TW201714730A - Polyester film - Google Patents
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- TW201714730A TW201714730A TW105124892A TW105124892A TW201714730A TW 201714730 A TW201714730 A TW 201714730A TW 105124892 A TW105124892 A TW 105124892A TW 105124892 A TW105124892 A TW 105124892A TW 201714730 A TW201714730 A TW 201714730A
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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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- 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
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/02—Thermal shrinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
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Abstract
Description
本發明係關於具有特殊熱特性之聚酯薄膜。 This invention relates to polyester films having special thermal properties.
熱收縮薄膜被廣泛地用於包裝用途、標籤用途等，但近年為了將水系油墨、特殊油墨、水系塗劑或特殊塗劑等、在塗布、乾燥步驟中伴隨加熱步驟之塗劑進行印刷、塗布，在坯材薄膜(raw film)方面，尋求具有所謂「在塗布乾燥步驟中約90℃的低溫下具有不造成收縮等變形的耐熱性，在之後收縮步驟中的高溫下則會大幅度收縮」之特徴的熱收縮性薄膜。例如，在以茶或清涼飲料水等之瓶容器為主的包裝用途、利用薄膜的收縮而對複雜形狀之構件賦予高創意設計的裝飾用途、形成所謂相位差形成層之光學層的光學用脫模薄膜的用途中，兼具低溫下之低熱收縮率、及高溫下之高熱收縮率的需求日益增加。就熱收縮薄膜而言，為了使其於特定方向收縮，已知有如專利文獻1及2所代表之單軸延伸薄膜及藉由於橫方向延伸後再於縱方向逐次雙軸延伸而只於特定方向熱收縮的薄膜。 The heat-shrinkable film is widely used for packaging applications, labeling applications, and the like, but in recent years, printing and coating of a coating agent accompanying a heating step in a coating and drying step, such as a water-based ink, a special ink, a water-based paint, or a special coating agent. In the case of a raw film, it is sought to have a heat resistance which does not cause deformation such as shrinkage at a low temperature of about 90 ° C in the coating drying step, and it shrinks greatly at a high temperature in the subsequent shrinking step. A special heat shrinkable film. For example, in the case of packaging for bottle containers such as tea or soft drink water, the use of a film having a high-intentional design for shrinking the film, and the use of an optical layer forming a phase difference forming layer In the use of the mold film, there is an increasing demand for both a low heat shrinkage rate at a low temperature and a high heat shrinkage rate at a high temperature. In the heat shrinkable film, in order to shrink in a specific direction, a uniaxially stretched film represented by Patent Documents 1 and 2 is known, and since it is extended in the lateral direction and then sequentially biaxially extended in the longitudinal direction, it is only in a specific direction. Heat shrinkable film.
然而，在將專利文獻1或2所記載之單軸延伸薄膜、橫縱逐次雙軸延伸薄膜作為尋求上述低溫耐熱性 及高溫收縮特性之收縮性薄膜使用的情況，由於在約90℃大幅度收縮，而在塗布特殊油墨或塗劑之步驟中有所謂變形、收縮的問題。於是，尋求耐熱溫度更高，且在加熱至高溫之情況可大幅度收縮的薄膜。 However, the uniaxially stretched film and the horizontally and longitudinally biaxially stretched film described in Patent Document 1 or 2 are sought as the above-mentioned low-temperature heat resistance. In the case where the shrinkable film of the high-temperature shrinkage property is used, there is a problem of deformation and shrinkage in the step of applying a special ink or a coating agent due to a large shrinkage at about 90 °C. Thus, a film which has a higher heat-resistant temperature and can be largely shrunk when heated to a high temperature is sought.
[專利文獻1]日本特開2011-79229號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-79229
[專利文獻2]國際公開第2014/021120號 [Patent Document 2] International Publication No. 2014/021120
於是，本發明之課題，在於提供在作為塗布步驟、乾燥步驟等步驟溫度之約90℃時不收縮或收縮率小，在收縮步驟溫度時大幅度收縮的聚酯薄膜。 Accordingly, an object of the present invention is to provide a polyester film which does not shrink or shrink at a temperature of about 90 ° C as a coating step or a drying step, and which shrinks greatly at the shrinking step temperature.
為了解決上述課題，本發明之聚酯薄膜，其特徵為主收縮方向之150℃熱收縮率為15%以上，且與主收縮方向垂直的方向之150℃熱收縮率小於15%，主收縮方向之90℃熱收縮率為14%以下。又，其特徵為主收縮方向之150℃熱收縮率為15%以上且與主收縮方向垂直的方向之150℃熱收縮率小於15%，藉由調溫式DSC所得到之玻璃轉移溫度為100℃以上。 In order to solve the above problems, the polyester film of the present invention is characterized in that the heat shrinkage ratio at 150 ° C in the main shrinkage direction is 15% or more, and the heat shrinkage ratio in the direction perpendicular to the main shrinkage direction is less than 15%, and the main shrinkage direction is 150%. The 90 ° C heat shrinkage rate is 14% or less. Further, it is characterized in that the heat shrinkage rate at 150 ° C in the main shrinkage direction is 15% or more, and the heat shrinkage ratio at 150 ° C in the direction perpendicular to the main shrinkage direction is less than 15%, and the glass transition temperature obtained by the temperature-controlled DSC is 100. Above °C.
本發明之聚酯薄膜具有在150℃時於主收縮方向收縮15%以上，且於與主收縮方向垂直的方向收縮 小於15%，在90℃時於主收縮方向收縮14%以下的特殊熱特性。又，本發明之聚酯薄膜，具有主收縮方向之150℃熱收縮率為15%以上且與主收縮方向垂直的方向之150℃熱收縮率小於15%，藉由調溫式DSC所得到之玻璃轉移溫度為100℃以上的特殊熱特性。藉此，而在90℃時收縮率小，在各種功能層之塗布步驟、乾燥步驟中，可為了塗劑之延展或乾燥而充分加熱，然後，於150℃，由於展現所謂在主收縮方向收縮15%以上、且在與主收縮方向垂直的方向收縮小於15%之在特定方向大幅度收縮的特殊熱收縮性，所以適合用於包裝用途、裝飾用途、光學用途。 The polyester film of the present invention has a shrinkage of 15% or more in the main shrinkage direction at 150 ° C and shrinks in a direction perpendicular to the main shrinkage direction. Less than 15%, at 90 ° C, shrinks by 14% or less in the main shrinkage direction. Further, the polyester film of the present invention has a heat shrinkage ratio of 150 ° C in a main shrinkage direction of 15 ° C or more and a direction perpendicular to the main shrinkage direction of 150 ° C of less than 15%, which is obtained by a temperature-controlled DSC. The glass transition temperature is a special thermal characteristic of 100 ° C or higher. Thereby, the shrinkage rate is small at 90 ° C, and in the coating step and the drying step of the various functional layers, it can be sufficiently heated for stretching or drying of the coating agent, and then, at 150 ° C, exhibits a so-called shrinkage in the main shrinkage direction. 15% or more, and shrinking in a direction perpendicular to the main shrinkage direction by less than 15%, which shrinks in a specific direction, is suitable for packaging applications, decorative applications, and optical applications.
以下，針對本發明之聚酯薄膜，與實施之形態一起詳細地說明。 Hereinafter, the polyester film of the present invention will be described in detail together with the embodiment.
就賦予本發明聚酯薄膜所用之聚酯的二醇(glycol)或其衍生物而言，以乙二醇為80莫耳%以上為較佳，但就其他成分而言，可包含例如：1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇等脂肪族二羥基化合物；二乙二醇、聚乙二醇、聚丙二醇、聚四亞甲基二醇等聚氧伸烷基二醇；1,4-環己烷二甲醇等脂環族二羥基化合物；雙酚A、雙酚S等芳香族二羥基化合物；以及彼等之衍生物。 The glycol or the derivative thereof to which the polyester film of the polyester film of the present invention is applied is preferably 80 mol% or more of ethylene glycol, but may contain, for example, 1 for other components. , 2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, etc. a dihydroxy compound; a polyoxyalkylene glycol such as diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol; an alicyclic dihydroxy compound such as 1,4-cyclohexanedimethanol; An aromatic dihydroxy compound such as bisphenol A or bisphenol S; and derivatives thereof.
又，就賦予本發明所用之聚酯的二羧酸或其衍生物而言，以對苯二甲酸為80莫耳%以上為較佳，但就其他成分而言，可列舉例如：間苯二甲酸、鄰苯二甲酸、2,6-萘二甲酸、二苯基二甲酸、二苯基碸二甲酸(diphenylsulfonedicarboxylic acid)、二苯氧基乙烷二甲酸等芳香族二羧酸；草酸、琥珀酸、己二酸、癸二酸、二聚酸、馬來酸、富馬酸等脂肪族二羧酸；1,4-環己烷二甲酸等脂環族二羧酸；對羥基苯甲酸等羥基羧酸(oxycarboxylic acid)；以及彼等之衍生物。就二羧酸之衍生物而言，可包含例如：對苯二甲酸二甲酯、對苯二甲酸二乙酯、對苯二甲酸2-羥乙基甲酯、2,6-萘二甲酸二甲酯、間苯二甲酸二甲酯、己二酸二甲酯、馬來酸二乙酯、二聚酸二甲酯等酯化物。 Further, the dicarboxylic acid or the derivative thereof to which the polyester used in the present invention is added is preferably 80 mol% or more of terephthalic acid, but other components may, for example, be isophthalic acid. Aromatic dicarboxylic acid such as formic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethane dicarboxylic acid; oxalic acid, amber An aliphatic dicarboxylic acid such as an acid, adipic acid, sebacic acid, dimer acid, maleic acid or fumaric acid; an alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; p-hydroxybenzoic acid or the like; Oxycarboxylic acid; and derivatives thereof. As the derivative of the dicarboxylic acid, for example, dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, 2,6-naphthalene dicarboxylic acid Esterified products such as methyl ester, dimethyl isophthalate, dimethyl adipate, diethyl maleate, dimethyl dimerate.
