TW200808551A

TW200808551A - Laminated polyester film for forming and method for producing the same

Info

Publication number: TW200808551A
Application number: TW096123967A
Authority: TW
Inventors: Katsufumi Kumano; Yuki Haraguchi; Yasushi Sasaki; Masatoshi Tanabe; Katsuya Ito
Original assignee: Toyo Boseki
Priority date: 2006-06-30
Filing date: 2007-07-02
Publication date: 2008-02-16
Also published as: JP4573144B2; CN101484317B; KR101086093B1; JP2010208341A; CN101484317A; JP4573145B1; KR20090031596A; TWI406766B; WO2008001932A1; JP2010253954A

Abstract

This invention provides a laminated polyester film for forming, which has an excellent forming ability, transparency, solvent resistance, figure stability (uneven thickness is one character of thermal shrinking), and excellent impact resistance, and a method for manufacturing the said laminated polyester film. The laminated polyester film is a laminated polyester film in biaxial orientation, which comprises layer B laminated on one or two sides of layer A. Any one of layer A and layer B is consisted of copolyester, or copolyester with homopolyester, in which the melting point of layer A (TmA: DEG C) and the melting point of layer B (TmB: DEG C) both satisfy with the formulae (1) and (2): 260 > TmB > TmA > 200 ...(1), 50 > TmB-TmA > 5...(2) Further, layer A and layer B have orientation structures in the laminated polyester film, a thermal shrinking rate less than 6.0%, and a thickness change rate less than 10% at 150 DEG C.

Description

200808551 九、發明說明：【發明所屬之技術領域】本發明係有關於一種成型用積層聚酯薄膜，成型性、特別是在低溫度及低壓力的成型性、特別是在低溫度及低壓力的成型性、透明性、耐溶劑性、形態安定性（熱收縮特性、厚度不均）優良，而且耐衝擊性優良，適合作爲家電、行動電話、汽車用內部裝飾材或外部裝飾材、或作爲建材用構件，及提供該成型用積層聚酯薄膜之製法。【先前技術】先前，聚氯乙烯薄膜係代表性的成型用薄片，就加工性等而言以往係良好地被使用。但是，薄膜燃燒時會產生有毒氣'體、.可塑劑滲出等環境適合性方面的問題。另一方面，作爲環境適合性優良的材料，由聚酯、聚碳酸酯、或丙烯酸系樹脂所構成的未拉伸薄膜，以往被使用於廣泛的領域。特別是由聚酯樹脂所構成的未拉伸薄膜具有優良成型性或層壓適合性。但是，因爲係未拉伸薄膜，在耐熱性或耐溶劑性方面較差。又，未拉伸薄膜之耐衝擊性或形態安定性（熱收縮特性）不充分。因此，會有（a)爲提高生產力而提高印刷或成型加工性時的速度時，在加工時會產生斷裂或破孔，（b)成型時的加熱會產生印刷偏移，或（c )成型品曝露在比常溫高的溫度時，成型品會產生變形等問題。而且，在未拉伸薄膜蒸鍍鋁等金屬時，若熱收縮性差時在蒸鍍時會包含小氣泡，會有卷取變爲困難，或是無法得 200808551 到充分的光澤等問題。進行真空蒸鍍時，因爲加工速度更快，若耐衝擊性不充分時在蒸鍍時會有薄片斷裂之情況。解決上述問題的方法，有揭示一種方法，係使用控制薄膜在10Ό %伸長時的應力在特定範圍而成之雙軸拉伸聚對酞酸乙二酯（例如，參照專利文獻1、2)。專利文獻1 :特開平2·2 04020號公報專利文獻2 :特開2 0 0 1 - 3 4 7 5 6 5號公報但是，專利文獻1所記載之發明，係藉由使用含有脂 ^ 肪族二醇之共聚合聚酯，並調整脂肪族二醇的調配量，來減小在150°C的環境下之100%伸長時的應力，能夠得到優良的成型性、平面性及耐熱性。但是就兼具成型性及耐熱性而言係不充分的。另一方面，專利文獻2所記載之發明，在成型溫度的低溫化或成型體的精加工性方面存在有問題點。本發明者已提案（例如，參照專利文獻3)揭示一種方法，係藉由使用以共聚合聚酯樹脂作爲構成成分，且使薄膜在1〇〇%伸長時之應力（25°<：、1〇〇°(：)、儲藏彈性模數（1〇〇 °C、180°c )、及長度方向於微小張力下之熱變形率（175°c ) 在特定範圍之雙軸配向積層聚酯薄膜，能夠改善前述問題點。專利文獻3 :特開2005-290354號公報藉由該方法，能夠大幅度地改善前述問題點，在成型時係高成型壓力模具成型法時，能夠提供工業上能夠滿足市場要求之薄膜。而且，在市場要求之強加壓成型法、或 200808551 真空成型法等成型時之低成型壓力成型方法都能夠提升精加工性。但是，得知上述的成型用雙軸配向聚酯薄膜，在連續長時間製造時，在對薄膜進行後加工時（印刷、金屬膜或金屬氧化物膜的層積等）、成型加工時、或成型品使用時會有容易產生薄膜破裂或黏結之情形。因此，要求提升薄膜的耐衝擊性，並更提高生產力或品質安定性。而且，有提案（例如，參照專利文獻4)，揭示使薄膜爲積層結構，並以使皮層具有耐藥品性、使芯層具有充分的成型性的方式來使各層分擔功能，其目標係兼具耐藥品性及成型性。專利文獻4:特開2005-335276號公報但是，因爲該發明係提高熱處理溫度至使芯層成爲實質上非配向結構的程度，會有（1)在室溫之延伸度極低，（2) 因爲加熱時白化，所以加工溫度的使用範圍狹窄，（3)因爲厚度均勻性變差，會有外觀品質、加工時的安定性、及再現性變差之問題。【發明內容】發明所欲解決之課題爲了解決前述先前的問題點，本發明之目的係提供一種成型用積層聚酯薄膜，成型性、特別是在低溫度及低壓力的成型性、特別是在低溫度及低壓力的成型性、透明性、耐溶劑性、形態安定性（熱收縮特性、厚度不均）優良，而且耐衝擊性優良，及提供該成型用積層聚酯薄膜之製法。200808551 IX. Description of the Invention: Technical Field of the Invention The present invention relates to a laminated polyester film for molding, which is moldable, particularly at low temperature and low pressure, particularly at low temperature and low pressure. Excellent in moldability, transparency, solvent resistance, form stability (heat shrinkage characteristics, thickness unevenness), and excellent impact resistance, suitable for use as home appliances, mobile phones, interior decorative materials for automobiles, exterior decorative materials, or as building materials. A member, and a method for producing the laminated polyester film for molding. [Prior Art] Conventionally, a sheet for forming a typical polyvinyl chloride film has been used satisfactorily in terms of workability and the like. However, when the film is burned, there are problems in environmental suitability such as toxic gas, plasticizer oozing. On the other hand, as a material excellent in environmental suitability, an unstretched film composed of a polyester, a polycarbonate or an acrylic resin has been conventionally used in a wide range of fields. In particular, the unstretched film composed of a polyester resin has excellent moldability or lamination suitability. However, since it is an unstretched film, it is inferior in heat resistance or solvent resistance. Further, the impact resistance or the form stability (heat shrinkage property) of the unstretched film is insufficient. Therefore, there are (a) when the speed at which printing or molding processability is improved to improve productivity, breakage or breakage occurs during processing, (b) heating during molding may cause printing offset, or (c) molding When the product is exposed to a temperature higher than normal temperature, the molded article may be deformed. Further, when a metal such as aluminum is vapor-deposited in an unstretched film, if the heat shrinkability is poor, small bubbles may be formed during vapor deposition, which may cause difficulty in winding, or may not provide sufficient gloss to 200808551. When vacuum vapor deposition is performed, the processing speed is faster, and if the impact resistance is insufficient, the sheet may be broken at the time of vapor deposition. In order to solve the above problems, there is disclosed a method of using a biaxially oriented polyethylene terephthalate (for example, see Patent Documents 1 and 2) by controlling the stress of a film at a tensile strength of 10% by weight. Patent Document 1: Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. 2 0 0 1 - 3 4 7 5 6 5 However, the invention described in Patent Document 1 is based on the use of a fat-containing compound. The copolymer of the diol is adjusted to adjust the amount of the aliphatic diol to reduce the stress at 100% elongation in an environment of 150 ° C, and excellent moldability, planarity, and heat resistance can be obtained. However, it is insufficient in terms of both moldability and heat resistance. On the other hand, the invention described in Patent Document 2 has a problem in that the molding temperature is lowered or the finish of the molded body is defective. The inventors of the present invention have proposed (for example, refer to Patent Document 3) to disclose a method of using a copolymerized polyester resin as a constituent component and stressing the film at a temperature of 1% by weight (25° <:, 1〇〇°(:), storage elastic modulus (1〇〇°C, 180°c), and thermal deformation rate (175°c) in the longitudinal direction under a slight tension. Biaxially oriented laminated polyester in a specific range In the film, the above-mentioned problem can be greatly improved by the method, and it is industrially possible to provide a high molding pressure mold molding method at the time of molding. A film that satisfies the requirements of the market. Moreover, the low-forming pressure molding method in the market, such as the strong press molding method or the 200808551 vacuum molding method, can improve the finish. However, the above-mentioned biaxial alignment for molding is known. When the polyester film is continuously produced for a long period of time, it is easy to produce when the film is post-processed (printing, lamination of a metal film or a metal oxide film, etc.), during molding, or when the molded article is used. In the case where the film is broken or bonded, it is required to improve the impact resistance of the film and to improve productivity or quality stability. Further, there is a proposal (for example, refer to Patent Document 4) to disclose that the film is a laminated structure and The skin layer has a chemical resistance and a sufficient moldability of the core layer, and the functions of the layers are shared, and the object is to have both chemical resistance and moldability. Patent Document 4: JP-A-2005-335276 When the heat treatment temperature is increased to such a degree that the core layer becomes substantially non-aligned, there is (1) the elongation at room temperature is extremely low, and (2) the whitening of the heating, the use range of the processing temperature is narrow, (3) The thickness uniformity is deteriorated, and there is a problem that the appearance quality, the stability at the time of processing, and the reproducibility are deteriorated. SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION In order to solve the aforementioned problems, the object of the present invention is to provide A laminated polyester film for molding, moldability, particularly at low temperature and low pressure, particularly at low temperature and low pressure, and transparency It is excellent in properties, solvent resistance, form stability (heat shrinkage characteristics, thickness unevenness), and excellent in impact resistance, and provides a method for producing the laminated polyester film for molding.

