F:連接對半摺疊薄膜兩端點的虛線的距離 Θ:部分對半摺疊薄膜的角度，可摺疊性While the present invention has been described above in terms of the preferred embodiments thereof, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention shall be subject to the definition of the scope of the patent application. X [Simple Description of the Drawings] FIG. 1 is a schematic diagram showing a calculation method of foldability. 16 1292409 17258pif.doc [Description of main component symbols] W: Width of film L: Distance to half-folded film F: Distance connecting dashed lines to the ends of the half-folded film Θ: Angle of partial-folded film, foldable Sex
1717
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| KR101511761B1 (en) | 2013-10-04 | 2015-04-14 | 도레이첨단소재 주식회사 | Biaxially-Oriented Polyester Film, Method for Manufacturing the Same and Method for Controlling the Bagginess at the Ends of the Film |
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