在本發明中，從降低於90℃之主收縮方向的熱收縮率，且提高於150℃之主收縮方向的熱收縮率的觀點而言，又，從使藉由調溫式DSC所得到之玻璃轉移溫度為100℃以上，且提高於150℃之主收縮方向的熱收縮率的觀點而言，以聚酯的結晶性較高者為較佳，因此就二醇成分而言，以乙二醇為85莫耳%以上為較佳，更佳為90莫耳%以上。又，就二羧酸成分而言，以對苯二甲酸為85莫耳%以上為較佳，更佳為90莫耳%以上。但是，在欲提高熱收縮率之情況，尤其是對於聚對苯二甲酸乙二酯可藉由導入共聚合成分，提高非晶性，而使熱收縮率提升，因此從兼具熱收縮性及耐熱性的觀點而言，以含有3莫耳%以上共聚合成分為較佳，更佳為5莫耳%以上 ，特佳為10莫耳%以上。在將共聚合成分導入聚對苯二甲酸乙二酯之情況，就共聚合成分而言，可使用以上列舉之二羧酸成分或二醇成分之任一種，但從耐熱性的觀點而言，較佳使用2,6-萘二甲酸、1,4-環己烷二甲醇。 In the present invention, from the viewpoint of lowering the heat shrinkage ratio in the main shrinkage direction of 90 ° C and increasing the heat shrinkage ratio in the main shrinkage direction of 150 ° C, it is obtained from the temperature-controlled DSC. From the viewpoint of a glass transition temperature of 100 ° C or more and an increase in the heat shrinkage ratio in the main shrinkage direction of 150 ° C, it is preferred that the crystallinity of the polyester is higher, so in terms of the diol component, The alcohol is preferably 85 mol% or more, more preferably 90 mol% or more. Further, the dicarboxylic acid component is preferably 85 mol% or more of terephthalic acid, more preferably 90 mol% or more. However, when it is desired to increase the heat shrinkage rate, in particular, polyethylene terephthalate can increase the heat shrinkage rate by introducing a copolymerization component, thereby improving the heat shrinkage ratio, and thus has heat shrinkage and From the viewpoint of heat resistance, it is preferably contained in a copolymerization ratio of 3 mol% or more, more preferably 5 mol% or more. , especially good for 10% or more. When the copolymerization component is introduced into the polyethylene terephthalate, the copolymerization component may be any of the above-exemplified dicarboxylic acid component or diol component, but from the viewpoint of heat resistance, Preferably, 2,6-naphthalenedicarboxylic acid or 1,4-cyclohexanedimethanol is used.
本發明之聚酯薄膜，從兼具耐熱性及熱收縮性的觀點而言，以藉由調溫式DSC所得到之玻璃轉移溫度為90℃以上為較佳。於此，玻璃轉移溫度可藉由在後述特性之測定方法之(6)調溫式DSC玻璃轉移溫度中所記載的方法得到。本發明之聚酯薄膜，其目的為在各種功能層之塗布步驟溫度或乾燥步驟溫度範圍內之約90℃不引起收縮變形。因此，因為較佳為於90℃時降低薄膜體(film bulk)中之分子運動性，而較佳為使藉由調溫式DSC所得到之玻璃轉移溫度為90℃以上。若小於90℃，則在塗布各種功能層等後之乾燥步驟中薄膜有變形的情況。從兼具耐熱性及熱收縮性的觀點而言，以藉由調溫式DSC所得到之玻璃轉移溫度為95℃以上為較佳，以100℃以上為更佳。再者，在朝需要高耐熱性之用途發展的情況，藉由調溫式DSC所得到之玻璃轉移溫度必須為100℃以上，較佳為103℃以上120℃以下，而以105℃以上115℃以下為更佳。若藉由調溫式DSC所得到之玻璃轉移溫度為120℃以上，則有於150℃之熱收縮性變低的可能性。另一方面，若低於100℃，則在塗布各種功能層等後之乾燥步驟中有薄膜變形的情況。就使玻璃轉移溫度為90℃以上之方法而言，可藉由例如將成為剛直的成分共聚合而進行控制。再者，藉由共聚合成分之選擇、共聚合量 之控制、延伸條件之調整，可使玻璃轉移溫度為100℃以上。例如，就對於聚對苯二甲酸乙二酯之較佳共聚合成分而言，可列舉2,6-萘二甲酸、1,4-環己烷二甲醇等。又，可藉由調整製膜時之延伸方式、延伸倍率、延伸及熱處理之溫度而達成。 The polyester film of the present invention preferably has a glass transition temperature of 90 ° C or higher by a temperature-controlled DSC from the viewpoint of heat resistance and heat shrinkability. Here, the glass transition temperature can be obtained by the method described in (6) Temperature-controlled DSC glass transition temperature of the measurement method of the characteristics described later. The polyester film of the present invention has an object of not causing shrinkage deformation at about 90 ° C in the coating step temperature or the drying step temperature range of the various functional layers. Therefore, since the molecular mobility in the film bulk is preferably lowered at 90 ° C, it is preferred that the glass transition temperature obtained by the temperature-modulated DSC is 90 ° C or higher. If it is less than 90 ° C, the film may be deformed in a drying step after applying various functional layers or the like. From the viewpoint of having heat resistance and heat shrinkability, the glass transition temperature obtained by the temperature-controlled DSC is preferably 95 ° C or higher, more preferably 100 ° C or higher. Furthermore, in the case of development in applications requiring high heat resistance, the glass transition temperature obtained by the temperature-regulating DSC must be 100 ° C or higher, preferably 103 ° C or higher and 120 ° C or lower, and 105 ° C or higher and 115 ° C. The following is better. When the glass transition temperature obtained by the temperature-regulating DSC is 120 ° C or more, the heat shrinkability at 150 ° C may be lowered. On the other hand, when it is less than 100 ° C, the film may be deformed in the drying step after applying various functional layers or the like. The method of setting the glass transition temperature to 90 ° C or higher can be controlled by, for example, copolymerizing a component which is rigid. Furthermore, by the choice of copolymerization components, the amount of copolymerization The control and extension conditions can be adjusted to achieve a glass transition temperature of 100 ° C or higher. For example, examples of preferred copolymerization components of polyethylene terephthalate include 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedimethanol, and the like. Further, it can be achieved by adjusting the stretching mode, the stretching ratio, the elongation, and the temperature of the heat treatment during film formation.
本發明之聚酯薄膜，以可動非晶量為25%以上為較佳。於此，可動非晶量如在後述之特性之測定方法(5)可動非晶量(分率)中所記載，可藉由於調溫式DSC所測定之玻璃轉移溫度的比熱差而算出。若可動非晶量小於25%，則熱收縮步驟中顯示收縮行為之非晶成分量少，在150℃時，有變得無法在主收縮方向收縮15%以上的情況。又上限雖無特別限定，但由於在超過40%時，有機械性強度降低的情況，而以40%以下為較佳。為了使可動非晶量為25%以上，可藉由調整製膜時之延伸方式、延伸倍率、延伸及熱處理之溫度而達成。 The polyester film of the present invention preferably has a movable amorphous content of 25% or more. Here, the movable amorphous amount is as described in the measurement method (5) movable amorphous amount (fraction rate) of the characteristics described later, and can be calculated by the specific heat difference of the glass transition temperature measured by the temperature-controlled DSC. When the amount of the movable amorphous material is less than 25%, the amount of the amorphous component which exhibits the shrinkage behavior in the heat shrinkage step is small, and when it is 150 ° C, the shrinkage does not become 15% or more in the main shrinkage direction. The upper limit is not particularly limited. However, when it exceeds 40%, the mechanical strength is lowered, and 40% or less is preferable. In order to make the amount of movable amorphous material 25% or more, it can be achieved by adjusting the stretching method, the stretching ratio, the elongation, and the temperature of the heat treatment at the time of film formation.