200808551 解決課題之手段爲了解決上述課題，本發明的成型用積層聚酯薄膜製法係由以下所構成。亦即，在本發明之第1發明係一種成型用積層聚膜，其特徵係在聚酯A層的一面或兩面，層積聚酯B 構成之雙軌配向積層聚酯薄膜，在A層及B層任一者都是以共聚合聚酯、或是共聚酯及同元聚酯作爲構成成分，A層的熔點（TmA ; B層的熔點（TmB; °C)係同時滿足下述式（1)及（2)，且積層聚酯薄膜係A層及B層同時具有配向結構，：g °C之熱收縮率係長度方向及寬度方向都爲6.0 %以下、方向的厚度變動率爲1 0%以下。 260>TmB>TmA>200 …⑴ 50>TmB-TmA>5 · · · ( 2 ) 第2發明係如第1發明之成型用積層聚酯薄膜，其共聚合聚酯係（a)由芳香族二羧酸、與乙二醇、與含窄狀脂肪族二醇或脂環族二醇之二醇成分所構成之共聚酯、或是（b)由含有對酞酸及異酞酸之芳香族二羧酸尽與含有乙二醇之二醇成分所構成。第3發明係如第1發明之成型用積層聚酯薄膜，其元聚酯係選自聚對酞酸乙二酯、聚對酞酸伸丁二酯、對酞酸丁二酯所組成群組中至少1種。第4發明係如第1發明之成型用積層聚酯薄膜，表層聚酯薄膜的總厚度爲1〇〜500微米，且B層的厚及其酯薄層而聚合。。）及 150 寬度中該分枝合聚分、中同及聚中積佔整 200808551 體的1〜3 0 %。第5發明係如第1發明之成型用積層聚酯薄膜’其中在積層聚酯薄膜的長度方向及寬度方向之100%拉伸時之應力，係任一者在25°C都爲40〜300MPa、且在l〇〇°C都爲1 〜lOOMPa 〇第6發明係如第1發明之成型用積層聚酯薄膜，其中積層聚酯薄膜的霧度爲2.0%以下。第7發明係一種成型用積層聚酯薄膜，其特徵係以第1 • 發明之積層聚酯薄膜作爲基材，在該基材的一面或兩面，更層積厚度爲0.01〜5微米的塗布層（C)而構成之成型用積層聚酯薄膜，塗布層係含有由選自聚酯、聚胺基甲酸酯、丙烯酸系聚合物、或其等的共聚物之至少1種樹脂及粒子之組成物所構成，且基材係實質上未含有粒子。 ^ _ 第8發明係一種第1發明之成型用積層聚酯薄膜之製法’其特徵係包含以下步驟所構成之成型用積層聚酯薄膜之製法：使用共擠壓法，來製造在聚酯A層的一面或兩面 β 層積聚酯Β層而構成之未拉伸薄膜之步驟；使該未拉伸薄膜在縱方向及橫方向進行雙軸拉伸步驟；及邊使用夾子把持雙軸拉伸過的薄膜邊進行熱處理之步驟；構成Α層及Β層之聚酯係共聚合聚酯、或共聚合聚酯與同元聚酯之混合物，熱處理步驟具有2階段以上的熱處理區段，控制在熱處理區段之最大升溫速度10〜3 {TC /秒，最大的熱處理溫度爲 (A層的熔點_1(rc )〜（a層的熔點+2(rc )。 -10- 200808551 第9發明係如第8發明之成型用積層聚酯薄膜之製法，其中在拉幅機內邊以夾子保持薄膜邊進行橫向拉伸及熱處理時，使用下述（i)〜（v)中至少1項的方法來冷卻夾子附近，接著在拉幅機出口將薄膜從夾子放開， (i) 在夾子部分設置熱遮蔽壁之方法 (ii) 在拉幅機附加夾子冷卻機構之方法 (iii) 加長設定熱固定後的冷卻區段，來使薄膜整體充分冷卻之方法 ' (iv) 增加冷卻區段的長度、及間隔數，來增加冷卻效率之方法 (v) 使用夾子之反轉部係在爐子的外側行進之方法，來強化夾子的冷卻之方法。發明之效果因爲本發明的成型用積層聚酯薄膜係採用在芯層（A 層）的一面或兩面具有皮層（B層），皮層的熔點比芯層的熔點高，且芯層亦具有配向結構之積層結構，能夠更提高皮層之耐藥品性及耐熱性，能夠賦與保護芯層等之功能。又，能夠賦予芯層（A層）充分的柔軟性，且更提高成型性。又，藉由雙軸拉伸，能夠改善厚度不均，藉由配向結晶化能夠顯現耐熱性及耐藥品性之功能。而且，藉由使皮層（B層）的熔點較高，且採用特定的熱處理條件，能夠抑制滑性變差、提高耐衝擊性。因此，連續地長時間製造薄膜時’能夠更提高對薄膜進行後加工時（印刷、層積金屬膜或金屬氧化物膜等）、成型加工時、或成型品的使用時之生產力或品 -11- 200808551 質安定性。藉由使用本發明的成型用積層聚酯薄膜，即便在成型時的成型壓力爲ίο氣壓以下之低壓真空成型或加壓成型等成型方法（先前的雙軸配向聚酯系薄膜係難以成型），亦能夠得到精加工性良好的成型品。又，因爲此等成型法的成型成本低廉，在成型品的製造時經濟性優良。因此，應用該等成型法最能夠有效地發揮本發明的成型用積層聚酯薄膜的特徵。 ® 另一方面’模具成型雖然模具或成型裝置價格高昂，就經濟性而品係不利的，但其特徵係能夠高精密度地成型比前述成型法更複雜形狀的成型品。因此，使用本發明所使用的成型用積層聚酯薄膜進行模具成型時，與先前的雙軸配向聚酯系薄膜比較時，能夠以較低的成型溫度來成型，且具有能夠顯現改善成型品的精加工性之顯著的效果。因此，本發明的成型用積層聚酯薄膜因爲加熱成型時的 0 成型、特別是在低溫度及低壓力的成型性優良，所以能夠應用模具成型、加壓成型、真空成型等廣範圍的成型方法。而且，因爲在常溫環境下使用藉由此種方法所成型的成型品’彈性及形態安定性（熱收縮特性、厚度不均）優良，且透明性、耐溶劑性及耐熱性優良，而且耐衝擊性優良，適合作爲家電、行動電話、汽車用的內部裝飾材或外部裝飾材’或建材用構件。又，本發明的成型用積層聚酯薄膜，除了上述的成型方法以外，亦適合作爲使用加壓成型、層壓成型、模內成型、 -12- 200808551 收縮成型、折彎成型等成型方法進行成型之成型用材料。【實施方式】首先，說明在本申請案的各發明所使用的特性値及評價時所使用之特性値的技術性意義。接著，說明製造本發明的成型用積層聚酯薄膜時所使用的原料、及薄膜的製法。 (1) 在150°C之熱收縮率（HS150) 在本發明的成型用積層聚酯薄膜，於15 0°C之熱收縮率 (HS 15 0)在長度方向及寬度方向任一者都是以6.0%以下爲佳。HS150的上限値以5.0%爲較佳，以4.0%爲更佳，以 3.0%爲特佳。另一方面，從實用上而言，HS 150的下限値以0.01%爲佳，以0.1%爲更佳，以0.5%爲特佳，從實用上的效果及生產力的觀點，可按照成型用薄膜之後加工時的熱處理溫度、成型品所使.用的溫度環境來設定適當的管理基準。但是，即便製造HS 150小於0.01 %的薄膜，在實用上的效果亦無法觀察到顯著的差異。寧可說因爲生產力非常低，不必使H S 1 5 0小於0.0 1 %。另一方面，藉由使薄膜的長度方向及寬度方向的HS150 爲6.0 %以下，在蒸鍍、濺鍍或印刷等施加熱的後處理步驟能夠抑制薄膜皺紋等變形。結果能夠以良好的狀態保持後加工後的薄膜之外觀或圖案設計性。而且，能夠抑制因成型時的加熱所引起的印刷偏移、或使成型品曝露在高溫環境下時成型品的變形。因此，能夠在廣闊溫度範圍使用成型品。 (2) 寬度方向的厚度變動率 200808551 在本發明，薄膜的厚度變動率係使用作爲與宏觀耐衝擊性有關的特性値。薄膜的厚度變動率（厚度不均）通常經常被使用作爲表示薄膜的外觀品質的特性値之一。薄膜的厚度變動率大時，係意指物性受到薄膜的厚度的影響而變動。薄膜的厚度變動率大時，在厚度較薄的部分之耐衝擊性下降。因此’ 連續地長時間製造薄膜時，對薄膜進行後加工時（印刷、金屬膜或金屬氧化物膜的層積等）、成型加工時、或成型品使 ® 用時，在厚度較薄的部分會容易產生薄膜破裂。又，將薄膜成型時，會因薄膜變形不均勻、成型性不均勻等而使安定性下降。藉由使薄膜的厚度變動率在寬度方向爲10%以下，能夠改善耐衝擊性。因此，在連續製造薄膜時、後加工時、成型加工時、或是成型品的使用時，能夠降低薄膜破裂的頻率。長度方向的厚度變動率亦同樣重要，但因爲係與寬度方向連動，在本發明係使用寬度方向的厚度變動率作爲代 ®表。 (3) 100%伸長時之應力（F 100) 在本發明，100%伸長時之應力（F100)係指與薄膜的成型性具有密切關係之標準。F 1 00與薄膜的成型性具有密切關係之理由，例如使用真空成形法來成型雙軸配向聚酯薄膜時，在模具的角隅附近薄膜會有局部性伸長至1 00%以上的情形。認爲F 1 〇〇高的薄膜時，因爲變形所必要的應力太高而導致變形不足、成形性下降。另一方面，F 1 00太小時 •14- 200808551 能夠低應力來加以變形，但是因爲只能夠產生極弱的張力，在該部分之薄膜無得到均勻的伸長’推定成型時會產生歪曲。因此，在本發明，對應成型時的溫度之與成型性有關的物性係使用在100°c時之100%伸長時應力（FlOOioo)。又，成型用的模具係在室溫附近的溫度使用時，即便在室溫附近亦要求F100値不可過大。因此，在室溫附近之成形性相關物性，係使用在25°C時之1〇〇%伸長時應力（F 1 0 025)。在本發明，成型用聚酯薄膜在薄膜的長度方向及寬度方向，於25°C之100%伸長時應力（F 1 0 02 5 )任一者都以40〜 3 00MPa 爲佳。薄膜的長度方向及寬度方向之F 1 0025之下限値，以 5〇MPa爲更佳，以60MPa爲特佳。另一方面，上限値以 250 MPa爲較佳，以200 MPa爲更佳，以180MPa爲特佳。藉由使F 1 002 5爲40MPa以上，在將卷物狀薄膜卷出時，能夠防止薄膜的伸長或破裂，使作業性變爲良好。另一方面使F 1 0 02 5爲300MPa以下時，成型性變爲良好。又，在本發明之成型用聚酯薄膜，於薄膜的長度方向及寬度方向在l〇〇°C時之100%伸長時應力（F1001()())，任一者都是以1〜lOOMPa爲佳。從成型性而言，薄膜的長度方向及寬度方向之F100100 之上限値，以90MPa爲較佳，以80MPa爲更佳，以70MPa 爲特佳。另一方面，從使用成型品之彈性或形態安定性而言，F1001G()之下限値以5MPa爲較佳，以l〇MPa爲更佳， 200808551 以20MPa爲特佳。 (4) 霧度本發明的成型用積層聚酯薄膜之霧度以2%以下爲佳。藉由使霧度爲2 %以下’能夠提局印刷、金屬蒸鍍、濺鑛層、轉印層等各種加添裝飾的鮮明性、高級感’使商品價値更加提高。霧度以1 · 8 %以下爲更佳，以1 · 6 %以下爲特佳。 (5) 在25°C的斷裂延伸度（TE25) 在本發明薄膜評價，在25°C的斷裂延伸度係薄膜在室 ® 溫附近之有關處理性的特性値。例如，藉由管理在25°C之斷裂延伸度，能夠以良好的狀態維持印刷、切條等後加的通過性。 (積層構成）本發明的成型用積層聚酯薄膜係在聚酯A層（芯層）的一面或兩面，層積聚酯B層（皮層）而構成之雙軸配向積層聚酯薄膜。200808551 Means for Solving the Problem In order to solve the above problems, the method for producing a laminated polyester film for molding of the present invention is constituted as follows. In the first aspect of the invention, the laminated film for molding is characterized in that a double-track alignment laminated polyester film composed of polyester B is laminated on one or both sides of the polyester A layer, in the layer A and the B. Any one of the layers is a copolymerized polyester, or a copolyester and a homopolyester as a constituent component, and the melting point of the layer A (TmA; the melting point of the layer B (TmB; °C) simultaneously satisfies the following formula ( 1) and (2), and the laminated polyester film A layer and B layer have an alignment structure at the same time, and the heat shrinkage ratio at g °C is 6.0% or less in the longitudinal direction and the width direction, and the thickness variation rate in the direction is 1 In the second invention, the laminated polyester film for molding according to the first aspect of the invention, which is a copolymerized polyester system (a), is a copolymerized polyester film (a). a copolyester composed of an aromatic dicarboxylic acid, ethylene glycol, a diol component containing a narrow aliphatic diol or an alicyclic diol, or (b) containing a para-citric acid and a different The aromatic dicarboxylic acid of citric acid is composed of a diol component containing ethylene glycol. The third aspect of the invention is a polyester film for molding according to the first invention, which is a polyester. At least one selected from the group consisting of polyethylene terephthalate, poly(p-butylene terephthalate), and p-butyl phthalate. The fourth invention is a laminate polyester film for molding according to the first aspect of the invention. The total thickness of the surface polyester film is from 1 〇 to 500 μm, and the thickness of the B layer and the thin layer of the ester are polymerized.) and the width of the branch in the width of 150, the same and the accumulation of the medium in the 200808551 body 1 to 3 0 %. According to a fifth aspect of the invention, in the laminated polyester film for molding of the first aspect of the invention, the stress in the longitudinal direction and the width direction of the laminated polyester film is 100% to 300 MPa at 25 ° C. In the first aspect of the invention, the laminated polyester film for molding according to the first aspect of the invention, wherein the laminated polyester film has a haze of 2.0% or less. According to a seventh aspect of the invention, there is provided a laminated polyester film for molding, characterized in that the laminated polyester film of the first aspect of the invention is used as a substrate, and a coating layer having a thickness of 0.01 to 5 μm is laminated on one or both sides of the substrate. (C) The laminated polyester film for molding comprising a composition comprising at least one resin selected from the group consisting of polyester, polyurethane, acrylic polymer, or the like, and particles. The composition is composed of a substance, and the substrate does not substantially contain particles. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ a step of forming an unstretched film by laminating a polyester layer on one or both sides of the layer; subjecting the unstretched film to a biaxial stretching step in the longitudinal direction and the transverse direction; and holding the biaxial stretching using a clip a step of heat-treating the film; a polyester-based copolymerized polyester constituting the ruthenium layer and the ruthenium layer, or a mixture of the copolymerized polyester and the homo-polyester, the heat treatment step having a heat treatment section of two or more stages, controlled in The maximum heating rate of the heat treatment zone is 10 to 3 {TC / sec, and the maximum heat treatment temperature is (the melting point of layer A _1 (rc ) ~ (the melting point of layer a + 2 (rc ). -10- 200808551 The method for producing a laminated polyester film for molding according to the eighth aspect of the invention, wherein at least one of the following (i) to (v) is used for lateral stretching and heat treatment while holding the film with a clip inside the tenter To cool the clip nearby, then the thinner at the exit of the tenter The film is released from the clip, (i) a method of providing a heat shielding wall in the clip portion (ii) a method of attaching a clip cooling mechanism to the tenter (iii) lengthening a cooling section after setting the heat fixing, to sufficiently cool the entire film Method (iv) Method of increasing the length of the cooling section and the number of intervals to increase the cooling efficiency (v) The method of using the reverse portion of the clip to travel outside the furnace to enhance the cooling of the clip. The effect of the present invention is that the laminated polyester film for molding of the present invention has a skin layer (layer B) on one or both sides of the core layer (layer A), the melting point of the skin layer is higher than the melting point of the core layer, and the core layer also has an alignment structure. The laminated structure can further improve the chemical resistance and heat resistance of the skin layer, and can impart a function of protecting the core layer, etc. Further, the core layer (layer A) can be sufficiently softened and the moldability can be further improved. Biaxial stretching can improve thickness unevenness, and can exhibit heat resistance and chemical resistance by alignment crystallization. Moreover, by making the skin layer (B layer) have a higher melting point and using a specific heat treatment strip In addition, when the film is continuously produced for a long period of time, it is possible to improve the post-processing of the film (printing, laminating a metal film or a metal oxide film, etc.) and molding. Or the productivity of the molded article or the product -11-200808551. The use of the laminated polyester film for molding of the present invention, even at the time of molding, the molding pressure is ίο, the pressure is lower than the vacuum forming or pressurizing A molding method such as molding (previously, the biaxially oriented polyester film is difficult to mold), and a molded article having excellent finishability can be obtained. Moreover, since the molding method has low molding cost and is economical in the production of the molded article. Therefore, the molding method is most effective in exerting the characteristics of the laminated polyester film for molding of the present invention. ® On the other hand, mold molding is economical and unfavorable because of its high price, but it is characterized by high-precision molding of molded articles having a more complicated shape than the above-mentioned molding method. Therefore, when the mold is formed by using the laminated polyester film for molding used in the present invention, it can be molded at a lower molding temperature than the conventional biaxially oriented polyester film, and has a molded article which can be improved. Significant effect of finish. Therefore, since the laminated polyester film for molding of the present invention is excellent in molding at the time of thermoforming, particularly in low temperature and low pressure, it is possible to apply a wide range of molding methods such as mold molding, press molding, and vacuum molding. . In addition, the molded article molded by such a method is excellent in elasticity and form stability (heat shrinkage characteristics, thickness unevenness) in a normal temperature environment, and is excellent in transparency, solvent resistance, and heat resistance, and is resistant to impact. It is excellent in properties and is suitable for use as an interior decoration material or an exterior decoration material for home appliances, mobile phones, automobiles, or for building materials. Further, in addition to the above-described molding method, the laminated polyester film for molding of the present invention is suitably molded by a molding method such as press molding, lamination molding, in-mold molding, shrink molding, or bending molding. The molding material. [Embodiment] First, the technical significance of the characteristics used in the inventions of the present application and the characteristics used in the evaluation will be described. Next, a method of producing a raw material and a film used in the production of the laminated polyester film for molding of the present invention will be described. (1) Heat shrinkage at 150 °C (HS150) In the laminated polyester film for molding of the present invention, the heat shrinkage ratio (HS 15 0) at 150 ° C is in either the longitudinal direction and the width direction. It is preferably 6.0% or less. The upper limit of HS150 is preferably 5.0%, more preferably 4.0%, and 3.0% is particularly good. On the other hand, practically, the lower limit of HS 150 is preferably 0.01%, more preferably 0.1%, and particularly preferably 0.5%. From the viewpoint of practical effects and productivity, it can be used as a film for molding. The heat treatment temperature at the time of processing and the temperature environment used for the molded product are used to set an appropriate management standard. However, even if a film having an HS 150 of less than 0.01% is produced, a significant difference cannot be observed in practical use. It is better to say that because the productivity is very low, it is not necessary to make H S 1 50 less than 0.01%. On the other hand, by setting the HS150 in the longitudinal direction and the width direction of the film to 6.0% or less, it is possible to suppress deformation such as wrinkles of the film by a post-treatment step of applying heat such as vapor deposition, sputtering, or printing. As a result, the appearance or pattern design of the post-processed film can be maintained in a good state. Further, it is possible to suppress the printing offset caused by heating at the time of molding or to deform the molded article when the molded article is exposed to a high temperature environment. Therefore, it is possible to use a molded article over a wide temperature range. (2) Thickness variation rate in the width direction 200808551 In the present invention, the thickness variation rate of the film is used as a property related to macro impact resistance. The thickness variation rate (thickness unevenness) of the film is often used as one of the characteristics indicating the appearance quality of the film. When the thickness variation rate of the film is large, it means that the physical properties are affected by the thickness of the film. When the thickness variation rate of the film is large, the impact resistance in the thin portion is lowered. Therefore, when the film is continuously produced for a long period of time, when the film is post-processed (printing, lamination of a metal film or a metal oxide film, etc.), during molding, or when the molded article is used, the thinner portion is used. It is easy to cause film cracking. Further, when the film is molded, the stability of the film is deteriorated due to uneven deformation of the film and uneven moldability. The impact resistance can be improved by making the thickness variation rate of the film 10% or less in the width direction. Therefore, the frequency of film breakage can be reduced during continuous film production, post-processing, molding processing, or use of a molded article. The thickness variation rate in the longitudinal direction is also important, but the thickness variation rate in the width direction is used as a substitute table in the present invention because it is interlocked with the width direction. (3) Stress at 100% elongation (F 100) In the present invention, the stress at 100% elongation (F100) means a standard closely related to the formability of the film. The reason why F 1 00 has a close relationship with the moldability of the film, for example, when a biaxially oriented polyester film is formed by a vacuum forming method, the film may locally extend to 100% or more in the vicinity of the corner of the mold. When a film having a high F 1 〇〇 is considered, the stress required for the deformation is too high, resulting in insufficient deformation and a decrease in formability. On the other hand, F 1 00 is too small • 14-200808551 can be deformed with low stress, but since only a very weak tensile force can be generated, the film in this portion is not uniformly stretched. Therefore, in the present invention, the physical properties relating to the moldability in accordance with the temperature at the time of molding are the stress at 100% elongation at 100 ° C (FlOOio). Further, when the mold for molding is used at a temperature near room temperature, F100 is not required to be too large even at room temperature. Therefore, the formability related property at room temperature is the stress (F 1 0 025) at 1% elongation at 25 °C. In the present invention, the polyester film for molding preferably has a stress (F 1 0 02 5 ) of 40 to 300 MPa in the longitudinal direction and the width direction of the film at 100% elongation at 25 °C. The lower limit F of F 1 0025 in the longitudinal direction and the width direction of the film is more preferably 5 MPa, and particularly preferably 60 MPa. On the other hand, the upper limit 値 is preferably 250 MPa, more preferably 200 MPa, and particularly preferably 180 MPa. When F 1 002 5 is 40 MPa or more, when the roll-shaped film is wound up, elongation or breakage of the film can be prevented, and workability can be improved. On the other hand, when F 1 0 02 5 is 300 MPa or less, the moldability becomes good. Further, in the polyester film for molding of the present invention, the stress (F1001 () ()) at 100% elongation at 10 ° C in the longitudinal direction and the width direction of the film, either is 1 to 100 MPa. It is better. From the viewpoint of moldability, the upper limit F of F100100 in the longitudinal direction and the width direction of the film is preferably 90 MPa, more preferably 80 MPa, and particularly preferably 70 MPa. On the other hand, from the viewpoint of the elasticity or form stability of the molded article, the lower limit of F1001G() is preferably 5 MPa, more preferably 10 MPa, and 200808551 is particularly preferably 20 MPa. (4) Haze The haze of the laminated polyester film for molding of the present invention is preferably 2% or less. By setting the haze to 2% or less, it is possible to improve the price of the product by adding various decorative and high-quality feelings such as printing, metal deposition, a splash layer, and a transfer layer. The haze is preferably 1 / 8 % or less, and more preferably 1 / 6 % or less. (5) Breaking elongation at 25 ° C (TE25) In the film of the present invention, the elongation at 25 ° C is the relevant handling property of the film near the chamber ® temperature. For example, by managing the elongation at break at 25 ° C, the passability of printing, slitting, etc. can be maintained in a good state. (Laminated structure) The laminated polyester film for molding of the present invention is a biaxially oriented laminated polyester film which is formed by laminating a polyester B layer (cortex) on one or both sides of a polyester A layer (core layer).

0 亦即，本發明的積層聚酯薄膜的積層構成係以B/A/B 之2種3層、或B/A的2種2層爲基本構成。又，亦能夠以前述積層薄膜作爲基材，在該基材的至少一面上設置塗布層（C層），用以對本發明薄膜的一面或兩面賦予改善品質或其他功能。在本發明的成型用積層聚酯薄膜，A層及B層任一者都是以共聚合聚酯、或是共聚合聚酯及同元聚酯作爲構成成分，A層的熔點（TmA ; °C )及B層的熔點（TmB ; °C )係同時滿足下述式（1 )、（ 2 )。 • 16- 200808551 260>TmB>TmA>200 · · · ( l ) 50>TmB-TmA>5 · · · (2) 亦即，在本發明，其特徵係使由聚酯B(熔點比芯層（A 層）的聚酯A高）所構成的皮層（B層），層積於芯層的一面或兩面，且芯層亦具有配向結構。使芯層（A層）保留配向結構之理由，將在後面詳細說明。而且，本發明的成型用積層聚酯薄膜係使A層的熔點 (°C )爲TmA、B層的熔點（°C )爲TmB時，滿足下述的關係式（1)係重要的。熔點能夠在差示掃描熱量測定（DSC)的一次升溫時檢測出，係意指熔化時之吸熱尖峰溫度。 260>TmB>TmA>200 · · · (1 ) 從薄膜整體的成型性而言，TmA及TmB以小於260 °C 爲佳。又，爲了維持薄膜整體的耐熱性，且減少在高溫的熱變形，高於200 °C係重要的。TmB及TmA以高於205 °C 爲佳，以高於21 0°C爲特佳。又，在本發明，從使柔軟性、滑性、耐藥品性、及耐熱性高度平衡而言，皮層（B層）的熔點（TmB)比芯層（A層）的熔點（TmA)高係重要的。而且，本發明的成型用積層聚酯薄膜，係使A層的熔點（°C )爲TmA、B層的熔點（°C )爲TmB時，滿足下述的關係式（2)係重要的。 50>TmB-TmA>5 …⑺ 「TmB-TmA」爲50°C以上時，因爲A層與B層的熔點差異太大時，無法使熱收縮率、柔軟性、耐衝撃性、經時 -17- 200808551 安定性、及加工安定性高度地滿足。「TmB-TmA」以小於 4〇°C爲佳，以小於35°C焉更佳。又，「TmB-TmA」爲5°C以 ί 下時’因爲熔點的差異太小，難以使柔軟性、滑性、耐藥品性、及耐熱性高度地平衡。「TmB-TmA」以大於1 0 °C爲In other words, the laminated structure of the laminated polyester film of the present invention is basically composed of two types of three layers of B/A/B or two types of two layers of B/A. Further, the laminated film may be used as a substrate, and a coating layer (C layer) may be provided on at least one surface of the substrate to impart improved quality or other functions to one or both sides of the film of the present invention. In the laminated polyester film for molding of the present invention, either of the A layer and the B layer is a copolymerized polyester or a copolymerized polyester and a homopolyester as a constituent component, and the melting point of the layer A (TmA; ° The melting points (TmB; °C) of the C) and B layers simultaneously satisfy the following formulas (1) and (2). • 16-200808551 260>TmB>TmA>200 · · · ( l ) 50 >TmB-TmA> 5 · · · (2) That is, in the present invention, it is characterized by polyester B (melting point ratio core layer) The skin layer (layer B) composed of (polyester A of the (A layer)) is laminated on one or both sides of the core layer, and the core layer also has an alignment structure. The reason why the core layer (layer A) retains the alignment structure will be described in detail later. Further, in the laminated polyester film for molding of the present invention, when the melting point (°C) of the layer A is TmA and the melting point (°C) of the layer B is TmB, it is important to satisfy the following relationship (1). The melting point can be detected at a single temperature rise of differential scanning calorimetry (DSC), which means the endothermic peak temperature at the time of melting. 260>TmB>TmA>200 · · · (1) From the viewpoint of moldability of the entire film, TmA and TmB are preferably less than 260 °C. Further, in order to maintain the heat resistance of the entire film and to reduce thermal deformation at a high temperature, it is important to be higher than 200 °C. TmB and TmA are preferably higher than 205 ° C, and particularly higher than 21 0 ° C. Further, in the present invention, the melting point (TmB) of the skin layer (layer B) is higher than the melting point (TmA) of the core layer (layer A) from the viewpoint of high balance of flexibility, slipperiness, chemical resistance, and heat resistance. important. Further, in the laminated polyester film for molding of the present invention, when the melting point (°C) of the layer A is TmA and the melting point (°C) of the layer B is TmB, it is important to satisfy the following relationship (2). 50>TmB-TmA>5 (7) When the "TmB-TmA" is 50 ° C or more, since the difference in melting point between the A layer and the B layer is too large, the heat shrinkage ratio, flexibility, impact resistance, and lapse of time cannot be obtained - 17- 200808551 Stability, and processing stability are highly satisfied. "TmB-TmA" is preferably less than 4 〇 ° C, and more preferably less than 35 ° C. Further, when "TmB-TmA" is 5 ° C or lower, the difference in melting point is too small, and it is difficult to highly balance flexibility, slipperiness, drug resistance, and heat resistance. "TmB-TmA" is greater than 10 °C

I 佳’以大於1 5 °c爲特佳。如本發明之使用含有5〜5 0莫耳％共聚合成分之共聚合聚酯作爲原料所得到聚酯薄膜，與聚對酞酸乙二酯薄膜比較時’結晶速度較慢、且結晶性低。又，爲了減少面配向度及在150°C的熱收縮率，使用專利文獻3所記載之在比通常更高的溫度進行熱處理之方法時，因爲在拉伸結束後急遽地在高溫進行熱處理，在熱處理區段構成較低結晶性的材料之分子的運動性變高。因此，在拉伸步驟因粒子（雙軸配向膜中的粒子或塗布層中的粒子）***所形成的表突起’在熱處理區段再次埋沒，而使薄膜表面的凹凸難以形成。因此，薄膜的滑性變差，將薄膜卷取成卷物狀時之外觀變差、且將已卷物狀卷取之薄膜卷出時，容易產生黏結響或破裂。爲了避免此等問題而將粒子的含有量增加至必要以上時，薄膜的透明性會變差。本發明係使用將熱處理步驟分成多段的熱處理區段，並使熱處理區段的升溫速度在特定範圍之製法，用以使薄膜在結晶化進行之同時，使配向鬆驰。藉由此方法，在粒子往內部埋没之前，能夠某種程度地促進薄膜的結晶化，能夠抑制粒子的沈入。而且，藉由提高熱處理溫度能夠促進結晶性，且得到熱收縮率低的薄膜。又，就從透明性而言， -18- 200808551 不必含有必要以上的粒子。決定聚酯的熔點（Tm)之重要因素雖有複數個，但是認爲藉由如何擾亂主體之聚酯的結晶性，能夠決定Tm。亦即，藉由在主體之同元聚酯混合共聚合聚酯，或是與同元聚酯共聚合，能使主體之聚酯的結晶性下降，來得到必要的T m 〇具體上’共聚合係完全無規地進行酯交換而成之情況的熔點，而混合係依照濟壓機的運轉條件、在熔融線之滯留時間、原料組成、分子量、原料水分率、觸媒等添加物、及酸價等來決定酯交換率。將此等重要因素全部固定時能夠得到再現性良好且一定的熔點。若只變更一個重要因素時，能夠得到對應的酯交換率，能夠得到在此條件下之再現性良好的熔點。 (薄膜之較佳製法）本發明之成型用積層聚酯薄膜在芯層（A層）及皮層（B 層）所使用的聚酯’係使用共聚合聚酯、或是共聚合聚酯及同元聚酯之混合物。共聚合聚酯較佳是（a)由芳香族二羧酸、與乙二醇、與含有分枝狀脂肪族二醇或脂環族二醇之二醇成分所構成之共聚合聚酯、或是（b)由含有對酞酸及異酞酸之芳香族二羧酸成分、與含有乙二醇之二醇成分所構成之共聚合聚酯。前述之共聚合聚酯的共聚合成分係分枝狀脂肪族二醇或脂環族二醇時，藉由該二醇之分子結構的體高度，能夠控制在高溫之分子運動。因此，使用含有分枝狀脂肪族二 -19- 200808551 醇或脂環族二醇作爲共聚合成分之共聚合聚酯而成的薄膜，其耐熱性提高。另一方面，共聚合成分之二羧酸成分係只有由芳香族二羧酸成分所構成的時亦能夠提高耐熱性。又，從能夠更提高成型性而言，構成雙軸配向聚酯薄膜之聚酯以更含有二醇成分之1，3·丙二醇單位或1，4 -丁二醇單位爲佳。又，藉由在共聚合聚酯導入此等單位，能夠在分子中形成微結晶，例如，能夠抑制在1 8 0 °C的彈性模數 ^ 下降。此等單位以共聚合聚酯的共聚合成分之方式導入，亦可使用混合如聚對酞酸丙二酯（PTT)、聚對酞酸丁二酯 (PBT)之同元聚酯的方法。在本發明，薄膜原料能夠使用共聚合聚酯單獨、混合2 種類以上的共聚合聚酯、或是混合至少1種同元聚酯與至少1種共聚合聚酯之任一種方法。從抑制熔點下降而言，此等之中，以混合同元聚酯及共聚合聚酯爲佳。 0 前述共聚合聚酯使用由芳香族二羧酸成分、與乙二醇、及含有分枝狀脂肪族二醇或脂環族二醇之二醇成分所構成之共聚合聚酯時’芳香族二竣酸成分以對酞酸、異酞酸、 2，6 -萘二羧酸或其等的酯形成性衍生物爲佳。相對於總二羧酸，對酞酸單位及/或2,6-萘二羧酸單位的量爲70莫耳 % ’以8 5莫耳％以上爲佳，以9 5莫耳％爲更佳，以1 〇〇莫耳％爲特佳。對酞酸單位與2，6 _萘二羧酸單位的莫耳比以 1 00/0 〜50/50 爲佳。又，分枝狀脂肪族二醇可例示的有新戊二醇、1，2-丙二 -20- 200808551 1，4 _ 。爲，而提升酸之之共耳％，以述之，對圍爲土類物、，以、鋁定劑有黏，以型性醇、1，3-丙二醇、1，4-丁二醇等。脂環族二醇可例示的有環己烷二甲醇、三環癸烷二羥甲基等。此等之中，以新戊二醇或1，4_環己烷二甲醇爲特佳賦予前述特性，以使用此等二醇作爲共聚合成分爲佳且，從透明性或耐熱性亦優良、設置有塗布層時能夠: 與塗布層的黏附性而言，亦是較佳。又，前述之共聚合聚酯，使用由含有對酞酸及異酞芳香族二羧酸成分、與含有乙二醇之二醇成分所構成 • 聚合聚酯時，相對於總二醇成分，乙二醇的量爲70莫以上，以85莫耳％以上爲佳，以95莫耳％以上爲特佳 100莫耳％以上爲最佳。乙二醇以外的二醇成分，以前分枝狀脂肪族二醇或脂環族二醇、或二甘醇爲佳。又酞酸單位及異酞酸單位的莫耳比以100/0〜50/5 0的範佳。製造前述共聚合聚酯所使用之觸媒，例如可使用鹼金屬化合物、錳化合物、鈷化合物、鋁化合物、銻化合 ^ 鈦化合物、鈦/矽複合氧化物、鍺化合物等。此等之中從觸媒活性而言，以鈦化合物、銻化合物、鍺化合物化合物爲佳。製造前述共聚合聚酯時，以添加磷化合物作爲熱安爲佳。前述磷化合物例如以磷酸、亞磷酸等爲佳。從成型性及製膜安定性而言，前述共聚合聚酯之固度以0.50dl/g以上爲佳，以〇.55dl/g以上爲更佳 0.60dl/g以上爲特佳。固有黏度小於0. 50dl/g時，成 -21 200808551 會有下降的傾向。另一方面，從耐衝擊性而言，藉由使薄膜的固有黏度爲〇· 6 0 dl/g以上，薄膜的衝擊強度提高能夠減少薄膜製膜時或加工時之斷裂頻率。又，爲了在熔融線除去異物而設置過濾器時，就熔融樹脂在壓出時之吐出安定性而言，固有黏度的上限以l.〇dl/g爲佳。在本發明，藉由使用至少1種同元聚酯及至少1種共聚合聚酯作爲薄膜原料，並將其等混合來製膜，能夠邊維持與只有使用共聚合聚酯時同等的柔軟性、邊實現透明性及 ® 高熔點（耐熱性）。相對於只有使用高熔點的同元聚酯（例如，聚對酞酸乙二酯）時，能夠邊維持高透明性、邊實現柔軟性及實用上無問題的熔點（耐熱性）。又，從成型性而言，以混合前述共聚合聚酯、及至少1 種以上聚對酞酸乙二酯以外的同元聚酯（例如聚對酞酸伸丁二酯或聚對酞酸丁二酯）作爲本發明之成型用積層聚酯薄膜的原料爲更佳。而且，亦可因必要而在前述共聚合聚酯並用1種或2 種以上下述二羧酸成分及/或二醇成分作爲共聚合成分。能夠與對酞酸或其酯形成性衍生物同時並用之其他二羧酸成分可舉出（1)異酞酸、2,6·萘二羧酸、二苯基-4,4，_ 二羧酸、二苯氧基乙烷二羧酸、二苯基礪二羧酸、5-鈉磺酸基異酞酸、酞酸等芳香族二羧酸或其等酯形成性衍生物、（2)草酸、琥珀酸、己二酸、癸二酸、二聚酸、順丁烯二酸、反丁烯二酸、戊二酸等脂肪族二羧酸或其等的酯形成性衍生物、（3)環己烷二羧酸等脂肪族二羧酸或其等的酯 -22- 200808551 形成性衍生物、（4)對羥基苯甲酸、羥基己酸等羥基羧酸或其等的酯形成性衍生物等。另一方面，能夠與乙二醇、及分枝狀脂肪族二醇及/或脂環族二醇同時並用之其他的二醇成分可舉出例如戊二醇、己二醇等脂肪族二‘醇、雙酚A、雙酚S等芳香族二醇及此等之環氧乙烷加成物、二甘醇、三甘醇等。而且，亦可因必要而使前述共聚合聚酯，進而與1，2,4-苯三甲酸、1，3,5-苯三甲酸、三羥甲基丙烷等多官能化合物 • 共聚合。又，爲了改善薄膜的滑性或卷取性等處理性，以在薄膜表面形成凹凸爲佳。在薄膜表面形成凹凸之方法通常能夠使用在薄膜中含有粒子之方法。但是，在薄膜中含有粒子，因爲通常折射率與聚酯不同，會成爲薄膜的透明性下降之重要因素。成型品爲了提高圖案設計性，多半的情況係在將薄膜成型之前對薄膜表面施行印刷。因爲此種印刷層多半係印刷在成型用薄膜的 ^ 背側，從印刷鮮明性而言，要求薄膜具有高透明性。因此，在本發明爲了改善透明性，以採用以下2種構成爲佳。第1構成係使積層聚酯薄膜之皮層（B層）的厚度1〜 5微米，並只有使該皮層（B層）含有粒子，芯層（A層）係實質上未含有粒子之構成。第2構成係以積層聚酯薄膜作爲基材，在該基材之一面或兩面更層積厚度爲0 · 0 1〜5微米的塗布層（C層），該塗布層係含有由選自聚酯、聚胺基甲酸酯、丙烯酸系聚合物、或其等的共聚物之至少1種樹脂及 -23- 200808551 粒子之組成物所構成，且在基材係實質上未含有粒子之構成。含有前述粒子之表面層厚度的上限’以3微米爲佳’ 以1微米爲特佳。使用塗布層（C層）之方法除了賦予透明性及滑性以外，亦有與印刷層之黏附性優良之優點。又，上述所稱「在基材係實質上未含有粒子」係意指例如無機粒子時，使用矽光X射線分析定量無機元素時，係能夠檢測出的界限以下的含量。這是即便未故意地在基材薄膜添加粒子，亦會有來自外來異物之污染成分混入之情 ⑩形。前述粒子可舉出平均粒徑（依據SEM之個數基準的平均粒徑）爲0.0 1〜1 0微米之眾所周知的內部粒子、無機粒子及/或有機粒子等外部粒子。使用平均粒徑大於微米的粒子時，會有薄膜容易產生缺陷、圖案設計性變差的傾向。另一方面，平均粒徑小於〇. 〇 1微米的粒子時，會有薄膜的滑性或卷取性等處理性下降低傾向。又，粒子的平均粒徑係藉由電子顯微鏡法對至少200 ^ 個以上的粒子拍攝複數張照片，在投影膠片（OHP film)追蹤粒子的輪廓，藉由圖像解析該追蹤像，換算圓相當直徑而算出。前述外部粒子可使用例如濕式及乾式二氧化矽、膠體二氧化矽、矽酸鋁、氧化鈦、碳酸鈣、磷酸鈣、硫酸鋇、氧化鎂、雲母、高嶺土、黏土、羥基磷灰石等無機粒子、以及苯乙烯、聚矽氧、丙烯酸類作爲構成成分之有機粒子等。其中，以使用乾式、濕式及乾式膠體狀二氧化矽、氧化鋁 -24- 200808551 等無機粒子及苯乙烯、聚矽氧、丙烯酸、甲基丙烯酸、聚酯、二乙烯基苯等作爲構成成分之有機粒子等爲佳。而且，因爲折射率比較接近聚酯，從透明性而言，以二氧化矽粒子、玻璃塡料、二氧化矽-氧化鋁複合氧化物粒子爲特佳。此等內部粒子、無機粒子及/或有機粒子在不損害特性的範圍內亦能夠並用二種以上。而且，在含有前述粒子之層中之粒子的含量，基於積層薄膜爲2.0%以下，在薄膜的滑性或卷取性不會成爲問題的 ® 範圍，以調整在0.001〜10質量％的範圍爲佳。本發明的成型用積層聚酯薄膜係雙軸拉伸薄膜是重要的〜在本發明，藉由雙軸拉伸之分子配向，能夠改善未拉伸薄膜的缺點之耐溶劑性或耐熱性。亦即，邊維持未拉伸薄膜之良好的成型性、邊改善未拉伸薄膜的缺點之耐溶劑性或耐熱性，係本發明的特徵之一。積層雙軸配向聚酯薄膜的製法係例如使用以下的方法。可例示將使用於聚酯A層及聚酯B層之聚酯乾燥後，各自分別供給至2台以上的熔融壓出機，藉由共擠出以B/A 或B/A/B的方式層積。將該等從狹縫狀的模頭以片狀擠出，再藉由施加靜電等方式使其黏附在鑄塑滾筒，並冷卻固化而得到未拉伸薄膜，隨後，使該未拉伸薄膜進行雙軸拉伸之方法。又，使用彎曲式擠壓機時，不一定須要乾燥薄膜料晶粒。在共擠出步驟，A層、B層都是配合所使用的原料來適當地調整熔融擠出條件，選擇能夠抑制加水分解、熱劣化 -25- 200808551 的進行’同時能夠將薄膜的熔點調整在適當的範圍之條件。具有熔點之原料時，係設定擠出溫度爲（熔點+1〇(rc ) 以下，較佳是（熔點+90°C )以下，更佳是（熔點+8(rc )以下，來抑制分解、及熔點下降。至模頭出口爲止之滯留時間爲 20分鐘以下’以18分鐘以下爲佳，以16分鐘以下爲更佳，能夠抑制分解、及熔點下降。 A層及B層所使用的熔融擠壓機係使用例如具有給料部、壓縮部、計量部、熔融線部之擠壓機。 ® 又，熔融擠壓機係從給料部至壓縮部使樹脂緩慢地升溫，並將樹脂溫度的上限控制在前述範圍，來使其完全熔融。又，在計量部或熔融線部，爲了抑制薄膜的固有黏度下降，例如芯層（A層）用的樹脂時，以使樹脂溫度爲小於 2 8 0°C爲佳。特別是熔融線部，爲了盡可能抑制樹脂劣化之進行，以在275 °C以下爲佳，以270 °C以下爲更佳。雙軸拉伸方法能夠採用將未拉伸薄片往薄膜的長度方向（MD)及寬度方向（TD)拉伸、熱處理，來得到具有目標物 ^ 性之雙軸拉伸薄膜。在此等方法之中，從薄膜品質而言，以在長度方向拉伸後，往寬度方向拉伸之MD/TD法，或是在寬度方向拉伸後，往長度方向拉伸之TD/MD法等依次雙軸拉伸方式、及大致同時往長度方向及寬度方向拉伸之同時雙軸拉伸方式爲佳。又，同時雙軸拉伸法時，亦可使用線性馬達驅動。而且，亦可按照必要採用將同一方向的拉伸分成多階段進行之多階段拉伸法。雙軸拉伸時之薄膜的拉伸倍率，以長度方向及寬度方向 -26- 200808551 係1.6〜4.2倍爲佳，以1.7〜4.0倍爲特佳。此時，長度方向及寬度方向的拉伸倍率係任一方向較大都可以，亦可以相同倍率。以長度方向的拉伸倍率爲2.8〜4.0倍、寬度方向的拉伸倍率爲3.0〜4.5倍來進行爲更佳。爲了使隨後之寬度方向的拉伸能夠順利，長度方向的拉伸以拉伸溫度爲50〜1 lOt：、拉伸倍率爲1.5〜4.0倍爲佳。通常，拉伸聚對酞酸乙二酯時，拉伸溫度比適當條件低時，因爲在橫向拉伸開始初期，屈服應力急遽地變高而無 ^ 法拉伸。又，即便能夠拉伸，厚度或拉伸倍率容易不均勻，乃是不佳。因此，在本發明以採用以下的拉伸條件爲佳。首先，預熱溫度以90〜140 °C爲佳。接著，在寬度方向的拉伸之前半部，拉伸溫度相對於預熱溫度，以-10〜25 °C 爲佳，以_1〇〜20 °C爲特佳。又，在寬度方向的拉伸之後半部，拉伸溫度相對於前半部的拉伸溫度，以〇〜+20 °c爲佳，以+5〜+2 5 °C爲特佳。藉由採用如此條件，在寬度方向的拉 ^ 伸之前半部的拉伸應力較大，能夠進行均勻的拉伸。又，藉由在後半提升溫度，能夠提高拉伸性。又，寬度方向的拉伸倍率以2.5〜5.0爲佳。而且，在雙軸拉伸後對薄膜進行熱處理。該熱處理能夠藉由在拉幅機中、或在已加熱的輥上等先前眾所周知的方法進行。又，熱處理溫度及熱處理時間能夠按照必要的熱收縮率程度而任意地設定。在本發明，係使熱處理步驟在2階段以上的熱處理區段進行，較佳是控制使熱處理區段之最大升溫速度爲10〜30 -27- 200808551 °C /秒、最大熱處理溫度爲（A層的熔點_i〇°c )〜（A層的熔點+2 0 °C )。又，熱處理區段以3區段以上爲更佳，以4區段以上爲特佳。熱處理時間係依照薄膜的運送速度及熱處理步驟的長度來決定適當的範圍，例如以進行1〜60秒爲佳。又，此種熱處理亦可邊使薄膜往其長度方向及/或寬度方向鬆驰、邊進行。爲了使薄膜之長度方向及橫向在150 °C的熱收縮率減小，以提高熱處理溫度、增長熱處理時間、及進行鬆弛處 ® 理爲佳。具體上’爲了使薄膜之長度方向及橫向在150 °C 的熱收縮率爲6.0%以下，以使熱處理步驟之最大熱處理溫度爲（A層的熔點-10 °C)〜（A層的熔點+20 °C)的範圍，並使鬆弛率爲1〜8 %邊鬆弛邊進行爲佳。而且，亦可對各方向進行1次以上的再拉伸，亦可隨後進行熱處理。又’爲了使A層保留配向結構，在熱處理步驟之最大的熱處理溫度上限以（A層的熔點+15°C )爲佳，以（A層的熔點+l〇°C )爲更佳，以（A層的熔點+5°C )爲特佳。而且，該熱 ^ 處理溫度係設定溫度而不是薄膜的實際溫度。但是，因爲增長製造線來增長熱處理時間受到設備上的限制，係困難的。又，降低薄膜的運送速度時，生產力會降低。因此，雖然在拉幅機內的拉伸區段係在1 0 0 °c附近以比較低的溫度加熱薄膜，但是通過拉伸區段後之薄膜進入熱處理區段，必須迅速地升溫至2 0 0 °c附近的高溫。因此，被推薦的較佳實施態樣係在熱處理區段設置紅外線加熱器，來增強對薄膜的加熱。 -28- 200808551 •例如，以採用在拉伸區段與熱處理區段之間設置1公尺以上的隔熱區段，用以提高以後的加熱效率之方法爲佳。亦即，藉由強化區段的間壁來減少熱流的洩漏，來提升加熱效率。藉由調整風量的平衡及強度，能夠邊確保風量、邊調整拉幅機內的壓力，來抑制熱流的洩漏。又，關於熱風加熱不足之加熱，以在強加熱區段附加紅外線加熱器爲佳。又，藉由增熱固定區段的長度、及區段數來使加熱量增加之方法亦是有效的。 ® 而且，薄膜的厚度爲5 0微米以下時，若從拉伸結束後之100°C附近的低溫，將熱處理區段的最大熱處理溫度急遽地升溫至（A層的熔點- l〇°C )以上（A層的熔點+20°C )以下的範圍時，會產生以下的問題。亦即，因爲本發明的積層薄膜係使用共聚合聚酯，結晶度較低，因此，會有在熱處理區段不僅是會產生薄膜的厚度均勻性變差、或衝擊強度下降，且於製膜中在熱處理區段會產生薄膜破孔，而無法連續製膜之情況。爲了解決此問題，在熱處理區段使溫度的升溫階段地進行’邊進行薄膜的結晶化、且邊藉由熱處理來使薄膜配向鬆弛係重要的。具體上，製造本發明的積層薄膜時，階段地升溫用以使在熱處理區段之升溫速度爲10〜3(TC /秒係重要的。在熱處理區段之升溫速度以15〜25 °C /秒爲佳。又’使熱處理區段之升溫速度加速時，在藉由熱處理來使薄膜配向鬆弛之前，薄膜結晶化。因此，構成薄膜之聚酯變脆’不僅是薄膜的衝擊強度下降，且，於製膜中在熱處 -29- 200808551 理區段產生薄膜破孔而難以連續製膜。另一方面，熱處理區段之升溫速度太慢時，受到設備上的限制，在到達必要的最大熱處理溫度之前，薄膜已通過熱處理區段。因此，由於熱處理溫度不足，薄膜在150 °C之長度方向及寬度方向的熱收縮率變大。又，爲了同時滿足本發明所規定之薄膜的特徵，抑制薄膜的固有黏度下降亦佳。例如，採用前述之熔融擠出時的溫度條件，來使薄膜的固有黏度爲0.50dl/g以上爲佳。又，藉由減少原料之聚酯的水分率，來抑制在熔融擠出時聚酯因加水分解所引起的固有黏度下降。又，本發明之積層薄膜的總厚度，可按照用途適當地設定在10〜5 00微米的範圍。通常的情況，薄膜的厚度多半是在20〜188微米的範圍使用。又，B層的厚度以佔總厚度之1〜30%的範圍爲佳，以2〜27%爲較佳，以3〜25%的範圍爲更佳。藉由使B層的厚度佔總厚度之1 %以上，能夠防止耐藥品性、耐熱性低落，又，製膜安定性亦優良。另一方面，藉由由使B層的厚度佔總厚度之30 %以下，能夠抑制成型性或熱收縮率的變差。爲了提升薄膜的成型性，通常可使用減小面配向度之方法。使面配向下降之手段，例如，已知有降低拉伸倍率之方法。但是該方法之薄膜的厚度均勻性變差。另一方面，本發明所採用的方法係使熱處理溫度比通常高，且將熱處理區段之升溫速度控制在一定範圍，邊使薄膜的結晶成、長、且邊進行配向鬆驰率。 -30- 200808551 本發明係藉由使用上述技術，並在熱處理溫度下功夫，來製造得到必要的物性，若熱處理溫度太高時，芯層變爲無配向，會產生許多缺點。 (1) 因爲在室溫之斷裂延伸度下降且變爲非常脆，所以在製程上難以卷取或切條。 (2) 因爲使用時亦容易斷裂，會產生處理上的問題。 (3) 厚度不均變爲非常差，會有處理性、外觀品質降低、加工品質、加工再現性變差。 (4) 成型時、印刷等伴隨加熱之後加工時、或是在高溫環境下使用成型品時，無配向部分因加熱會有白化變質的情形，而引起外觀不良。因此，使用或加工時的溫度範圍受到限定。爲了避免此等問題，必須選擇適當的熱處理溫度，不可使芯層成爲無配向狀態。又，在本發明，使用作爲薄膜的原料之共聚合聚酯，因爲熔點比同元聚合物低，若提高熱處理溫度時，於拉幅機內在保持薄膜之夾子，薄膜會有黏附而難以剝離之問題。因此，連續製膜時，於拉幅機出口將薄膜放開時對夾子附近進行充分冷卻係重要的。具體上，爲了防止薄膜與夾子黏附，以採用以下方法爲佳，（1)在夾子部分設置熱遮蔽壁，使夾子不容易受到加熱之方法，（2)在拉幅機附加夾子冷卻機構之方法，（3)設定將熱固定後的冷卻區段增長，用以強化冷卻能力來對整體充分地進行冷卻之方法，（4)增加冷卻區段的長度、及區段 200808551 數，來增加冷卻效率之方法，（5)使用夾子的反轉部分係在爐子的外側行進之形式，來強化夾子的冷卻之方法等。實施例以下，藉由實施例來詳細地說明本發明。又，在各實施例所得到的薄膜特性係藉由以下方法來測定、評價。 (1) 固有黏度精稱0 · 1克晶粒試樣，並溶解在2 5毫升的苯酚/四氯乙烷=6M(質量比）的混合溶劑中，使用奧氏黏度計在30°C測 φ 定。又，測定係進行3次，來求得其平均値。 (2) 薄膜的熔點使用差示掃描熱量測定器（DUPONT公司製、V4 OB2000 型），以試樣量約0.0 1 0克、測定溫度範圍爲室溫至3 0 0 °C、升溫速度爲i 〇 °C /分鐘的條件進行測定。A層及B層的熔點之判定，係藉由切取A4尺寸的薄膜，並黏著固定在平板後，使用刮鬍刀片削取表面，進行D S C測定來測定B層的熔點。接著，藉由D S C測定薄膜整體的熔點，藉由消除B φ 層熔點之熔化尖峰的資訊來求得A層的熔點。 (3) A層（芯層）有無配向製作判定用試樣係使用切薄片機，於薄膜的MD方向平行地製作薄片（厚度：10微米）用以對厚度方向剖面進行透射觀察。接著，使用透射型偏光顯微鏡藉由以下基準來目視判定使偏光板旋轉時在A層之影像的明亮度。又，擴大倍率係以2 0 0倍進行。無配向：A層之影像明亮度實質上無變化有配向：A層之影像明亮度實質上有變化 -32- 200808551 (4) 薄膜的厚度依據JIS K 7105「塑膠薄膜及薄片厚度測定方法」機械式掃描測定方法（A法）來測定。測定器係使用電子測微計 (MAHR公司製、MINITRON 1240)。薄膜的厚度係每1薄膜測定5點，合計測定3片1 5點，求取其平均値。 (5) 10 0%拉伸時之應力（F 100)及斷裂延伸度（TE) 對雙軸拉伸膜的長度方向及寬度方向，使用刮鬍刀片切取各自長度爲180毫米及寬度爲10毫米之薄長方形試樣。接著使用拉伸試驗機（東洋精機股份公司製）來拉伸薄長方形試樣，從所得到的負荷-歪曲線求取各方向之1 〇〇%拉伸時應力（MPa)及斷裂延伸度（％)。又，測定係在25 °C的環境下，以初期長40毫米、夾頭間距離爲100毫米、十字頭速度爲100毫米/分鐘、記錄計之夾頭速度爲200毫米/分鐘、測力傳感器25kgf的條件進行。又，該測定係進行1 〇次，並採用平均値。又，100°C之環境下，係使用上述同樣的條件來進行拉伸試驗。此時，試樣係在1〇〇°C的環境下保持30秒後進行 / 測定。又，測定係進行1 0次，並採用平均値。 (6) 在150°C之熱收縮率依據JIS C 238-1997 5.3.4(尺寸變化），依照以下順序測定在薄膜的長度方向及寬度方向之1 50°C時的熱收縮率。對薄膜的長度方向及寬度方向，各自切取長度250毫米及寬度20毫米之薄長方形試樣。在各試樣的長度方向以 200毫米間隔記上2個記號，在5克之一定張力（長度方向 -33- 200808551 的張力）下測定2個記號的間隔A。隨後，將薄長方形各試樣之一側，在無負荷下使用夾子吊於筐架，放入150°C環境下的齒輪烘箱中，同時計測時間。3 0分鐘後，從齒輪烘箱取出筐架並在室溫下放置3 0分鐘。接著，對熱處理後的各試樣，在5gf之一定張力（長度方向的張力）下，使用鐵尺以0.25毫米單位讀取2個記號的間隔B(熱處理後之2個記號的間隔）。藉由讀取的間隔A及6，藉由下述式來算出各試樣在1 5 0 °C之熱收縮率，並依照以下基準判定。測定係進行3次，並求取其平均値。數値係對小數點第2位四捨五入，而湊齊爲小數第1位。熱收縮率（％) = ((A-B)/A)x 100 (7) 寬度方向的厚度變動率卷取薄膜的寬度方向3公尺、長度方向5公分之連續的帶狀試樣，使用薄膜厚度連續測定機（ANRITSU股份公司製），來測定薄膜的厚度，並記錄於記錄器。藉由圖表求得厚度的最大値（dmax)、最小値（dmin)、平均値（d)，並藉由下述式算出下厚度變動率（％)。又，測定係進行3次，並求取其平均値。又，寬度方向的長度小於3公尺時，係連接而進行。又，將連接部分從數據剔除。厚度變動率（％) = ((dmax-dmin)/d)xl〇〇 (8) 霧度依據JIS K 7 136，使用霧度計（日本電色工業股份公司製、3 00A)進行測定，測定係進行2次，並求取其平均値。 (9) 衝擊強度 -34- 200808551 使用薄膜衝擊測試器（東洋精機股份公司製、製造號碼 T-84-3)，使用夾鉗將測定用薄膜壓住，使用1/2英吋直徑之半球衝擊頭進行刺扎，來測定試樣的衝撃強度。試樣係切取100毫米X100毫米以上，固定試樣之固定環的內徑爲 3 0毫米。又，測定係進行1 〇次，並採用平均値。將該平均値換算成每1毫米厚度，來求取薄膜的衝擊強度（J/mm)，並依據以下基準判定。〇：10 J/mm以上 • X :小於 1 0 J / m m (10)成型性 (a)真空成型性在薄膜上進行5毫米四方之方形格印刷後，使用已加熱至5 00 °C之紅外線加熱器將薄膜加熱10〜15秒後，在模具溫度30〜100°C進行真空成型。又，加熱條件係在上述範圍內選擇對各薄膜最適當的條件。模具的形狀係杯型，且開口部之直徑爲50毫米，底面部之直徑爲40毫米，深度 W 爲50毫米，使用全部的角具有直徑0.5毫米的彎曲之物。在最適當條件下，對5個真空成型而成的成型品評價成型性及精加工性，依據下述基準進行等級判定。又，◎及〇爲合格，X爲不合格。 ◎ : (i)成型品無破裂 (Π)角的曲率半徑爲1毫米以下，且印刷偏移爲〇·1毫米以下 (iii)且無符合x之外觀不良 -35- 200808551 〇：（i)成型品無破裂 (ii) 角的曲率半徑爲大於1毫米且1.5毫米以下.，或是印刷偏移爲大於〇 · 1毫米且0.2毫米以下 (iii) 且無符合X之外觀不良’係實用上無問題的程度 X :成型品破裂，或是雖無破裂但符合以下項目（i)〜（iv) 中任一者之物 (i)角的曲率半徑大於1.5毫米 (Π)產生大皺紋而外觀差 • (Hi)薄膜白化而透明性下降 (W)印刷偏移大於0.2毫米 (b)壓空成型性在薄膜上進行5毫米四方之方形格印刷後，使用已加熱至5 00 °C之紅外線加熱器將薄膜加熱10〜15秒後，在模具溫度3 0〜1 0 0 °C進行真空成型，在4氣壓的加壓下進行加壓成型。又，加熱條件係在上述範圍內選擇對各薄膜最適當的條件。模具的形狀係杯型，且開口部之直徑爲60毫 ^ 米，底面部之直徑爲55毫米，深度爲50毫米，使用全部的角具有直徑〇 . 5毫米的彎曲之物。在最適當條件下，對5個真空成型而成的成型品評價成型性及精加工性，依據下述基準進行等級判定。又，◎及〇爲合格，X爲不合格。 ◎ : (i)成型品無破裂 (Π)角的曲率半徑爲1毫米以下，且印刷偏移爲〇·1毫米以下 -36- 200808551 (iii)且無符合X之外觀不良〇：（i )成型品無破裂 (ii) 角的曲率半徑爲大於1毫米且1 .5毫米以下，或是印刷偏移爲大於0.1毫米且0.2毫米以下 (iii) 且無符合X之外觀不良，係實用上無問題的程度 X :成型品破裂，或是雖無破裂但符合以下項目（i)〜（iv) 中任一者 (i)角的曲率半徑大於1.5毫米 • (Π)產生大鈹紋而外觀差 (iii) 薄膜白化而透明性下降 (iv) 印刷偏移大於0.2毫米 (c)模具成型性在薄膜上進行印刷後，使用已加熱至1 00〜1 40°C之熱板接觸加熱4秒鐘後，以模具溫度3 0〜7 0 °C、保壓時間5 秒進行加壓成型。又，加熱條件係在上述範圍內選擇對各薄膜最適當的條件。模具的形狀係杯型，且開口部之直徑 ^ 爲50毫米，底面部之直徑爲40毫米，深度爲30毫米’使用全部的角具有直徑0.5毫米的彎曲之物。在最適當條件下，對5個模具成型而成的成型品評價成型性及精加工性，依據下述基準進行等級判定。又’ ◎及〇爲合格，X爲不合格。 ◎ : (i)成型品無破裂 (ii)角的曲率半徑爲1毫米以下，且印刷偏移爲0,1毫米以下 -37- 200808551 (iii)且無符合X之外觀不良〇：（i)成型品無破裂 (ii) 角的曲率半徑爲大於1毫米且1.5毫米以下，或是印刷偏移爲大於〇 . 1毫米且〇 · 2毫米以下 (iii) 且無符合X之外觀不良，係實用上無問題的程度 X :成型品破裂，或是雖無破裂但符合以下項目（i)〜（iv) 中任一者 (iv)角的曲率半徑大於1.5毫米 • (ii)產生大皺紋而外觀差 (iii) 薄膜白化而透明性下降 (iv) 印刷偏移大於〇·2毫米 (11) 耐溶劑性將試樣浸漬在調溫至25 °C之甲苯中3 0分鐘，依據以下基準判定浸漬前後的外觀變化，〇爲合格。霧度係使用前述方法測定。〇··外觀幾乎無變化，且霧度値的變化小於1 % ® X :認定有外觀變化，或霧度値的變化爲1 %以上 (12) 靜摩擦係數μ s及動磨察係數/zd 依據JIS-C2151，使用以下條件進行評價。平板用試片：寬度130毫米、長度250毫米且使用非印刷面側翹曲用試片：寬度12〇毫米、長度120毫米且使用印刷面側 ’I 佳' is especially good at more than 15 °C. The polyester film obtained by using the copolymerized polyester containing 5 to 50% by mole of the copolymerization component as a raw material of the present invention has a slower crystallization rate and lower crystallinity when compared with the polyethylene terephthalate film. . In addition, in order to reduce the surface alignment degree and the heat shrinkage rate at 150 ° C, when the heat treatment is performed at a temperature higher than usual as described in Patent Document 3, the heat treatment is performed at a high temperature after the end of the stretching. The mobility of the molecules constituting the material having lower crystallinity in the heat treatment zone becomes high. Therefore, in the stretching step, the surface protrusion formed by the bulging of the particles (particles in the biaxial alignment film or particles in the coating layer) is buried again in the heat treatment section, and the unevenness of the surface of the film is difficult to form. Therefore, the slipperiness of the film is deteriorated, and when the film is wound into a roll, the appearance is deteriorated, and when the film wound up in the form of a roll is taken up, sticking or cracking easily occurs. In order to avoid such problems and increase the content of the particles more than necessary, the transparency of the film is deteriorated. The present invention is a method in which the heat treatment step is divided into a plurality of heat treatment sections, and the temperature increase rate of the heat treatment section is in a specific range, so that the film is relaxed while the crystallization is progressing. By this method, the crystallization of the film can be promoted to some extent before the particles are buried inside, and the sinking of the particles can be suppressed. Further, by increasing the heat treatment temperature, crystallinity can be promoted, and a film having a low heat shrinkage rate can be obtained. Moreover, in terms of transparency, -18-200808551 does not have to contain more than necessary particles. Although there are a plurality of important factors determining the melting point (Tm) of the polyester, it is considered that Tm can be determined by how to disturb the crystallinity of the main polyester. That is, by copolymerizing the polyester in the main polyester of the main body or copolymerizing with the homopolyester, the crystallinity of the polyester of the main body can be lowered to obtain the necessary T m 〇 The polymerization system is a melting point in which the transesterification is carried out completely randomly, and the mixing system is in accordance with the operating conditions of the press, the residence time in the melting line, the raw material composition, the molecular weight, the raw material moisture content, the catalyst, and the like, and The acid value and the like determine the transesterification rate. When these important factors are all fixed, a good reproducibility and a certain melting point can be obtained. When only one important factor is changed, the corresponding transesterification ratio can be obtained, and a melting point excellent in reproducibility under these conditions can be obtained. (Prepared method for producing a film) The polyester film for molding of the present invention uses a copolymerized polyester or a copolymerized polyester and a polyester used in the core layer (layer A) and the skin layer (layer B). a mixture of polyesters. The copolymerized polyester is preferably (a) a copolymerized polyester composed of an aromatic dicarboxylic acid, ethylene glycol, a diol component containing a branched aliphatic diol or an alicyclic diol, or (b) A copolymerized polyester composed of an aromatic dicarboxylic acid component containing p-citric acid and isophthalic acid and a glycol component containing ethylene glycol. When the copolymerization component of the above-mentioned copolymerized polyester is a branched aliphatic diol or an alicyclic diol, molecular motion at a high temperature can be controlled by the bulk height of the molecular structure of the diol. Therefore, a film obtained by using a copolymerized polyester containing a branched aliphatic -19-200808551 alcohol or an alicyclic diol as a copolymerization component has improved heat resistance. On the other hand, when the dicarboxylic acid component of the copolymerization component is composed only of an aromatic dicarboxylic acid component, heat resistance can be improved. Further, from the viewpoint of further improving the moldability, the polyester constituting the biaxially oriented polyester film preferably contains a 1,3-glycol unit or a 1,4-butanediol unit of a diol component. Further, by introducing these units into the copolymerized polyester, it is possible to form microcrystals in the molecule, and for example, it is possible to suppress a decrease in the elastic modulus at 18 °C. These units are introduced as a copolymerized component of the copolymerized polyester, and a method of mixing a homopolyester such as poly(p-propyl phthalate) (PTT) or polybutylene terephthalate (PBT) may also be used. In the present invention, the film raw material can be either a copolymerized polyester alone or a mixture of two or more kinds of copolymerized polyesters, or a method of mixing at least one of the homopolyesters and at least one of the copolymerized polyesters. From the viewpoint of suppressing a decrease in the melting point, it is preferred to mix the homopolyester and the copolymerized polyester. 