本發明之聚酯薄膜，主收縮方向之150℃熱收縮率必須為15%以上。藉由使主收縮方向之150℃熱收縮率為15%以上，在使用於包裝用途、裝飾用途、光學用途等之情況，可顯示優良的收縮特性。較佳為20%以上，進一步更佳為25%以上，最佳為30%以上。為了使主收縮方向之150℃熱收縮率為15%以上，只要在延伸步驟中於收縮方向延伸即可。例如，若欲使其收縮15%，則必須延伸至少1.15倍以上，若為同元聚酯、尤其是聚對苯二甲酸乙二酯，則以使主收縮方向之折射率為1.6以上為較佳。又，在主收縮方向之折射率超過1.64而定向時， 在使與主收縮方向垂直的方向之150℃熱收縮率為小於15%的情況下，難以使主收縮方向之150℃熱收縮率為15%以上。因此，本發明中之聚酯薄膜之主收縮方向的折射率，以1.60以上1.64以下為較佳。於此，本發明中之主收縮方向，係指將薄膜之某一任意方向當作0°，在從其開始以5°間隔至180°為止之各方向測定150℃熱收縮率時，收縮率最高的方向。在本發明中，以主收縮方向為薄膜縱軸方向，與主收縮方向垂直的方向為薄膜寬度方向為較佳。藉由於薄膜縱軸方向顯示高收縮性，而在各種油墨或塗劑之塗布步驟、與其他功能層之貼合等的加工步驟中，可進行輥對輥(roll-to-roll)方式之貼合或加工，尤其是在光學用途中，能以輥對輥方式形成相位差層，因而較佳。 The polyester film of the present invention must have a heat shrinkage ratio of 150 ° C in the main shrinkage direction of 15% or more. When the heat shrinkage rate at 150 ° C in the main shrinkage direction is 15% or more, excellent shrinkage characteristics can be exhibited when used for packaging applications, decorative applications, optical applications, and the like. It is preferably 20% or more, further preferably 25% or more, and most preferably 30% or more. In order to make the heat shrinkage rate of 150 ° C in the main shrinkage direction 15% or more, it is sufficient to extend in the shrinkage direction in the stretching step. For example, if it is intended to shrink by 15%, it must be extended by at least 1.15 times. If it is a homopolyester, especially polyethylene terephthalate, the refractive index in the main shrinkage direction is 1.6 or more. good. Moreover, when the refractive index in the main contraction direction is more than 1.64 and oriented, When the heat shrinkage rate at 150 ° C in the direction perpendicular to the main shrinkage direction is less than 15%, it is difficult to set the heat shrinkage ratio at 150 ° C in the main shrinkage direction to 15% or more. Therefore, the refractive index of the polyester film of the present invention in the main shrinkage direction is preferably 1.60 or more and 1.64 or less. Here, the main shrinkage direction in the present invention means a shrinkage ratio when the heat shrinkage rate at 150 ° C is measured in any direction from the beginning of the film from 0° to 180° in any arbitrary direction of the film. The highest direction. In the present invention, the main shrinkage direction is the film longitudinal axis direction, and the direction perpendicular to the main shrinkage direction is preferably the film width direction. By exhibiting high shrinkage in the direction of the longitudinal axis of the film, in a processing step of coating processes of various inks or coatings, bonding with other functional layers, etc., roll-to-roll bonding can be performed. It is preferred to combine or process, especially in optical applications, to form a retardation layer in a roll-to-roll manner.
本發明之聚酯薄膜，與主收縮方向垂直的方向之150℃熱收縮率必須小於15%。通常若為依縱橫之順序逐次雙軸延伸的薄膜、或使縱橫之延伸倍率或延伸速度為相同而同時雙軸延伸的薄膜，在使與主收縮方向垂直的方向為薄膜寬度方向的情況，在寬度方向亦收縮。與此相對，例如，藉由使其為包含至少在寬度方向延伸後，在作為與其垂直的方向之縱軸方向延伸之步驟的逐次雙軸延伸方法，可使與主收縮方向垂直的方向之150℃熱收縮率為小於15%。推測此係藉由在使其暫時於寬度方向定向、結晶化之狀態下，使其於縱軸方向延伸，可使被認為是收縮成分之非晶成分選擇性地在縱軸方向歪曲。因此，就樹脂組成而言，以使用具有可定向結晶化 程度之結晶性的樹脂為較佳。又，定向結晶化係指以折射率或平面定向係數(plane orientation coefficient)所定義者，平面定向係數較佳為0.1以上，於不使非晶成分結晶化而使其歪曲之點，平面定向係數較佳為0.14以下。 The polyester film of the present invention must have a heat shrinkage ratio of 150 ° C in a direction perpendicular to the main shrinkage direction of less than 15%. In general, in the case of a film which is biaxially stretched in the order of vertical and horizontal directions, or a film in which the stretching ratio or the stretching speed of the longitudinal and lateral directions are the same and biaxially stretched, the direction perpendicular to the main shrinkage direction is the film width direction, The width direction also shrinks. On the other hand, for example, by making it a sequential biaxial stretching method including a step of extending at least in the width direction and extending in the direction of the longitudinal axis perpendicular to the direction perpendicular thereto, 150 directions perpendicular to the main contraction direction can be obtained. °C thermal shrinkage is less than 15%. It is presumed that the amorphous component, which is considered to be a contraction component, is selectively bent in the longitudinal direction by being stretched in the longitudinal direction while being temporarily oriented and crystallized in the width direction. Therefore, in terms of resin composition, the use of directional crystallization A degree of crystalline resin is preferred. Further, the directional crystallization refers to a plane orientation coefficient which is defined by a refractive index or a plane orientation coefficient, and preferably has a plane orientation coefficient of 0.1 or more, which is not distorted by crystallization of an amorphous component, and a plane orientation coefficient. It is preferably 0.14 or less.
本發明之聚酯薄膜，以主收縮方向之90℃熱收縮率為14%以下為較佳。本發明中，要求於各種功能層之塗布步驟或乾燥步驟的溫度下不收縮變形。與此相對，若超過14%，則由於塗布各種功能層後之乾燥步驟中會收縮變形，而有無法耐受該步驟的情況。又，從皺紋的減低等、使經塗布步驟、乾燥步驟之薄膜外觀提升的觀點而言，主收縮方向之90℃熱收縮率有必須為14%以下的情況。主收縮方向之90℃熱收縮率更佳為10%以下，進一步更佳為5%以下。為了使於90℃的主收縮方向之熱收縮率為14%以下，可藉由例如使薄膜之從調溫式DSC所得到之玻璃轉移溫度為90℃以上而達成。 The polyester film of the present invention preferably has a heat shrinkage ratio at 90 ° C in the main shrinkage direction of 14% or less. In the present invention, it is required to not shrink and deform at the temperature of the coating step or the drying step of the various functional layers. On the other hand, when it exceeds 14%, it will shrink and deform in the drying process after apply|coating various functional layers, and this step cannot be received. Moreover, from the viewpoint of the reduction of the wrinkles and the like, the appearance of the film in the coating step and the drying step is improved, and the 90° C. heat shrinkage rate in the main shrinkage direction must be 14% or less. The 90 ° C heat shrinkage ratio in the main shrinkage direction is more preferably 10% or less, still more preferably 5% or less. In order to make the heat shrinkage rate in the main shrinkage direction at 90 ° C 14% or less, it can be achieved, for example, by setting the glass transition temperature of the film from the temperature-controlled DSC to 90 ° C or higher.
本發明之聚酯薄膜，從耐熱性的觀點而言，以主收縮方向之於80℃之熱收縮應力為1MPa以下為較佳。若於80℃之熱收縮應力為1MPa以下，則可將在各種功能層之塗布步驟或乾燥步驟溫度下的收縮變形抑制至非常低。若主收縮方向之於80℃之熱收縮應力為0.9MPa以下，則為更佳，若為0.001MPa以上0.8MPa以下，則為進一步更佳，若為0.01MPa以上0.2MPa以下，則為最佳。在本發明之聚酯薄膜中，就使主收縮方向之於80℃之熱收縮應力為1MPa以下的方法而言，可列舉例如：延伸後於80℃以上105℃以下進行熱處理，然後以比105℃更 高溫進行熱處理的階段熱處理之方法。藉由進行低溫/高溫之階段熱處理，可抑制熱結晶化，同時亦可緩和非晶部分之一部分，因此能在高度維持主收縮方向之高溫下的熱收縮性的狀態下，將低溫下的熱收縮應力抑制至非常低。 The polyester film of the present invention preferably has a heat shrinkage stress at 80 ° C in a main shrinkage direction of from 1 MPa or less from the viewpoint of heat resistance. When the heat shrinkage stress at 80 ° C is 1 MPa or less, the shrinkage deformation at the coating step or the drying step temperature of various functional layers can be suppressed to be extremely low. The heat shrinkage stress at 80 ° C in the main shrinkage direction is preferably 0.9 MPa or less, more preferably 0.001 MPa or more and 0.8 MPa or less, and more preferably 0.01 MPa or more and 0.2 MPa or less. . In the polyester film of the present invention, the heat shrinkage stress at 80 ° C in the main shrinkage direction is 1 MPa or less, and for example, heat treatment is carried out at 80 ° C or higher and 105 ° C or lower after stretching, and then the ratio is 105. °C more A method of heat treatment at a high temperature for heat treatment. By performing the heat treatment at the low temperature/high temperature stage, thermal crystallization can be suppressed, and at the same time, one part of the amorphous portion can be alleviated, so that the heat at a low temperature can be maintained in a state where the heat shrinkage at a high temperature in the main shrinkage direction is maintained at a high height. The shrinkage stress is suppressed to very low.