0 When the copolymerized polyester is a copolymerized polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol, 'aromatic The diterpene acid component is preferably an ester-forming derivative of citric acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid or the like. The amount of the unit of decanoic acid and/or the unit of 2,6-naphthalenedicarboxylic acid is 70 mol% with respect to the total dicarboxylic acid, preferably 8 5 mol% or more, more preferably 95 mol%. It is especially good with 1% Mo. The molar ratio of the unit of citric acid to the unit of 2,6-naphthalenedicarboxylic acid is preferably from 1 00/0 to 50/50. Further, as the branched aliphatic diol, neopentyl glycol, 1,2-propane-20-200808551 1,4 _ can be exemplified. For the purpose of raising the total amount of acid, it is stated that the surrounding material is clay, and the aluminum fixing agent is sticky, and the type alcohol, 1,3-propanediol, 1,4-butanediol, etc. . The alicyclic diol may, for example, be cyclohexanedimethanol or tricyclodecane dimethylol. Among these, it is preferable to impart the above characteristics with neopentyl glycol or 1,4-cyclohexanedimethanol, and it is preferable to use these diols as a copolymerization synthesis, and it is excellent in transparency or heat resistance. When the coating layer is provided, it is also preferable in terms of adhesion to the coating layer. Further, when the above-mentioned copolymerized polyester is composed of a polymerized polyester comprising a terephthalic acid and an isoindole aromatic dicarboxylic acid component and a glycol component containing ethylene glycol, the total diol component is used. The amount of the diol is preferably 70 mol or more, preferably 85 mol% or more, and more preferably 95 mol% or more, particularly preferably 100 mol% or more. The diol component other than ethylene glycol is preferably a branched aliphatic diol, an alicyclic diol or diethylene glycol. Moreover, the molar ratio of the citric acid unit and the isononanoic acid unit is 100/0 to 50/5 0. For the catalyst used for the above-mentioned copolymerized polyester, for example, an alkali metal compound, a manganese compound, a cobalt compound, an aluminum compound, a ruthenium compound titanium compound, a titanium/ruthenium composite oxide, a ruthenium compound or the like can be used. Among these, from the catalyst activity, a titanium compound, a ruthenium compound or a ruthenium compound compound is preferred. When the above copolymerized polyester is produced, it is preferred to add a phosphorus compound as the heat. The phosphorus compound is preferably, for example, phosphoric acid, phosphorous acid or the like. In terms of moldability and film stability, the solidity of the aforementioned copolymerized polyester is 0. 50dl / g or more is better, to 〇. More than 55dl/g is better. More than 60 dl / g is particularly good. Intrinsic viscosity is less than 0. At 50 dl/g, there is a tendency to fall to -21 200808551. On the other hand, in terms of impact resistance, by setting the intrinsic viscosity of the film to 〇·60 dl/g or more, the impact strength of the film can be reduced to reduce the fracture frequency at the time of film formation or processing. Further, in order to provide a filter for removing foreign matter from the molten wire, the upper limit of the intrinsic viscosity of the molten resin at the time of extrusion is 1. 〇 dl / g is better. In the present invention, by using at least one homopolyester and at least one copolymerized polyester as a film raw material, and mixing them to form a film, it is possible to maintain the same flexibility as when only a copolymerized polyester is used. , achieving transparency and high melting point (heat resistance). When a homopolymer polyester having a high melting point (for example, polyethylene terephthalate) is used, it is possible to achieve high flexibility while achieving flexibility and a practically problem-free melting point (heat resistance). Further, in terms of moldability, the copolymerized polyester and at least one of the homopolyesters other than the polyethylene terephthalate (for example, polybutylene terephthalate or polypyristate) are mixed. The diester) is more preferably used as a raw material of the laminated polyester film for molding of the present invention. Further, if necessary, one or two or more kinds of the following dicarboxylic acid component and/or diol component may be used as a copolymerization component in the copolymerization of the polyester. Examples of other dicarboxylic acid components which can be used in combination with a phthalic acid or an ester-forming derivative thereof include (1) isononanoic acid, 2,6-naphthalenedicarboxylic acid, and diphenyl-4,4,-dicarboxylic acid. An aromatic dicarboxylic acid such as an acid, a diphenoxyethane dicarboxylic acid, a diphenylphosphonium dicarboxylic acid, a 5-sodium sulfonate isophthalic acid or a decanoic acid or an ester-forming derivative thereof, (2) An ester-forming derivative of an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, azelaic acid, dimer acid, maleic acid, fumaric acid or glutaric acid or the like, (3) An ester-forming derivative of an aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid or an ester thereof such as an ester-22-200808551 forming derivative, (4) a hydroxycarboxylic acid such as p-hydroxybenzoic acid or hydroxycaproic acid or the like Things and so on. On the other hand, other diol components which can be used together with ethylene glycol and a branched aliphatic diol and/or an alicyclic diol can be mentioned, for example, aliphatic diols such as pentanediol and hexanediol. An aromatic diol such as an alcohol, bisphenol A or bisphenol S, or an ethylene oxide adduct thereof, diethylene glycol or triethylene glycol. Further, the copolymerized polyester may be copolymerized with a polyfunctional compound such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid or trimethylolpropane, if necessary. Further, in order to improve the handleability such as the smoothness or the take-up property of the film, it is preferred to form irregularities on the surface of the film. A method of forming irregularities on the surface of a film can usually be carried out by using a method of containing particles in a film. However, since the film contains particles, since the refractive index is usually different from that of the polyester, it becomes an important factor for the decrease in transparency of the film. In order to improve the design of the molded article, most of the molded articles are printed on the surface of the film before the film is formed. Since such a printing layer is mostly printed on the back side of the film for molding, the film is required to have high transparency in terms of printing sharpness. Therefore, in the present invention, in order to improve the transparency, it is preferred to adopt the following two configurations. In the first configuration, the thickness of the skin layer (layer B) of the laminated polyester film is 1 to 5 μm, and only the skin layer (layer B) contains particles, and the core layer (layer A) has a structure in which particles are not substantially contained. In the second embodiment, a laminated polyester film is used as a substrate, and a coating layer (C layer) having a thickness of 0·0 1 to 5 μm is laminated on one surface or both surfaces of the substrate, and the coating layer is selected from the group consisting of poly At least one resin of a copolymer, a polyurethane, an acrylic polymer, or a copolymer thereof, and a composition of -23-200808551 particles, and the substrate is substantially free of particles. The upper limit 'the thickness of the surface layer containing the aforementioned particles is preferably 3 μm' is particularly preferable at 1 μm. The method of using the coating layer (C layer) has an advantage of being excellent in adhesion to the printing layer in addition to imparting transparency and slipperiness. Further, the above-mentioned "substantially no particles are contained in the substrate" means, for example, inorganic particles, and when the inorganic elements are quantified by calender X-ray analysis, the content can be detected below the limit. This is because even if particles are not intentionally added to the substrate film, there is a mixture of contaminated components from foreign matter. The particles may have an average particle diameter (average particle diameter based on the number of SEMs) of 0. 0 1 to 1 0 micrometers of well-known internal particles such as internal particles, inorganic particles, and/or organic particles. When particles having an average particle diameter of more than micrometers are used, the film tends to be defective and the pattern design tends to be deteriorated. On the other hand, the average particle size is less than 〇 When the particles of 1 μm are used, there is a tendency that the handleability such as slipperiness or take-up property of the film is lowered. Further, the average particle diameter of the particles is obtained by taking a plurality of photographs of at least 200 ^ or more particles by electron microscopy, and tracking the contour of the particles on a transparencies (OHP film), and analyzing the tracking image by an image, and the scale is equivalent. Calculated by diameter. As the external particles, for example, wet and dry cerium oxide, colloidal cerium oxide, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, magnesium oxide, mica, kaolin, clay, hydroxyapatite or the like can be used. Particles, and organic particles such as styrene, polyfluorene, and acrylic as constituent components. Among them, inorganic particles such as dry, wet and dry colloidal cerium oxide, alumina-24-200808551, and styrene, polyfluorene oxide, acrylic acid, methacrylic acid, polyester, divinylbenzene, etc. are used as constituent components. Organic particles and the like are preferred. Further, since the refractive index is relatively close to the polyester, it is particularly preferable from the viewpoint of transparency, such as cerium oxide particles, glass cerium, and cerium oxide-alumina composite oxide particles. These internal particles, inorganic particles, and/or organic particles can be used in combination of two or more kinds within a range that does not impair the properties. Further, the content of the particles in the layer containing the aforementioned particles is 2. Below 0%, the slipperiness or take-up of the film does not become a problem in the ® range to adjust at 0. A range of 001 to 10% by mass is preferred. The laminated polyester film for molding of the present invention is important as a biaxially stretched film. In the present invention, solvent resistance or heat resistance which is disadvantageous of the unstretched film can be improved by molecular alignment by biaxial stretching. That is, it is one of the features of the present invention to maintain good moldability of the unstretched film and to improve solvent resistance or heat resistance of the unstretched film. The method for producing a laminated biaxially oriented polyester film is, for example, the following method. It is exemplified that the polyester used in the polyester A layer and the polyester B layer is dried and then supplied to two or more melt extruders by coextrusion in a B/A or B/A/B manner. Lamination. The slit-shaped die is extruded in a sheet shape, adhered to the casting drum by applying static electricity or the like, and solidified by cooling to obtain an unstretched film, and then the unstretched film is subjected to the unstretched film. Biaxial stretching method. Also, when a curved extruder is used, it is not necessary to dry the film grain. In the co-extrusion step, both the A layer and the B layer are appropriately adjusted to the melt extrusion conditions in combination with the raw materials used, and it is possible to suppress the progress of hydrolysis and thermal degradation -25-200808551 while adjusting the melting point of the film. The appropriate range of conditions. In the case of a raw material having a melting point, the extrusion temperature is set to be (melting point + 1 〇 (rc) or less, preferably (melting point + 90 ° C) or less, more preferably (melting point + 8 (rc) or less) to suppress decomposition, And the melting point is decreased. The residence time until the exit of the die is 20 minutes or less. It is preferably 18 minutes or less, more preferably 16 minutes or less, and the decomposition and the melting point can be suppressed. The melt extrusion used in the A layer and the B layer. For the press, for example, an extruder having a feed portion, a compression portion, a metering portion, and a melt line portion is used. Further, the melt extruder slowly heats the resin from the feed portion to the compression portion, and controls the upper limit of the resin temperature. In the above range, it is completely melted. Further, in order to suppress the decrease in the inherent viscosity of the film in the metering portion or the melting line portion, for example, the resin for the core layer (layer A) is such that the resin temperature is less than 280 °. In particular, in order to suppress the deterioration of the resin as much as possible, the melting line portion is preferably 275 ° C or lower, more preferably 270 ° C or lower. The biaxial stretching method can be carried out by using unstretched sheets. The length direction (MD) and width of the film The (TD) is stretched and heat-treated to obtain a biaxially stretched film having a target property. Among these methods, in terms of film quality, after stretching in the longitudinal direction, the film is stretched in the width direction. The MD/TD method is a biaxial stretching method in which the TD/MD method is stretched in the longitudinal direction after stretching in the width direction, and the biaxial stretching method is performed while stretching in the longitudinal direction and the width direction at substantially the same time. Further, in the case of the simultaneous biaxial stretching method, a linear motor drive may be used, and a multi-stage stretching method in which the stretching in the same direction is divided into a plurality of stages may be employed as necessary. The stretching ratio of the film is in the length direction and the width direction -26- 200808551. 6~4. 2 times is better, to 1. 7~4. 0 times is especially good. In this case, the stretching ratio in the longitudinal direction and the width direction may be larger in either direction, or may be the same magnification. The stretching ratio in the longitudinal direction is 2. 8~4. 0 times, the stretching ratio in the width direction is 3. 0~4. 5 times to perform better. In order to make the subsequent stretching in the width direction smooth, the stretching in the longitudinal direction is carried out at a stretching temperature of 50 to 1 lOt: and the stretching ratio is 1. 5~4. 0 times is better. In general, when the polyethylene terephthalate is stretched, when the stretching temperature is lower than the appropriate condition, the yield stress is rapidly increased and the film is not stretched at the beginning of the transverse stretching. Further, even if it can be stretched, the thickness or the stretching ratio is likely to be uneven, which is not preferable. Therefore, in the present invention, it is preferred to employ the following stretching conditions. First, the preheating temperature is preferably 90 to 140 °C. Next, in the first half of the stretching in the width direction, the stretching temperature is preferably -10 to 25 °C with respect to the preheating temperature, and particularly preferably _1 Torr to 20 °C. Further, in the half after stretching in the width direction, the stretching temperature is preferably 〇~+20 °c with respect to the stretching temperature of the first half, and particularly preferably +5 to +25 °C. By adopting such a condition, the tensile stress in the half portion before stretching in the width direction is large, and uniform stretching can be performed. Moreover, the stretchability can be improved by raising the temperature in the latter half. Further, the stretching ratio in the width direction is 2. 5~5. 0 is better. Moreover, the film is heat treated after biaxial stretching. This heat treatment can be carried out by a previously known method such as in a tenter or on a heated roll. Further, the heat treatment temperature and the heat treatment time can be arbitrarily set in accordance with the degree of heat shrinkage required. In the present invention, the heat treatment step is performed in the heat treatment section of two or more stages, preferably, the maximum temperature increase rate of the heat treatment section is controlled to be 10 to 30 -27 to 200808551 ° C / sec, and the maximum heat treatment temperature is (A layer). Melting point _i 〇 ° c ) ~ (A layer of melting point + 2 0 ° C). Further, the heat treatment zone is preferably three or more segments, and more preferably four or more segments. The heat treatment time is determined in accordance with the transport speed of the film and the length of the heat treatment step, and is preferably, for example, 1 to 60 seconds. Further, such heat treatment can be carried out while relaxing the film in the longitudinal direction and/or the width direction. In order to reduce the heat shrinkage rate at 150 °C in the longitudinal direction and the transverse direction of the film, it is preferable to increase the heat treatment temperature, increase the heat treatment time, and perform the relaxation. Specifically, the heat shrinkage rate at a temperature of 150 ° C in the longitudinal direction and the transverse direction of the film was 6. 0% or less, so that the maximum heat treatment temperature in the heat treatment step is (the melting point of layer A - 10 ° C) ~ (the melting point of layer A + 20 ° C), and the relaxation rate is 1 to 8 % while relaxing. It is better. Further, it is also possible to perform re-stretching for one or more times in each direction, or to perform heat treatment subsequently. Further, in order to maintain the alignment structure of the layer A, the upper limit of the maximum heat treatment temperature in the heat treatment step is preferably (the melting point of layer A + 15 ° C), and the melting point of layer A (l熔点 ° C) is more preferable. (The melting point of layer A + 5 ° C) is particularly good. Moreover, the heat treatment temperature sets the temperature rather than the actual temperature of the film. However, it is difficult to increase the manufacturing time to increase the heat treatment time by the equipment. Also, when the transport speed of the film is lowered, the productivity is lowered. Therefore, although the stretched section in the tenter heats the film at a relatively low temperature around 100 °c, the film after the stretched section enters the heat treatment zone, and must be rapidly heated to 2 0. High temperature near 0 °c. Therefore, the preferred embodiment is to provide an infrared heater in the heat treatment section to enhance the heating of the film. -28- 200808551 • For example, it is preferable to use a heat insulating section of 1 m or more between the stretching section and the heat treatment section to improve the heating efficiency in the future. That is, the heat transfer efficiency is improved by reducing the leakage of the heat flow by strengthening the partition walls. By adjusting the balance and strength of the air volume, it is possible to suppress the leakage of the heat flow while ensuring the air volume and adjusting the pressure in the tenter. Further, regarding the heating of insufficient hot air heating, it is preferable to add an infrared heater to the strong heating section. Further, a method of increasing the amount of heating by increasing the length of the fixed section and the number of sections is also effective. ® When the thickness of the film is 50 μm or less, the maximum heat treatment temperature of the heat treatment zone is rapidly increased to a temperature of 100 ° C after the end of stretching (the melting point of layer A - l 〇 ° C ) When the above range (melting point of layer A + 20 ° C) is less than the following, the following problems occur. That is, since the laminated film of the present invention uses a copolymerized polyester and has a low degree of crystallinity, not only the thickness uniformity of the film may be deteriorated in the heat-treated section, but also the impact strength may be lowered, and the film may be formed. In the heat treatment section, film breakage occurs, and the film cannot be continuously formed. In order to solve this problem, it is important to carry out crystallization of the film while the temperature is raised in the heat treatment zone, and to align the film by heat treatment. Specifically, when the laminated film of the present invention is produced, the temperature is raised in stages to increase the temperature in the heat treatment zone to 10 to 3 (TC / sec is important. The heating rate in the heat treatment zone is 15 to 25 ° C / In the second step, when the temperature increase rate of the heat treatment zone is accelerated, the film is crystallized before the film is relaxed by the heat treatment. Therefore, the polyester constituting the film becomes brittle, not only the impact strength of the film is lowered, but also In the film formation, in the hot section -29-200808551, the film section is broken and it is difficult to form a film continuously. On the other hand, when the temperature rise rate of the heat treatment section is too slow, it is limited by the equipment and reaches the maximum necessary. Before the heat treatment temperature, the film has passed through the heat treatment zone. Therefore, since the heat treatment temperature is insufficient, the heat shrinkage rate of the film in the longitudinal direction and the width direction at 150 ° C becomes large. Further, in order to simultaneously satisfy the characteristics of the film specified by the present invention, It is also preferable to suppress the intrinsic viscosity of the film. For example, the temperature condition at the time of melt extrusion is used to make the film have an intrinsic viscosity of 0. More than 50 dl / g is preferred. Further, by reducing the moisture content of the polyester of the raw material, the inherent viscosity drop of the polyester due to hydrolysis by hydrolysis during melt extrusion is suppressed. Further, the total thickness of the laminated film of the present invention can be appropriately set in the range of 10 to 500 μm in accordance with the use. In general, the thickness of the film is mostly used in the range of 20 to 188 μm. Further, the thickness of the layer B is preferably in the range of 1 to 30% of the total thickness, preferably 2 to 27%, more preferably 3 to 25%. When the thickness of the layer B is 1% or more of the total thickness, chemical resistance and heat resistance can be prevented from being lowered, and film forming stability is also excellent. On the other hand, by making the thickness of the layer B 30% or less of the total thickness, deterioration of moldability or heat shrinkage rate can be suppressed. In order to improve the formability of the film, a method of reducing the face alignment degree can be usually used. As means for lowering the surface alignment, for example, a method of lowering the stretching ratio is known. However, the thickness uniformity of the film of this method is deteriorated. On the other hand, the method used in the present invention is such that the heat treatment temperature is higher than usual, and the temperature increase rate of the heat treatment zone is controlled within a certain range, and the film is crystallized and formed while being subjected to the alignment relaxation ratio. -30- 200808551 The present invention produces the necessary physical properties by using the above technique and working at a heat treatment temperature. If the heat treatment temperature is too high, the core layer becomes unaligned, which causes many disadvantages. (1) Since the elongation at break at room temperature decreases and becomes very brittle, it is difficult to take up or cut a strip in the process. (2) It is easy to break when used, which causes handling problems. (3) Unevenness in thickness becomes very poor, and there are handling properties, deterioration in appearance quality, deterioration in processing quality, and process reproducibility. (4) When molding, such as molding, printing, etc., or when using a molded article in a high-temperature environment, the unaligned portion may be whitened and deteriorated due to heating, resulting in poor appearance. Therefore, the temperature range at the time of use or processing is limited. In order to avoid such problems, it is necessary to select an appropriate heat treatment temperature and not to make the core layer unaligned. Further, in the present invention, a copolymerized polyester which is a raw material of a film is used because the melting point is lower than that of the homopolymer, and when the heat treatment temperature is raised, the film is held in the tenter, and the film adheres and is difficult to peel off. problem. Therefore, it is important to sufficiently cool the vicinity of the clip when the film is released at the tenter exit when the film is continuously formed. Specifically, in order to prevent the film from sticking to the clip, it is preferable to use the following method: (1) a method of providing a heat shielding wall in the clip portion so that the clip is not easily heated, and (2) a method of attaching a clip cooling mechanism to the tenter (3) setting the cooling section after heat fixation to enhance the cooling capacity to fully cool the whole, (4) increasing the length of the cooling section, and the number of sections 200808551 to increase the cooling efficiency The method (5) is to use a form in which the reverse portion of the clip travels on the outside of the furnace to enhance the cooling of the clip. EXAMPLES Hereinafter, the present invention will be described in detail by way of examples. Further, the film properties obtained in the respective examples were measured and evaluated by the following methods. (1) Intrinsic viscosity is called 0 · 1 g of crystal grain sample, and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 6 M (mass ratio), measured at 30 ° C using an Austenitic viscometer φ fixed. Further, the measurement system was carried out three times to obtain the average enthalpy. (2) Melting point of the film A differential scanning calorimeter (manufactured by DUPONT, V4 OB2000 type) was used, and the sample amount was about 0. 0 1 0 g, the measurement temperature range was room temperature to 300 ° C, and the temperature increase rate was i 〇 ° C / min. The melting points of the A layer and the B layer were determined by cutting an A4 size film and adhering it to a flat plate, and then using a razor blade to cut the surface, and performing D S C measurement to determine the melting point of the B layer. Next, the melting point of the entire film was measured by D S C , and the melting point of the layer A was determined by eliminating the information of the melting peak of the melting point of the B φ layer. (3) A layer (core layer) with or without alignment The sample for the determination was produced by using a slitter, and a sheet (thickness: 10 μm) was formed in parallel in the MD direction of the film to observe the cross section in the thickness direction. Next, the brightness of the image in the layer A when the polarizing plate was rotated was visually determined by the following reference using a transmission type polarization microscope. Further, the expansion magnification is performed at 200 times. No alignment: The brightness of the image of the A layer is substantially unchanged. There is a change in the brightness of the image of the A layer. -32- 200808551 (4) The thickness of the film is based on JIS K 7105 "Measuring method for measuring the thickness of plastic film and sheet". The method of the scanning method (A method) was used for the measurement. The measuring instrument was an electronic micrometer (manufactured by MAHR, MINITRON 1240). The thickness of the film was measured at 5 points per 1 film, and a total of 3 pieces of 15 points were measured to obtain an average enthalpy. (5) Stress at 10% stretch (F 100) and elongation at break (TE) For the length direction and width direction of the biaxially stretched film, use a razor blade to cut each length to 180 mm and width to 10 mm. Thin rectangular specimen. Then, a thin rectangular sample was stretched using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress (MPa) and the elongation at break (1%) in each direction were obtained from the obtained load-歪 curve. %). In addition, the measurement system is in the environment of 25 ° C, with an initial length of 40 mm, a distance between the chucks of 100 mm, a crosshead speed of 100 mm/min, and a chuck speed of 200 mm/min. The condition of 25kgf is carried out. Further, the measurement was carried out 1 time, and the average enthalpy was employed. Further, in the environment of 100 ° C, the tensile test was carried out under the same conditions as above. At this time, the sample was subjected to / measurement in an environment of 1 ° C for 30 seconds. Further, the measurement system was carried out 10 times, and the average enthalpy was employed. (6) Thermal shrinkage at 150 ° C according to JIS C 238-1997 5. 3. 4 (Dimensional change), the heat shrinkage ratio at a temperature of 150 ° C in the longitudinal direction and the width direction of the film was measured in the following order. Thin rectangular specimens having a length of 250 mm and a width of 20 mm were cut out in the longitudinal direction and the width direction of the film. Two marks were placed at intervals of 200 mm in the longitudinal direction of each sample, and the interval A between the two marks was measured at a constant tension of 5 g (the tension in the longitudinal direction - 33 - 200808551). Subsequently, one side of each sample of the thin rectangular shape was used, and the clip was hung on the basket under no load, and placed in a gear oven at 150 ° C, and the time was measured. After 30 minutes, the rack was removed from the gear oven and allowed to stand at room temperature for 30 minutes. Next, for each sample after the heat treatment, a steel ruler was used at a constant tension (tension in the longitudinal direction) of 5 gf. The interval B of the two marks is read in 25 mm units (the interval between the two marks after the heat treatment). The heat shrinkage ratio of each sample at 150 °C was calculated by the following equation by the intervals A and 6 read, and judged according to the following criteria. The assay was performed 3 times and the average enthalpy was determined. The number of digits is rounded off to the second decimal place, and is rounded to the first decimal place. Heat shrinkage rate (%) = ((AB)/A) x 100 (7) Thickness variation rate in the width direction Winding film strips of 3 m in the width direction and 5 cm in the longitudinal direction of the film, using film thickness A continuous measuring machine (manufactured by ANRITSU AG) was used to measure the thickness of the film and recorded on a recorder. The maximum enthalpy (dmax), minimum enthalpy (dmin), and average enthalpy (d) of the thickness were obtained from the graph, and the lower thickness variation rate (%) was calculated by the following formula. Further, the measurement system was carried out 3 times, and the average enthalpy was determined. Further, when the length in the width direction is less than 3 m, it is connected. Also, the connected portion is culled from the data. The thickness variation rate (%) = ((dmax - dmin) / d) xl 〇〇 (8) The haze is measured according to JIS K 7 136 using a haze meter (made by Nippon Denshoku Industries Co., Ltd., 300 A). The system is carried out 2 times and the average 値 is obtained. (9) Impact strength -34- 200808551 Using a film impact tester (manufactured by Toyo Seiki Co., Ltd., manufacturing number T-84-3), the measuring film is pressed with a clamp, and a hemispherical impact of 1/2 inch diameter is used. The head is punctured to determine the punching strength of the sample. The sample was cut to a size of 100 mm X 100 mm or more, and the inner diameter of the fixing ring of the fixed sample was 30 mm. Further, the measurement system was carried out 1 time, and the average enthalpy was used. The average enthalpy was converted into a thickness per 1 mm to determine the impact strength (J/mm) of the film, and it was judged based on the following criteria. 〇: 10 J/mm or more • X: less than 10 J / mm (10) Formability (a) Vacuum formability After 5 mm square square printing on the film, use infrared rays heated to 500 ° C The heater heats the film for 10 to 15 seconds, and then vacuum-forms at a mold temperature of 30 to 100 °C. Further, the heating conditions are selected within the above range to select the most appropriate conditions for each film. The shape of the mold is cup type, and the diameter of the opening is 50 mm, the diameter of the bottom portion is 40 mm, the depth W is 50 mm, and the entire corner has a diameter of 0. 5 mm curved object. Under the most appropriate conditions, the molded articles obtained by vacuum molding were evaluated for moldability and finishability, and the grades were judged according to the following criteria. Also, ◎ and 〇 are qualified, and X is unqualified. ◎ : (i) The molded article has no crack (Π) angle of curvature of 1 mm or less, and the printing offset is 〇·1 mm or less (iii) and there is no appearance defect in conformity with x-35-200808551 〇: (i) The molded article has no crack (ii) The radius of curvature of the corner is greater than 1 mm and 1. 5 mm or less. , or the print offset is greater than 〇 · 1 mm and 0. 2 mm or less (iii) and no appearance defect conforming to X' is a practically problem-free degree X: the molded product is broken, or is not broken but conforms to any of the following items (i) to (iv) ( i) The radius of curvature of the corner is greater than 1. 5 mm (Π) produces large wrinkles and poor appearance • (Hi) film whitens and decreases transparency (W) print offset is greater than 0. 2 mm (b) Pressure Formability After 5 mm square square printing on the film, the film is heated for 10 to 15 seconds using an infrared heater heated to 500 ° C, at a mold temperature of 3 0 to 1 Vacuum molding was carried out at 0 ° C, and press molding was carried out under a pressure of 4 atm. Further, the heating conditions are selected within the above range to select the optimum conditions for each film. The shape of the mold was a cup type, and the diameter of the opening was 60 mm, the diameter of the bottom portion was 55 mm, and the depth was 50 mm, and the diameter was used for all the corners. 5 mm curved object. Under the most appropriate conditions, the molded articles obtained by vacuum molding were evaluated for moldability and finishability, and the grades were judged according to the following criteria. Also, ◎ and 〇 are qualified, and X is unqualified. ◎ : (i) The radius of curvature of the molded article without crack (Π) angle is 1 mm or less, and the printing offset is 〇·1 mm or less -36-200808551 (iii) and there is no appearance defect conforming to X: (i) The molded article has no crack (ii) The radius of curvature of the corner is greater than 1 mm and 1 . Below 5 mm, or the print offset is greater than 0. 1 mm and 0. 2 mm or less (iii) and no conformity with X, which is practically problem-free. X: The molded product is broken, or it is not broken but meets any of the following items (i) to (iv) (i) The radius of curvature of the corner is greater than 1. 5 mm • (Π) produces large crepe and poor appearance (iii) film whitening and decreased transparency (iv) print offset greater than 0. 2 mm (c) Mold formability After printing on the film, after heating for 4 seconds using a hot plate heated to 100 ° to 40 ° C, the mold temperature is 3 0 to 70 ° C, holding time Pressurized molding in 5 seconds. Further, the heating conditions are selected within the above range to select the most suitable conditions for each film. The shape of the mold is cup-shaped, and the diameter of the opening is 50 mm, the diameter of the bottom portion is 40 mm, and the depth is 30 mm. The entire corner has a diameter of 0. 5 mm curved object. Under the most appropriate conditions, the molded articles formed by the five molds were evaluated for formability and finishability, and the grades were judged according to the following criteria. Also ◎ and 〇 are qualified, X is unqualified. ◎ : (i) The molded article has no crack (ii) The radius of curvature of the corner is 1 mm or less, and the printing offset is 0,1 mm or less -37-200808551 (iii) and there is no appearance defect conforming to X: (i) The molded article has no crack (ii) The radius of curvature of the corner is greater than 1 mm and 1. Below 5 mm, or the print offset is greater than 〇. 1 mm and 〇 · 2 mm or less (iii) and no conformity with X, which is practically problem-free. X: The molded product is broken, or it is not broken but meets the following items (i) to (iv) The radius of curvature of one (iv) angle is greater than 1. 5 mm • (ii) Large wrinkles and poor appearance (iii) Thin film whitening and decreased transparency (iv) Print offset is greater than 〇·2 mm (11) Solvent resistance The sample is immersed in a temperature adjustment to 25 °C. After 30 minutes in toluene, the change in appearance before and after the immersion was judged based on the following criteria, and 〇 was qualified. The haze was measured using the method described above. 〇··The appearance is almost unchanged, and the change in haze is less than 1 % ® X : Appearance change, or haze change is 1% or more (12) Static friction coefficient μ s and dynamic friction coefficient / zd basis JIS-C2151 was evaluated using the following conditions. Test piece for flat plate: 130 mm in width and 250 mm in length and using non-printing side. Test piece for warpage: width 12 mm, length 120 mm and use of printed side ‘