本發明之聚酯薄膜，從高韌性的觀點而言，以與主收縮方向垂直的方向之斷裂伸長率為100%以上為較佳。又，藉由使主收縮方向之斷裂伸長率為100%以上，而薄膜之韌性提高，變得容易抑制加工時之薄膜破裂，因而較佳。與主收縮方向垂直的方向之斷裂伸長率若為120%以上，則為進一步更佳，若為150%以上則為最佳。於本發明之聚酯薄膜，就使與主收縮方向垂直的方向之斷裂伸長率為100%以上之方法而言，較佳使用使與主收縮方向垂直的方向之延伸溫度為90℃以上的方法。又，在與主收縮方向垂直的方向進行複數次延伸的情況，於延伸溫度最高之與主收縮方向垂直的方向之延伸步驟中，以使延伸溫度為90℃以上為較佳。藉由將與主收縮方向垂直的方向之延伸溫度設定為高達90℃以上，可不進行與主收縮方向垂直的方向之定向，而提高斷裂伸長率。更佳為與主收縮方向垂直的方向之延伸溫度為95℃以上。 The polyester film of the present invention preferably has a breaking elongation in a direction perpendicular to the main shrinkage direction of 100% or more from the viewpoint of high toughness. Moreover, since the elongation at break in the main shrinkage direction is 100% or more, the toughness of the film is improved, and it is easy to suppress film breakage during processing, which is preferable. The elongation at break in the direction perpendicular to the main shrinkage direction is more preferably 120% or more, and more preferably 150% or more. In the polyester film of the present invention, in the method of making the elongation at break perpendicular to the main shrinkage direction 100% or more, it is preferred to use a method in which the elongation temperature in the direction perpendicular to the main shrinkage direction is 90° C. or higher. . Further, in the case where the stretching is performed plural times in the direction perpendicular to the main shrinkage direction, it is preferable that the stretching temperature is 90 ° C or more in the extending step in the direction perpendicular to the main shrinkage direction in which the stretching temperature is the highest. By setting the stretching temperature in the direction perpendicular to the main shrinkage direction to be higher than 90 ° C or higher, the orientation in the direction perpendicular to the main shrinkage direction can be prevented, and the elongation at break can be improved. More preferably, the extension temperature in the direction perpendicular to the main shrinkage direction is 95 ° C or higher.
本發明之聚酯薄膜，為了進一步提高韌性，以主收縮方向之斷裂伸長率為150%以上，且比與主收縮方向垂直的方向之斷裂伸長率高為較佳。藉由使主收縮方向之斷裂伸長率為150%以上、比與主收縮方向垂直的 方向之斷裂伸長率高，可進一步提高薄膜之韌性，大幅度地減低加工時之薄膜破損。本發明之聚酯薄膜之主收縮方向的斷裂伸長率，若為170%以上則進一步更佳，若為200%以上則為最佳。 In order to further improve the toughness, the polyester film of the present invention preferably has a breaking elongation in the main shrinkage direction of 150% or more and a tensile elongation in a direction perpendicular to the main shrinkage direction. By making the elongation at break in the main shrinkage direction 150% or more, perpendicular to the main shrinkage direction The elongation at break in the direction is high, and the toughness of the film can be further improved, and the film breakage during processing can be greatly reduced. The elongation at break in the main shrinkage direction of the polyester film of the present invention is further preferably 170% or more, and more preferably 200% or more.
本發明之聚酯薄膜，以因雙軸延伸而在薄膜表面形成微小刮痕之情況等的表面平滑化為目的，可於至少一側之面具有表面層，該表面層係展現選自包含硬塗(hardcoat)性、自修復性、防眩性、抗反射性、低反射性、紫外線遮蔽性、及抗靜電性之群組中的1種以上的功能。表面層從因薄膜坯材收縮所致之追隨性的觀點而言，以可追隨收縮而變形之程度的柔軟者為較佳。 The polyester film of the present invention has a surface layer on at least one side for the purpose of smoothing a surface such as a micro scratch on the surface of the film by biaxial stretching, and the surface layer exhibits a surface selected from the group consisting of hard One or more functions in the group of hardcoat, self-healing, anti-glare, anti-reflective, low-reflective, ultraviolet shielding, and antistatic properties. From the viewpoint of the followability due to shrinkage of the film material, the surface layer is preferably soft to the extent that it can be deformed following shrinkage.
接著，將本發明之薄膜的較佳製造方法說明於下。本發明並不受限於該例而解釋。 Next, a preferred method of producing the film of the present invention will be described below. The invention is not to be construed as being limited to the examples.
就聚酯而言，例如係將聚對苯二甲酸乙二酯供給至擠壓機，進行熔融擠壓。此時，樹脂溫度以控制於265℃~295℃為較佳。接著，通過過濾器及齒輪泵，而分別進行異物之除去、擠壓量之均衡化，從T字模以片狀吐出至冷卻輥上。此時，係藉由下述方法，使片狀聚合物密合於鑄造輥，冷卻固化，得到未延伸薄膜：使用施加高電壓之電極，而以靜電使冷卻輥與樹脂密合的施加靜電法；在鑄造輥與擠出的聚合物片間設置水膜的鑄造法；將鑄造輥溫度設為低於聚酯樹脂的玻璃轉移點，而使擠出之聚合物黏著的方法；或者將此等方法之複數種組合的方法。在此等鑄造法中，使用聚酯之情況，從生產性或平面性的觀點而言，較佳使用施加靜電之方法。 In the case of polyester, for example, polyethylene terephthalate is supplied to an extruder for melt extrusion. At this time, the resin temperature is preferably controlled at 265 ° C to 295 ° C. Then, the filter and the gear pump are used to remove the foreign matter and equalize the amount of the squeeze, and discharge the sheet from the T-die to the cooling roll. At this time, the sheet-like polymer is adhered to the casting roll by the following method, and solidified by cooling to obtain an unstretched film: an electrostatic application method in which the cooling roll is adhered to the resin by static electricity using an electrode to which a high voltage is applied. a method of casting a water film between a casting roll and an extruded polymer sheet; a method of setting the temperature of the casting roll to be lower than a glass transition point of the polyester resin to adhere the extruded polymer; or A method of combining multiple methods. In the case of using the polyester in the casting method, a method of applying static electricity is preferably used from the viewpoint of productivity or planarity.
本發明之聚酯薄膜，係使主收縮方向之150℃熱收縮率為15%以上，且與主收縮方向垂直的方向之150℃熱收縮率小於15%，90℃主收縮方向熱收縮率為14%以下。又，其特徵為主收縮方向之150℃熱收縮率為15%以上且與主收縮方向垂直的方向之150℃熱收縮率小於15%，藉由調溫式DSC所得到之玻璃轉移溫度為100℃以上。為達成此等條件，就藉由前述鑄造法所得到之片的延伸方法而言，較佳使用例如：在薄膜縱軸方向-寬度方向-縱軸方向逐次雙軸延伸、或在薄膜寬度方向-縱軸方向逐次雙軸延伸後，於101℃以上160℃以下進行熱處理的方法；維持住薄膜寬度方向之端部，將縱軸方向及寬度方向延伸，使自全延伸步驟之最終點起5%區間之縱軸方向延伸倍率為寬度方向延伸倍率以上，並進行101℃以上160℃以下之熱處理的方法等。 The polyester film of the present invention has a heat shrinkage ratio of 150 ° C in the main shrinkage direction of 15% or more, and a heat shrinkage ratio of 150 ° C in a direction perpendicular to the main shrinkage direction of less than 15%, and a heat shrinkage ratio of 90 ° C in the main shrinkage direction. 14% or less. Further, it is characterized in that the heat shrinkage rate at 150 ° C in the main shrinkage direction is 15% or more, and the heat shrinkage ratio at 150 ° C in the direction perpendicular to the main shrinkage direction is less than 15%, and the glass transition temperature obtained by the temperature-controlled DSC is 100. Above °C. In order to achieve such conditions, it is preferable to use a stretching method of the sheet obtained by the above casting method, for example, to sequentially biaxially extend in the direction of the longitudinal axis of the film - the width direction - the longitudinal axis direction, or in the film width direction - After the longitudinal axis direction is sequentially biaxially stretched, the heat treatment is performed at 101 ° C or more and 160 ° C or less; the end portion in the film width direction is maintained, and the longitudinal axis direction and the width direction are extended so that the final point of the full extension step is 5%. In the longitudinal direction of the section, the stretching ratio is equal to or greater than the width direction expansion ratio, and a method of heat treatment of 101° C. or more and 160° C. or less is performed.
在本發明中，尤其是應用於重視主收縮方向的高收縮性之用途的情況，就片之延伸方法而言，較佳為在於縱軸方向-寬度方向-縱軸方向逐次雙軸延伸後，於101℃以上160℃以下熱處理之方法中，使最初之縱軸方向的延伸倍率為後續之縱軸方向的延伸倍率以下。具體而言，較佳為使最初之縱軸方向的延伸倍率為1.01倍以上3倍以下，使後續之縱軸方向的延伸倍率為1.1倍以上4倍以下，且使最初之縱軸方向的延伸倍率為後續之縱軸方向的延伸倍率以下。又，較佳為使片之延伸方法，為在於薄膜寬度方向-縱軸方向逐次雙軸延伸後，於101℃以上160℃以下熱處理的方法。在此情況，較佳為 於寬度方向延伸1.5倍以上6倍以下，然後於縱軸方向延伸1.1倍以上4倍以下，於縱軸方向延伸後，具有100℃以下之冷卻步驟、101℃以上160℃以下之熱處理步驟。再者，亦較佳為使片之延伸方法為下述方法：維持住片之寬度方向端部，將縱軸方向及寬度方向延伸，使自全延伸步驟之最終點起5%區間之縱軸方向延伸倍率為寬度方向延伸倍率以上，使總縱軸方向延伸倍率為比總寬度方向延伸倍率低，延伸後進行於101℃以上160℃以下之熱處理的方法。 In the present invention, in particular, in the case of application to the use of high shrinkage in the main shrinkage direction, it is preferable that the sheet extending method is such that the longitudinal axis direction-width direction-vertical axis direction is sequentially biaxially stretched. In the method of heat treatment at 101 ° C or more and 160 ° C or less, the stretching ratio in the first vertical axis direction is equal to or less than the stretching ratio in the subsequent vertical axis direction. Specifically, it is preferable that the stretching ratio in the first vertical axis direction is 1.01 times or more and 3 times or less, and the stretching ratio in the subsequent vertical axis direction is 1.1 times or more and 4 times or less, and the first vertical axis direction is extended. The magnification is equal to or less than the stretching ratio in the subsequent vertical axis direction. Moreover, it is preferable that the method of extending the sheet is a method of heat-treating at 101 ° C or more and 160 ° C or less after sequentially biaxially stretching in the film width direction and the vertical axis direction. In this case, it is preferably After extending 1.5 times or more and 6 times or less in the width direction, the film is extended by 1.1 times or more and 4 times or less in the longitudinal direction, and has a cooling step of 100° C. or less and a heat treatment step of 101° C. or more and 160° C. or less after extending in the vertical axis direction. Further, it is preferable that the method of extending the sheet is a method of maintaining the end portion in the width direction of the sheet and extending the longitudinal axis direction and the width direction so that the final point of the full extension step is a vertical axis of 5% interval. The direction stretch ratio is equal to or greater than the width direction stretch ratio, and the total longitudinal axis direction stretch ratio is lower than the total width direction stretch ratio, and the heat treatment is performed at 101 ° C or more and 160 ° C or less after stretching.