測定環境：23°C、50%RH -38- 200808551 翹曲質量：200克試驗速度：150毫米/分鐘使用以下基準判定測定値。〇：/z s、// d都小於0 · 8 X : // s、β d任一者都是0.8以上 (1 3 )加熱白化在150°C熱處理30分鐘後，依照以下基準藉由目視進行觀察外觀。又，〇爲合格。〇：無變化 X :薄膜白化，可觀察到變化。實施例1 (水分而成的聚酯系接枝共聚物之調製）在具備有攪拌機、溫度計、回流裝置及定量滴加裝置之反應器，添加75質量份疏水性共聚合聚酯、56質量份甲基乙基酮、及19質量份異丙醇，在651：加熱、攪拌，來使樹脂溶解。樹脂完全溶解後，在聚酯溶液中添加1 5質量份順丁烯二酸酐。接著，以0.1毫升/分鐘將在12質量份甲基乙基酮中溶解10質苯乙烯及1·5質量份偶氮雙二甲基戊腈而成之溶液滴加在聚酯溶液中，進而繼續攪拌2小時。從反應溶液進行分析用取樣後，添加5質量份甲醇。接著，在反應溶液添加300質量份離子交換水及15質量份三乙胺’攪拌1小時。隨後，將反應器內溫上升至1 0 0乞，藉由蒸餾餾去甲基乙基酮、異丙醇、及過剩的三乙胺，而得到水分散而成的聚酯系接枝共聚物。所得到的聚酯系接枝 -39- 200808551 共聚物係淡黃色透明，且玻璃轉移溫度爲40 °C。 (印刷性改良層用塗布液（X的調製）在離子交換水及異丙醇的混合溶劑（質量比爲60/40)，以總固體成分濃度成爲5質量％的方式，將水分散而成的聚酯系接枝共聚物、粒子平均粒徑爲2.2微米之苯乙烯-苯并胍胺系球狀有機粒子（日本觸媒工業公司製）、及平均粒徑爲0.02微米之膠體二氧化矽（觸媒化成公司製）混合，使各自固體成分質量比爲50/1/3，來調製塗布液A。 • (易滑性改良層用塗布液b的調製）在離子交換水及異丙醇的混合溶劑（質量比爲60/40)，以總固體成分濃度成爲5質量％的方式，將水分散性聚酯系共聚物（東洋紡績公司製、VAIRONAL MD-16)、磺酸金屬鹽之千二烷基二苯醚磺酸鈉（松本油脂公司製、陰離子系防靜電劑）、高分子系蠟劑之聚乙烯系乳膠蠟（東邦化學公司製、粒子之平均粒徑爲2.2微米.之苯乙烯-苯并胍胺系球狀有機粒子（日本觸媒工業公司製）、及平均粒徑爲0.04微米 W 之膠體二氧化矽（日產化學公司製）混合，使各自固體成分質量比爲50/2.5/2.5/0· 5/5，來調製塗布液B。 (薄膜原料的製造）乾燥表1所記載組成的樹脂，使用作爲芯層（A層）及皮層（B層）。 (積層薄膜的製造）使用具有給料塊及T模頭且能夠共擠出的擠壓機，將β 層用原料以表2的B層擠出條件、及同樣地將A層用原料 -40- 200808551 以表2的A層擠出條件共擠出。層的構成係B/A/B的2種 3層。又，調整熔融擠出時之樹脂的吐出量，使最後薄膜厚度爲1〇〇微米、各層的厚度爲B/A/B = 8/8 4/8的比率。皮層（B層）之滯留時間爲18分鐘，芯層（A層）之滯留時間爲8 分鐘，在表面溫度爲40 °C之鑄塑滾筒急冷固化而得到無定形薄膜。將所得到的薄膜在預熱輥與冷卻輥之間，藉由旋轉速度差在8 3 °C往縱向拉伸3.3倍。使用逆輥塗布法在所得到的單軸拉伸薄膜的一面塗布上述的塗布液a、對另一面塗布塗布液b。又，各塗布液係在輥間隙之間施加1 000(1/秒）以上的剪切速度，在2秒以內塗布在基材薄膜上，並在65 °C、6 0%RH、風速15公尺/秒的環境下，乾燥2秒鐘。進而，在130°C藉由在風速20公尺/秒的環境下乾燥3秒鐘來除去水分，導入拉幅機並在1〇〇 °C預熱3秒，在橫向拉伸的前半部以100 °C、後半部以95 °C拉伸3.8倍，在熱處理區段以140它3秒、17〇°C3秒、205 Ό3秒升溫，在205它進行熱處理，並進行5%的橫向鬆驰而得到一面具有塗布液 a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇.65dl/g。又，塗布液a 及塗布液b之最後乾燥塗布量都是0.1克/平方公尺。又，在拉幅機，夾子反軟部係外部反轉方式，並設置夾子冷卻裝置，以20°C的冷風強制冷卻，並使TD出口的夾子溫度爲40 °C以下，採取防止與夾子黏附之對策。所得到薄膜的特性及評價結果係如表3所示。 -41 - 200808551 實施例2 在實施例1，除了變更爲表1所示原料及表4所示製膜條件以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.66dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇.1克/平方公尺。所得到薄膜的特性及評價結果係如表6所示。實施例3 Φ 在實施例1，除了變更爲表1所示原料及表4所示製膜條件以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.6 6dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇.1克/平方公尺。所得到薄膜的特性及評價結果係如表6所示。實施例4 在實施例1，除了變更爲表1所示原料及表4所示製膜 W 條件以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.70 dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇.1克/平方公尺。所得到薄膜的特性及評價結果係如表6所示。實施例5 在實施例1，除了變更爲表1所示原料，並調整熔融擠出時之吐出量來變更拉伸薄片的厚度，變更爲表4所示製 -42- 200808551 膜條件，及未設置塗布層以外，與實施例1同樣地進行，得到具有厚度25微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇.65dl/g。又，所得到薄膜的特性及評價結果係如表6所示。實施例6 在實施例1，除了使用與實施例2相同的原料，並調整熔融擠出時之吐出量來變更拉伸薄片的厚度，變更爲表4 所不製膜條件，及未設置塗布層以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度5 0微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇·64 dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是0 · 1克/平方公尺。所得到薄膜的特性及評價結果係如表6所示。實施例7 在實施例1，除了將B層的原料變更爲表2所示之原料以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度50微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.70dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇 · 1克/平方公尺。所得到薄膜的特性及評價結果係如表6所示。比較例1 在實施例1，除了變更爲表2所示原料及表5所示製膜條件，並且未設置皮層（B層）以外，與實施例1同樣地進行，得到具有厚度100微米的單層構成之雙軸拉伸聚酯薄 -43- 200808551 膜。所得到薄膜的特性及評價結果係如表7所示。比較例2 在實施例1，除了變更爲表2所示原料及表5所示製膜條件，並且未設置皮層（B層）以外，與實施例1同樣地進行，得到具有厚度1 〇〇微米的單層構成之雙軸拉伸聚酯薄膜。所得到薄膜的特性及評價結果係如表7所示。比較例3 在實施例1，除了變更爲表5所示之製膜條件以外，與 • 實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度1〇〇微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇.71dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是0 · 1克/平方公尺。所得到薄膜的特性及評價結果係如表7所示。比較例4 在實施例1，除了將B層用原料變更爲表3所示原料，進而變更爲表5所示之製膜條件以外，與實施例1同樣地 • 進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度1 〇 0微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.71 dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是0 · 1克/平方公尺。所得到薄膜的特性及評價結果係如表7所示。比較例5 在實施例4，除了變更爲表5所示之製膜條件以外，與實施例4同樣地進行，得到在一面具有塗布液a、另一面 -44- 200808551 具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲0.71 dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇. 1克/平方公尺。所得到薄膜的特性及評價結果係如表7所示。比較例6 在實施例1，除了變更爲表3所示之原料及表5所示之製膜條件以外，與實施例1同樣地進行，得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇.70dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是〇.1克/平方公尺。所得到薄膜的特性及評價結果係如表7所示。比較例7 準備表3所記載之樹脂，並乾燥作爲a層及B層所使用的原料。接著，使用具有給料塊及T模頭且能夠共擠出的擠壓機，將B層用原料以2 8 5 °C、A層用原料以2 8 5 t：在各自分別的熔融擠出壓熔融。接著，使層的構成爲B/A/B，使B層/A層的厚度比爲〇 · 1 1來進行共擠出，在鑄塑滾筒上急冷固化而得到未拉伸積層薄片。將所得到的未拉伸積層薄片在1 1 〇往縱向拉伸3 . 〇倍、在1 2 0 °C往橫向拉伸3 · 2倍來進行依次雙軸拉伸後，在 23 5 °C進行熱處理，而得到2種3層構成之積層雙軸拉伸聚酯薄膜。所得到薄膜的特性及評價結果係如表7所示。比較例8 在實施例1，除了變更爲表3所示之原料及表5所示之 -45- 200808551 製膜條件以外，與實施例1同樣地進行’得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜。所得到薄膜的固有黏度爲〇.7〇dl/g。又，塗布液a及塗布液b之最後乾燥塗布量都是0.1克/平方公尺。所得到薄膜的特性及評價結果係如表7所示。比較例9 在實施例1，除了變更爲表3所示之原料及表5所示之製膜條件以外，與實施例1同樣地進行，欲得到在一面具有塗布液a、另一面具有塗布液b之厚度100微米的積層雙軸拉伸聚酯薄膜，但是在拉幅機內產生斷裂，而無法得到薄膜。Measurement environment: 23 ° C, 50% RH - 38 - 200808551 Warpage mass: 200 g Test speed: 150 mm / min The measurement was determined using the following criteria. 〇: /zs, / / d are less than 0 · 8 X : / / s, β d are 0.8 or more (1 3) heating whitening after heat treatment at 150 ° C for 30 minutes, according to the following criteria by visual inspection Observe the appearance. Also, 〇 is qualified. 〇: No change X: The film is whitened and a change can be observed. Example 1 (Preparation of a polyester-based graft copolymer obtained by moisture) In a reactor equipped with a stirrer, a thermometer, a reflux device, and a quantitative dropping device, 75 parts by mass of a hydrophobic copolymerized polyester and 56 parts by mass were added. Methyl ethyl ketone and 19 parts by mass of isopropyl alcohol were dissolved in 651: heating and stirring to dissolve the resin. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Next, a solution obtained by dissolving 10 styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 12 parts by mass of methyl ethyl ketone is added dropwise to the polyester solution at 0.1 ml/min. Stirring was continued for 2 hours. After the sample was analyzed from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution for stirring for 1 hour. Subsequently, the internal temperature of the reactor was raised to 100 Torr, and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off by distillation to obtain a water-dispersed polyester-based graft copolymer. . The obtained polyester-based graft-39-200808551 copolymer was light yellow transparent and had a glass transition temperature of 40 °C. (Preparation of a coating layer for a printed layer (X) In a mixed solvent of ion-exchanged water and isopropyl alcohol (mass ratio: 60/40), water is dispersed so that the total solid content concentration is 5% by mass. Polyester-based graft copolymer, styrene-benzoguanamine-based spherical organic particles having an average particle diameter of 2.2 μm (manufactured by Nippon Shokubai Co., Ltd.), and colloidal cerium oxide having an average particle diameter of 0.02 μm It is mixed with the solid content ratio of 50/1/3 to prepare the coating liquid A. • (Preparation of coating liquid b for slip-friendly layer) In ion-exchanged water and isopropyl alcohol The mixed solvent (mass ratio: 60/40), and the water-dispersible polyester copolymer (VAIRONAL MD-16, manufactured by Toyobo Co., Ltd.) and the metal sulfonate are used so that the total solid content concentration is 5% by mass. Sodium dialkyl diphenyl ether sulfonate (made by Matsumoto Oil Co., Ltd., anionic antistatic agent), polyethylene wax of polymer wax (made by Toho Chemical Co., Ltd., the average particle size of the particles is 2.2 μm. Styrene-benzoguanamine-based spherical organic particles (Day Manufactured by a catalyst company, and a colloidal cerium oxide (manufactured by Nissan Chemical Co., Ltd.) having an average particle diameter of 0.04 μm, and the solid content ratio of each solid component is 50/2.5/2.5/0·5/5 to prepare a coating. Liquid B. (Production of film raw material) The resin having the composition described in Table 1 was dried and used as a core layer (layer A) and a skin layer (layer B). (Production of laminated film) Using a feed block and a T die In the extrusion extruder, the raw material for the β layer was coextruded under the conditions of the B layer of Table 2 and the raw material of the layer A-40-200808551 in the same manner as in the extrusion of the layer A of Table 2. Two kinds of three layers of B/A/B. In addition, the discharge amount of the resin during melt extrusion is adjusted so that the final film thickness is 1 〇〇 micron and the thickness of each layer is B/A/B = 8/8 4 / The ratio of 8 is 18. The retention time of the skin layer (B layer) is 18 minutes, the residence time of the core layer (layer A) is 8 minutes, and the casting drum at a surface temperature of 40 ° C is quenched and solidified to obtain an amorphous film. The obtained film was stretched 3.3 times in the longitudinal direction between the preheating roll and the cooling roll by a difference in rotational speed at 83 ° C. Using reverse roll coating The coating liquid a was applied to one surface of the obtained uniaxially stretched film, and the coating liquid b was applied to the other surface. Further, each coating liquid was applied with a shear rate of 1 000 (1/sec) or more between the roll gaps. , coated on the substrate film within 2 seconds, and dried for 2 seconds at 65 ° C, 60% RH, and wind speed of 15 meters / sec. Further, at 130 ° C by wind speed of 20 gong Dry in a ruler/second environment for 3 seconds to remove moisture, introduce into a tenter and preheat for 3 seconds at 1 °C, stretch at 100 °C in the first half of the transverse stretch and 95 °C in the second half. 3.8 times, in the heat treatment section, the temperature was raised by 140, 3 seconds, 17 ° C 3 seconds, 205 Ό 3 seconds, and heat treatment was performed at 205, and 5% lateral relaxation was performed to obtain a coating liquid a on one side and a coating surface on the other side. A laminated biaxially oriented polyester film having a thickness of 100 μm of liquid b. The intrinsic viscosity of the obtained film was 〇.65 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . In addition, in the tenter, the clip anti-soft part is externally reversed, and a clip cooling device is provided, and forced cooling is performed by cold air of 20 ° C, and the clip temperature of the TD outlet is 40 ° C or less, and the adhesion to the clip is prevented. Countermeasures. The characteristics and evaluation results of the obtained film are shown in Table 3. -41 - 200808551 Example 2 In the same manner as in Example 1, except that the material shown in Table 1 and the film forming conditions shown in Table 4 were changed, the coating liquid a was provided on one surface and the other surface was coated. A laminated biaxially oriented polyester film having a thickness of 100 μm of liquid b. The intrinsic viscosity of the obtained film was 0.66 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 6. Example 3 Φ In the same manner as in Example 1, except that the material shown in Table 1 and the film forming conditions shown in Table 4 were changed, the coating liquid a was provided on one surface and the coating liquid b was provided on the other surface. A laminated biaxially oriented polyester film having a thickness of 100 μm. The film obtained had an intrinsic viscosity of 0.66 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 6. [Example 4] In the same manner as in Example 1, except that the material shown in Table 1 and the film W shown in Table 4 were changed, the coating liquid a was provided on one surface and the coating liquid b was provided on the other surface. A laminated biaxially oriented polyester film having a thickness of 100 μm. The intrinsic viscosity of the obtained film was 0.70 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 6. Example 5 In the first embodiment, the raw material shown in Table 1 was changed, and the discharge amount at the time of melt extrusion was adjusted to change the thickness of the stretched sheet, and the film condition was changed to -42-200808551 as shown in Table 4, and A laminate biaxially stretched polyester film having a thickness of 25 μm was obtained in the same manner as in Example 1 except that the coating layer was provided. The intrinsic viscosity of the obtained film was 〇.65 dl/g. Further, the characteristics and evaluation results of the obtained film are shown in Table 6. [Example 6] In Example 1, except that the same raw material as in Example 2 was used, the discharge amount at the time of melt extrusion was adjusted to change the thickness of the stretched sheet, and the film formation conditions in Table 4 were not changed, and the coating layer was not provided. In the same manner as in Example 1, a laminated biaxially stretched polyester film having a coating liquid a on one surface and a coating liquid b on the other surface having a thickness of 50 μm was obtained. The intrinsic viscosity of the obtained film was 〇·64 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 6. Example 7 In the same manner as in Example 1, except that the raw material of the layer B was changed to the raw material shown in Table 2, the coating liquid a was provided on one surface and the coating liquid b on the other surface was 50 μm thick. The laminated biaxially stretched polyester film. The intrinsic viscosity of the obtained film was 0.70 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 〇 1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 6. Comparative Example 1 A sample having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the material shown in Table 2 and the film forming conditions shown in Table 5 were changed and the skin layer (layer B) was not provided. The layer consists of a biaxially stretched polyester film-43-200808551 film. The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 2 In the same manner as in Example 1, except that the material shown in Table 2 and the film forming conditions shown in Table 5 were changed and the skin layer (layer B) was not provided, the thickness of 1 μm was obtained. A biaxially stretched polyester film composed of a single layer. The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 3 In the same manner as in Example 1, except that the film formation conditions shown in Table 5 were changed, the thickness of the coating liquid a on one surface and the thickness of the coating liquid b on the other surface were obtained. The laminated biaxially stretched polyester film. The intrinsic viscosity of the obtained film was 71.71 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 4 In the same manner as in Example 1, except that the material for the layer B was changed to the material shown in Table 3 and the conditions for the film formation shown in Table 5 were changed, the coating liquid was obtained on one side. a. The other side has a laminated biaxially stretched polyester film having a thickness of the coating liquid b of 1 〇 0 μm. The obtained film had a solid viscosity of 0.71 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 5 In the same manner as in Example 4 except that the film formation conditions shown in Table 5 were changed, the thickness of the coating liquid b having the coating liquid a on one surface and the other surface -44 to 200808551 was obtained. Micron laminated biaxially oriented polyester film. The intrinsic viscosity of the obtained film was 0.71 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 6 In the same manner as in Example 1, except that the raw material shown in Table 3 and the film forming conditions shown in Table 5 were changed, the coating liquid a was provided on one surface and the coating liquid b was provided on the other surface. A laminated biaxially oriented polyester film having a thickness of 100 μm. The intrinsic viscosity of the obtained film was 〇.70 dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 7 The resin described in Table 3 was prepared, and the raw materials used as the a layer and the layer B were dried. Next, using an extruder having a feed block and a T die and capable of co-extrusion, the raw material for the layer B is used at 2 8 5 ° C, and the raw material for the layer A is used as 2 8 5 t: in respective respective melt extrusion pressures. Melt. Next, the layer was formed into a B/A/B, and the thickness ratio of the layer B/A layer was 〇·1 1 , co-extruded, and rapidly solidified on a casting drum to obtain an unstretched laminated sheet. The obtained unstretched laminated sheet was stretched by 3 纵向 in the longitudinal direction at 1 1 、, and stretched 3 2 times in the transverse direction at 120 ° C to carry out sequential biaxial stretching, at 23 5 ° C. The heat treatment was carried out to obtain two layers of a three-layer stretched polyester film having a three-layer structure. The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 8 In the same manner as in Example 1, except that the material shown in Table 3 and the film forming conditions of -45 to 200808551 shown in Table 5 were changed, the obtained Example 1 was obtained to have a coating liquid a on one side and the other side. A laminated biaxially stretched polyester film having a coating liquid b having a thickness of 100 μm. The intrinsic viscosity of the obtained film was 〇.7〇dl/g. Further, the final dry coating amount of the coating liquid a and the coating liquid b was 0.1 g/m 2 . The characteristics and evaluation results of the obtained film are shown in Table 7. Comparative Example 9 In the same manner as in Example 1, except that the material shown in Table 3 and the film forming conditions shown in Table 5 were changed, the coating liquid a was provided on one surface and the coating liquid was provided on the other surface. b. A laminated biaxially stretched polyester film having a thickness of 100 μm, but breakage occurred in the tenter, and a film could not be obtained.

-46- 200808551-46- 200808551

【15 固有黏度 (dl/g) 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.71 0.69 0.69 調配比 (質量％) O ο ο ο 〇芯層(A層二醇成分 (莫耳％) 〇〇 ω 〇〇 o i—H 〇 a-. EG 70 CHDM 30 i ο Ο w ο τ—Η Ο EG 70 NPG 30 ο 1 Ο ω ο ι—Η Ο EG 70 NPG 30 ο r—4 Ο m 〇 a w 〇 1—4 o o r—H o CL, 二羧酸成分 (莫耳％) ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 TPA 100 TPA 100 TPA 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 TPA 70 IPA 30 TPA 100 TPA 100 皮層(B層）固有黏度 (dl/g) 0.71 i 1 0.71 0.69 I 0.71 '0.69 I 0.71 0.69 0.71 1 1 調配比 (質量％) ο r丨丨Η i 1 O xo 1 1 O i 1 1 粒子含量 (ppm) 1 1 1 I 1 1 I I 1 I ι o 〇vl 1 1 平均粒徑 (微米） 1 I I 1 1 I 1 1 1 1 I 1 1 種類 » 1 1 1 1 1 1 1 1 1 I 真球狀二氧化矽 1 1 二醇成分 (莫耳％) EG 93 CHDM 7 1 1 EG 70 CHDM 30 Ο ι-H α ω 1 EG 70 CHDM 30 ο τ-Η Ο W 1 EG 70 CHDM 30 o o w EG 93 CHDM 7 1 1 二羧酸| 成分1 (莫耳％) — ΤΡΑ 100 1 1 TPA 100 ΤΡΑ 100 1 TPA 100 ι- ί ΤΡΑ 100 I TPA 100 TPA 100 TPA 100 I t 實施例1 實施例2 實施例3 實施例4 實施例5 200808551[15 intrinsic viscosity (dl/g) 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.71 0.69 0.69 compounding ratio (% by mass) O ο ο ο 〇 core layer (A layer diol component (mol%) 〇〇 ω 〇〇oi—H 〇a-. EG 70 CHDM 30 i ο Ο w ο τ—Η Ο EG 70 NPG 30 ο 1 Ο ω ο ι—Η Ο EG 70 NPG 30 ο r—4 Ο m 〇aw 〇1— 4 oor—H o CL, dicarboxylic acid component (mol%) ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 TPA 100 TPA 100 TPA 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 100 TPA 70 IPA 30 TPA 100 TPA 100 Cortex ( Layer B) Intrinsic viscosity (dl/g) 0.71 i 1 0.71 0.69 I 0.71 '0.69 I 0.71 0.69 0.71 1 1 Formulation ratio (% by mass) ο r丨丨Η i 1 O xo 1 1 O i 1 1 Particle content (ppm ) 1 1 1 I 1 1 II 1 I ι o 〇vl 1 1 Average particle size (micron) 1 II 1 1 I 1 1 1 1 I 1 1 Type » 1 1 1 1 1 1 1 1 1 I True spherical Cerium oxide 1 1 diol component (mol%) EG 93 CHDM 7 1 1 EG 70 CHDM 30 Ο ι-H α ω 1 EG 70 CHDM 30 ο τ-Η Ο W 1 EG 70 CHDM 30 oow EG 93 CHDM 7 1 Dicarboxylic acid Example 3 Example 45200808551 embodiment ΤΡΑ 100 1 1 TPA 100 ΤΡΑ 100 1 TPA 100 ι- ί ΤΡΑ 100 I TPA 100 TPA 100 TPA 100 I t Example 1 Example 2 Example - component 1 (mole%) |

【CN嗽】芯層(A層）固有黏度 (dl/g) 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.69 1 0.71 0.69 〇\ ο 0.71 0.69 0.69 調配比 (質量％) ο ο ο ο ο ο ο 二醇成分 (莫耳％) EG 70 CHDM 30 〇 ο 1—( ο τ-Η ο ι—Η ο ι—Η ο r-H ο τ—^ ο \ "4 ο r-H ο < < ο ο r-H ο ι—Η ο r-H 〇 ω Ο Ρ-. Ο ω Ο pq Ο Ο W Ο PQ Ο 〇Η Ο ρρ Ο W Ο PL, Ο m ο m Ο Ρη 二羧酸成分 (莫耳％) TPA 100 TPA 100 TPA 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 皮層(B層）固有黏度 (dl/g) 0.71 0.69 I 0.71 I I I I » I I I 0.71 t I 調配比 (質量％) I ο t—< 1 1 I I I 1 1 1 Ο r-H I I 粒子含量 (ppm) 1 1 1 ο 寸 1 1 I I I 1 1 1 1 i 1 平均粒徑 (微米） I 1 * 1 1 1 II 1 1 1 1 1 1 1 種類 1 1 1 二氧化矽 _1 1 1 1 1 1 1 1 V 1 I 1 二醇成分 (莫耳％) EG 70 CHDM 30 〇 Η Ο W 1 EG 93 CHDM 7 1 1 1 1 1 1 1 ) EG 93 CHDM 7 I 1 二羧酸成分 (莫耳％) TPA 100 TPA 100 1 TPA 100 1 1 1 1 I 1 I 1 ΤΡΑ 100 1 1 實施例6 實施例7 比較例1 比較例2 比較例3 丨oo寸， 200808551[CN嗽] Core layer (layer A) Intrinsic viscosity (dl/g) 0.71 0.69 0.69 0.71 0.69 0.69 0.71 0.69 0.69 1 0.71 0.69 〇\ ο 0.71 0.69 0.69 Mixing ratio (% by mass) ο ο ο ο ο ο ο diol Ingredients (% by mole) EG 70 CHDM 30 〇ο 1—( ο τ-Η ο ι—Η ο ι—Η ο rH ο τ—^ ο \ "4 ο rH ο << ο ο rH ο ι —Η ο rH 〇ω Ο Ρ-. Ο ω Ο pq Ο Ο W Ο PQ Ο 〇Η Ο ρρ Ο W Ο PL, Ο m ο m Ο Ρη Dicarboxylic acid component (mol%) TPA 100 TPA 100 TPA 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 ΤΡΑ 70 ΙΡΑ 30 ΤΡΑ 100 ΤΡΑ 100 Cortex (B layer) Intrinsic viscosity (dl/g) 0.71 0.69 I 0.71 IIII » III 0.71 t I compounding ratio (% by mass) I ο t—< 1 1 III 1 1 1 Ο rH II Particle content (ppm) 1 1 1 ο 1 1 1 1 1 1 1 1 1 Average particle size (μm) I 1 * 1 1 1 II 1 1 1 1 1 1 1 Type 1 1 1 Ceria 1 1 1 1 1 1 1 1 V 1 I 1 Glycol component (% by mole) EG 70 CHDM 30 Η Ο W 1 EG 93 CHDM 7 1 1 1 1 1 1 1 ) EG 93 CHDM 7 I 1 Dicarboxylic acid component (mol%) TPA 100 TPA 100 1 TPA 100 1 1 1 1 I 1 I 1 ΤΡΑ 100 1 1 Example 6 Example 7 Comparative Example 1 Comparative Example 2 Comparative Example 3 丨oo inch, 200808551

m W- 3 画 T—Η 〇\ VO 〇 σ\ νο ο 1 i \ο ο % ^ I ； t 〇 o 1—< 卜 ON VO 〇 σ\ v〇〇 t—1 ON VO o ON o 調配比 (質量％) ο ο 沄 ο ι—Η 1 1 o r i 〇沄 o 芯層(A層二醇成分 (莫耳％) 〇 1 < 〇 W 〇 T—1 〇 ο Η Ο CU ο S ο τ-^ Ο W EG 93 CHDM 7 1 1 ON t—ι 〇\ 〇〇 PQ W Q Ο r—Η Ο W o 〇 ω 〇 i i o PU o ι—H ϋ m o T-H 〇 ω o T—i 〇 Oh 二羧酸成分 (莫耳％) 〇 r-H < Η ο r—i < Η ο r_H ο τ—ί < Ρη ο τ^Η < Η 1 1 TPA 88 IPA 12 ο ο CO <1 <· 〇 H o g 〇〇 c^ m 〇 H < Pk 〇 r—H < Ph 皮層(B層）固有黏度 (dl/g) 1—^ τ—Η t τ-Η ΟΝ VD Ο '4 ON VO ο a\ vo 〇〇 o r _Η 卜· 1 t t—H r-； 1 1 調配比 (質量％) 1 o o T-H Ο ι Ή 1 1 o r—H 1 1 m 含量 (ppm) 〇 r-H ο VD 1 1 1 I I 1 I t 1 1 1 1 1 平均粒徑 (微米） v〇 r-H 1 1 1 1 I 1 » 1 1 1 1 1 ) 騷驛真球狀二氧化矽真球狀二氧化矽 1 1 1 1 1 1 1 1 1 1 1 1 I 二醇成分 (莫耳％) EG 93 CHDM 7 EG 93 CHDM 7 1 EG 70 CHDM 30 ο 1—Η Ο ΡΡ ο τ—Η Ο W ο t—Η Ο o r—1 〇 PL, 〇 CD m W Q EG 93 CHDM 7 1 1 EG 93 CHDM 7 1 1 鏈您 11 成分 (莫耳％) TPA 100 TPA 100 1 TPA 100 ΤΡΑ 100 TPA 100 TPA 100 <1 TPA 100 1 1 TPA 100 1 1 比較例4 比較例5 比較例6 比較例7 比較例8 比較例9 丨6寸丨 200808551m W- 3 D_Η 〇\ VO 〇σ\ νο ο 1 i \ο ο % ^ I ; t 〇o 1—< Bu ON VO 〇σ\ v〇〇t-1 ON VO o ON o Ratio (% by mass) ο ο 沄ο ι—Η 1 1 ori 〇沄o Core layer (A layer diol component (mole%) 〇1 < 〇W 〇T-1 〇ο Η Ο CU ο S ο τ -^ Ο W EG 93 CHDM 7 1 1 ON t—ι 〇\ 〇〇PQ WQ Ο r—Η Ο W o 〇ω 〇iio PU o ι—H ϋ mo TH 〇ω o T—i 〇Oh Dicarboxylic acid Ingredient (mole%) 〇rH < Η ο r—i < Η ο r_H ο τ — ί < Ρη ο τ^Η < Η 1 1 TPA 88 IPA 12 ο ο CO <1 <· 〇 H og 〇〇c^ m 〇H < Pk 〇r-H < Ph Cortex (B layer) Intrinsic viscosity (dl/g) 1—^ τ—Η t τ-Η ΟΝ VD Ο '4 ON VO ο a \ vo 〇〇or _Η Bu· 1 tt—H r-; 1 1 Mixing ratio (% by mass) 1 oo TH Ο ι Ή 1 1 or—H 1 1 m Content (ppm) 〇rH ο VD 1 1 1 II 1 I t 1 1 1 1 1 Average particle size (micron) v〇rH 1 1 1 1 I 1 » 1 1 1 1 1 ) Sao 驿 true spherical cerium oxide true spherical cerium oxide 1 1 1 1 1 1 1 1 1 1 1 1 I diol component (mol%) EG 93 CHDM 7 EG 93 CHDM 7 1 EG 70 CHDM 30 ο 1—Η Ο ο ο τ—Η Ο W ο t—Η Ο or—1 〇PL , 〇CD m WQ EG 93 CHDM 7 1 1 EG 93 CHDM 7 1 1 Chain 11 ingredients (mole %) TPA 100 TPA 100 1 TPA 100 ΤΡΑ 100 TPA 100 TPA 100 <1 TPA 100 1 1 TPA 100 1 1 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 丨 6 inch 丨 200808551