另一方面，在本發明中，在應用於重要的是兼具主收縮方向之高收縮性，以及機械強度、操作性之用途的情況，較佳為使延伸方法為於縱軸方向-寬度方向-縱軸方向逐次雙軸延伸後，於101℃以上160℃以下熱處理之方法，並使最初之縱軸方向的延伸倍率為比後續之縱軸方向的延伸倍率高。具體而言，較佳為使最初之縱軸方向的延伸倍率為1.11倍以上4倍以下，使後續之縱軸方向的延伸倍率為1.01倍以上3倍以下，且使最初之縱軸方向的延伸倍率為比後續之縱軸方向的延伸倍率高。又，就其他延伸方法而言，亦較佳為下述方法：維持住薄膜之寬度方向端部，將薄膜縱軸方向及寬度方向延伸，使自全延伸步驟之最終點起5%區間之縱軸方向延伸倍率為寬度方向延伸倍率以上，並使總縱軸方向延伸倍率為比總寬度方向延伸倍率高，延伸後於101℃以上160℃以下進行熱處理的方法。於此較佳之熱處理溫度係表示進行雙軸延伸後之熱處理溫度中，成為最高溫之溫度。 又，熱處理時間在不使特性劣化之範圍內，可設為任意之時間，較佳可在5秒以上60秒以下、更佳為10秒以上40秒以下、最佳為15秒以上30秒以下進行。 On the other hand, in the present invention, in the case where it is important to have high shrinkage in the main shrinkage direction and use of mechanical strength and workability, it is preferable to extend the method in the longitudinal direction-width direction. - The longitudinal axis direction is sequentially biaxially stretched, and the heat treatment is performed at 101 ° C or more and 160 ° C or less, and the stretching ratio in the first vertical axis direction is higher than the stretching ratio in the subsequent vertical axis direction. Specifically, it is preferable that the stretching ratio in the first vertical axis direction is 1.11 times or more and 4 times or less, and the subsequent stretching ratio in the vertical axis direction is 1.01 times or more and 3 times or less, and the first vertical axis direction is extended. The magnification is higher than the stretching ratio in the subsequent vertical axis direction. Further, in other extension methods, it is also preferred to maintain the film in the width direction end portion and extend the film in the longitudinal direction and the width direction so as to extend from the final point of the full extension step by 5%. The axial direction stretching magnification is equal to or greater than the width direction stretching magnification, and the total longitudinal axis direction stretching magnification is higher than the total width direction stretching magnification, and the method of heat treatment after stretching is performed at 101 ° C or more and 160 ° C or less. The preferred heat treatment temperature here means the temperature which becomes the highest temperature among the heat treatment temperatures after the biaxial stretching. Further, the heat treatment time may be any time within a range in which the characteristics are not deteriorated, and is preferably 5 seconds or longer and 60 seconds or shorter, more preferably 10 seconds or longer and 40 seconds or shorter, and most preferably 15 seconds or longer and 30 seconds or shorter. get on.
本發明之聚酯薄膜之厚度，只要在不阻礙本發明之目的的範圍內，則無特別限制，只要設為如就雙軸延伸薄膜而言一般使用之約3μm~300μm即可。又，薄膜之厚度可依據用途或塗布之油墨、塗劑等而選擇。 The thickness of the polyester film of the present invention is not particularly limited as long as it does not inhibit the object of the present invention, and may be about 3 μm to 300 μm which is generally used for a biaxially stretched film. Further, the thickness of the film can be selected depending on the application or the applied ink, the paint, and the like.
本發明之聚酯薄膜，能以襯底材料等加以補強。就襯底材料而言，可列舉雙軸定向聚酯薄膜或雙軸定向聚丙烯薄膜等。 The polyester film of the present invention can be reinforced with a substrate material or the like. As the substrate material, a biaxially oriented polyester film or a biaxially oriented polypropylene film or the like can be cited.
本發明之聚酯薄膜，由於在低溫區域熱收縮率低，在高溫區域顯示均勻之熱收縮性，而可適合使用於包裝用途。在印刷層、耐候層、黏著層、接著層、氣相沉積層等各種功能層之塗布、形成步驟或乾燥步驟中，由於具有不會熱收縮之耐熱性，而亦可對應於例如水系溶劑之塗布劑。再者，由於藉由高溫加熱而顯示高熱收縮性，故對瓶等容器之裝配性優良，因此可適合用於以標籤用為中心的各種包裝用途。 The polyester film of the present invention can be suitably used for packaging applications because of its low heat shrinkage rate in a low temperature region and uniform heat shrinkage in a high temperature region. In the coating, forming step or drying step of various functional layers such as a printing layer, a weatherable layer, an adhesive layer, an adhesive layer, a vapor deposited layer, etc., since it has heat resistance which does not heat shrink, it may correspond to, for example, an aqueous solvent. Coating agent. In addition, since it exhibits high heat shrinkability by heating at a high temperature, it has excellent assembly property to a container such as a bottle, and thus can be suitably used for various packaging applications centering on labels.
又，本發明之聚酯薄膜亦可適合用於裝飾用途。在印刷層、耐候層、黏著層、接著層、氣相沉積層、防刮層、防指紋層等各種功能層之塗布、形成步驟或乾燥步驟中，由於具有不會熱收縮之耐熱性，而亦可對應於例如水系溶劑之塗布劑，且由於在各種功能層塗布後之乾燥步驟中的耐熱性優良，在高溫加熱時顯示高熱收縮性，而可適用於對複雜形狀之構件的高創意性裝飾。 Further, the polyester film of the present invention can also be suitably used for decorative purposes. In the coating, forming step or drying step of various functional layers such as a printing layer, a weathering layer, an adhesive layer, an adhesive layer, a vapor deposited layer, a scratch-resistant layer, an anti-fingerprint layer, etc., since there is heat resistance which does not shrink by heat, It may also correspond to a coating agent such as an aqueous solvent, and is excellent in heat resistance in a drying step after application of various functional layers, exhibits high heat shrinkability upon heating at a high temperature, and is applicable to high creativity of a member having a complicated shape. decoration.
又，本發明之聚酯薄膜亦可適合使用於光學用途。在所謂相位差形成層等各種功能層之塗布步驟或乾燥步驟的耐熱性優良，可利用高溫加熱時之收縮特性而形成相位差層。 Further, the polyester film of the present invention can also be suitably used for optical applications. The coating step or the drying step of various functional layers such as a phase difference forming layer is excellent in heat resistance, and the phase difference layer can be formed by shrinkage characteristics at the time of high-temperature heating.
(特性之測定方法及效果之評價方法) (Method for measuring characteristics and method for evaluating effects)
本發明中的特性之測定方法、及效果之評價方法，如以下說明。 The method for measuring the characteristics of the present invention and the method for evaluating the effects are as follows.
(1)聚酯之組成 (1) Composition of polyester
可將聚酯薄膜溶解於六氟異丙醇(HFIP)，使用1H-NMR及13C-NMR，針對各單體殘基成分及副產之二乙二醇，而定量含量。在積層薄膜之情況，可依據積層厚度，削取薄膜之各層，藉此採取構成各層單體之成分，進行評價。再者，關於本發明之薄膜，藉由從薄膜製造時之混合比率計算，而算出組成。 The polyester film can be dissolved in hexafluoroisopropanol (HFIP) and quantified by 1 H-NMR and 13 C-NMR for each monomer residue component and by-product diethylene glycol. In the case of a laminated film, each layer of the film can be cut according to the thickness of the laminate, and the components constituting the respective layers can be used for evaluation. Further, regarding the film of the present invention, the composition was calculated by calculating the mixing ratio at the time of film production.
(2)薄膜主收縮方向 (2) The main shrinkage direction of the film
以薄膜之任一方向當作0°，在針對從其開始以每5°間隔至180°為止的方向而切出為150mm(測定方向)×寬度10mm(與測定方向垂直的方向)大小之樣本上，在100mm(L0)間隔之兩端位置標示標記(標線)，懸吊3g之錘，於加熱至150℃之熱風烘箱內放置30分鐘，進行加熱處理。測定熱處理後之標線間距離(L1)，從加熱前後之標線間距離的變化，以下式算出熱收縮率。 A sample having a size of 150 mm (measurement direction) × width 10 mm (direction perpendicular to the measurement direction) is cut out in any direction from the beginning of the film to 0° in any direction from the film. On the top, the mark (marking line) is placed at both ends of the interval of 100 mm (L0), and the hammer of 3 g is suspended and placed in a hot air oven heated to 150 ° C for 30 minutes for heat treatment. The distance between the lines after the heat treatment (L1) was measured, and the heat shrinkage ratio was calculated from the change in the distance between the lines before and after the heating.
熱收縮率(%)=100×(L0-L1)/L0 Heat shrinkage rate (%) = 100 × (L0 - L1) / L0
測定係各方向均各進行5次，以熱收縮率最高之方向作為主收縮方向。 The measurement system was carried out 5 times in each direction, and the direction in which the heat shrinkage rate was the highest was taken as the main shrinkage direction.
(3)90℃及150℃熱收縮率 (3) 90 ° C and 150 ° C heat shrinkage rate
針對薄膜之主收縮方向及與主收縮方向垂直的方向進行測定。在切出為150mm(測定方向)×寬度10mm(垂直於測定方向的方向)之大小的樣本上，在100mm(L0)間隔之兩端位置標示標記(標線)，懸吊3g之錘，於加熱至測定溫度之熱風烘箱內放置30分鐘，進行加熱處理。測定熱處理後之標線間距離(L1)，從加熱前後之標線間距離的變化，以下式算出熱收縮率。測定係各方向均以5樣本實施，以平均值進行評價。 The measurement was performed on the main shrinkage direction of the film and the direction perpendicular to the main shrinkage direction. On a sample cut to a size of 150 mm (measuring direction) × width 10 mm (direction perpendicular to the direction of measurement), mark (marking) is placed at both ends of the interval of 100 mm (L0), and the hammer of 3 g is suspended. The mixture was allowed to stand in a hot air oven heated to a measured temperature for 30 minutes, and heat-treated. The distance between the lines after the heat treatment (L1) was measured, and the heat shrinkage ratio was calculated from the change in the distance between the lines before and after the heating. The measurement system was carried out in 5 samples in each direction and evaluated as an average value.
熱收縮率(%)=100×(L0-L1)/L0 Heat shrinkage rate (%) = 100 × (L0 - L1) / L0
(4)斷裂伸長率 (4) Elongation at break
針對薄膜之主收縮方向及與主收縮方向垂直的方向進行測定。使用拉伸試驗機(Orientec公司製TENSILON UCT-100)，將寬度10mm之樣本薄膜以於測定方向夾頭間長度成為50mm(初期試驗長度)之方式設置，在溫度25℃、濕度65%RH之條件下，以拉伸速度300mm/分鐘進行拉伸試驗，將斷裂時之伸長率作為斷裂伸長率。各測定分別各進行5次，使用其平均值。 The measurement was performed on the main shrinkage direction of the film and the direction perpendicular to the main shrinkage direction. Using a tensile tester (TENSILON UCT-100, manufactured by Orientec Co., Ltd.), a sample film having a width of 10 mm was set so that the length between the chucks in the measurement direction was 50 mm (initial test length) at a temperature of 25 ° C and a humidity of 65% RH. Under the conditions, the tensile test was carried out at a tensile speed of 300 mm/min, and the elongation at break was taken as the elongation at break. Each measurement was performed 5 times each, and the average value was used.
(5)可動非晶量(分率) (5) Movable amorphous amount (fraction rate)
使用TA Instruments公司製調溫式DSC而測定。將5mg試料於氮氣體環境下，以0℃至150℃、2℃/分鐘之升溫速度、調溫振幅±1℃，調溫週期60秒進行測定。求取於玻璃轉移溫度之比熱差，由以下之式算出。 The measurement was carried out using a temperature-adjusted DSC manufactured by TA Instruments. 5 mg of the sample was measured under a nitrogen atmosphere at a temperature elevation rate of 0 ° C to 150 ° C, 2 ° C / min, a temperature modulation amplitude of ± 1 ° C, and a temperature adjustment period of 60 seconds. The specific heat difference at the glass transition temperature was calculated and calculated by the following formula.
可動非晶量(%)=(比熱差)/(聚酯完全非晶物之比熱差理論值)×100 Movable amorphous amount (%) = (specific heat difference) / (comparative heat difference theoretical value of polyester completely amorphous) × 100
聚對苯二甲酸乙二酯完全非晶物之比熱差理論值=0.4052J/(g℃) The specific heat difference of polyethylene terephthalate complete amorphous material = 0.4052J / (g ° C)
又，本發明中針對聚對苯二甲酸乙二酯單元為89莫耳%以上者，係參照聚對苯二甲酸乙二酯之完全非晶物的比熱差理論值。又，在聚對苯二甲酸乙二酯單元為小於89莫耳%之情況，係將該樹脂在非晶狀態，依照下述(6)記載之方法測定玻璃轉移溫度，將此時所得到之玻璃轉移溫度前後的比熱差，作為該樹脂之完全非晶物之比熱差理論值。再者，為了使樹脂為非晶狀態，可列舉例如將該樹脂加熱至熔點以上使其熔融後，於3秒以內急冷至20℃以下而得到等之方法。此外，只要為一般作成非晶狀態之手段，不受上述方法限定，均可使用。 Further, in the present invention, the polyethylene terephthalate unit is 89 mol% or more, and the specific heat difference of the complete amorphous material of polyethylene terephthalate is referred to. Further, when the polyethylene terephthalate unit is less than 89 mol%, the resin is in an amorphous state, and the glass transition temperature is measured according to the method described in the following (6). The specific heat difference before and after the glass transition temperature is the theoretical value of the specific heat difference of the completely amorphous material of the resin. In addition, in order to make the resin into an amorphous state, for example, the resin is heated to a melting point or higher and melted, and then quenched to 20° C. or less in 3 seconds to obtain a method. Further, any means for forming an amorphous state in general can be used without being limited by the above method.
(6)調溫式DSC玻璃轉移溫度 (6) Temperature-controlled DSC glass transfer temperature
使用TA Instrument公司製調溫式DSC，以下述條件進行測定。 The measurement was carried out under the following conditions using a temperature-adjusting DSC manufactured by TA Instrument.
加熱溫度：270~570K(RCS冷卻法) Heating temperature: 270~570K (RCS cooling method)
溫度校正：高純度銦及錫之熔點 Temperature correction: high purity indium and tin melting point
調溫振幅：±1K Temperature regulation amplitude: ±1K
調溫週期：60秒 Temperature adjustment cycle: 60 seconds
溫階(temperature step)：5K Temperature step: 5K
試料重量：5mg Sample weight: 5mg
試料容器：鋁製開放型容器(22mg) Sample container: aluminum open container (22mg)
參照容器：鋁製開放型容器(18mg) Reference container: aluminum open container (18mg)
再者，玻璃轉移點係由下式算出。 Further, the glass transition point was calculated by the following formula.
玻璃轉移溫度=(外推玻璃轉移開始溫度+外推玻璃 轉移完成溫度)/2 Glass transfer temperature = (extra push glass transfer start temperature + extrapolated glass Transfer completion temperature)/2
(7)薄膜折射率及平面定向係數 (7) Film refractive index and plane orientation coefficient
以鈉D線(波長589nm)作為光源，使用二碘甲烷作為安裝液，於25℃使用阿貝折射計求取薄膜縱軸方向、寬度方向及厚度方向之折射率(分別為nMD、nTD、nZD)。從所求得之折射率，依照下述之式，算出平面定向係數(fn)。 Using sodium D line (wavelength 589 nm) as the light source and diiodomethane as the mounting liquid, the refractive index in the longitudinal direction, the width direction and the thickness direction of the film was obtained at 25 ° C using an Abbe refractometer (nMD, nTD, nZD, respectively). ). From the obtained refractive index, the plane orientation coefficient (fn) was calculated according to the following equation.
fn=(nMD+nTD)/2-nZD Fn=(nMD+nTD)/2-nZD
(8)包裝用途適性 (8) Applicability of packaging use
(i)乾燥耐熱性 (i) Dry heat resistance
在薄膜表面進行網版印刷。印刷係使用Mino Group(股)製油墨U-PET(517)、網版SX270T，以刮板(squeegee)速度300mm/秒、刮板角度45°之條件進行，接著於90℃條件下之熱風烘箱中乾燥5分鐘，得到印刷層積層薄膜。針對關於所得到之印刷層積層薄膜的外觀，以下述基準進行評價。 Screen printing is performed on the surface of the film. The printing system uses Mino Group ink U-PET (517), screen SX270T, with a squeegee speed of 300 mm / sec and a squeegee angle of 45 °, followed by a hot air oven at 90 ° C. The film was dried for 5 minutes to obtain a printed layer laminated film. The appearance of the obtained printed layer laminated film was evaluated based on the following criteria.
A：乾燥後亦未確認到皺紋產生，為良好外觀。 A: No wrinkles were observed after drying, which was a good appearance.
B：乾燥後雖確認有若干皺紋，但為良好外觀。 B: Although some wrinkles were confirmed after drying, it was a good appearance.
C：乾燥後雖確認有皺紋，但為實用上無問題之程度。 C: Although wrinkles were confirmed after drying, it was practically no problem.
D：乾燥後確認有皺紋，為無法實用之程度。 D: Wrinkles were confirmed after drying, which was not practical.
A、B、C為合格程度。 A, B, and C are qualified.
(ii)熱收縮性 (ii) heat shrinkage
針對(i)所製成之印刷層積層薄膜，將薄膜兩端部藉由熔斷封接而接著，製成圓筒狀之標籤。將該標籤被覆於圓筒形鋁瓶之胴部(底面直徑150mm)，以通過時間3秒 使其通過150℃氣體環境下之隧道爐，而裝配於瓶，以下述基準評價收縮外觀。 For the printed laminate film produced in (i), both ends of the film were sealed by fusing, and then a cylindrical label was formed. The label was covered on the crotch portion of the cylindrical aluminum bottle (bottom diameter 150 mm) to pass the time 3 seconds This was passed through a tunnel furnace under a gas atmosphere of 150 ° C, and assembled in a bottle, and the shrinkage appearance was evaluated on the basis of the following criteria.
A：未發生皺紋、扭曲、收縮不足，為創意性優良之外觀。 A: There is no wrinkles, distortion, and insufficient shrinkage, and it is a creative and excellent appearance.
B：可確認有皺紋、扭曲、收縮不足之至少任一者，但為創意性優良之外觀。 B: At least one of wrinkles, distortion, and insufficient shrinkage can be confirmed, but the appearance is excellent in creativity.
C：可確認有皺紋、扭曲、收縮不足之至少任一者，但實用上無問題。 C: At least one of wrinkles, distortion, and insufficient shrinkage can be confirmed, but there is no problem in practical use.
D：可確認有皺紋、扭曲、收縮不足之至少任一者，為無法實用之程度。 D: At least one of wrinkles, distortion, and insufficient shrinkage can be confirmed, and it is not practical.
A、B、C為合格程度。 A, B, and C are qualified.
(9)裝飾用途適性 (9) Applicability of decorative use
(i)乾燥耐熱性 (i) Dry heat resistance
在薄膜表面，使用施用器(applicator)，塗布Nippon Chemical公司製892L，並於90℃進行5分鐘乾燥，形成接著層。針對關於接著層積層薄膜之外觀，以下述基準進行評價。 On the surface of the film, 892 L manufactured by Nippon Chemical Co., Ltd. was applied using an applicator, and dried at 90 ° C for 5 minutes to form an adhesive layer. The evaluation was carried out on the basis of the following criteria regarding the appearance of the laminate film.
A：乾燥後亦未確認到皺紋產生，為良好外觀。 A: No wrinkles were observed after drying, which was a good appearance.
B：乾燥後雖確認有若干皺紋，但為良好外觀。 B: Although some wrinkles were confirmed after drying, it was a good appearance.
C：乾燥後雖確認有皺紋，但為實用上無問題之程度。 C: Although wrinkles were confirmed after drying, it was practically no problem.
D：乾燥後確認有皺紋，為無法實用之程度。 D: Wrinkles were confirmed after drying, which was not practical.
A、B、C為合格程度。 A, B, and C are qualified.
(ii)形狀追隨性 (ii) shape followability
針對(i)所製成之接著層積層薄膜，將接著層積層薄膜被覆於加熱至80℃之鎂殼體(底面200mm×100mm×高 度30mm之長方體)，以通過時間10秒使其通過150℃氣體環境下之隧道爐，而使其追隨形狀，針對收縮外觀，以下述基準評價。 For the laminated film produced by (i), the laminated film is coated on a magnesium casing heated to 80 ° C (bottom 200 mm × 100 mm × height) The rectangular parallelepiped of 30 mm was passed through a tunnel furnace under a gas atmosphere of 150 ° C for 10 seconds to follow the shape, and the shrinkage appearance was evaluated on the basis of the following criteria.
A：可追隨至高度30mm。 A: Can follow up to a height of 30mm.
B：可追隨至高度25mm以上且小於30mm。 B: It can follow up to a height of 25 mm or more and less than 30 mm.
C：可追隨至高度20mm以上且小於25mm。 C: It can follow up to a height of 20 mm or more and less than 25 mm.
D：追隨性低，無法追隨至高度20mm。 D: Low followability, unable to follow up to a height of 20mm.
A、B、C為合格程度。 A, B, and C are qualified.
(10)光學用途適性 (10) Optical suitability
(i)操作性 (i) Operational
針對切下實施例及比較例所得到之熱收縮性薄膜之端部的薄膜捲，將捲出張力設為100N/m，將捲取張力設為100N/m、200N/m、250N/m、300N/m而輸送，針對操作性，以下述基準進行評價。 The film roll of the end portion of the heat-shrinkable film obtained in the examples and the comparative examples was cut to have a take-up tension of 100 N/m and a take-up tension of 100 N/m, 200 N/m, and 250 N/m. The product was transported at 300 N/m, and evaluated for the operability based on the following criteria.
A：以捲取張力300N/m，可捲取1000m。 A: The winding tension is 300 N/m, and the coiling speed is 1000 m.
B：在捲取張力250N/m時可捲取1000m，但在300N/m時於捲取1000m前發生薄膜斷裂。 B: 1000 m can be taken up when the take-up tension is 250 N/m, but film breakage occurs at 1000 N/m before winding up to 1000 m.
C：在捲取張力200N/m時可捲取1000m，但在250N/m時於捲取1000m前發生薄膜斷裂。 C: 1000 m can be taken up when the take-up tension is 200 N/m, but film breakage occurs at 250 N/m before winding up to 1000 m.
D：即使在捲取張力100N/m時於捲取1000m前亦發生薄膜斷裂。 D: Film fracture occurred even before winding up to 1000 m at a take-up tension of 100 N/m.
A、B、C為合格程度。 A, B, and C are qualified.
(ii)乾燥耐熱性 (ii) Dry heat resistance
在薄膜表面將聚碳酸酯/甲苯分散體以模塗布器(die coater)進行塗布‧乾燥(乾燥溫度：90℃，乾燥時間：1 分鐘，捲出張力：200N/m，捲取張力：100N/m)。針對所得到之聚碳酸酯積層薄膜的外觀，以下述基準進行評價。 The polycarbonate/toluene dispersion was coated on a film surface by a die coater ‧ drying (drying temperature: 90 ° C, drying time: 1 Minute, roll-out tension: 200 N/m, take-up tension: 100 N/m). The appearance of the obtained polycarbonate laminated film was evaluated based on the following criteria.
A：乾燥後亦未確認到皺紋產生，為良好外觀。 A: No wrinkles were observed after drying, which was a good appearance.
B：乾燥後雖確認有若干皺紋，但為良好外觀。 B: Although some wrinkles were confirmed after drying, it was a good appearance.
C：乾燥後雖確認有皺紋，但為實用上無問題之程度。 C: Although wrinkles were confirmed after drying, it was practically no problem.
D：乾燥後確認有皺紋，為無法實用之程度。 D: Wrinkles were confirmed after drying, which was not practical.
A、B、C為合格程度。 A, B, and C are qualified.
(iii)韌性 (iii) Resilience
針對(ii)所製成之聚碳酸酯積層薄膜，於150℃之烘箱中一邊使其於主收縮方向收縮，一邊於與主收縮方向垂直的方向微延伸，而形成相位差層。此時，以下述基準評價韌性。 The polycarbonate laminated film produced in (ii) was subjected to shrinkage in the main shrinkage direction in an oven at 150 ° C, and slightly extended in a direction perpendicular to the main shrinkage direction to form a retardation layer. At this time, the toughness was evaluated by the following criteria.
A：能在與主收縮方向垂直的方向延伸1.2倍以上。 A: It can extend 1.2 times or more in a direction perpendicular to the main contraction direction.
B：能在與主收縮方向垂直的方向延伸1.1倍以上且小於1.2倍。 B: It can extend 1.1 times or more and less than 1.2 times in the direction perpendicular to the main contraction direction.
C：能在與主收縮方向垂直的方向延伸1.05倍以上且小於1.1倍。 C: It can extend 1.05 times or more and less than 1.1 times in the direction perpendicular to the main contraction direction.
D：無法在與主收縮方向垂直的方向延伸1.05倍。 D: It is not possible to extend 1.05 times in the direction perpendicular to the main contraction direction.
即使延伸至指定之倍率，薄膜亦未斷裂之情況，評價為能延伸。 Even if the film was not broken even if it was extended to the specified magnification, it was evaluated as being stretchable.
A、B、C為合格程度。 A, B, and C are qualified.
(iv)熱收縮性 (iv) heat shrinkage
以與(iii)同樣之方式，針對在150℃之烘箱中使其於主方向收縮之薄膜的熱收縮性，以下述基準評價。 In the same manner as in (iii), the heat shrinkability of the film which was shrunk in the main direction in an oven at 150 ° C was evaluated on the basis of the following criteria.
A：主收縮方向之熱收縮率為30%以上，在收縮後之薄膜外觀未見到皺紋。 A: The heat shrinkage rate in the main shrinkage direction was 30% or more, and no wrinkles were observed in the film appearance after shrinkage.
B：主收縮方向之熱收縮率為20%以上且收縮小於30%，在收縮後之薄膜外觀未見到皺紋。 B: The heat shrinkage ratio in the main shrinkage direction was 20% or more and the shrinkage was less than 30%, and wrinkles were not observed in the appearance of the film after shrinkage.
C：主收縮方向之熱收縮率為15%以上且小於20%，在收縮後之薄膜外觀未見到皺紋。 C: The heat shrinkage ratio in the main shrinkage direction was 15% or more and less than 20%, and wrinkles were not observed in the appearance of the film after shrinkage.
D：主收縮方向之熱收縮率小於15%，或者在薄膜外觀可見到皺紋。 D: The heat shrinkage rate in the main shrinkage direction is less than 15%, or wrinkles are visible in the appearance of the film.
A、B、C為合格程度。 A, B, and C are qualified.
(11)於80℃之熱收縮應力 (11) Thermal shrinkage stress at 80 ° C
將於溫度23℃、相對濕度65%靜置24小時之薄膜，使用TMA/SS6000(Seiko Instruments公司製)測定，將樣本之初期長度設為20mm、寬度設為2mm，從23℃至170℃為止，以升溫速度5℃/分鐘測定，從所得到之熱收縮力曲線讀取於80℃之熱收縮力[N]，將其除以從薄膜厚度及測定寬度所求得之截面積，算出熱收縮應力[MPa]。 The film which was allowed to stand at a temperature of 23 ° C and a relative humidity of 65% for 24 hours was measured by TMA/SS6000 (manufactured by Seiko Instruments Co., Ltd.), and the initial length of the sample was set to 20 mm, and the width was set to 2 mm, from 23 ° C to 170 ° C. The heat shrinkage force [N] was read from the obtained heat shrinkage force curve at a heating rate of 5 ° C / minute, and the heat shrinkage force [N] was measured by dividing the film thickness and the measured width to calculate the heat. Shrinkage stress [MPa].
(聚酯之製造) (Manufacture of polyester)
供給製膜之聚酯樹脂係如以下而準備。 The polyester resin supplied to the film formation was prepared as follows.
(聚酯A) (Polyester A)
以100莫耳%之對苯二甲酸成分作為二羧酸成分，以100莫耳%之乙二醇成分作為二醇成分的聚對苯二甲酸乙二酯樹脂(固有黏度0.65)。 A polyethylene terephthalate resin having a terephthalic acid component of 100 mol% as a dicarboxylic acid component and a glycol component of 100 mol% as a diol component (inherent viscosity: 0.65).
(聚酯B) (Polyester B)
以90莫耳%之對苯二甲酸成分及10莫耳%之間苯二 甲酸成分作為二羧酸成分，以100莫耳%之乙二醇成分作為二醇成分的聚酯樹脂(固有黏度0.65)。 Between 90 mol% of terephthalic acid and 10 mol% of benzene The formic acid component is a polyester resin having a glycol component of 100 mol% as a dicarboxylic acid component (intrinsic viscosity: 0.65).
(聚酯C) (Polyester C)
以100莫耳%之對苯二甲酸成分作為二羧酸成分，以90莫耳%之乙二醇成分及10莫耳%之1,4-環己烷二甲醇成分作為二醇成分的聚酯樹脂(固有黏度0.65)。 a polyester having a terephthalic acid component of 100 mol% as a dicarboxylic acid component, a glycol component of 90 mol%, and a 1,4-cyclohexanedimethanol component of 10 mol% as a diol component Resin (inherent viscosity 0.65).
(粒子母料之製造) (Manufacture of particle masterbatch)
(粒子母料A) (particle masterbatch A)
在聚酯A中以粒子濃度5質量%含有數平均粒徑0.2μm之凝集矽石的聚對苯二甲酸乙二酯粒子母料(固有黏度0.63)。 In the polyester A, a polyethylene terephthalate particle masterbatch (intrinsic viscosity: 0.63) of agglomerated vermiculite having a number average particle diameter of 0.2 μm was contained at a particle concentration of 5 mass%.
(實施例1~11、比較例1、2) (Examples 1 to 11, Comparative Examples 1, 2)
使所用之聚酯及粒子母料之組成如表1所示，將原料供給至擠壓機，於擠壓機圓筒(cylinder)溫度270℃熔融，短管溫度為275℃，噴嘴溫度為280℃，從T字模以片狀吐出至溫度控制於25℃之冷卻輥上。此時，使用直徑0.1mm之線狀電極施加靜電，使其密合於冷卻輥，得到未延伸片。依序進行1縱延伸、1橫延伸、熱處理、2縱延伸、2橫延伸、熱處理，分別得到設為如表1所示之延伸倍率、延伸溫度、熱處理溫度的聚酯薄膜。再者，延伸倍率1.0倍表示不進行延伸，而以表1所記載之溫度進行熱處理。 The composition of the polyester and the particle masterbatch used was as shown in Table 1, and the raw material was supplied to an extruder, and melted at a cylinder temperature of 270 ° C, a short tube temperature of 275 ° C, and a nozzle temperature of 280. °C, discharged from the T-shaped mold in a sheet form to a cooling roll controlled to a temperature of 25 °C. At this time, static electricity was applied using a linear electrode having a diameter of 0.1 mm, and it was adhered to the cooling roll to obtain an unstretched sheet. First, the longitudinal stretching, the one transverse stretching, the heat treatment, the two longitudinal stretching, the two transverse stretching, and the heat treatment were carried out, and a polyester film having a stretching ratio, an extension temperature, and a heat treatment temperature as shown in Table 1 was obtained. Further, a draw ratio of 1.0 times indicates that heat treatment is performed at the temperatures shown in Table 1 without stretching.
將所得到之薄膜的物性、特性之測定、評價結果示於表2、表3。實施例全部的90℃熱收縮率小於15%，且150℃熱收縮率為25%以上，對此熱收縮特性為必要 之用途的適合性優良。 The measurement of the physical properties and characteristics of the obtained film and the evaluation results are shown in Table 2 and Table 3. All of the examples have a heat shrinkage ratio of less than 15% at 90 ° C and a heat shrinkage ratio of 25% or more at 150 ° C, which is necessary for heat shrinkage characteristics. The suitability of the application is excellent.
另一方面，比較例1由於1縱延伸之倍率為3.0倍，且由於1橫延伸中收縮成分偏向而歪曲，而最終所取得的薄膜縱軸方向之150℃熱收縮率變得小於15%。 On the other hand, in Comparative Example 1, the magnification of the one longitudinal extension was 3.0 times, and the shrinkage component in one lateral stretch was deflected, and the heat shrinkage ratio at 150 ° C in the longitudinal direction of the film finally obtained was less than 15%.
又，比較例2由於玻璃轉移溫度低於90℃，而於90℃之熱收縮率變大。 Further, in Comparative Example 2, since the glass transition temperature was lower than 90 ° C, the heat shrinkage ratio at 90 ° C became large.
實施例係在各種功能層塗布後之乾燥適當度優良，且在之後於150℃大幅度收縮的收縮性亦佳。 In the examples, the drying property after application of various functional layers was excellent, and the shrinkage property after shrinking at 150 ° C was also good.
又，實施例11雖然無法滿足在裝飾用途方面所要求之實用性，但由於在80℃之熱收縮應力小於1MPa，而在包裝用途及光學用途方面沒有實用上的問題。 Further, although the practical value required for decorative use was not satisfied in Example 11, the thermal shrinkage stress at 80 ° C was less than 1 MPa, and there was no practical problem in packaging use and optical use.
本發明之聚酯薄膜，具有在約90℃不會收縮，而於約150℃大幅度收縮的特殊熱收縮特性。藉此，可使用於必須在約90℃時不收縮變形，以進行各種功能層塗布後之乾燥，然後，於約150℃時大幅度收縮的用途。 The polyester film of the present invention has a special heat shrinkage property which does not shrink at about 90 ° C and shrinks at about 150 ° C. Thereby, it can be used for the purpose of not shrinking and deforming at about 90 ° C, drying after application of various functional layers, and then shrinking at about 150 ° C.
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| CN108665810A (en) * | 2018-05-31 | 2018-10-16 | 昆山国显光电有限公司 | Metal wire, display screen, metal wire production method and metal wire restorative procedure |
| KR20220038066A (en) * | 2019-07-26 | 2022-03-25 | 도요보 가부시키가이샤 | Heat-shrinkable polyester film |
| JP7537094B2 (en) | 2020-02-18 | 2024-08-21 | 東レ株式会社 | Polyester Film |
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| JP4809419B2 (en) * | 2007-12-13 | 2011-11-09 | 東洋紡績株式会社 | Heat-shrinkable polyester film and method for producing the same |
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| US9920162B2 (en) * | 2012-08-29 | 2018-03-20 | Toyobo Co., Ltd. | Heat-shrinkable polyester film |
-
2016
- 2016-08-02 KR KR1020187001935A patent/KR102538384B1/en active IP Right Grant
- 2016-08-02 JP JP2016560834A patent/JP6789821B2/en active Active
- 2016-08-02 WO PCT/JP2016/072608 patent/WO2017022742A1/en active Application Filing
- 2016-08-02 CN CN201680040931.1A patent/CN107848193B/en active Active
- 2016-08-05 TW TW105124892A patent/TWI720006B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401212A (en) * | 2017-08-16 | 2019-03-01 | 中国石油化工股份有限公司 | Polymer blend and heat-shrinkable film and preparation method thereof |
| CN109401212B (en) * | 2017-08-16 | 2022-12-13 | 中国石油化工股份有限公司 | Polyester composition, heat-shrinkable film and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6789821B2 (en) | 2020-11-25 |
| KR20180037181A (en) | 2018-04-11 |
| TWI720006B (en) | 2021-03-01 |
| WO2017022742A1 (en) | 2017-02-09 |
| CN107848193A (en) | 2018-03-27 |
| CN107848193B (en) | 2020-01-10 |
| JPWO2017022742A1 (en) | 2018-05-24 |
| KR102538384B1 (en) | 2023-05-31 |
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