[表4] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 製膜條件皮層(B層）的擠出條件給料部溫度(°C) 210 210 210 200 210 210 210 壓縮部溫度(°C) 285 285 285 285 285 295 285 計量部溫度(°c) 260 260 260 260 260 282 260 芯層(A層）的擠出條件給料部溫度(°c) 210 210 210 200 210 210 210 壓縮部溫度(°c) 285 265 265 265 285 275 285 計量部溫度(°c) 260 260 260 260 260 280 260 合流線的擠出條件熔融線部溫度(°c) 255 255 255 255 255 270 255 T模頭部溫度(°c) 255 255 255 255 255 270 255 芯層(A層)的厚度比率(％) 85 85 85 85 95 85 85 長度方向拉伸拉伸溫度(°c) 83 90 90 87 83 90 83 拉伸倍率(倍） 3.3 3.3 3.5 3.5 3.3 3.3 3.3 有無塗布層有有有有 Μ y\\\ 有有寬度方向拉伸預熱溫度(°c) 100 110 110 95 100 105 100 預熱時間(秒） 3 3 3 3 3 3 3 拉伸溫度前半re) 100 110 110 80 100 110 100 拉伸溫度後半re) 95 100 100 75 95 100 95 拉伸倍率(倍） .3.8 3.8 3.8 3.8 3.8 3.8 3.8 熱處理 #桌1區溫度（C) 140 140 140 140 140 140 140 #第2區溫度(°C) 170 170 170 170 170 170 170 #第3區溫度(°C) 205 210 210 205 205 210 205 #第4區溫度(°C) 205 210 210 205 205 210 205 #第5區溫度(°C) 205 210 210 205 205 210 205 最大升溫速度 (。〇/秒） 15.0 13.3 13.3 21.7 15.0 13.3 15.0 鬆驰率(％) 5 5 5 5 5 5 5 -50- 200808551[Table 4] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Film forming conditions Skin condition (B layer) Extrusion conditions Feeding section temperature (°C) 210 210 210 200 210 210 210 Compressor temperature (°C) 285 285 285 285 285 295 285 Metering temperature (°c) 260 260 260 260 260 282 260 Extrusion condition of the core layer (layer A) Feeder temperature (°c) 210 210 210 200 210 210 210 Compressor temperature (°c) 285 265 265 265 285 275 285 Metering temperature (°c) 260 260 260 260 260 280 260 Extrusion conditions for the joining line Melting line temperature (°c) 255 255 255 255 255 270 255 T-die head temperature (°c) 255 255 255 255 255 270 255 Thickness ratio (%) of core layer (layer A) 85 85 85 85 95 85 85 Tensile stretching temperature in length (°c) 83 90 90 87 83 90 83 Stretching magnification (times) 3.3 3.3 3.5 3.5 3.3 3.3 3.3 Whether or not the coating layer is present Μ y\\\ There is a stretching direction in the width direction (°c) 100 110 110 95 100 105 100 Preheating time (seconds) 3 3 3 3 3 3 3 stretching temperature first half re) 100 110 110 80 100 110 100 stretching temperature second half re) 95 100 100 75 95 100 95 Stretching ratio (times) .3.8 3.8 3.8 3.8 3.8 3.8 3.8 Heat treatment #Table 1 zone temperature (C) 140 140 140 140 140 140 140 #2nd zone temperature (°C) 170 170 170 170 170 170 170 #第3区温度(°C) 205 210 210 205 205 210 205 #第4区温度(°C) 205 210 210 205 205 210 205 #第5区温度(°C) 205 210 210 205 205 210 205 Maximum temperature rise Speed (.〇/sec) 15.0 13.3 13.3 21.7 15.0 13.3 15.0 Relaxation rate (%) 5 5 5 5 5 5 5 -50- 200808551

[表5] 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例8 比較例9 製膜條件皮層(B層）的擠出條件給料部溫度(°C) - - 210 210 200 210 210 210 壓縮部溫度(°C) 一 - 285 285 275 285 285 285 計量部溫度(°c) • 260 260 260 260 260 260 芯層(A層）的擠出條件給料部溫度(°c) 200 200 210 210 200 210 210 210 壓縮部溫度(°c) 265 265 285 285 295 285 285 285 計量部溫度(°c) 260 260 260 260 300 260 260 260 合流線的擠出條件熔融線部溫度 (°C) 255 255 255 255 295 255 255 255 T模頭部溫度 CC) 255 255 255 255 285 255 255 255 芯層(A層)的厚度比率(％) 85 85 85 85 85 85 85 85 長度方向拉伸拉伸溫度(°c) 83 83 83 83 87 83 83 83 拉伸倍率(倍） 3.5 3.5 3.3 3.3 3.5 3.3 3.3 3.3 有無塗布層有有有有有有有有寬度方向拉伸預熱溫度(°c) 95 95 100 100 95 100 100 100 預熱時間(秒） 3 3 3 3 3 3 3 3 拉伸溫度前半 CC) 80 80 100 100 80 100 100 100 拉伸溫度後半 (°C) 75 75 95 95 75 95 95 95 拉伸倍率(倍） 3.8 3.8 3.8 3.8 3.8 3,8 3.8 3.8 熱處理 #第1區溫度(°c) 140 140 140 140 140 140 110 200 #第2區溫度(°C) 170 170 170 170 170 170 120 200 #第3區溫度(°C) 205 180 230 180 205 205 130 205 #第4區溫度(°C) 205 180 230 180 205 205 140 205 #第5區溫度(°C) 205 180 230 180 205 205 150 205 最大升溫速度 cc/m 21.7 21.7 20.0 15.0 21.7 15.0 3.0 35.0 鬆弛率(％) 5 5 5 5 5 5 5 5 -51- 200808551[Table 5] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 8 Comparative Example 9 Film forming conditions Skin condition (B layer) Extrusion conditions Feeding unit temperature (°C) - - 210 210 200 210 210 210 Compressor temperature (°C) I-285 285 275 285 285 285 Metering temperature (°c) • 260 260 260 260 260 260 Extrusion condition of the core layer (layer A) Feeder temperature (°c 200 200 210 210 200 210 210 210 Compressor temperature (°c) 265 265 285 285 295 285 285 285 Metering temperature (°c) 260 260 260 260 300 260 260 260 Extrusion line extrusion condition Melting line temperature ( °C) 255 255 255 255 295 255 255 255 T die head temperature CC) 255 255 255 255 285 255 255 255 Thickness ratio (%) of core layer (layer A) 85 85 85 85 85 85 85 85 Length stretching Stretching temperature (°c) 83 83 83 83 87 83 83 83 Drawing ratio (times) 3.5 3.5 3.3 3.3 3.5 3.3 3.3 3.3 Whether there are coating layers with or without stretching direction in the width direction (°c 95 95 100 100 95 100 100 100 Warm-up time (seconds) 3 3 3 3 3 3 3 3 Stretching temperature first half CC) 80 80 100 100 80 100 100 100 The second half of the stretching temperature (°C) 75 75 95 95 75 95 95 95 Stretching ratio (times) 3.8 3.8 3.8 3.8 3.8 3,8 3.8 3.8 Heat treatment #1st zone temperature (°c) 140 140 140 140 140 140 110 200 #2nd zone temperature (°C) 170 170 170 170 170 170 120 200 #3rd zone temperature (°C) 205 180 230 180 205 205 130 205 #4zone temperature (°C) 205 180 230 180 205 205 140 205 #第5区温度(°C) 205 180 230 180 205 205 150 205 Maximum heating rate cc/m 21.7 21.7 20.0 15.0 21.7 15.0 3.0 35.0 Relaxation rate (%) 5 5 5 5 5 5 5 5 -51- 200808551

[表6] 實施例 1 實施例 2 實施例 3 實施例 4 實施例 5 實施例 6 實施例 7 厚度(微米） 100 100 100 100 25 50 100 皮層的熔點(TmB)°C 240 245 245 245 238 226 240 芯層的熔點(TmA)t： 212 220 211 202 208 208 205 熔點差(TmB-TmA)°C 28 25 34 43 30 18 35 薄芯層有無配向結構有有有有有有有膜 HS150(%) : MD/TD 1.7/0.0 1.9/0.0 L5/L1 2.3/L4 1.8/0.2 1.9/1.0 2.571.8 特寬度方向之厚度變動率(％) 3 3 3 4 4 4 4 性霧度(％) 0.9 0.9 0.9 0.9 1.2 0.9 3.0 衝擊強度(〗/mm) 21 22 22 22 21 20 29 TE(%) MD/TD 平均(25°C) 256 256 256 256 250 223 256 F100 MD/TD (25 °C) 80/85 82/88 72/78 68/70 80/76 72/65 68/72 (MPa) MD/TD (100°C) 30/30 35/38 25/28 23/24 30/25 20/18 30/32 真空成型性〇〇〇〇 ◎ ◎ 〇評加壓成型性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 價模具成型性 ◎ ◎ ◎ ◎ ◎ ◎ ◎ 結耐溶劑性〇〇〇〇〇〇〇果滑性〇〇〇〇〇〇〇加熱白化〇〇〇〇〇〇〇 -52- 200808551[Table 6] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Thickness (micrometer) 100 100 100 100 25 50 100 Melting point of skin layer (TmB) °C 240 245 245 245 238 226 Melting point of 240 core layer (TmA) t: 212 220 211 202 208 208 205 Melting point difference (TmB-TmA) °C 28 25 34 43 30 18 35 Thin core layer with or without alignment structure There are some films HS150 (% ) : MD/TD 1.7/0.0 1.9/0.0 L5/L1 2.3/L4 1.8/0.2 1.9/1.0 2.571.8 Thickness variation rate in the width direction (%) 3 3 3 4 4 4 4 Sex haze (%) 0.9 0.9 0.9 0.9 1.2 0.9 3.0 Impact strength (〗/mm) 21 22 22 22 21 20 29 TE (%) MD/TD Average (25°C) 256 256 256 256 250 223 256 F100 MD/TD (25 °C) 80 /85 82/88 72/78 68/70 80/76 72/65 68/72 (MPa) MD/TD (100°C) 30/30 35/38 25/28 23/24 30/25 20/18 30 /32 Vacuum moldability 〇〇〇〇 ◎ ◎ Evaluation of press formability ◎ ◎ ◎ ◎ ◎ ◎ ◎ Price mold moldability ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐耐耐耐耐滑滑滑耐〇〇〇〇〇〇heating albino 〇〇〇〇〇〇 -52- 200808551

[表7] 比較例 1 比較例 2 比較例 3 比較例 4 比較例 5 比較例 6 比較例 7 比較例 8 厚度(微米) 100 100 100 100 100 100 100 / 100 皮層的熔點(TmB)°C _ 240 240 248 199 245 240 芯層的熔點(TmA)°C 198 198 205 205 196 246 223 212 熔點差(TmB-TmA)°C • 35 35 52 -47 22 28 薄芯層有無配向結構有有有有有有無有膜 HS150(%) ： MD/TD 2.3/1.4 7.3/3.4 1.5/1.1 8.5/3.1 6.4/3.6 4.8/2.2 2.5/1.8 1.6 特寬度方向之厚度變動率(％) 10 4 11 3 11 8 28 3 性霧度(％) 0.9 0.9 0.9 0.9 0.9 0.9 1.0 0.9 衝擊強度(J/mm) 14 22 12 22 6 28 3 20 TE(%) MD/TD平均(25°C) 170 257 84 244 256 256 4 270 F100 MD/TD (25 °C) 52/58 103/110 70/75 118/119 62/64 105/110 -/- 150/160 (MPa) MD/TD (100°C) 15/24 36/38 17/19 39/40 19/21 20/30 18/23 30/40 真空成型性〇 X 〇 X 〇〇〇 X 評加壓成型性 ◎ Δ ◎ Δ ◎ Δ ◎ 〇價模具成型性 ◎ 〇 ◎ 〇 ◎ 〇 ◎ 〇結耐溶劑性 X X 〇〇〇〇〇〇果滑性 X 〇 X 〇〇 X 〇〇加熱白化〇〇〇〇〇〇 X 〇產業上之利用可能性依照本發明之成型用積層聚酯薄膜，加熱成型性時之成型性、特別是在低溫度及低壓力的成型性之成型性優良，能夠應用於廣泛的成型方法，且在常溫環境下作爲成型體使用於時，彈性及形態安定性（熱收縮特性、厚度不均）優良，且透明性、印刷性、耐溶劑性及耐熱性優良，而且耐衝擊性優良，具有適合作爲家電、行動電話、汽車用內 -53 - 200808551 部裝飾材或外部裝飾材、或作爲建材用構件之優點，對產業界有重大貢獻。【圖式簡單說明】無。【元件符號說明】無0[Table 7] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Thickness (micrometer) 100 100 100 100 100 100 100 / 100 Melting point of skin layer (TmB) °C _ 240 240 248 199 245 240 melting point of the core layer (TmA) °C 198 198 205 205 196 246 223 212 Melting point difference (TmB-TmA) °C • 35 35 52 -47 22 28 Thin core layer with or without alignment structure With or without membrane HS150 (%) : MD/TD 2.3/1.4 7.3/3.4 1.5/1.1 8.5/3.1 6.4/3.6 4.8/2.2 2.5/1.8 1.6 Thickness variation rate in the width direction (%) 10 4 11 3 11 8 28 3 Sexual haze (%) 0.9 0.9 0.9 0.9 0.9 0.9 1.0 0.9 Impact strength (J/mm) 14 22 12 22 6 28 3 20 TE (%) MD/TD average (25 ° C) 170 257 84 244 256 256 4 270 F100 MD/TD (25 °C) 52/58 103/110 70/75 118/119 62/64 105/110 -/- 150/160 (MPa) MD/TD (100°C) 15/24 36 /38 17/19 39/40 19/21 20/30 18/23 30/40 Vacuum moldability 〇X 〇X 〇〇〇X Evaluation of press formability ◎ Δ ◎ Δ ◎ Δ ◎ 〇模具 mold moldability ◎ 〇 ◎ 〇◎ 〇◎ 〇 knot solvent resistance XX 〇〇〇滑滑 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X It is excellent in moldability at low temperature and low pressure, and can be applied to a wide range of molding methods. It is excellent in elasticity and form stability (heat shrinkage characteristics and thickness unevenness) when it is used as a molded body in a normal temperature environment. It is excellent in transparency, printability, solvent resistance, and heat resistance, and is excellent in impact resistance. It is suitable as a decorative material or exterior decorative material for home appliances, mobile phones, and automobiles, or as a building material member. The advantages have a significant contribution to the industry. [Simple description of the diagram] None. [Component Symbol Description] No 0

-54--54-

Claims

200808551 十、申請專利範圍： 1· 一種成型用積層聚酯薄膜，其特徵係在聚酯A層的一面或兩面，層積聚酯B層而構成之雙軸配向積層聚酯薄膜，在A層及B層任一者都是以共聚合聚酯、或是共聚合聚酯及同元聚酯作爲構成成分，A層的熔點（TmA : °C )及 B層的熔點（TmB: °C)係同時滿足下述式（1)及（2)，且積層聚酯薄膜係A層及B層同時具有配向結構，在150 °C之熱收縮率係長度方向及寬度方向都爲6.0%以下、寬 ® 度方向的厚度變動率爲10%以下， 2 6 0 > T m B > T m A > 2 0 0 · · · (1 ) 5 0>T mB-T m Α>5 ·*·(2)。 2.如申請專利範圍第1項之成型用積層聚酯薄膜，其中該共聚合聚酯係U)由芳香族二羧酸成分、與乙二醇、與含有分枝狀脂肪族二醇或脂環族二醇之二醇成分所構成之共聚合聚酯、或是（b)由含有對酞酸及異酞酸之芳香族二羧酸成分、與含有乙二醇之二醇成分所構成。 ^ 3.如申請專利範圍第1項之成型用積層聚酯薄膜，其中該同元聚酯係選自聚對酞酸乙二酯、聚對酞酸伸丁二酯、及聚對酞酸丁二酯所組成群組中至少1種。 4. 如申請專利範圍第1項之成型用積層聚酯薄膜，其中該積層聚酯薄膜的總厚度爲10〜500微米，且B層的厚度佔整體的1〜3 0 %。 5. 如申請專利範圍第1項之成型用積層聚酯薄膜，其中在積層聚酯薄膜的長度方向及寬度方向之1〇〇%拉伸時之應 -55- 200808551 力，係任一者在25。(：都爲40〜300MPa、且在l〇〇°C都爲 1 〜lOOMPa 〇 6.如申請專利範圍第1項之成型用積層聚酯薄膜，其中該積層聚酯薄膜的霧度爲2.0%以下。 7· —種如申請專利範圍第1項之成型用積層聚酯薄膜之製法，其特徵係包含以下步驟所構成之成型用積層聚酯薄膜之製法：使用共擠壓法，來製造在聚酯A層的一面或兩面層積聚酯B層而構成之未拉伸薄膜之步驟；使該未 ® 拉伸薄膜在縱方向及橫方向進行雙軸拉伸步驟；及邊使用夾子把持雙軸拉伸過的薄膜邊進行熱處理之步驟；構成A層及B層之聚酯係共聚合聚酯、或共聚合聚酯與同元聚酯之混合物，熱處理步驟具有2階段以上的熱處理區段，控制在熱處理區段之最大升溫速度〜30 °C/秒，最大的熱處理溫度爲（A層的熔點-10°C )〜（A層的熔點+ 20°C )。 8·如申請專利範圍第7項之成型用積層聚酯薄膜之製法， ^ 其中在拉幅機內邊以夾子保持薄膜邊進行橫向拉伸及熱處理時，使用下述（i)〜（v)中至少1項的方法來冷卻夾子附近，接著在拉幅機出口將薄膜從夾子放開， (i) 在夾子部分設置熱遮蔽壁之方法 (Π)在拉幅機附加夾子冷卻機構之方法 (iii) 加長設定熱固定後的冷卻區段，來使薄膜整體充分冷卻之方法 (iv) 增加冷卻區段的長度、及間隔數，來增加冷卻效率 -56- 200808551 之方法 (V) 使用夾子之反轉部係在爐子的外側行進之方法，來強化夾子的冷卻之方法。.200808551 X. Patent application scope: 1. A laminated polyester film for molding, characterized in that a polyester B layer is laminated on one or both sides of a polyester A layer to form a biaxial alignment laminated polyester film, in the A layer. And the B layer is composed of a copolymerized polyester or a copolymerized polyester and a homopolyester as a constituent component, the melting point of the layer A (TmA: °C) and the melting point of the layer B (TmB: °C). The following formulas (1) and (2) are satisfied, and the laminated polyester film A layer and the B layer have an alignment structure at the same time, and the heat shrinkage ratio at 150 ° C is 6.0% or less in both the longitudinal direction and the width direction. The thickness variation rate in the width direction is 10% or less, 2 6 0 > T m B > T m A > 2 0 0 · · · (1) 5 0>T mB-T m Α>5 ·* ·(2). 2. The laminated polyester film for molding according to claim 1, wherein the copolymerized polyester U) is composed of an aromatic dicarboxylic acid component, ethylene glycol, and a branched aliphatic diol or fat. The copolymerized polyester composed of the diol component of the cyclodiol or (b) is composed of an aromatic dicarboxylic acid component containing p-citric acid and isononic acid, and a glycol component containing ethylene glycol. 3. The laminated polyester film for molding according to claim 1, wherein the homopolyester is selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polypyristate. At least one of the groups consisting of diesters. 4. The laminated polyester film for molding according to the first aspect of the invention, wherein the laminated polyester film has a total thickness of 10 to 500 μm, and the thickness of the B layer accounts for 1 to 30% of the whole. 5. The laminated polyester film for molding according to the first aspect of the patent application, wherein the laminate polyester film is stretched by 1% in the longitudinal direction and the width direction, and is preferably -55-200808551. 25. (: Both are 40 to 300 MPa, and both are 1 to 100 MPa at 10 ° C. 〇 6. The laminated polyester film for molding according to the first aspect of the patent application, wherein the laminated polyester film has a haze of 2.0%. The method for producing a laminated polyester film for molding according to the first aspect of the patent application, characterized in that the method for producing a laminated polyester film for molding comprising the following steps is as follows: a co-extrusion method is used to manufacture a step of laminating a polyester B layer on one or both sides of the polyester A layer to form an unstretched film; subjecting the un-stretched film to a biaxial stretching step in the longitudinal direction and the transverse direction; and using a clip to hold the double a step of heat-treating the axially stretched film; a polyester-based copolymerized polyester constituting the A layer and the B layer, or a mixture of a copolymerized polyester and a homopolyester, and a heat treatment step having a heat treatment section of 2 or more stages , control the maximum heating rate in the heat treatment section ~ 30 ° C / sec, the maximum heat treatment temperature is (the melting point of layer A - 10 ° C) ~ (the melting point of layer A + 20 ° C). 8 · If the scope of application The method for producing a laminated polyester film for molding according to item 7, ^ When the film is stretched and heat-treated while holding the film inside the tenter, use at least one of the following (i) to (v) to cool the vicinity of the clip, and then take the film from the clip at the exit of the tenter. Release, (i) a method of providing a heat shielding wall in the clip portion (Π) a method of adding a clip cooling mechanism to the tenter (iii) a method of lengthening the cooling section after heat setting to sufficiently cool the entire film ( Iv) Increasing the length of the cooling section and the number of intervals to increase the cooling efficiency -56- 200808551 Method (V) The method of using the reversing part of the clip to travel outside the furnace to enhance the cooling of the clip.

-57- 200808551 七、指定代表圖： (一）本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： Μ 。 \Ν 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：-57- 200808551 VII. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ . \Ν 八. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: