TW202229432A - Readily adhesive polyester film - Google Patents

Abstract

To provide a readily adhesive polyester film that is suitable for use in optical applications, etc., by suppressing a decrease in adhesion over time. A readily adhesive polyester film having, on at least one surface of a polyester film, a coating layer obtained by curing a composition including a polyester having a polycyclic aromatic skeleton and a crosslinking agent having at least one skeleton selected from an aliphatic skeleton, an alicyclic skeleton, and a heterocyclic skeleton, wherein, when the surface of the coating layer on the side thereof not in contact with the polyester film is measured by a Fourier-transform infrared spectroscopy (FT-IR) method, a prescribed relative absorption intensity ratio (I1640/I1410) of the absorption intensity (I1640) having a peak at 1640 cm<SP>-1</SP> pertaining to urea groups and the absorption intensity (I1410) having a peak at 1410 cm<SP>-1</SP> pertaining to polyester CH expansion and contraction satisfies a specific relationship.

Description

易接著性聚酯薄膜Easy Adhesive Polyester Film

本發明係關於一種易接著性聚酯薄膜，其可確保能消除在積層硬塗層等功能層時的虹斑問題之低干涉性，且與前述功能層的密著性、抗黏連性(blocking resistance)、透明性優異。更詳細而言，係關於一種易接著性聚酯薄膜，其即使在更透明的光學用途中也可適用。The present invention relates to an easy-adhesive polyester film, which can ensure low interference properties that can eliminate the problem of rainbow spots when a functional layer such as a hard coat layer is laminated, and has adhesion and anti-blocking properties ( excellent blocking resistance) and transparency. More specifically, it is about an easy-adhesive polyester film which can be applied to more transparent optical applications.

於觸控面板、電腦、電視、液晶顯示裝置等之顯示器、裝飾材料等之正面，使用積層有透明的硬塗層之硬塗薄膜。又，作為基材之透明塑膠薄膜，一般使用透明的聚酯薄膜，為了提升基材的聚酯薄膜與硬塗層之密著性，作為此等之中間層，在聚酯薄膜表面設置具有易接著性的塗布層之情況多。A hard coat film with a transparent hard coat layer is used on the front side of monitors and decorative materials such as touch panels, computers, televisions, and liquid crystal display devices. In addition, as the transparent plastic film of the base material, a transparent polyester film is generally used. In order to improve the adhesion between the polyester film of the base material and the hard coat layer, as these intermediate layers, an easy-to-use polyester film is provided on the surface of the polyester film. There are many cases of adhesive coating layers.

於前述之硬塗薄膜，係要求對於溫度、濕度、光的耐久性、透明性、耐化學性、耐擦傷性、防污性等。又，由於多使用於顯示器及裝飾材料之表面，而要求視覺辨認性及設計性。因此，為了抑制從任意角度來觀看時之反射光所致的眩光或虹彩狀色彩等，而一般亦進行在硬塗層之上層設置交替地積層有高折射率層與低折射率層之多層構造的抗反射層。In the aforementioned hard coat film, durability against temperature, humidity, light, transparency, chemical resistance, scratch resistance, stain resistance, and the like are required. Moreover, since it is used for the surface of a display and a decorative material in many cases, visibility and design are required. Therefore, in order to suppress glare or iridescent color due to reflected light when viewed from any angle, a multilayer structure in which high-refractive index layers and low-refractive index layers are alternately laminated on top of a hard coat layer is generally also performed. anti-reflection layer.

近年來，開發出具有各式各樣的骨架之硬塗層，每次都會討論基材與硬塗層之密著性。不僅是積層後立即的初期密著性，亦要求耐濕熱耐性、密著保持性、隨著時間經過的密著性降低小等之對於製品的長期使用之可靠性，且要求具有各種評價耐性之製品。In recent years, hard coats with various skeletons have been developed, and the adhesion between the substrate and the hard coat is always discussed. Not only the initial adhesion immediately after lamination, but also the reliability for long-term use of the product, such as resistance to moisture and heat, adhesion retention, and a small decrease in adhesion over time, and various evaluation resistances are required. product.

於以往之易接著性聚酯薄膜之領域中，將採用萘二甲酸作為共聚合成分之聚酯樹脂使用於具有易接著性的塗布層時，與基材聚酯薄膜的密著性亦優異，被提案作為合適例(例如，參照專利文獻1)。又，作為柔軟性優異且密著性高之樹脂，有提案使用具有聚碳酸酯成分的聚胺基甲酸酯樹脂之方法(例如，參照專利文獻2)。 然而，雖然皆確認有密著性，但得不到擔保對於長期使用的可靠性之易接著性聚酯薄膜。 [先前技術文獻] [專利文獻] In the field of conventional easy-adhesive polyester films, when a polyester resin using naphthalenedicarboxylic acid as a copolymerization component is used in a coating layer with easy-adhesion, the adhesion to the base polyester film is also excellent. It is proposed as a suitable example (for example, refer to Patent Document 1). Moreover, as resin which is excellent in flexibility and high in adhesiveness, a method of using a polyurethane resin having a polycarbonate component is proposed (for example, refer to Patent Document 2). However, although the adhesiveness was confirmed, the easy-adhesive polyester film that guarantees reliability for long-term use was not obtained. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本特開2011-246663號公報 [專利文獻2]日本特開2011-168053號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2011-246663 [Patent Document 2] Japanese Patent Laid-Open No. 2011-168053

[發明欲解決之課題][The problem to be solved by the invention]

本發明係以如此的習知技術之課題為背景而完成者。即，本發明之目的在於提供一種密著性的可靠性經提升之易接著性聚酯薄膜，特別地，提供一種易接著性聚酯薄膜，其藉由抑制隨著時間經過的密著性降低，而適用於光學用途等。The present invention has been made on the background of such a conventional problem. That is, an object of the present invention is to provide an easy-adhesive polyester film in which the reliability of adhesiveness is improved, and in particular, to provide an easy-adhesive polyester film which suppresses the decrease in adhesiveness with time , while suitable for optical applications, etc.

本發明者為了達成如此之目的而專心致力地檢討，結果完成本發明。 即，本發明包含以下之構成。 1.一種易接著性聚酯薄膜，其係在聚酯薄膜之至少一面上具有塗布層之易接著性聚酯薄膜，該塗布層係將包含具有多環芳香族骨架的聚酯與具有選自脂肪族、脂環族、雜環族的至少一個骨架的交聯劑之組成物硬化而成者，以傅立葉轉換型紅外光譜法(FT-IR)測定前述塗布層之未與聚酯薄膜相接側之表面時，規定以歸屬於脲基的1640cm ^-1為波峰的吸收強度(I ₁₆₄₀)與以歸屬於聚酯之CH伸縮的1410cm ^-1為波峰的吸收強度(I ₁₄₁₀)之相對吸收強度比(I ₁₆₄₀/I ₁₄₁₀)時，滿足以下之關係； 評價製膜後的易接著性聚酯薄膜而得之相對吸收強度比(X)與評價80℃90%RH環境下放置24小時後的聚酯薄膜而得之相對吸收強度比(Y)滿足下述式(1)之關係； 110 ≦ (Y/X)×100 ≦ 140・・・(1)。 2.如上述第1記載之易接著性聚酯薄膜，其中前述具有多環芳香族骨架的聚酯為具有萘骨架的聚酯。 3.如上述第1或第2記載之易接著性聚酯薄膜，其中前述具有選自脂肪族、脂環族、雜環族的至少一個骨架的交聯劑為具有選自脂肪族、脂環族、雜環族的至少一個骨架的異氰酸酯交聯劑。 4.如上述第1～第3中任一項記載之易接著性聚酯薄膜，其中在前述塗布層表面上設置包含具有芳香族骨架的樹脂之硬塗層時，其密著性為95%以上。 [發明之效果] In order to achieve such an object, the inventors of the present invention have made intensive studies, and as a result, they have completed the present invention. That is, the present invention includes the following configurations. 1. An easy-adhesive polyester film, which is an easy-adhesive polyester film having a coating layer on at least one side of the polyester film, and the coating layer will comprise a polyester having a polycyclic aromatic skeleton and a polyester having a The composition of the cross-linking agent with at least one skeleton of aliphatic, alicyclic and heterocyclic is hardened, and it is determined by Fourier transform infrared spectroscopy (FT-IR) that the coating layer is not in contact with the polyester film In the case of the surface of the side, the relative absorption intensity (I ₁₆₄₀ ) of the peak at 1640 cm ^-1 attributed to the urea group and the absorption intensity (I ₁₄₁₀ ) of the peak at 1410 cm ^-1 attributed to the CH stretch of polyester is defined When the ratio (I ₁₆₄₀ /I ₁₄₁₀ ), the following relationship is satisfied: The relative absorption strength ratio (X) obtained by evaluating the easy-adhesive polyester film after film formation and evaluating the The relative absorption intensity ratio (Y) obtained from the polyester film satisfies the relationship of the following formula (1): 110≦(Y/X)×100≦140・・・(1). 2. The easily adhesive polyester film according to the above 1st item, wherein the polyester having a polycyclic aromatic skeleton is a polyester having a naphthalene skeleton. 3. The easily adhesive polyester film according to the above 1 or 2, wherein the crosslinking agent having at least one skeleton selected from aliphatic, alicyclic and heterocyclic Isocyanate cross-linking agent of at least one skeleton of the heterocyclic group. 4. The easily adhesive polyester film according to any one of the above 1 to 3, wherein when a hard coat layer comprising a resin having an aromatic skeleton is provided on the surface of the coating layer, the adhesion is 95% above. [Effect of invention]

根據本發明，可提供一種長期間確保密著可靠性之易接著性聚酯薄膜，可廣泛應用於光學用途等。ADVANTAGE OF THE INVENTION According to this invention, the easy-adhesion polyester film which can ensure adhesion reliability for a long period of time can be provided, and can be widely used for optical applications, etc.

[用以實施發明的形態][Form for carrying out the invention]

(聚酯薄膜) 本發明中作為基材使用的聚酯薄膜係主要由聚酯樹脂所構成的薄膜。此處，所謂「主要由聚酯樹脂所構成的薄膜」，意指由含有50質量%以上的聚酯樹脂之樹脂組成物所形成的薄膜。與其它聚合物摻合時，意指含有50質量%以上的聚酯樹脂，與其它單體共聚合時，意指含有50莫耳%以上的聚酯結構單元。聚酯薄膜較佳為含有90質量%以上的聚酯樹脂，更佳為95質量%以上，進一步較佳為含有100質量%。 (Polyester film) The polyester film used as the base material in the present invention is a film mainly composed of a polyester resin. Here, the "film mainly composed of polyester resin" means a film formed from a resin composition containing 50% by mass or more of polyester resin. When blending with other polymers, it means containing 50 mass % or more of polyester resin, and when copolymerizing with other monomers, means containing 50 mol % or more of polyester structural units. The polyester film preferably contains 90% by mass or more of the polyester resin, more preferably 95% by mass or more, and still more preferably 100% by mass.

聚酯樹脂之材料係沒有特別的限定，可使用將二羧酸成分與二醇成分予以聚縮合而形成的共聚物或其之摻合樹脂。作為二羧酸成分，例如可舉出對苯二甲酸、間苯二甲酸、鄰苯二甲酸、2,5-萘二甲酸、2,6-萘二甲酸、1,4-萘二甲酸、1,5-萘二甲酸、二苯基羧酸、二苯氧基乙烷二甲酸、二苯基碸羧酸、蒽二甲酸、1,3-環戊烷二甲酸、1,3-環己烷二甲酸、1,4-環己烷二甲酸、六氫對苯二甲酸、六氫間苯二甲酸、丙二酸、二甲基丙二酸、琥珀酸、3,3-二乙基琥珀酸、戊二酸、2,2-二甲基戊二酸、己二酸、2-甲基己二酸、三甲基己二酸、庚二酸、壬二酸、二聚物酸、癸二酸、辛二酸、十二烷二甲酸等。The material of the polyester resin is not particularly limited, and a copolymer formed by polycondensing a dicarboxylic acid component and a diol component or a blended resin thereof can be used. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1 ,5-Naphthalenedicarboxylic acid, Diphenylcarboxylic acid, Diphenoxyethanedicarboxylic acid, Diphenylethylenedicarboxylic acid, Anthracenedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid , glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, azelaic acid, dimer acid, sebacic acid acid, suberic acid, dodecanedicarboxylic acid, etc.

作為構成聚酯樹脂之二醇成分，例如可舉出乙二醇、丙二醇、六亞甲基二醇、新戊二醇、1,2-環己烷二甲醇、1,4-環己烷二甲醇、1,10-癸二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-雙(4-羥基苯基)丙烷、雙(4-羥基苯基)碸等。Examples of glycol components constituting the polyester resin include ethylene glycol, propylene glycol, hexamethylene glycol, neopentyl glycol, 1,2-cyclohexanedimethanol, and 1,4-cyclohexanediol. Methanol, 1,10-decanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-bis(4-hydroxybenzene) base) propane, bis(4-hydroxyphenyl) bismuth, etc.

構成聚酯樹脂之二羧酸成分與二醇成分，可各自使用1種或2種以上。又，亦可適宜添加偏苯三酸等其它的酸成分或三羥甲基丙烷等其它的羥基成分。The dicarboxylic acid component and the diol component that constitute the polyester resin can be used individually by one type or two or more types. Moreover, other acid components, such as trimellitic acid, and other hydroxyl components, such as trimethylolpropane, may be added suitably.

作為聚酯樹脂，具體而言可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等，於此等之中，從物性與成本的平衡來看，較佳為聚對苯二甲酸乙二酯。又，為了控制偏光性等光學特性，包含其它的共聚合成分或其它的聚合物者亦為較佳的態樣。從控制聚酯薄膜的光學特性之觀點來看，作為較佳的共聚合成分，可舉出二乙二醇或在側鏈具有降莰烯的共聚合成分等。Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. Among them, polyethylene terephthalate is preferred from the viewpoint of the balance between physical properties and cost. Moreover, in order to control optical characteristics, such as polarizing property, what contains other copolymerization components or other polymers is also a preferable aspect. From the viewpoint of controlling the optical properties of the polyester film, as a preferable copolymerization component, diethylene glycol, a copolymerization component having norbornene in a side chain, etc. are mentioned.

為了改善聚酯薄膜之滑動性、捲繞性等的處理性，有使薄膜中含有惰性粒子之情況，但為了保持高的透明性，薄膜中的惰性粒子含量較佳為儘可能地少。因此，較佳係成為僅使薄膜的表層中含有粒子之多層構成，或者使薄膜中實質上不含粒子、僅使積層在聚酯薄膜之至少一面上的被覆層中含有微粒子。In order to improve the handling properties of the polyester film such as sliding property and winding property, inert particles may be contained in the film, but in order to maintain high transparency, the content of inert particles in the film is preferably as small as possible. Therefore, it is preferable to use a multilayer structure in which particles are contained only in the surface layer of the film, or the film contains substantially no particles and only fine particles are contained in the coating layer laminated on at least one side of the polyester film.

此外，所謂「實質上不含粒子」，例如於無機粒子之情況，意指當以螢光X射線分析來定量分析來自粒子的元素時為50ppm以下、較佳為10ppm以下、最佳為檢測極限以下之含量。此係因為即使在基材薄膜中不積極地添加粒子，也有來自外來異物的污染成分，或者原料樹脂或薄膜之製程中的生產線或裝置上附著的污垢剝離而不可避免地混入薄膜中之情況。In addition, "substantially free of particles", for example, in the case of inorganic particles, means 50 ppm or less, preferably 10 ppm or less, and optimally the detection limit when elements derived from particles are quantitatively analyzed by X-ray fluorescence analysis the following content. This is because, even if particles are not actively added to the base film, contamination from foreign matter, or contamination from raw resin or film production lines or equipment is peeled off and inevitably mixed into the film.

又，使聚酯薄膜成為多層構成時，在內層實質上不含惰性粒子而僅在最外層含有惰性粒子之兩種三層的構成，可兼顧透明性與加工性而較佳。Moreover, when a polyester film is made into a multilayer structure, the structure of two types of three layers in which the inner layer does not substantially contain the inert particles and only the outermost layer contains the inert particles is preferable because both transparency and workability can be achieved.

成為基材的聚酯薄膜可為單層，也可為積層有2種以上之層者。又，只要是達成本發明的效果之範圍內，則視需要可使薄膜中含有各種添加劑。作為添加劑，例如可舉出抗氧化劑、耐光劑、防凝膠化劑、有機濕潤劑、抗靜電劑、紫外線吸收劑、界面活性劑等。於薄膜具有積層構成時，亦較佳為視需要因應各層的功能而使其含有添加劑。例如，為了防止偏光鏡之光降解，於內層添加紫外線吸收劑等者亦為較佳的態樣。The polyester film used as the base material may be a single layer, or may be one in which two or more types of layers are laminated. Moreover, as long as the effect of this invention is achieved, various additives can be contained in a film as needed. As an additive, an antioxidant, a lightfast agent, an antigelling agent, an organic wetting agent, an antistatic agent, an ultraviolet absorber, a surfactant, etc. are mentioned, for example. When the film has a layered structure, it is also preferable to contain an additive according to the function of each layer as necessary. For example, in order to prevent the photodegradation of the polarizer, it is also preferable to add an ultraviolet absorber to the inner layer.

聚酯薄膜可依照常用方法製造。例如，藉由將上述的聚酯樹脂熔融擠出成薄膜狀，以澆鑄滾筒使其冷卻固化而形成薄膜之方法等來獲得。作為本發明中的聚酯薄膜，可使用無延伸薄膜、延伸薄膜之任一者，但從機械強度或耐化學性等耐久性之點來看，較佳為延伸薄膜。於聚酯薄膜為延伸薄膜時，其延伸方法係沒有特別的限定，可採用縱單軸延伸法、橫單軸延伸法、縱橫逐次雙軸延伸法、縱橫同時雙軸延伸法等。將聚酯薄膜延伸時，延伸可在積層後述的易接著層之前實施，也可在積層易接著層之後實施。亦可在積層易接著層之前於縱或橫向上單軸延伸，在積層被覆層之後，於另一方向上延伸。The polyester film can be produced according to the usual methods. For example, it can be obtained by a method of melt-extruding the above-mentioned polyester resin into a film form, and cooling and solidifying it with a casting roll to form a film. As the polyester film in the present invention, either a non-stretched film or a stretched film can be used, but a stretched film is preferred from the viewpoint of durability such as mechanical strength and chemical resistance. When the polyester film is a stretched film, the stretching method is not particularly limited, and vertical uniaxial stretching, horizontal uniaxial stretching, vertical and horizontal sequential biaxial stretching, vertical and horizontal simultaneous biaxial stretching, and the like can be used. When the polyester film is stretched, the stretching may be performed before laminating the easily bonding layer described later, or may be performed after laminating the easily bonding layer. It is also possible to extend uniaxially in the vertical or horizontal direction before laminating the easily bonding layer, and extend in the other direction after laminating the coating layer.

(塗布層) 本發明之易接著性聚酯薄膜係在如上述的聚酯製基材薄膜上積層有易接著性塗布層者。塗布層中包含黏結劑樹脂及添加劑。 (coating layer) The easily-adhesive polyester film of the present invention is obtained by laminating an easily-adhesive coating layer on the above-mentioned polyester base film. The coating layer contains binder resin and additives.

以下，詳細說明塗布層之各組成。 作為構成塗布層的黏結劑樹脂，係具有易接著性的樹脂，從粒子的保持、密著性之觀點來看，較佳為聚酯，再者於本發明中，最佳為具有多環芳香族骨架的聚酯。其亦有與後述硬塗層之組成的相容性，但硬塗層之組成具有芳香族骨架時，從共軛相互作用的觀點來看亦較佳。 Hereinafter, each composition of the coating layer will be described in detail. The binder resin constituting the coating layer is a resin having easy adhesion, and from the viewpoint of particle retention and adhesion, polyester is preferred, and in the present invention, polycyclic aromatic resin is preferred. family skeleton polyester. It also has compatibility with the composition of the hard coat layer described later, but when the composition of the hard coat layer has an aromatic skeleton, it is also preferable from the viewpoint of conjugated interaction.

作為具有多環芳香族骨架的聚酯之具體例，可舉出具有萘骨架的聚酯、具有茀骨架的聚酯、具有蒽骨架的聚酯、具有菲骨架的聚酯等。Specific examples of the polyester having a polycyclic aromatic skeleton include a polyester having a naphthalene skeleton, a polyester having a pyrene skeleton, a polyester having an anthracene skeleton, a polyester having a phenanthrene skeleton, and the like.

於本發明中，作為構成塗布層的黏結劑樹脂，較佳為不含胺基甲酸酯樹脂。胺基甲酸酯樹脂有時基於塗膜的彈性或易成形性之觀點而被使用，但顯然藉由胺基甲酸酯樹脂而脲化合物作為雜質混入，若塗布層中存在的脲化合物量變得過多，則有變得難以滿足與後述相對吸收強度比有關的特性之情況，從維持密著性之隨著時間經過的安定性之觀點來看，較佳為不含胺基甲酸酯樹脂。In the present invention, the binder resin constituting the coating layer is preferably a urethane-free resin. Urethane resins are sometimes used from the viewpoint of elasticity or formability of the coating film, but it is clear that urea compounds are mixed in as impurities by the urethane resins, and the amount of urea compounds present in the coating layer becomes If it is too large, it may become difficult to satisfy the properties related to the relative absorption intensity ratio described later. From the viewpoint of maintaining the stability over time of the adhesiveness, it is preferable not to contain a urethane resin.

前述聚酯在塗布層中，相對於樹脂與交聯劑的固體成分質量之和，就聚酯樹脂的固體成分質量之百分率而言較佳為含有10質量%以上90質量%以下。更佳為15%質量%以上85質量%以下。聚酯樹脂之含量為90質量%以下時，保持高溫高濕下之與硬塗層的密著性而較佳。相反地，若含量為10質量%以上，則容易保持常溫及高溫高濕下之與聚酯薄膜的密著性而較佳。The polyester is preferably contained in the coating layer in an amount of 10 mass % or more and 90 mass % or less in terms of the solid content mass percentage of the polyester resin relative to the sum of the solid content mass of the resin and the crosslinking agent. More preferably, it is 15% by mass or more and 85% by mass or less. When the content of the polyester resin is 90% by mass or less, it is preferable to maintain the adhesion to the hard coat layer under high temperature and high humidity. Conversely, when the content is 10% by mass or more, it is easy to maintain the adhesion to the polyester film at normal temperature and high temperature and high humidity, which is preferable.

於本發明中，為了在塗布層中形成交聯結構，較佳為使其含有交聯劑。適合為可藉由交聯的副反應而生成脲基之交聯劑，作為具體的交聯劑，可舉出異氰酸酯系交聯劑及碳二亞胺系交聯劑。於此等之中，從塗液之隨著時間經過的安定性、高溫高濕處理下之密著性提升效果來看，較佳為異氰酸酯交聯劑。再者，於本發明中，最佳為具有選自脂肪族、脂環族、雜環族的至少一個骨架之異氰酸酯。又，為了促進交聯反應，於塗布層形成用組成物中，可視需要適宜地使用觸媒等。In this invention, in order to form a crosslinked structure in a coating layer, it is preferable to contain a crosslinking agent. A crosslinking agent which can generate a urea group by the side reaction of crosslinking is suitable, and an isocyanate type crosslinking agent and a carbodiimide type crosslinking agent are mentioned as a specific crosslinking agent. Among these, an isocyanate crosslinking agent is preferable in view of the stability of the coating solution over time and the effect of improving the adhesion under high temperature and high humidity treatment. Furthermore, in this invention, the isocyanate which has at least one skeleton selected from aliphatic, alicyclic, and heterocyclic is preferable. Moreover, in order to accelerate a crosslinking reaction, a catalyst etc. are used suitably as needed in the composition for coating layer formation.

作為脂肪族異氰酸酯之具體例，可舉出1,4-二異氰酸基丁烷、1,5-五亞甲基二異氰酸酯、2-甲基-1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,12-十二烷二異氰酸酯、2,2,4-三甲基-1,6-六亞甲基二異氰酸酯、2,4,4-三甲基-1,6-六亞甲基二異氰酸酯、3,5,5-三甲基-1,6-六亞甲基二異氰酸酯等。Specific examples of aliphatic isocyanates include 1,4-diisocyanatobutane, 1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl base-1,6-hexamethylene diisocyanate, 3,5,5-trimethyl-1,6-hexamethylene diisocyanate, etc.

作為脂環族異氰酸酯之具體例，可舉出環己烷二異氰酸酯、異佛爾酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、1,3-雙(異氰酸酯甲基)環己烷、1,4-雙(異氰酸酯甲基)環己烷、環己基1,4-二異氰酸酯、1,1-雙(異氰酸基甲基)環己烷、2,4-六氫甲苯二異氰酸酯、2,6-六氫甲苯二異氰酸酯等。Specific examples of alicyclic isocyanates include cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,3-bis(isocyanate methyl)cyclohexane , 1,4-bis(isocyanatomethyl)cyclohexane, cyclohexyl 1,4-diisocyanate, 1,1-bis(isocyanatomethyl)cyclohexane, 2,4-hexahydrotoluene diisocyanate , 2,6-hexahydrotoluene diisocyanate, etc.

作為雜環族異氰酸酯之具體例，可舉出2,5-二異氰酸基噻吩、2,5-雙(異氰酸基甲基)噻吩、2,5-二異氰酸基四氫噻吩、2,5-雙(異氰酸基甲基)四氫噻吩、3,4-雙(異氰酸基甲基)四氫噻吩、2,5-二異氰酸基-1,4-二噻𠮿、2,5-雙(異氰酸基甲基)-1,4-二噻𠮿、4,5-二異氰酸基-1,3-二噻

、4,5-雙(異氰酸基甲基)-1,3-二噻

、4,5-雙(異氰酸基甲基)-2-甲基-1,3-二噻

、2,6-二(異氰酸酯甲基)呋喃、5,5’-亞甲基雙糠基異氰酸酯、5,5’-亞異丙基雙糠基異氰酸酯或二異氰酸酯類之三聚物，被稱為三聚異氰酸酯(isocyanurate)體的具有三

環之2,4,6-三側氧六氫-1,3,5-三

-1,3,5-三基參(6,1-己烷二基)參異氰酸酯、1,3,5-參[(5-異氰酸基-1,3,3-三甲基環己基)甲基]-1,3,5-三

-2,4,6(1H,3H,5H)-三酮等。Specific examples of heterocyclic isocyanates include 2,5-diisocyanatothiophene, 2,5-bis(isocyanatomethyl)thiophene, and 2,5-diisocyanatotetrahydrothiophene , 2,5-bis(isocyanatomethyl)tetrahydrothiophene, 3,4-bis(isocyanatomethyl)tetrahydrothiophene, 2,5-diisocyanato-1,4-di thiocyanate, 2,5-bis(isocyanatomethyl)-1,4-dithiocyanate, 4,5-diisocyanato-1,3-dithiocyanate

, 4,5-bis(isocyanatomethyl)-1,3-dithiane

, 4,5-bis(isocyanatomethyl)-2-methyl-1,3-dithione

, 2,6-bis(isocyanate methyl)furan, 5,5'-methylenebisfurfuryl isocyanate, 5,5'-isopropylidenebisfurfuryl isocyanate or trimer of diisocyanates, known as It is a trimeric isocyanate (isocyanurate) body with three

Cyclic 2,4,6-tri-oxohexahydro-1,3,5-tri

-1,3,5-Trimethylpara(6,1-hexanediyl)paraisocyanate, 1,3,5-para[(5-isocyanato-1,3,3-trimethylcyclohexyl) )methyl]-1,3,5-tri

-2,4,6(1H,3H,5H)-triketone, etc.

於本發明中，具有芳香族骨架的異氰酸酯因其反應性高而容易與空氣中的水分反應，超出需要地促進脲化合物之生成，故較佳為不含於塗布層形成用組成物中。再者，從耐候性之觀點來看，亦較佳為具有脂肪族、脂環族、雜環族的至少一個骨架之異氰酸酯。In the present invention, since the isocyanate having an aromatic skeleton is highly reactive, it easily reacts with moisture in the air and promotes the formation of the urea compound more than necessary, so it is preferably not contained in the composition for forming a coating layer. Furthermore, from the viewpoint of weather resistance, an isocyanate having at least one skeleton of aliphatic, alicyclic, and heterocyclic is also preferred.

作為交聯劑在塗布層形成用組成物中之固體成分含量，相對於樹脂與交聯劑的固體成分質量之和，就交聯劑的固體成分質量之百分率而言較佳為5質量%以上50質量%以下。更佳為10質量%以上45質量%以下。進一步較佳為10質量%以上30質量%以下，最佳為10質量%以上20質量%以下。若為5質量%以上，則保持塗布層的樹脂強度，高溫高濕下的密著性良好，若為50質量%以下，則保持塗布層的樹脂柔軟性，保持常溫、高溫高濕下的密著性而較佳。The solid content of the crosslinking agent in the composition for forming a coating layer is preferably 5% by mass or more in terms of the solid content mass percentage of the crosslinking agent relative to the sum of the solid content mass of the resin and the crosslinking agent 50 mass % or less. More preferably, it is 10 mass % or more and 45 mass % or less. More preferably, it is 10 mass % or more and 30 mass % or less, and most preferably 10 mass % or more and 20 mass % or less. If it is 5 mass % or more, the resin strength of the coating layer is maintained, and the adhesion under high temperature and high humidity is good. Adherence is better.

本發明之易接著性聚酯薄膜中的塗布層較佳為將包含聚酯與交聯劑之組成物硬化而成者，該聚酯具有多環芳香族骨架，該交聯劑具有選自脂肪族、脂環族、雜環族的至少一個骨架。此將組成物硬化而成者之表現，係由於難以適當地表現交聯劑所致的反應硬化後之化學組成，而作為如此的記載。The coating layer in the easy-adhesive polyester film of the present invention is preferably obtained by curing a composition comprising polyester and a cross-linking agent, the polyester has a polycyclic aromatic skeleton, and the cross-linking agent has a compound selected from aliphatic At least one skeleton of alicyclic, alicyclic, and heterocyclic. The expression of the composition obtained by curing the composition is described as such because it is difficult to appropriately express the chemical composition after reaction curing by the crosslinking agent.

(添加劑) 於本發明中的塗布層中，在不妨礙本發明的效果之範圍內，可添加眾所周知的添加劑，例如界面活性劑、抗氧化劑、耐熱安定劑、耐候安定劑、紫外線吸收劑、有機的易滑劑、顏料、染料、有機或無機的粒子、抗靜電劑、成核劑等。然而，較佳為不使用不利環境等的物質。 (additive) In the coating layer of the present invention, well-known additives such as surfactants, antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic slippery agents, etc. agents, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, etc. However, it is preferable not to use a substance that is unfavorable to the environment or the like.

於本發明中，為了更提升塗布層的抗黏連性，在塗布層中添加粒子者亦為較佳的態樣。於本發明中，作為使塗布層中含有的粒子，例如為氧化鈦、硫酸鋇、碳酸鈣、硫酸鈣、矽石、氧化鋁、滑石、高嶺土、黏土等或此等之混合物，再者，可舉出其它一般的無機粒子，例如與磷酸鈣、雲母、水輝石、氧化鋯、氧化鎢、氟化鋰、氟化鈣等併用等之無機粒子，或者苯乙烯系、丙烯酸系、三聚氰胺系、苯并胍胺(benzoguanamine)系、聚矽氧系等之有機聚合物系粒子等。In the present invention, in order to further enhance the anti-blocking property of the coating layer, it is also a preferred aspect to add particles to the coating layer. In the present invention, as the particles to be contained in the coating layer, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, etc., or a mixture of these, may be used. Other general inorganic particles, such as inorganic particles used in combination with calcium phosphate, mica, hectorite, zirconia, tungsten oxide, lithium fluoride, calcium fluoride, etc., or styrene-based, acrylic-based, melamine-based, benzene-based, etc. And guanamine (benzoguanamine), polysiloxane and other organic polymer particles and the like.

塗布層中的惰性粒子之平均粒徑(利用SEM的個數基準之平均粒徑；以下相同)較佳為0.04～2.0μm，進一步較佳為0.1～1.0μm。若惰性粒子之平均粒徑為0.04μm以上，則容易對於薄膜表面形成凹凸，故薄膜的滑動性或捲取性等之處理性提升，貼合時的加工性良好而較佳。另一方面，若惰性粒子之平均粒徑為2.0μm以下，則難以發生粒子的脫落而較佳。塗布層中的粒子濃度較佳為固體成分中1～20質量%。The average particle diameter of the inert particles in the coating layer (average particle diameter based on the number of objects by SEM; the same applies hereinafter) is preferably 0.04 to 2.0 μm, more preferably 0.1 to 1.0 μm. When the average particle diameter of the inert particles is 0.04 μm or more, irregularities are likely to be formed on the surface of the film, so that the slipperiness of the film and the rollability of the film are improved, and the processability at the time of lamination is good, which is preferable. On the other hand, when the average particle diameter of the inert particles is 2.0 μm or less, the particles are less likely to fall off, which is preferable. The particle concentration in the coating layer is preferably 1 to 20% by mass in the solid content.

本發明中塗布層之厚度可在0.001～2.00μm之範圍中適宜設定，但為了兼顧加工性與接著性，較佳為0.01～1.00μm之範圍，更佳為0.02～0.80μm，進一步較佳為0.05～0.50μm。若塗布層之厚度為0.001μm以上，則接著性良好而較佳。若塗布層之厚度為2.00μm以下，則難以發生黏連而較佳。In the present invention, the thickness of the coating layer can be appropriately set in the range of 0.001 to 2.00 μm, but in order to take both workability and adhesiveness into consideration, it is preferably in the range of 0.01 to 1.00 μm, more preferably 0.02 to 0.80 μm, and still more preferably 0.05～0.50μm. When the thickness of the coating layer is 0.001 μm or more, the adhesiveness is good, which is preferable. If the thickness of the coating layer is 2.00 μm or less, blocking is difficult to occur, which is preferable.

本發明係對於塗布層形成用組成物中存在的交聯劑成分因與空氣中的水分等的反應而變形的脲化合物，著眼於其存在量的變化。The present invention pays attention to changes in the amount of the urea compound in which the crosslinking agent component present in the composition for forming a coating layer is deformed by the reaction with moisture in the air or the like.

以傅立葉轉換型紅外光譜法(FT-IR)測定本發明之易接著性聚酯薄膜的塗布層之表面時，若藉由以歸屬於脲基的1640cm ^-1為波峰的吸收強度(I ₁₆₄₀)與以歸屬於具有多環芳香族骨架的聚酯之CH伸縮的1410cm ^-1為波峰的吸收強度(I ₁₄₁₀)之相對吸收強度比(I ₁₆₄₀/I ₁₄₁₀)來規定，則此相對吸收強度比愈大，意指塗布層中愈多脲化合物生成。歸屬於脲化合物的1640cm ^-1之波峰未必恰好出現在1640cm ^-1，而存在1640±5cm ^-1左右的幅度。又，歸屬於具有多環芳香族骨架的聚酯樹脂的1410cm ^-1之波峰未必恰好出現在1410cm ^-1，而存在1410±5cm ^-1左右的幅度。 When measuring the surface of the coating layer of the easy-adhesive polyester film of the present invention by Fourier transform infrared spectroscopy (FT-IR), if the absorption intensity (I ₁₆₄₀ ) at 1640 cm ^-1 attributed to the urea group is taken as the peak The relative absorption intensity ratio (I ₁₆₄₀ /I ₁₄₁₀ ) is defined as the relative absorption intensity ratio (I 1640 /I 1410 ) with the absorption intensity (I ₁₄₁₀ ) at 1410 cm ⁻¹ attributable to the CH stretching of the polyester having a polycyclic aromatic skeleton as the peak. Larger means more urea compound is generated in the coating layer. The peak at 1640 cm ^-1 attributed to the urea compound does not necessarily appear exactly at 1640 cm ^-1 , but has an amplitude around 1640±5 cm ^-1 . In addition, the peak at 1410 cm ^-1 attributed to the polyester resin having a polycyclic aromatic skeleton does not necessarily appear exactly at 1410 cm ^-1 , but has a width of about 1410±5 cm ^-1 .

較佳為使評價製膜後的易接著聚酯薄膜而得之相對吸收強度比(X)與評價80℃、90%RH環境下保持24小時後的易接著聚酯薄膜而得之相對吸收強度比(Y)滿足下述(1)之關係。 110 ≦ (Y/X)×100 ≦ 140・・・(1) Preferably, the ratio (X) of the relative absorption strength obtained by evaluating the easily bondable polyester film after film formation to the relative absorption strength obtained by evaluating the easily bondable polyester film after being kept at 80°C and 90% RH for 24 hours The ratio (Y) satisfies the relation of the following (1). 110 ≦ (Y/X)×100 ≦ 140・・・(1)

本發明所言之「製膜後」，係指在薄膜製造後，放置於一定環境下的樣品，為240小時以內者。前述所謂一定環境下，具體而言，係指就溫度而言5℃以上40℃以下、就濕度而言30%RH至60%RH以下之環境下。若為保持於此等範圍的樣品，則確認不到隨著時間經過的變化，可確認到可謂初期狀態而較佳。The term "after film formation" as used in the present invention refers to a sample placed under a certain environment after film production, within 240 hours. Specifically, the above-mentioned so-called certain environment refers to an environment of 5°C or higher and 40°C or lower in terms of temperature and 30% RH to 60% RH or lower in terms of humidity. If it is a sample which maintains these ranges, the change with the passage of time cannot be confirmed, and it can be confirmed that it can be said to be an initial state, which is preferable.

本發明之易接著聚酯薄膜較佳係存在於薄膜表面的塗布層之前述(Y/X)×100為140以下，進一步較佳為130以下。若為140以下，則塗布層中的脲之比例不過大，可防止具有極性基的脲化合物吸附更多的空氣中之水分等而使密著性之隨著時間經過的安定性、可靠性降低之問題，因此較佳。若前述(Y/X)×100為110以上，則原本的交聯劑之含有率無不足，可適當地進行交聯等之反應，得到密著性、密著可靠性而較佳。In the easily adhesive polyester film of the present invention, the above-mentioned (Y/X)×100 of the coating layer present on the film surface is preferably 140 or less, more preferably 130 or less. If it is 140 or less, the ratio of urea in the coating layer will not be too large, and the urea compound having a polar group can be prevented from adsorbing more moisture in the air, thereby reducing the stability and reliability of the adhesion over time. problem, so it is better. When the above-mentioned (Y/X)×100 is 110 or more, the content of the original crosslinking agent is not insufficient, reactions such as crosslinking can be appropriately performed, and adhesion and adhesion reliability are obtained.

本來，如果能以數週～數個月左右在通常放置的室溫環境中放置前後的相對吸收强度之比來評價易接著性聚酯薄膜的話，可能會比較理想，但是因為難以放置測定，而作為其代用測量，設為加速地在80℃、90%RH的高溫高濕度環境下放置24小時來進行評價。Originally, it may be ideal if the ratio of the relative absorption strength before and after being left in a normal room temperature environment for several weeks to several months can be used to evaluate the easy-adhesive polyester film, but it is difficult to measure. As a substitute measurement, evaluation was performed by being left to stand for 24 hours in a high-temperature and high-humidity environment of 80° C. and 90% RH at an accelerated rate.

為了滿足相對吸收強度比之關係式(1)，較佳為控制塗布層中的樹脂與交聯劑之比率。藉由使塗布層形成用組成物中的樹脂成分增加，而X及Y之值增加，將樹脂成分與交聯劑成分的固體成分總和當作100質量%時，較佳為將樹脂成分的固體成分設為70質量%以上。更佳為75質量%以上，進一步較佳為80質量%以上。若為70質量%以上，則交聯劑比率不過大，可減少多餘的脲化合物之比例，變得容易滿足關係式(1)。惟，此等手段終究僅為一例，並非將採用其它達成手段者排除在外。將樹脂成分與交聯劑成分之固體成分總和當作100質量%時，交聯劑成分之固體成分較佳為30質量%以下，更佳為25質量%以下，進一步較佳為20質量%以下。In order to satisfy the relational formula (1) of the relative absorption intensity ratio, it is preferable to control the ratio of the resin to the crosslinking agent in the coating layer. By increasing the resin component in the composition for forming a coating layer, the values of X and Y increase, and when the total solid content of the resin component and the crosslinking agent component is taken as 100% by mass, the solid content of the resin component is preferably A component shall be 70 mass % or more. More preferably, it is 75 mass % or more, More preferably, it is 80 mass % or more. If it is 70 mass % or more, the ratio of the crosslinking agent is not too large, the ratio of the excess urea compound can be reduced, and the relational formula (1) can be easily satisfied. However, these means are only an example after all, and do not exclude those who use other means of achieving it. When the total solid content of the resin component and the crosslinking agent component is taken as 100% by mass, the solid content of the crosslinking agent component is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less .

此時，就X之值而言較佳為1.78以下。更佳為1.60以下，進一步較佳為1.41以下。藉由樹脂成分增加，交聯劑成分變少，可減少多餘的脲化合物之比例，硬塗密著性變得良好而較佳。另一方面，X之值較佳為1.10以上，可滿足作為用於構築與樹脂的交聯反應之添加比率，容易滿足高溫高濕下之與硬塗層的密著性而較佳。X之值更佳為1.15以上，進一步較佳為1.20以上。In this case, the value of X is preferably 1.78 or less. More preferably, it is 1.60 or less, and still more preferably 1.41 or less. By increasing the resin component, the crosslinking agent component is reduced, the ratio of the excess urea compound can be reduced, and the hard coat adhesion becomes good and preferable. On the other hand, the value of X is preferably 1.10 or more, which can satisfy the addition ratio for building the crosslinking reaction with the resin and easily satisfy the adhesion to the hard coat layer under high temperature and high humidity. The value of X is more preferably 1.15 or more, and still more preferably 1.20 or more.

又，就Y之值而言較佳為2.70以下。更佳為2.30以下，進一步較佳為1.85以下。藉由交聯劑成分變少，隨著時間經過後亦可減少多餘的脲化合物之發生比例，硬塗密著性變得良好而較佳。另一方面，若Y之值為0.90以上，則可滿足作為用於構築與樹脂的交聯反應之添加比率，容易滿足高溫高濕下之與硬塗層的密著性而較佳。Y之值更佳為1.20以上，進一步較佳為1.40以上。Moreover, it is preferable that the value of Y is 2.70 or less. More preferably, it is 2.30 or less, and still more preferably 1.85 or less. By reducing the amount of the crosslinking agent component, the generation ratio of the excess urea compound can also be reduced with the passage of time, and the hard coat adhesion becomes good, which is preferable. On the other hand, when the value of Y is 0.90 or more, the addition ratio for building the crosslinking reaction with the resin can be satisfied, and the adhesion to the hard coat layer under high temperature and high humidity can be easily satisfied, which is preferable. The value of Y is more preferably 1.20 or more, and still more preferably 1.40 or more.

於塗布層形成用組成物中，以塗布時的調平性之提升、塗布液之脫泡為目的，亦可含有界面活性劑。界面活性劑可為陽離子系、陰離子系、非離子系等之任一者，但較佳為聚矽氧系、乙炔二醇系或氟系界面活性劑。此等之界面活性劑較佳為以不損害螢光燈下的虹彩狀色彩之抑制效果或密著性的程度之範圍而含於塗布層形成用組成物中。In the composition for forming a coating layer, a surfactant may be contained for the purpose of improving the leveling property at the time of coating and defoaming of the coating liquid. The surfactant may be any of cationic, anionic, and nonionic surfactants, but is preferably a polysiloxane-based, acetylene glycol-based or fluorine-based surfactant. These surfactants are preferably contained in the composition for forming a coating layer in a range of such a degree that they do not impair the effect of suppressing the iridescent color under a fluorescent lamp or the adhesiveness.

作為塗覆方法，可應用在聚酯基材薄膜製膜時同時塗覆的所謂線內(in‐line)塗布法、及在將聚酯基材薄膜予以製膜後另外以塗布機塗覆的所謂離線(off-line)塗布法之任一者，但線內塗布法效率上更佳。As the coating method, a so-called in-line coating method in which the polyester base film is simultaneously applied during film formation, and a method in which the polyester base film is formed into a film and coated with a coater separately can be applied. Any of the so-called off-line coating methods, but the in-line coating method is more efficient.

作為塗覆方法，用以將塗布液塗布於聚對苯二甲酸乙二酯(以下，簡稱為PET)薄膜之方法，可使用眾所周知之任意方法。例如，可舉出反向輥塗布(reverse roll coating)法、凹版塗布法、吻合塗布(kiss coating)法、模塗法、輥刷法、噴塗法、氣刀塗布法、線棒塗布法、管刮法、含浸塗布法、簾塗法等。可將此等之方法單獨或組合進行塗覆。As a coating method, the method for coating a coating liquid on a polyethylene terephthalate (hereinafter, abbreviated as PET) film can be any well-known method. For example, a reverse roll coating method, a gravure coating method, a kiss coating method, a die coating method, a roll brush method, a spray coating method, an air knife coating method, a wire bar coating method, a pipe coating method, a Scraping method, dip coating method, curtain coating method, etc. These methods can be applied individually or in combination.

於本發明中，作為在聚酯薄膜上設置塗布層之方法，可舉出將含有溶媒、粒子、樹脂的塗布液塗布於聚酯薄膜上並乾燥之方法。作為溶媒，可舉出水或者水與有機溶劑之混合系，但較佳係從環境問題之點來看，以水單獨或者混合有水與水溶性有機溶劑者為較佳。 例如，作為水溶性有機溶劑之例，可舉出異丙醇、乙醇等之醇系、甲基乙基酮等之酮系、丁基賽珞蘇等之醚系、三乙醇胺等之胺系、N-甲基吡咯啶酮等之醯胺系。 In the present invention, as a method of providing a coating layer on a polyester film, a method of applying a coating liquid containing a solvent, particles, and resin on a polyester film and drying it is exemplified. Examples of the solvent include water or a mixture of water and an organic solvent, but from the viewpoint of environmental problems, water alone or a mixture of water and a water-soluble organic solvent is preferred. For example, examples of the water-soluble organic solvent include alcohols such as isopropanol and ethanol, ketones such as methyl ethyl ketone, ethers such as butyl selenium, amines such as triethanolamine, Amide series such as N-methylpyrrolidone.

塗布液之固體成分濃度亦取決於黏結劑樹脂之種類或溶媒之種類等，但較佳為2質量%以上，更佳為4質量%。塗布液之固體成分濃度較佳為35質量%以下，更佳為15質量%以下。The solid content concentration of the coating liquid also depends on the type of binder resin, the type of solvent, and the like, but is preferably 2 mass % or more, more preferably 4 mass %. The solid content concentration of the coating liquid is preferably 35% by mass or less, more preferably 15% by mass or less.

關於塗布後之乾燥溫度，雖然亦取決於黏結劑樹脂之種類、溶媒之種類、有無交聯劑、固體成分濃度等，但較佳為80℃以上，且較佳為250℃以下。The drying temperature after coating also depends on the type of binder resin, the type of solvent, the presence or absence of a crosslinking agent, the solid content concentration, etc., but is preferably 80°C or higher, and preferably 250°C or lower.

(易接著性聚酯薄膜之製造) 成為本發明之易接著性聚酯薄膜的基材之聚酯薄膜，可依照一般的聚酯薄膜之製造方法來製造。例如，可舉出將聚酯樹脂熔融，擠出成薄片狀，將經成形的無配向聚酯在玻璃轉移溫度以上之溫度，利用輥之速度差在縱向上延伸後，藉由拉幅機在橫向上延伸，施予熱處理之方法。 (Manufacture of Easy Adhesive Polyester Film) The polyester film which becomes the base material of the easily adhesive polyester film of this invention can be manufactured according to the manufacturing method of a general polyester film. For example, the polyester resin is melted and extruded into a sheet shape, and the formed non-oriented polyester is stretched in the longitudinal direction at a temperature equal to or higher than the glass transition temperature by means of the speed difference of the rolls, and then stretched by a tenter in the longitudinal direction. A method of extending laterally and applying heat treatment.

本發明之聚酯薄膜可為單軸延伸薄膜，也可為雙軸延伸薄膜，但使用雙軸延伸薄膜作為液晶面板正面的保護膜時，即使從薄膜面之正上方來觀察，也看不到虹狀色斑，但由於有從傾斜方向觀察時觀察到虹狀色斑之情況而必須注意。The polyester film of the present invention can be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as the protective film on the front surface of the liquid crystal panel, even if it is viewed from right above the film surface, it is not visible Iridescent spots are observed, but caution is required because iridescent spots are observed when viewed from an oblique direction.

此現象係因為雙軸延伸薄膜包含在行進方向、寬度方向、厚度方向上具有不同折射率的折射率橢圓體，有依在薄膜內部的光之穿透方向而遲滯成為零的(折射率橢圓體被看成真圓的)方向存在。因此，若從傾斜方向的特定方向來觀察液晶顯示畫面，則有發生遲滯成為零之點的情況，以該點為中心，同心圓狀地發生虹狀色斑。而若將從薄膜面之正上方(法線方向)起到看見虹狀色斑之位置為止的角度當作θ，則薄膜面內的雙折射愈大而此角度θ變得愈大，變得難以看見虹狀色斑。在雙軸延伸薄膜中有角度θ變小之傾向，因此單軸延伸薄膜者變得較難以看見虹狀色斑而較佳。This phenomenon is caused by the fact that the biaxially stretched film contains refractive index ellipsoids with different refractive indices in the advancing direction, width direction, and thickness direction, and the retardation becomes zero according to the transmission direction of light inside the film (refractive index ellipsoid). seen as a true circle) direction exists. Therefore, when the liquid crystal display screen is viewed from a specific direction in the oblique direction, a point at which the hysteresis becomes zero may occur, and rainbow-like color unevenness occurs concentrically around the point. On the other hand, if the angle from directly above the film surface (the direction of the normal line) to the position where the iridescent color spot is seen is regarded as θ, the larger the birefringence in the film surface, the larger this angle θ becomes, and the angle θ becomes larger. Iridescent spots are difficult to see. In a biaxially stretched film, the angle θ tends to become smaller, so it is more difficult to see iridescent spots in a uniaxially stretched film.

然而，完全單軸性(單軸對稱)薄膜由於與配向方向呈正交的方向之機械強度顯著地降低而不佳。本發明較佳為在實質上不發生虹狀色斑的範圍內、或在液晶顯示畫面所要求的視角範圍中不發生虹狀色斑的範圍內，具有雙軸性(雙軸對稱性)。However, fully uniaxial (uniaxially symmetric) films are not good because the mechanical strength in the direction orthogonal to the alignment direction is significantly reduced. The present invention preferably has biaxiality (biaxial symmetry) within a range in which rainbow unevenness does not substantially occur, or within a range where rainbow unevenness does not occur in a viewing angle range required for a liquid crystal display screen.

(積層聚酯薄膜) 本發明中主要用於光學用途的積層聚酯薄膜，係藉由在本發明之易接著性聚酯薄膜的塗布層上，設置由電子束或紫外線硬化型丙烯酸樹脂或者矽氧烷系熱硬化性樹脂等所構成之硬塗層等而得。 (Laminated polyester film) The laminated polyester film mainly used for optical applications in the present invention is formed by providing an electron beam or ultraviolet curable acrylic resin or a siloxane-based thermosetting property on the coating layer of the easy-adhesive polyester film of the present invention. A hard coat layer composed of resin or the like is obtained.

在本發明之易接著性聚酯薄膜的塗布層上設置功能層者亦為較佳形態。所謂功能層，係以防止映入或抑制眩光、抑制虹斑、抑制傷痕等為目的，除了前述硬塗層之外，亦指防眩層、防眩性抗反射層、抗反射層、低反射層及抗靜電層等之具有功能性的層。功能層可使用該技術領域中眾所周知之各種者，其種類係沒有特別的限制。以下，說明各功能層。It is also a preferable form to provide a functional layer on the coating layer of the easily adhesive polyester film of the present invention. The so-called functional layer is for the purpose of preventing reflection or suppressing glare, suppressing rainbow spots, suppressing scars, etc. In addition to the aforementioned hard coating, it also refers to anti-glare layer, anti-glare anti-reflection layer, anti-reflection layer, low-reflection layer, etc. functional layers such as layers and antistatic layers. As the functional layer, various well-known ones in the technical field can be used, and the type thereof is not particularly limited. Hereinafter, each functional layer will be described.

例如，於硬塗層之形成中，可使用眾所周知的硬塗層，並沒有特別的限定，但可使用藉由乾燥、熱、化學反應或者照射電子束、放射線、紫外線之任一者而聚合及/或反應之樹脂化合物。作為如此的硬化性樹脂，可舉出三聚氰胺系、丙烯酸系、聚矽氧系、聚乙烯醇系之硬化性樹脂，但於得到高的表面硬度或光學設計之點上，較佳為光硬化性型的丙烯酸系硬化性樹脂。作為如此的丙烯酸系硬化性樹脂，可使用多官能(甲基)丙烯酸酯系單體或丙烯酸酯系寡聚物，作為丙烯酸酯系寡聚物之例，可舉出聚酯丙烯酸酯系、環氧丙烯酸酯系、胺基甲酸酯丙烯酸酯系、聚醚丙烯酸酯系、聚丁二烯丙烯酸酯系、聚矽氧丙烯酸酯系等。可藉由於此等丙烯酸系硬化性樹脂中混合反應稀釋劑、光聚合起始劑、增感劑等，而得到用於形成前述光學功能層的塗布用組成物。For example, in the formation of the hard coat layer, a well-known hard coat layer can be used, but it is not particularly limited, but polymerization and /or reacted resin compound. Examples of such curable resins include melamine-based, acrylic-based, polysiloxane-based, and polyvinyl alcohol-based curable resins, but photocurable resins are preferred from the viewpoint of obtaining high surface hardness and optical design. type of acrylic curable resin. As such acrylic curable resins, polyfunctional (meth)acrylate-based monomers or acrylate-based oligomers can be used, and examples of acrylate-based oligomers include polyester acrylate-based, cyclic Oxyacrylate, urethane acrylate, polyether acrylate, polybutadiene acrylate, polysiloxane acrylate, etc. The coating composition for forming the aforementioned optical functional layer can be obtained by mixing a reactive diluent, a photopolymerization initiator, a sensitizer, etc. with these acrylic curable resins.

上述硬塗層可具有使外光散射之防眩功能(防眩光(anti-glare)功能)。防眩功能(防眩光功能)係藉由在硬塗層之表面上形成凹凸而得。此時，薄膜之霧度理想上較佳為0～50%，更佳為0～40%，特佳為0～30%。當然，0%為理想者，0.2%以上也無妨，0.5%以上也無妨。The above-mentioned hard coat layer may have an anti-glare function (anti-glare function) that scatters external light. The anti-glare function (anti-glare function) is obtained by forming unevenness on the surface of the hard coat layer. In this case, ideally, the haze of the film is preferably 0 to 50%, more preferably 0 to 40%, and particularly preferably 0 to 30%. Of course, 0% is ideal, 0.2% or more is fine, and 0.5% or more is fine.

又，為了施予藉由賦予折射率不同的層，改變光的穿透特性而抑制光的反射之低反射加工(抗反射加工)，較佳為對於硬塗層及功能層調整折射率且理想上實現0～1.0%的反射率，更佳為0～0.8%，特佳為0～0.5%。當然，0%為理想者，0.05%以上也無妨，0.1%以上也無妨。In addition, in order to apply low-reflection processing (anti-reflection processing) that suppresses reflection of light by changing the transmission characteristics of light by imparting layers with different refractive indices, it is preferable to adjust the refractive index for the hard coat layer and the functional layer, and ideal A reflectance of 0 to 1.0% is achieved, more preferably 0 to 0.8%, and particularly preferably 0 to 0.5%. Of course, 0% is ideal, 0.05% or more is fine, and 0.1% or more is fine.

特別地，作為本發明所使用的硬塗用組成物，為了調整折射率，一般使用：相對於構成樹脂的單體、寡聚物之總莫耳數，以5莫耳%以上20莫耳%以下之比例包含芳香族成分之樹脂。In particular, as the hard coating composition used in the present invention, in order to adjust the refractive index, it is generally used: 5 mol % or more and 20 mol % with respect to the total moles of monomers and oligomers constituting the resin. The following ratios contain resins containing aromatic components.

本發明之易接著性聚酯薄膜及在其塗布層上積層有功能層之積層聚酯薄膜之用途主要涵蓋光學用薄膜全體，特別可適用於稜鏡透鏡薄片、AR(抗反射)薄膜、硬塗薄膜、擴散板、防破碎薄膜等之LCD或平面TV、CRT等之光學用構件的基底薄膜、電漿顯示器用的正面板中作為構件的近紅外線吸收濾光片、觸控面板或電致發光等之透明導電性薄膜等。The application of the easy-adhesive polyester film of the present invention and the laminated polyester film with a functional layer laminated on the coating layer of the present invention mainly covers the entire optical film, and is especially suitable for lens sheets, AR (anti-reflection) films, hard Coating films, diffusers, anti-fragmentation films, etc., base films for optical components such as LCDs, flat-screen TVs, CRTs, etc., near-infrared absorbing filters used as components in front panels for plasma displays, touch panels or electro-optics Transparent conductive films for light emission, etc.

作為上述硬塗層形成用的藉由電子束或紫外線進行硬化之丙烯酸樹脂，更詳細而言，為具有丙烯酸酯系的官能基者，例如可使用含有下述者：對於比較低分子量的聚酯樹脂、聚醚樹脂、丙烯酸樹脂、環氧樹脂、胺基甲酸酯樹脂、醇酸樹脂、螺縮醛樹脂、聚丁二烯樹脂、聚硫醇多烯樹脂、多元醇等的多官能化合物之(甲基)丙烯酸酯等之寡聚物或預聚物；及作為反應性稀釋劑之(甲基)丙烯酸乙酯、(甲基)丙烯酸乙基己酯、苯乙烯、甲基苯乙烯、N-乙烯基吡咯啶酮等之單官能單體以及多官能單體，例如三羥甲基丙烷三(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等者。As the acrylic resin to be cured by electron beam or ultraviolet rays for forming the above-mentioned hard coat layer, more specifically, one having an acrylate-based functional group, for example, one containing a polyester having a relatively low molecular weight can be used. Resin, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, polyol and other polyfunctional compounds Oligomers or prepolymers of (meth)acrylates, etc.; and as reactive diluents ethyl (meth)acrylate, ethylhexyl (meth)acrylate, styrene, methylstyrene, N - Monofunctional monomers such as vinylpyrrolidone as well as polyfunctional monomers such as trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate Esters, diethylene glycol di(meth)acrylate, neotaerythritol tri(meth)acrylate, dipeotaerythritol hexa(meth)acrylate, 1,6-hexanediol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, etc.

而且，於電子束或紫外線硬化型樹脂之情況，在前述樹脂中作為光聚合起始劑，可混合苯乙酮類、二苯基酮類、米其勒苯甲醯基苯甲酸酯、α-戊基肟酯、一硫化四甲胺硫甲醯基(tetramethylthiuram monosulfide)、氧硫𠮿

類，或作為光增感劑，可混合正丁胺、三乙胺、三正丁基膦等而使用。Furthermore, in the case of electron beam or ultraviolet curable resins, acetophenones, benzophenones, Michels benzyl benzoate, α -Pentyl oxime ester, tetramethylthiuram monosulfide, oxygen sulfur

or as a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used.

又，聚矽氧系(矽氧烷系)熱硬化性樹脂可藉由在酸或鹼觸媒下，將有機矽烷化合物單獨或混合2種以上進行水解及縮合反應而製造。特別地，於低反射用之情況中，混合1種以上的氟矽烷化合物進行水解及縮合反應者，係在低折射率性、耐污染性等之提升上進一步較佳。In addition, polysiloxane-based (siloxane-based) thermosetting resin can be produced by hydrolyzing and condensing an organosilane compound alone or in combination of two or more kinds under an acid or alkali catalyst. In particular, in the case of low reflection, mixing one or more fluorosilane compounds for hydrolysis and condensation reaction is more preferable in terms of improvement of low refractive index, contamination resistance, and the like.

(積層聚酯薄膜之製造) 對於本發明中使用易接著性聚酯薄膜的積層聚酯薄膜之製造方法進行說明，但不受說明的具體例所限定。 (Manufacture of laminated polyester film) Although the manufacturing method of the laminated polyester film using the easily adhesive polyester film in this invention is demonstrated, it is not limited to the specific example demonstrated.

在前述易接著性聚酯薄膜的塗布層面上，塗布前述之電子束或紫外線硬化型丙烯酸樹脂、寡聚物、單體或者矽氧烷系熱硬化性樹脂。於兩面設有塗布層時，塗布於至少一塗布層面。塗布液係沒有特別稀釋之必要，但即使因應塗布液的黏度、潤濕性、塗膜厚等之需要而藉由有機溶劑稀釋也沒有特別的問題。塗布層係在前述之薄膜上塗布前述塗布液後，視需要使其乾燥後，配合塗布液之硬化條件，藉由電子束或紫外線照射及加熱而使塗布層硬化，藉此形成硬塗層。The above-mentioned electron beam or ultraviolet curable acrylic resin, oligomer, monomer or siloxane-based thermosetting resin is coated on the coating layer of the aforementioned easy-adhesive polyester film. When there are coating layers on both sides, it is coated on at least one coating layer. The coating liquid does not need to be particularly diluted, but there is no particular problem even if it is diluted with an organic solvent according to the needs of the viscosity, wettability, coating film thickness, etc. of the coating liquid. The coating layer is formed by applying the coating liquid on the thin film, drying it if necessary, and curing the coating layer by electron beam or ultraviolet irradiation and heating according to the curing conditions of the coating liquid, thereby forming a hard coat layer.

於本發明中，硬塗層之厚度較佳為1～15μm。若硬塗層之厚度為1μm以上，則有效率地發揮作為硬塗層的對於耐化學性、耐擦傷性、防污性等之效果而較佳。另一方面，若厚度為15μm以下，則保持硬塗層的可撓性，沒有發生龜裂等之虞而較佳。In the present invention, the thickness of the hard coat layer is preferably 1-15 μm. When the thickness of the hard coat layer is 1 μm or more, the effects of the hard coat layer on chemical resistance, scratch resistance, antifouling properties, and the like are effectively exhibited. On the other hand, when the thickness is 15 μm or less, the flexibility of the hard coat layer is maintained and there is no risk of cracking or the like occurring.

作為耐刮傷性，將塗布面以黑襯紙磨耗時，較佳為目視下傷痕不顯眼者。若在前述評價中傷痕不顯眼，則在通過導輥時不易刮傷，於處理性等之觀點上較佳。As scratch resistance, when the coated surface is abraded with black backing paper, it is preferable that the scratches are inconspicuous by visual observation. If scratches are not conspicuous in the said evaluation, it is hard to be scratched when passing through a guide roll, and it is preferable from a viewpoint of handleability etc..

本發明之易接著性聚酯薄膜及積層聚酯薄膜由於主要使用於光學用途，較佳為具有高的透明性。霧度之下限理想上為0%，愈接近0%愈佳。霧度之上限較佳為2%，若為2%以下，則透光率良好，於液晶顯示裝置中可得到鮮明的影像而較佳。聚酯薄膜之霧度例如可依照後述之方法測定。Since the easily adhesive polyester film and the laminated polyester film of the present invention are mainly used for optical applications, it is preferable that they have high transparency. The lower limit of the haze is ideally 0%, and the closer it is to 0%, the better. The upper limit of the haze is preferably 2%, and if it is 2% or less, the light transmittance is good, and a clear image can be obtained in a liquid crystal display device, which is preferable. The haze of the polyester film can be measured, for example, by the method described later.

易接著層性的塗布層與硬塗層之密著性較佳係藉由利用後述測定法的評價而為95%以上。更佳為98%以上，進一步較佳為100%。若為95%以上，則可說是充分保持塗布層與硬塗層的密著性之狀態。It is preferable that the adhesiveness of the coating layer of easy-bonding layer property and a hard-coat layer is 95% or more by evaluation by the measurement method mentioned later. More preferably, it is 98% or more, and still more preferably, it is 100%. If it is 95% or more, it can be said that the adhesiveness between the coating layer and the hard coat layer is sufficiently maintained.

關於依照後述方法評價的易接著層與硬塗層在80℃、95%RH高溫高濕條件下的密著性，亦與前述同樣地密著性較佳為95%以上。更佳為98%以上，進一步較佳為100%。若為95%以上，則大致滿足高溫高濕條件下的易接著層與硬塗層之密著性，大致滿足後加工步驟的通過性。Regarding the adhesion between the easily bonding layer and the hard coat layer evaluated by the method described later under high temperature and high humidity conditions of 80° C. and 95% RH, the adhesion is preferably 95% or more in the same manner as described above. More preferably, it is 98% or more, and still more preferably, it is 100%. If it is 95% or more, the adhesion between the easy-bonding layer and the hard coat layer under high temperature and high humidity conditions is generally satisfied, and the passability of the post-processing step is generally satisfied.

本來，如果能以數週～數個月左右在通常放置的室溫環境中放置後的密著性來評價易接著性聚酯薄膜的話，可能會比較理想，但是因為難以放置測定，而作為其代用測量，設為加速地在80℃、90%RH的高溫高濕度環境下放置24小時來進行評價。Originally, it may be ideal to evaluate the adhesion of the easy-adhesive polyester film after being left in a normal room temperature environment for several weeks to several months. As a substitute for measurement, evaluation was performed by being left to stand for 24 hours in a high-temperature and high-humidity environment of 80° C. and 90% RH at an accelerated rate.

本發明之易接著性聚酯薄膜可用於各種的用途，但較佳係在液晶顯示裝置所用的偏光板之製造步驟中使用，特佳係使用作為構成偏光板的偏光鏡之保護膜。通常，偏光鏡多為聚乙烯醇製者，本發明之易接著性聚酯薄膜係在偏光鏡上，視需要使用聚乙烯醇製或在其中加有交聯劑等之接著劑而接著。此時，本發明之易接著性聚酯薄膜的塗布層更佳為不是向與偏光鏡接著之側的面，而是向其相反面使用。在本發明之易接著性聚酯薄膜之與偏光鏡接著的表面，較佳為例如積層如國際公開第2012/105607號中記載之包含聚酯系樹脂、聚乙烯醇系樹脂及交聯劑之易接著層。The easily adhesive polyester film of the present invention can be used in various applications, but is preferably used in the production process of polarizers used in liquid crystal display devices, and is particularly preferably used as a protective film for polarizers constituting polarizers. Usually, polarizers are mostly made of polyvinyl alcohol, and the easy-adhesive polyester film of the present invention is attached to the polarizer by using polyvinyl alcohol or an adhesive added with a crosslinking agent or the like as necessary. In this case, it is more preferable to use the coating layer of the easily adhesive polyester film of the present invention not on the surface on the side adhering to the polarizer, but on the opposite surface. On the surface of the easy-adhesive polyester film of the present invention to be bonded to the polarizer, it is preferable to laminate, for example, a film comprising a polyester-based resin, a polyvinyl alcohol-based resin and a cross-linking agent as described in International Publication No. 2012/105607. Easy to attach layer.

[實施例] 接著，使用實施例、比較例及參考例，詳細說明本發明，惟本發明當然不受以下的實施例所限定。又，本發明所用之評價方法係如以下。 [Example] Next, the present invention will be described in detail using Examples, Comparative Examples, and Reference Examples, but it goes without saying that the present invention is not limited to the following Examples. In addition, the evaluation method used in this invention is as follows.

(1)平均粒徑 [利用掃描型電子顯微鏡之測定法] 上述粒子之平均粒徑的測定可藉由下述之方法進行。對於粒子，以掃描型電子顯微鏡(SEM)拍攝照片，以最小粒子1個之大小成為2～5mm的倍率，測定300～500個粒子的最大徑(最遠離的2點間之距離)，將其平均值當作平均粒徑。本發明之塗布層中存在的粒子之平均粒徑可藉由該測定法測定。 (1) Average particle size [Measurement method using scanning electron microscope] The measurement of the average particle diameter of the said particle|grains can be performed by the following method. The particles are photographed with a scanning electron microscope (SEM), the size of one smallest particle is set to a magnification of 2 to 5 mm, the maximum diameter (the distance between the two farthest points) of 300 to 500 particles is measured, and the The average value was taken as the average particle size. The average particle diameter of the particles present in the coating layer of the present invention can be measured by this measuring method.

[動態光散射法] 粒子之平均粒徑係在粒子或薄膜之製造時，亦可藉由動態散射法求出。將溶膠以分散介質稀釋，使用分散介質之參數，以次微米粒子分析器N4 PLUS(Beckman Coulter公司製)測定，以累積量法演算，藉此得到平均粒徑。於動態光散射法中觀測溶膠中的粒子之平均粒徑，當粒子彼此有凝聚時，觀測彼等的凝聚粒子之平均粒徑。 [Dynamic light scattering method] The average particle diameter of the particles can also be obtained by the dynamic scattering method at the time of production of the particles or thin films. The sol is diluted with a dispersion medium, measured with a submicron particle analyzer N4 PLUS (manufactured by Beckman Coulter) using the parameters of the dispersion medium, and calculated by the cumulant method to obtain the average particle diameter. The average particle diameter of the particles in the sol was observed by the dynamic light scattering method, and when the particles were aggregated with each other, the average particle diameter of the aggregated particles was observed.

(2)粒子之折射率 粒子之折射率測定可藉由下述之方法進行。將無機粒子在150℃下乾燥後，將經研缽粉碎的粉末浸漬於溶媒1(比粒子更低折射率者)中後，少量一點一點地添加溶媒2(比粒子更高折射率者)直到微粒子幾乎變得透明為止。使用阿貝折射計(ATAGO股份有限公司製阿貝折射率計)，測定此液之折射率。測定係以23℃、D線(波長589nm)進行。上述溶媒1與溶媒2係選定能互相混合者，因應折射率，例如可舉出1,1,1,3,3,3-六氟-2-丙醇、2-丙醇、氯仿、四氯化碳、甲苯、甘油等之溶媒。 (2) Refractive index of particles The measurement of the refractive index of particles can be performed by the following method. After drying the inorganic particles at 150°C, the powder pulverized in a mortar was immersed in solvent 1 (those with a lower refractive index than the particles), and then the solvent 2 (those with a higher refractive index than the particles) was added little by little. ) until the particles become almost transparent. The refractive index of this liquid was measured using an Abbe refractometer (Abbe refractometer manufactured by ATAGO Co., Ltd.). The measurement was performed at 23° C. and D line (wavelength: 589 nm). The above-mentioned solvent 1 and solvent 2 are selected to be able to be mixed with each other, and according to the refractive index, for example, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-propanol, chloroform, tetrachloro Carbon, toluene, glycerol and other solvents.

(3)光學用易接著性聚酯薄膜之霧度 易接著性聚酯薄膜之霧度係依據JIS K 7136：2000，使用濁度計(日本電色製，NDH2000)測定。 (3) Haze of easy-adhesive polyester film for optics The haze of the easy-adhesive polyester film was measured according to JIS K 7136:2000 using a turbidity meter (Nihon Denshoku, NDH2000).

(4)密著性 於實施例所得之聚酯薄膜的易接著層上，形成前述硬塗層之形成的項目中所記述的硬塗層。對於形成硬塗的易接著用聚酯薄膜，依據JIS-K5400-1990的8.5.1之記載，求出硬塗層與基材薄膜之密著性。 (4) Adhesion On the easily bonding layer of the polyester film obtained in the Example, the hard coat layer described in the item of formation of the above-mentioned hard coat layer was formed. The adhesion between the hard coat layer and the base film was determined according to the description in 8.5.1 of JIS-K5400-1990 about the polyester film for easy bonding to form a hard coat layer.

具體而言，使用間隙間隔2mm的刀具導軌(cutter guide)，對於硬塗層面，加上貫穿硬塗層而到達基材薄膜的100個方格狀切傷。接著，將賽璐玢黏著膠帶(NICHIBAN製，405號；24mm寬)貼附於方格狀之切傷面，以橡皮擦擦過而使其完全附著。然後，垂直地從硬塗積層偏光鏡保護膜之硬塗層面撕下賽璐玢黏著膠帶，目視計數從硬塗積層偏光鏡保護膜的硬塗層面剝落的方格之數，由下式求出硬塗層與基材薄膜之密著性。此外，將方格中部分地剝離者亦計數為剝落的方格。 密著性(%)={1-(剝落的方格之數/100)}×100 Specifically, using a cutter guide with a clearance interval of 2 mm, 100 square-shaped cuts penetrating the hard coating layer and reaching the base film were added to the hard coating surface. Next, a cellophane adhesive tape (made by NICHIBAN, No. 405; 24 mm in width) was attached to the cut surface of the checkered shape, and wiped with an eraser to make it completely attached. Then, vertically peel off the cellophane adhesive tape from the hard coat surface of the hard coat laminated polarizer protective film, and count the number of squares peeled off from the hard coat surface of the hard coat laminated polarizer protective film by the following formula: The adhesion between the hard coat layer and the base film was determined. In addition, the partially peeled off squares are also counted as peeled squares. Adhesion (%)={1-(Number of peeled squares/100)}×100

(5)耐濕熱性(80℃、90%RH放置後之密著性) 將所得之易接著性聚酯薄膜在高溫高濕槽中，於80℃、90%RH之環境下放置24小時，接著在室溫(20℃、65%RH)下放置12小時。然後，以與前述同樣之方法形成硬塗層，求出與基材薄膜的密著性。 (5) Moisture and heat resistance (adhesion after standing at 80°C and 90%RH) The obtained easily adhesive polyester film was placed in a high temperature and high humidity tank in an environment of 80°C and 90% RH for 24 hours, and then at room temperature (20°C, 65% RH) for 12 hours. Then, the hard coat layer was formed in the same manner as described above, and the adhesion to the base film was determined.

(6)數量平均分子量 將0.03g的樹脂溶於10ml的四氫呋喃中，使用GPC-LALLS裝置低角度光散射光度計LS-8000(東曹股份有限公司製，四氫呋喃溶媒，參考：聚苯乙烯)，以管柱溫度30℃、流量1ml/分鐘，使用管柱(昭和電工公司製Shodex KF-802、804、806)，測定數量平均分子量。 (6) Number average molecular weight 0.03 g of resin was dissolved in 10 ml of tetrahydrofuran, and the column temperature was 30° C. using a GPC-LALLS apparatus low-angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene). and a flow rate of 1 ml/min, and the number average molecular weight was measured using a column (Shodex KF-802, 804, and 806 manufactured by Showa Denko Co., Ltd.).

(7)利用紅外光譜法的吸光度測定 對於所得之光學用易接著性聚酯薄膜，於以下之條件下進行FT-IR ATR測定。 裝置：Cary670FTIR(Agilent公司製) 配件：SPECTRA-Tech Foundation Thunder Dome Ge45° 一次反射 檢測器：TGS 解析力：4cm ^-1累計次數：128次 1640cm ^-1的波峰強度係從約1540cm ^-1之谷水平地畫基線，求出從基線起的峰頂之高度(I ₁₆₄₀)。 1410cm ^-1的波峰強度係將連接約1420cm ^-1的谷與約1390cm ^-1的谷之線當作基線，求出從基線起的峰頂之高度(I ₁₄₁₀)。 相對吸收強度比係算出I ₁₆₄₀與I ₁₄₁₀之比(I ₁₆₄₀/I ₁₄₁₀)而求得。 測定係得到在製膜後所立即測定、算出的數據「I ₁₆₄₀/I ₁₄₁₀(X)」，與使用在製膜後於高溫高濕槽中在80℃、90%RH之環境下放置24小時，接著在室溫(20℃、65%RH)下放置12小時的試料所測定、算出的數據「I ₁₆₄₀/I ₁₄₁₀(Y)」，而算出「(Y/X)×100」。 (7) Absorbance measurement by infrared spectroscopy About the obtained easily adhesive polyester film for optics, FT-IR ATR measurement was performed under the following conditions. Device: Cary670FTIR (manufactured by Agilent) Accessories: SPECTRA-Tech Foundation Thunder Dome Ge45° Primary reflection detector: TGS Resolution: 4cm ^-1 Accumulation times: 128 times The peak intensity at 1640cm ^-1 is from the valley level of about 1540cm ^-1 The base line was drawn, and the height of the peak from the base line was obtained (I ₁₆₄₀ ). The peak intensity at 1410 cm ^-1 was used as a base line connecting a valley of about 1420 cm ^-1 and a valley of about 1390 cm ^-1 , and the height of the peak from the base line (I ₁₄₁₀ ) was determined. The relative absorption intensity ratio was obtained by calculating the ratio of I ₁₆₄₀ to I ₁₄₁₀ (I ₁₆₄₀ /I ₁₄₁₀ ). The measurement system obtains the data "I ₁₆₄₀ /I ₁₄₁₀ (X)" that is measured and calculated immediately after film formation, and is placed in a high-temperature and high-humidity tank at 80°C and 90% RH for 24 hours after film formation. , and then calculated the data "I ₁₆₄₀ /I ₁₄₁₀ (Y)" of the sample that was left at room temperature (20°C, 65% RH) for 12 hours, and calculated "(Y/X)×100".

(塗布層用共聚合聚酯樹脂(A)之聚合) 於具備攪拌機、溫度計及部分回流式冷卻器之不銹鋼製高壓釜中，加入342.0質量份的2,6-萘二甲酸二甲酯、35.0質量份的對苯二甲酸二甲酯、35.5質量份的5-鈉磺基間苯二甲酸二甲酯、198.6質量份的乙二醇、118.2質量份的1,6-己二醇及0.4質量份的鈦酸四正丁酯，於160℃至220℃之溫度下費時4小時進行酯交換反應。再者，添加60.7質量份的癸二酸，進行酯化反應。接著，升溫到255℃為止，將反應系統徐徐地減壓後，於30Pa之減壓下反應1小時30分鐘，得到共聚合聚酯樹脂(A)。所得之共聚合聚酯樹脂(A)為淡黃色透明。測定共聚合聚酯樹脂(A)之還原黏度(reduced viscosity)，結果為0.72dl/g。利用DSC的玻璃轉移溫度為40℃，數量平均分子量為20000。 (Polymerization of Copolymerized Polyester Resin (A) for Coating Layer) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux cooler, 342.0 parts by mass of dimethyl 2,6-naphthalate, 35.0 parts by mass of dimethyl terephthalate, and 35.5 parts by mass of Dimethyl 5-sodiumsulfoisophthalate, 198.6 parts by mass of ethylene glycol, 118.2 parts by mass of 1,6-hexanediol, and 0.4 parts by mass of tetra-n-butyl titanate, at 160°C to 220°C The transesterification reaction took 4 hours at the same temperature. Furthermore, 60.7 parts by mass of sebacic acid was added to perform an esterification reaction. Next, the temperature was raised to 255° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (A). The obtained copolymerized polyester resin (A) was light yellow and transparent. The reduced viscosity of the copolymerized polyester resin (A) was measured and found to be 0.72 dl/g. The glass transition temperature by DSC was 40°C, and the number average molecular weight was 20,000.

(塗布層用共聚合聚酯樹脂(B)之聚合) 於具備攪拌機、溫度計及部分回流式冷卻器之不銹鋼製高壓釜中，加入293.0質量份的2,6-萘二甲酸二甲酯、128.0質量份的對苯二甲酸二甲酯、41.6質量份的5-鈉磺基間苯二甲酸二甲酯、125.0質量份的乙二醇、105.0質量份的二乙二醇、142.0質量份的1,6-己二醇及0.4質量份的鈦酸四正丁酯，於160℃至220℃之溫度下費時4小時進行酯交換反應。接著，升溫到255℃為止，將反應系統徐徐地減壓後，於30Pa之減壓下反應1小時30分鐘，得到共聚合聚酯樹脂(B)。所得之共聚合聚酯樹脂(B)為淡黃色透明。測定共聚合聚酯樹脂(B)之還原黏度，結果為0.69dl/g。利用DSC的玻璃轉移溫度為30℃，數量平均分子量為21000。 (Polymerization of Copolymerized Polyester Resin (B) for Coating Layer) In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux cooler, 293.0 parts by mass of dimethyl 2,6-naphthalate, 128.0 parts by mass of dimethyl terephthalate, and 41.6 parts by mass of Dimethyl 5-sodiumsulfoisophthalate, 125.0 parts by mass of ethylene glycol, 105.0 parts by mass of diethylene glycol, 142.0 parts by mass of 1,6-hexanediol, and 0.4 parts by mass of tetra-n-titanate Butyl ester was transesterified at a temperature of 160°C to 220°C for 4 hours. Next, the temperature was raised to 255° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (B). The obtained copolymerized polyester resin (B) was light yellow and transparent. The reduced viscosity of the copolymerized polyester resin (B) was measured and found to be 0.69 dl/g. The glass transition temperature by DSC was 30°C, and the number average molecular weight was 21,000.

(塗布層用共聚合聚酯樹脂(C)之聚合) 於具備攪拌機、溫度計及部分回流式冷卻器之不銹鋼製高壓釜中，加入145.6質量份的對苯二甲酸二甲酯、14.8質量份的5-鈉磺基間苯二甲酸二甲酯、43.3質量份的壬二酸二甲酯、80.7質量份的乙二醇、131.6質量份的9,9-雙[4-(2-羥基乙氧基)苯基]茀、70.9質量份的3-甲基-1,5-戊二醇及0.4質量份的鈦酸四正丁酯，於160℃至220℃之溫度下費時4小時進行酯交換反應。接著，升溫到255℃為止，將反應系統徐徐地減壓後，於30Pa之減壓下反應1小時30分鐘，得到共聚合聚酯樹脂(C)。所得之共聚合聚酯樹脂(C)為淡黃色透明。測定共聚合聚酯樹脂(C)之還原黏度，結果為0.65dl/g。利用DSC的玻璃轉移溫度為40℃，數量平均分子量為19000。 (Polymerization of Copolymerized Polyester Resin (C) for Coating Layer) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux cooler, 145.6 parts by mass of dimethyl terephthalate, 14.8 parts by mass of dimethyl 5-sodiumsulfoisophthalate, and 43.3 parts by mass were added. parts of dimethyl azelaic acid, 80.7 parts by mass of ethylene glycol, 131.6 parts by mass of 9,9-bis[4-(2-hydroxyethoxy)phenyl]pyridine, 70.9 parts by mass of 3-methyl -1,5-pentanediol and 0.4 parts by mass of tetra-n-butyl titanate were subjected to transesterification at a temperature of 160°C to 220°C for 4 hours. Next, the temperature was raised to 255° C., the pressure of the reaction system was gradually reduced, and the reaction was carried out under a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymerized polyester resin (C). The obtained copolymerized polyester resin (C) was pale yellow and transparent. The reduced viscosity of the copolymerized polyester resin (C) was measured and found to be 0.65 dl/g. The glass transition temperature by DSC was 40°C, and the number average molecular weight was 19,000.

(塗布層用共聚合聚酯樹脂(D)之聚合) 除了設為194.2質量份的對苯二甲酸二甲酯、184.5質量份的間苯二甲酸二甲酯、14.8質量份的5-鈉磺基間苯二甲酸二甲酯、233.5質量份的二乙二醇、136.6質量份的乙二醇及0.2質量份的鈦酸四正丁酯以外，與樹脂(A)之聚合同樣地，得到共聚合聚酯樹脂(D)。測定所得之共聚合聚酯樹脂(D)之還原黏度，結果為0.70dl/g。利用DSC的玻璃轉移溫度為40℃。 (Polymerization of Copolymerized Polyester Resin (D) for Coating Layer) Except for 194.2 parts by mass of dimethyl terephthalate, 184.5 parts by mass of dimethyl isophthalate, 14.8 parts by mass of dimethyl 5-sodiumsulfoisophthalate, and 233.5 parts by mass of diethyl Except for the diol, 136.6 parts by mass of ethylene glycol, and 0.2 part by mass of tetra-n-butyl titanate, a copolymerized polyester resin (D) was obtained in the same manner as in the polymerization of the resin (A). The reduced viscosity of the obtained copolymerized polyester resin (D) was measured and found to be 0.70 dl/g. The glass transition temperature by DSC was 40°C.

(聚酯水分散體(Aw)、(Bw)、(Cw)、(Dw)之調製) 於具備攪拌機、溫度計與回流裝置之反應器中，加入30質量份的共聚合聚酯樹脂(A)、15質量份的乙二醇正丁基醚，在110℃下加熱、攪拌而溶解樹脂。於樹脂完全溶解後，將55質量份的水一邊攪拌一邊徐徐地添加至聚酯溶液。添加後，一邊攪拌一邊冷卻到室溫為止，製作固體成分25.0質量%的乳白色聚酯樹脂(A)水分散體(樹脂A溶液)(Aw)。 (Preparation of polyester aqueous dispersion (Aw), (Bw), (Cw), (Dw)) In a reactor equipped with a stirrer, a thermometer and a reflux device, 30 parts by mass of the copolymerized polyester resin (A) and 15 parts by mass of ethylene glycol n-butyl ether were added, and the resin was dissolved by heating and stirring at 110°C. After the resin was completely dissolved, 55 parts by mass of water was gradually added to the polyester solution while stirring. After addition, it cooled to room temperature while stirring, and produced the milky white polyester resin (A) aqueous dispersion (resin A solution) (Aw) with a solid content of 25.0 mass %.

以同樣之方法，製作共聚合聚酯樹脂(B)而成的聚酯樹脂(B)水分散體(樹脂B溶液)(Bw)。In the same manner, a polyester resin (B) aqueous dispersion (resin B solution) (Bw) obtained by copolymerizing the polyester resin (B) was produced.

以同樣之方法，製作溶解共聚合聚酯樹脂(C)而成的聚酯樹脂(C)水分散體(樹脂C溶液)(Cw)。In the same manner, a polyester resin (C) aqueous dispersion (resin C solution) (Cw) obtained by dissolving the copolymerized polyester resin (C) was prepared.

以同樣之方法，製作溶解共聚合聚酯樹脂(D)而成的聚酯樹脂(D)水分散體(樹脂D溶液)(Dw)。In the same manner, a polyester resin (D) aqueous dispersion (resin D solution) (Dw) obtained by dissolving the copolymerized polyester resin (D) was prepared.

(聚胺基甲酸酯水分散體(E)之製造) [以脂肪族系聚碳酸酯多元醇作為構成成分的水分散聚胺基甲酸酯樹脂之聚合] 於具備攪拌機、戴氏冷凝器、氮氣導入管、矽凝膠乾燥管及溫度計之四口燒瓶中，投入43.75質量份的4,4’-二苯基甲烷二異氰酸酯、12.85質量份的二羥甲基丁酸、153.41質量份的數量平均分子量2000之聚六亞甲基碳酸酯二醇、0.03質量份的二月桂酸二丁錫及84.00質量份作為溶劑的丙酮，於氮氣環境下，在75℃下攪拌3小時，確認反應液到達指定的胺當量。接著，將此反應液降溫到40℃為止後，添加8.77質量份的三乙胺，得到聚胺基甲酸酯預聚物溶液。接著，於具備能高速攪拌的均質分散機之反應容器中，添加450g的水，調整至25℃，一邊以2000min ^-1攪拌混合，一邊添加聚胺基甲酸酯預聚物溶液，進行水分散。然後，於減壓下，藉由去除丙酮及水的一部分，而調製固體成分37質量%的水溶性聚胺基甲酸酯樹脂溶液(樹脂E溶液)。所得之聚胺基甲酸酯樹脂的玻璃轉移溫度為-30℃。 (Manufacture of Aqueous Polyurethane Dispersion (E)) [Polymerization of Water-dispersed Polyurethane Resin Containing Aliphatic Polycarbonate Polyol as a Component] , nitrogen introduction tube, silicone gel drying tube and thermometer four-necked flask, put 43.75 parts by mass of 4,4'-diphenylmethane diisocyanate, 12.85 parts by mass of dimethylol butyric acid, 153.41 parts by mass of Polyhexamethylene carbonate diol having a number average molecular weight of 2,000, 0.03 parts by mass of dibutyltin dilaurate, and 84.00 parts by mass of acetone as a solvent were stirred at 75° C. for 3 hours under a nitrogen atmosphere, and the reaction solution was confirmed. to the specified amine equivalent weight. Next, after cooling this reaction liquid to 40 degreeC, 8.77 mass parts of triethylamines were added, and the polyurethane prepolymer solution was obtained. Next, 450 g of water was added to a reaction vessel equipped with a homodisperser capable of high-speed stirring, and the temperature was adjusted to 25° C. While stirring and mixing at 2000 min ⁻¹ , the polyurethane prepolymer solution was added to conduct water dispersion. . Then, by removing a part of acetone and water under reduced pressure, a water-soluble polyurethane resin solution (resin E solution) having a solid content of 37% by mass was prepared. The glass transition temperature of the obtained polyurethane resin was -30°C.

(交聯劑P之合成) 於具備攪拌機、溫度計、回流冷卻管之燒瓶中，在100質量份的藉由既有的方法由1,6-六亞甲基二異氰酸酯所製作之具有三聚異氰酸酯結構的聚異氰酸酯化合物(NCO濃度23.1%)、17.5質量份的N-甲基吡咯啶酮中，滴下35.00質量份的3,5-二甲基吡唑，於氮氣環境下，在70℃下保持1小時。然後，滴下12.50質量份的二羥甲基丙酸。測定反應液的紅外光譜，確認異氰酸酯基之吸收消失後，添加8.72質量份的N,N-二甲基乙醇胺。就那樣攪拌1小時後，適量添加水，得到固體成分40質量%的封端異氰酸酯系水分散液(交聯劑P溶液)。 (Synthesis of Crosslinker P) In a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, in 100 parts by mass of a polyisocyanate compound (NCO concentration) prepared from 1,6-hexamethylene diisocyanate by an existing method 23.1%) and 17.5 parts by mass of N-methylpyrrolidone, 35.00 parts by mass of 3,5-dimethylpyrazole was dropped, and kept at 70° C. for 1 hour under a nitrogen atmosphere. Then, 12.50 parts by mass of dimethylolpropionic acid was dropped. The infrared spectrum of the reaction liquid was measured, and after confirming that the absorption of the isocyanate group disappeared, 8.72 parts by mass of N,N-dimethylethanolamine was added. After stirring for 1 hour, an appropriate amount of water was added to obtain a blocked isocyanate-based aqueous dispersion (crosslinking agent P solution) with a solid content of 40% by mass.

(交聯劑Q之合成) 於具備攪拌機、溫度計、回流冷卻管之燒瓶中，在100質量份的藉由既有的方法由環己烷二異氰酸酯所作成之具有三聚異氰酸酯結構的聚異氰酸酯化合物(NCO濃度23.3%)、17.5質量份的N-甲基吡咯啶酮中，滴下35.00質量份的3,5-二甲基吡唑，於氮氣環境下，在70℃下保持1小時。 然後，滴下12.50質量份的二羥甲基丙酸。測定反應液的紅外光譜，確認異氰酸酯基之吸收消失後，添加8.72質量份的N,N-二甲基乙醇胺。就那樣攪拌1小時後，適量添加水，得到固體成分40質量%的封端異氰酸酯系水分散液(交聯劑Q溶液)。 (Synthesis of Crosslinker Q) In a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, in 100 parts by mass of a polyisocyanate compound (NCO concentration: 23.3%) having a trimeric isocyanate structure made from cyclohexane diisocyanate by an existing method, 17.5 To the mass part of N-methylpyrrolidone, 35.00 mass parts of 3,5-dimethylpyrazoles were dripped, and it was hold|maintained at 70 degreeC for 1 hour under nitrogen atmosphere. Then, 12.50 parts by mass of dimethylolpropionic acid was dropped. The infrared spectrum of the reaction liquid was measured, and after confirming that the absorption of the isocyanate group disappeared, 8.72 parts by mass of N,N-dimethylethanolamine was added. After stirring for 1 hour, an appropriate amount of water was added to obtain a blocked isocyanate-based aqueous dispersion (crosslinking agent Q solution) with a solid content of 40% by mass.

(交聯劑R之合成) 於具備攪拌機、溫度計、回流冷卻管之燒瓶中，在100質量份的藉由既有的方法由2,5-二異氰酸基噻吩所作成之具有三聚異氰酸酯結構的聚異氰酸酯化合物(NCO濃度23.1%)、17.5質量份的N-甲基吡咯啶酮中，滴下35.00質量份的3,5-二甲基吡唑，於氮氣環境下，在70℃下保持1小時。 然後，滴下12.50質量份的二羥甲基丙酸。測定反應液的紅外光譜，確認異氰酸酯基之吸收消失後，添加8.72質量份的N,N-二甲基乙醇胺。就那樣攪拌1小時後，適量添加水，得到固體成分40質量%的封端異氰酸酯系水分散液(交聯劑R溶液)。 (Synthesis of crosslinking agent R) In a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, in 100 parts by mass of a polyisocyanate compound (NCO concentration) prepared from 2,5-diisocyanatothiophene by an existing method 23.1%) and 17.5 parts by mass of N-methylpyrrolidone, 35.00 parts by mass of 3,5-dimethylpyrazole was dropped, and kept at 70° C. for 1 hour under a nitrogen atmosphere. Then, 12.50 parts by mass of dimethylolpropionic acid was dropped. The infrared spectrum of the reaction liquid was measured, and after confirming that the absorption of the isocyanate group disappeared, 8.72 parts by mass of N,N-dimethylethanolamine was added. After stirring for 1 hour, an appropriate amount of water was added to obtain a blocked isocyanate-based aqueous dispersion (crosslinking agent R solution) with a solid content of 40% by mass.

(交聯劑S之合成) 於具備攪拌機、溫度計、回流冷卻管之燒瓶中，加入168質量份的六亞甲基二異氰酸酯與220質量份的聚乙二醇單甲基醚(平均分子量400)，在120℃下攪拌1小時，更添加26質量份的4,4’-二環己基甲烷二異氰酸酯與3.8質量份(相對於全部異氰酸酯而言2質量%)作為碳二亞胺化觸媒的3-甲基-1-苯基-2-磷雜環戊烯(phospholene)-1-氧化物，於氮氣流下在185℃更攪拌5小時。測定反應液之紅外光譜，確認異氰酸酯基之吸收消失。放置冷卻到60℃為止，添加567質量份的離子交換水，得到固體成分40質量%的碳二亞胺系交聯劑(交聯劑S溶液)。 (Synthesis of Crosslinking Agent S) In a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, 168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 400) were added, and the mixture was stirred at 120° C. for 1 hour. , and 26 parts by mass of 4,4'-dicyclohexylmethane diisocyanate and 3.8 parts by mass (2 mass % relative to all isocyanates) of 3-methyl-1-benzene as a carbodiimide catalyst were added yl-2-phospholene-1-oxide and stirred for 5 hours at 185°C under nitrogen flow. The infrared spectrum of the reaction solution was measured, and it was confirmed that the absorption of the isocyanate group disappeared. It was left to cool to 60° C., and 567 parts by mass of ion-exchanged water was added to obtain a carbodiimide-based crosslinking agent (crosslinking agent S solution) with a solid content of 40% by mass.

(交聯劑T之合成) 於具備攪拌機、溫度計、回流冷卻管之燒瓶中，在100質量份的藉由既有的方法由2,4-甲苯二異氰酸酯所作成之具有三聚異氰酸酯結構的聚異氰酸酯化合物(NCO濃度22.3%)、17.5質量份的N-甲基吡咯啶酮中，滴下35.00質量份的3,5-二甲基吡唑，於氮氣環境下，在70℃下保持1小時。 然後，滴下12.50質量份的二羥甲基丙酸。測定反應液的紅外光譜，確認異氰酸酯基之吸收消失後，添加8.72質量份的N,N-二甲基乙醇胺。就那樣攪拌1小時後，適量添加水，得到固體成分40質量%的封端異氰酸酯系水分散液(交聯劑T溶液)。 (Synthesis of Crosslinking Agent T) In a flask equipped with a stirrer, a thermometer, and a reflux cooling tube, 100 parts by mass of a polyisocyanate compound having a trimeric isocyanate structure (NCO concentration: 22.3%) was prepared from 2,4-toluene diisocyanate by an existing method. and 17.5 parts by mass of N-methylpyrrolidone, 35.00 parts by mass of 3,5-dimethylpyrazole was dropped, and kept at 70° C. for 1 hour under a nitrogen atmosphere. Then, 12.50 parts by mass of dimethylolpropionic acid was dropped. The infrared spectrum of the reaction liquid was measured, and after confirming that the absorption of the isocyanate group disappeared, 8.72 parts by mass of N,N-dimethylethanolamine was added. After stirring for 1 hour, an appropriate amount of water was added to obtain a blocked isocyanate-based aqueous dispersion (crosslinking agent T solution) with a solid content of 40% by mass.

(氧化鋯粒子) 於3公升的玻璃製容器中，投入2283.6g的純水與403.4g的草酸二水合物，加熱到40℃，調製10.72質量%草酸水溶液。一邊攪拌此水溶液，一邊徐徐地添加495.8g的碳酸氧鋯粉末(ZrOCO ₃，AMR International Corp.製，換算成ZrO ₂，含有39.76質量%)，混合30分鐘後，在90℃下進行30分鐘的加熱。接著，費時1小時徐徐地添加1747.2g的25.0質量%氫氧化四甲銨水溶液(多摩化學工業(股)製)。於此時間點，混合液為漿體狀，以ZrO ₂換算含有4.0質量%。將此漿體移到不銹鋼製高壓釜容器，在145℃下進行5小時的水熱處理。此水熱處理後之生成物係沒有未解膠物而完全地溶膠化。所得之溶膠就ZrO ₂而言含有4.0質量%，pH6.8，利用動態光散射法的平均粒徑為19nm。又，以純水將溶膠調整至ZrO ₂濃度2.0質量%，所測定的穿透率為88%。藉由穿透型電子顯微鏡觀察粒子，結果幾乎都是7nm左右的ZrO ₂一次粒子之凝聚粒子。將上述進行水熱處理而得之ZrO ₂濃度4.0質量%的氧化鋯溶膠4000g，使用超濾裝置，一邊徐徐地添加純水一邊進行洗淨及濃縮，得到ZrO ₂濃度13.1質量%、pH4.9、ZrO ₂濃度13.1質量%時之穿透率76%的氧化鋯溶膠953g。所得之氧化鋯系微粒子的折射率為1.75。 (Zirconium oxide particles) 2283.6 g of pure water and 403.4 g of oxalic acid dihydrate were put into a 3-liter glass container, and heated to 40° C. to prepare a 10.72 mass % oxalic acid aqueous solution. While stirring this aqueous solution, 495.8 g of zirconium oxycarbonate powder (ZrOCO ₃ , manufactured by AMR International Corp., converted to ZrO ₂ , containing 39.76 mass %) was gradually added, and after mixing for 30 minutes, the mixture was mixed at 90° C. for 30 minutes. heating. Next, 1747.2 g of a 25.0 mass % aqueous tetramethylammonium hydroxide solution (manufactured by Tama Chemical Industry Co., Ltd.) was gradually added over 1 hour. At this point in time, the mixed solution was in a slurry state and contained 4.0 mass % in terms of ZrO ₂ . This slurry was transferred to a stainless steel autoclave vessel, and hydrothermally treated at 145° C. for 5 hours. The product after this hydrothermal treatment is completely sol-free without unsolved matter. The obtained sol contained 4.0 mass % of ZrO ₂ , had a pH of 6.8, and had an average particle diameter of 19 nm by the dynamic light scattering method. In addition, the sol was adjusted to a ZrO ₂ concentration of 2.0 mass % with pure water, and the measured transmittance was 88%. Observation of the particles with a transmission electron microscope revealed that most of the particles were aggregated particles of ZrO ₂ primary particles of about 7 nm. 4000 g of zirconia sol with a ZrO ₂ concentration of 4.0 mass % obtained by the above-mentioned hydrothermal treatment was washed and concentrated while gradually adding pure water using an ultrafiltration apparatus to obtain a ZrO ₂ concentration of 13.1 mass %, pH 4.9, 953 g of zirconia sol with a penetration rate of 76% at a ZrO ₂ concentration of 13.1 mass %. The refractive index of the obtained zirconia-based fine particles was 1.75.

(氧化鋯溶膠) 於上述進行洗淨及濃縮而得之ZrO ₂濃度13.1質量%的氧化鋯溶膠300g中，添加3.93g的20質量%檸檬酸水溶液及11.0g的25質量%氫氧化四甲銨水溶液後，更以超濾裝置進行濃縮，結果得到ZrO ₂濃度30.5質量%之高濃度的氧化鋯溶膠129g。此所得之高濃度的氧化鋯溶膠為pH9.3，利用動態光散射法的平均粒徑為19nm。又，此氧化鋯溶膠係無沉降物，在50℃之條件下1個月以上為安定。 (Zirconium oxide sol) To 300 g of zirconia sol having a ZrO ₂ concentration of 13.1 mass % obtained by washing and concentrating above, 3.93 g of a 20 mass % citric acid aqueous solution and 11.0 g of a 25 mass % tetramethylammonium hydroxide were added After the aqueous solution, it was further concentrated by an ultrafiltration apparatus, and as a result, 129 g of a high-concentration zirconia sol with a ZrO ₂ concentration of 30.5 mass % was obtained. The obtained high-concentration zirconia sol had a pH of 9.3 and an average particle diameter of 19 nm by the dynamic light scattering method. In addition, this zirconia sol system has no sediment and is stable under the condition of 50°C for more than one month.

(氧化鈦粒子) 混合12.09kg的以TiO ₂換算基準包含7.75質量%的四氯化鈦(OSAKA Titanium technologies(股)製)之四氯化鈦水溶液與4.69kg的包含15質量%的氨之氨水(宇部興產(股)製)，調製pH9.5之白色漿體液。接著，過濾此漿體後，以純水洗淨，得到固體成分含量為10質量%之含水鈦酸濾餅9.87kg。接著，對此濾餅加入11.28kg的包含35質量%過氧化氫的雙氧水(三菱瓦斯化學(股)製)與20.00kg的純水後，在80℃之溫度，於攪拌下加熱1小時，更添加57.52kg的純水，得到98.67kg的以TiO ₂換算基準包含1質量%的過氧化鈦酸之過氧化鈦酸水溶液。此過氧化鈦酸水溶液為透明的黃褐色，pH為8.5。 (Titanium oxide particles) 12.09 kg of titanium tetrachloride aqueous solution containing 7.75 mass % of titanium tetrachloride (manufactured by OSAKA Titanium technologies Co., Ltd.) on a TiO ₂ conversion basis and 4.69 kg of ammonia water containing 15 mass % of ammonia were mixed (manufactured by Ube Industries, Ltd.), and prepared a white slurry with pH 9.5. Next, after filtering the slurry, it was washed with pure water to obtain 9.87 kg of a hydrated titanic acid cake having a solid content of 10% by mass. Next, 11.28 kg of hydrogen peroxide containing 35% by mass of hydrogen peroxide (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 20.00 kg of pure water were added to this filter cake, and then heated at a temperature of 80° C. for 1 hour with stirring, and further 57.52 kg of pure water was added to obtain 98.67 kg of an aqueous titanic acid peroxide solution containing 1 mass % of titanic acid peroxide based on TiO ₂ conversion. The aqueous titanic acid peroxide solution was transparent yellowish brown and had a pH of 8.5.

接著，於98.67kg的前述過氧化鈦酸水溶液中，混合4.70kg的陽離子交換樹脂(三菱化學(股)製)，於其中在攪拌下徐徐地添加12.33kg的以SnO ₂換算基準包含1質量%的錫酸鉀(昭和化工(股)製)之錫酸鉀水溶液。接著，分離已吸入鉀離子等的陽離子交換樹脂後，置入高壓釜(Taiatsu Techno(股)製，120L)中，在165℃之溫度下加熱18小時。 Next, 4.70 kg of cation exchange resin (manufactured by Mitsubishi Chemical Co., Ltd.) was mixed with 98.67 kg of the aforementioned titanic acid peroxide solution, and 12.33 kg of 1 mass % based on SnO ₂ conversion was gradually added thereto under stirring. Aqueous potassium stannate solution of potassium stannate (manufactured by Showa Chemical Co., Ltd.). Next, after separating the cation exchange resin into which potassium ions and the like have been absorbed, it was placed in an autoclave (manufactured by Taiatsu Techno Co., Ltd., 120 L), and heated at a temperature of 165° C. for 18 hours.

(氧化鈦溶膠) 接著，將所得之混合水溶液冷卻到室溫後，以超濾裝置(旭化成(股)製，ACV-3010)進行濃縮，得到固體成分含量為10質量%之包含鈦系微粒子(以下，稱為「P-1」)的水分散溶膠9.90kg。以上述方法測定如此所得之溶膠中所含的固體物，結果為由具有金紅石型結晶結構之包含鈦及錫的複合氧化物所構成之鈦系微粒子(一次粒子)。再者，測定此鈦系微粒子中所含的金屬成分之含量，結果以各金屬成分之氧化物換算基準，為TiO ₂87.2質量%、SnO ₂11.0質量%及K ₂O 1.8質量%。又，該混合水溶液之pH為10.0。再者，前述包含鈦系微粒子的水分散溶膠為透明的乳白色，此水分散溶膠中所含的前述鈦系微粒子的平均粒徑為35nm，再者具有100nm以上的粒徑之粗大粒子的分布頻率為0%。再者，所得之鈦系微粒子的折射率為2.42。 (Titanium oxide sol) Next, the obtained mixed aqueous solution was cooled to room temperature, and then concentrated with an ultrafiltration apparatus (manufactured by Asahi Kasei Co., Ltd., ACV-3010) to obtain titanium-based fine particles ( Hereinafter, referred to as "P-1"), 9.90 kg of the water-dispersed sol. The solid matter contained in the sol thus obtained was measured by the above-mentioned method, and the result was titanium-based fine particles (primary particles) composed of a composite oxide containing titanium and tin having a rutile-type crystal structure. Furthermore, when the content of the metal component contained in the titanium-based fine particles was measured, it was 87.2 mass % of TiO ₂ , 11.0 mass % of SnO ₂ , and 1.8 mass % of K ₂ O based on the oxide conversion of each metal component. In addition, the pH of this mixed aqueous solution was 10.0. Furthermore, the water-dispersed sol containing the titanium-based fine particles was transparent and milky white, the titanium-based fine particles contained in the water-dispersed sol had an average particle diameter of 35 nm, and the distribution frequency of the coarse particles having a particle diameter of 100 nm or more. is 0%. Furthermore, the refractive index of the obtained titanium-based fine particles was 2.42.

(氧化鋯/氧化鈦混合溶膠) 將上述所得之氧化鋯粒子與氧化鈦粒子以各自之比率混合，而製作固體成分濃度13質量%的氧化鋯/氧化鈦混合溶膠。 (Zirconium oxide/Titanium oxide mixed sol) The zirconia particles and the titania particles obtained above were mixed at respective ratios to prepare a zirconia/titania mixed sol having a solid content concentration of 13% by mass.

(硬塗層之形成) 於後述實施例所製造的聚酯薄膜之與偏光鏡接著面的相反側之面上，使用＃14線棒塗布下述組成之硬塗層形成用塗布液，在70℃下乾燥1分鐘，去除溶劑。接著，對於塗布有硬塗層的薄膜，使用高壓水銀燈照射300mJ/cm ²的紫外線，得到具有厚度7μm的硬塗層之偏光鏡保護膜。 (Formation of hard coat layer) On the opposite side of the polyester film produced in the examples described later and the polarizer bonding surface, the coating liquid for forming a hard coat layer of the following composition was applied using a #14 wire bar, and the temperature was 70 It was dried at °C for 1 minute and the solvent was removed. Next, the film coated with the hard coat layer was irradiated with ultraviolet rays of 300 mJ/cm ² using a high-pressure mercury lamp to obtain a polarizer protective film having a hard coat layer with a thickness of 7 μm.

硬塗形成用的塗布液係如以下地調製。The coating liquid system for hard coat formation was prepared as follows.

(硬塗層形成用塗布液L之調製) 甲基乙基酮                        64.40質量% 二新戊四醇六丙烯酸酯        27.20質量% (新中村化學製A-DPH) 聚乙二醇二丙烯酸酯             3.40質量% (共榮社化學製Light Acrylate 9EG-A) 雙酚A二丙烯酸酯               4.00質量% (共榮社化學製Light Acrylate BP-4PA) 光聚合起始劑                      1.00質量% (Ciba Specialty Chemicals公司製Irgacure 184) 所調製的硬塗層形成用塗布液L中之全部樹脂中的芳香族成分係以莫耳比計為13.3%。 (Preparation of coating liquid L for hard coat layer formation) Methyl ethyl ketone 64.40% by mass Dipivalerythritol hexaacrylate 27.20% by mass (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) Polyethylene glycol diacrylate 3.40% by mass (Light Acrylate 9EG-A, manufactured by Kyōeisha Chemical Co., Ltd.) Bisphenol A diacrylate 4.00% by mass (Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.) Photopolymerization initiator 1.00% by mass (Irgacure 184 by Ciba Specialty Chemicals) The aromatic component in the whole resin in the prepared coating liquid L for hard-coat layer formation was 13.3 % in molar ratio.

(硬塗層形成用塗布液M之調製) 甲基乙基酮                      64.90質量% 二新戊四醇六丙烯酸酯       27.20質量% (新中村化學製A-DPH) 聚乙二醇二丙烯酸酯           5.30質量% (共榮社化學製Light Acrylate 9EG-A) 雙酚A二丙烯酸酯              1.60質量% (共榮社化學製Light Acrylate BP-4PA) 光聚合起始劑                     1.00質量% (Ciba Specialty Chemicals公司製Irgacure 184) 所調製的硬塗層形成用塗布液M中之全部樹脂中的芳香族成分係以莫耳比計為5.4%。 (Preparation of Coating Liquid M for Hard Coat Layer Formation) Methyl ethyl ketone 64.90% by mass Dipivalerythritol hexaacrylate 27.20% by mass (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) Polyethylene glycol diacrylate 5.30% by mass (Light Acrylate 9EG-A, manufactured by Kyōeisha Chemical Co., Ltd.) Bisphenol A diacrylate 1.60% by mass (Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.) Photopolymerization initiator 1.00% by mass (Irgacure 184 by Ciba Specialty Chemicals) The aromatic component in all resins in the prepared coating liquid M for forming a hard coat layer was 5.4% in molar ratio.

(硬塗層形成用塗布液N之調製) 甲基乙基酮                      64.10質量% 二新戊四醇六丙烯酸酯       27.20質量% (新中村化學製A-DPH) 聚乙二醇二丙烯酸酯           1.90質量% (共榮社化學製Light Acrylate 9EG-A) 雙酚A二丙烯酸酯              5.80質量% (共榮社化學製Light Acrylate BP-4PA) 光聚合起始劑                     1.00質量% (Ciba Specialty Chemicals公司製Irgacure 184) 所調製的硬塗層形成用塗布液N中之全部樹脂中的芳香族成分係以莫耳比計為19.3%。 (Preparation of Coating Liquid N for Hard Coat Layer Formation) Methyl ethyl ketone 64.10% by mass Dipivalerythritol hexaacrylate 27.20% by mass (A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.) Polyethylene glycol diacrylate 1.90% by mass (Light Acrylate 9EG-A, manufactured by Kyōeisha Chemical Co., Ltd.) Bisphenol A diacrylate 5.80% by mass (Light Acrylate BP-4PA manufactured by Kyoeisha Chemical Co., Ltd.) Photopolymerization initiator 1.00% by mass (Irgacure 184 by Ciba Specialty Chemicals) The aromatic component in the whole resin in the prepared coating liquid N for hard-coat layer formation was 19.3 % in molar ratio.

(實施例1) (塗布液之調製) 調製下述組成之塗布液。 水                                  36.47質量份 異丙醇                            37.42質量份 矽溶膠                              1.21質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     20.06質量份 (固體成分濃度25質量%) 交聯劑P溶液                    3.14質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 1) (Preparation of coating liquid) The coating liquid of the following composition was prepared. Water 36.47 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

(易接著性聚酯薄膜之製造) 作為薄膜原料聚合物，將固有黏度(溶媒：苯酚/四氯乙烷=60/40)為0.62dl/g且實質上不含粒子的PET樹脂丸粒，於133Pa之減壓下，在135℃下乾燥6小時。然後，供給至擠壓機，在約280℃下熔融擠出成片狀，於保持在表面溫度20℃的旋轉冷卻金屬輥上使其急速冷卻密著固化，得到未延伸PET薄片。 (Manufacture of Easy Adhesive Polyester Film) As the film raw material polymer, PET resin pellets with an intrinsic viscosity (solvent: phenol/tetrachloroethane=60/40) of 0.62 dl/g and substantially no particles were used under a reduced pressure of 133 Pa at 135°C. dry for 6 hours. Then, it was supplied to an extruder, melt-extruded into a sheet form at about 280°C, and rapidly cooled on a rotating cooling metal roll maintained at a surface temperature of 20°C, adhered and solidified to obtain an unstretched PET sheet.

以加熱的輥群及紅外線加熱器將此未延伸PET薄片加熱到100℃，然後以具有圓周速度差的輥群，在長度方向上延伸3.5倍，得到單軸延伸PET薄膜。The unstretched PET sheet was heated to 100° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a peripheral speed difference to obtain a uniaxially stretched PET film.

接著，以輥塗法，將上述塗布液塗布於PET薄膜之單面後，在80℃下乾燥，並以最終延伸後的乾燥後塗布量成為0.12g/m ²之方式調整。隨後，以拉幅機在150℃下於寬度方向上延伸至4.0倍，以固定薄膜的寬度方向之長度的狀態，在230℃下加熱，更在230℃下進行寬度方向的鬆弛處理，得到厚度38μm之易接著性聚酯薄膜。 Next, the above-mentioned coating liquid was applied to one side of a PET film by a roll coating method, dried at 80° C., and adjusted so that the coating amount after drying after final stretching was 0.12 g/m ² . Subsequently, the film was stretched 4.0 times in the width direction at 150°C with a tenter, heated at 230°C with the length of the film in the width direction fixed, and further relaxed in the width direction at 230°C to obtain a thickness of the film. 38μm easy-adhesive polyester film.

對所得之易接著性聚酯薄膜的易接著層上，以紅外光譜法測定吸光度，算出以歸屬於脲化合物的1640cm ^-1為波峰的吸收強度(I ₁₆₄₀)與以歸屬於聚酯樹脂的1410cm ^-1為波峰的吸收強度(I ₁₄₁₀)之相對吸收強度比「(I ₁₆₄₀/I ₁₄₁₀)(X)」，結果為1.375。 On the easy-bond layer of the easily-bonded polyester film obtained, the absorbance was measured by infrared spectroscopy, and the absorption intensity (I ₁₆₄₀ ) at 1640 cm ⁻¹ attributable to the urea compound as the peak and at 1410 cm attributable to the polyester resin were calculated. ^-1 is the relative absorption intensity ratio "(I ₁₆₄₀ /I ₁₄₁₀ )(X)" of the absorption intensity (I ₁₄₁₀ ) of the peak, and the result is 1.375.

接著，使用前述硬塗層形成用塗布液A，得到依照前述形成方法於所得之易接著性聚酯薄膜的易接著層上形成有硬塗層之積層聚酯薄膜。Next, using the said coating liquid A for hard-coat layer formation, the laminated polyester film which formed the hard-coat layer on the easy-bond layer of the obtained easily-bond polyester film in accordance with the said formation method was obtained.

評價所得之積層聚酯薄膜的硬塗層之密著性，結果密著力為100%。The adhesiveness of the hard coat layer of the obtained laminated polyester film was evaluated, and as a result, the adhesive strength was 100%.

再者，將所得之易接著性聚酯薄膜在高溫高濕槽中於80℃、90RH%之環境下放置24小時，接著在室溫下放置12小時。然後，對處理後的易接著性聚酯薄膜之易接著層上，以紅外光譜法測定吸光度，算出相對吸收強度比「(I ₁₆₄₀/I ₁₄₁₀)(Y)」，結果為1.750。 Furthermore, the easily adhesive polyester film obtained was left to stand in an environment of 80° C. and 90 RH% for 24 hours in a high-temperature and high-humidity tank, and then left to stand at room temperature for 12 hours. Then, the absorbance was measured by infrared spectroscopy on the easily adhesive layer of the easily adhesive polyester film after the treatment, and the relative absorption intensity ratio "(I ₁₆₄₀ /I ₁₄₁₀ )(Y)" was calculated and found to be 1.750.

由此結果，算出(Y/X)×100時，成為127。From this result, when (Y/X)×100 is calculated, it becomes 127.

接著，於處理後的易接著性聚酯薄膜整易接著層上，使用硬塗層形成用塗布液L，形成硬塗層，得到積層聚酯薄膜。Next, on the easily-adhesive layer of the easily-adhesive polyester film after the treatment, a hard-coat layer was formed using the coating liquid L for hard-coat layer formation, and a laminated polyester film was obtained.

評價所得之積層聚酯薄膜的硬塗層之密著性，結果密著力為100%。又，評價將易接著性聚酯薄膜在80℃、90%RH環境放置後的密著性(耐濕熱性)，結果為100%。The adhesiveness of the hard coat layer of the obtained laminated polyester film was evaluated, and as a result, the adhesive strength was 100%. Moreover, the adhesiveness (moisture-heat resistance) after leaving the easily adhesive polyester film to stand in 80 degreeC and 90%RH environment was evaluated, and it was 100%.

(實施例2) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.00質量份 異丙醇                            37.42質量份 矽溶膠                              1.21質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     21.32質量份 (固體成分濃度25質量%) 交聯劑P溶液                    2.35質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 2) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.00 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 21.32 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 2.35 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例3) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.94質量份 異丙醇                            37.42質量份 矽溶膠                              1.21質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     18.81質量份 (固體成分濃度25質量%) 交聯劑P溶液                    3.92質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 3) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.94 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 18.81 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 3.92 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例4) 除了使用交聯劑Q溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Example 4) Except having used the crosslinking agent Q solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例5) 除了使用交聯劑R溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Example 5) Except having used the crosslinking agent R solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例6) 除了使用交聯劑S溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Example 6) Except having used the crosslinking agent S solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例7) 除了使用樹脂B溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Example 7) Except having used the resin B solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例8) 除了使用樹脂C溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Example 8) Except having used the resin C solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例9) 除了調製下述組成之塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.47質量份 異丙醇                            37.42質量份 氧化鋯溶膠                       1.21質量份 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     20.06質量份 (固體成分濃度25質量%) 交聯劑P溶液                    3.14質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 9) Except having prepared the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.47 parts by mass Isopropyl alcohol 37.42 parts by mass Zirconia sol 1.21 parts by mass Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例10) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.47質量份 異丙醇                            37.42質量份 氧化鈦溶膠                       1.21質量份 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     20.06質量份 (固體成分濃度25質量%) 交聯劑P溶液                    3.14質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 10) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.47 parts by mass Isopropyl alcohol 37.42 parts by mass Titanium oxide sol 1.21 parts by mass Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例11) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.47質量份 異丙醇                            37.42質量份 氧化鋯/氧化鈦混合溶膠      1.21質量份 (相對於氧化鋯/氧化鈦合計質量而言氧化鋯質量75質量%，固體成分濃度13質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     20.06質量份 (固體成分濃度25質量%) 交聯劑P溶液                    3.14質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Example 11) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.47 parts by mass Isopropyl alcohol 37.42 parts by mass Zirconia/titania mixed sol 1.21 parts by mass (Zirconium oxide mass 75 mass %, solid content concentration 13 mass % relative to the total mass of zirconium oxide/titanium oxide) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 20.06 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 3.14 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(實施例12～13) 除了將塗布於所得之易接著性聚酯薄膜上的硬塗液之種類如表1中記載地變更以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Examples 12 to 13) An easily adhesive polyester film was obtained in the same manner as in Example 1, except that the type of the hard coating liquid to be applied on the obtained easily adhesive polyester film was changed as described in Table 1. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(比較例1) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  35.53質量份 異丙醇                            37.42質量份 矽溶膠                              1.21質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     22.57質量份 (固體成分濃度25質量%) 交聯劑P溶液                    1.57質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Comparative Example 1) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 35.53 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 22.57 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 1.57 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(比較例2) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  38.63質量份 異丙醇                            37.42質量份 矽溶膠                              1.21質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.11質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     14.30質量份 (固體成分濃度25質量%) 交聯劑P溶液                    6.74質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Comparative Example 2) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 38.63 parts by mass Isopropyl alcohol 37.42 parts by mass Silica sol 1.21 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.11 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 14.30 parts by mass (solid content concentration 25% by mass) Cross-linking agent P solution 6.74 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(比較例3) 除了使用樹脂D溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Comparative Example 3) An easily adhesive polyester film was obtained in the same manner as in Example 1, except that the coating liquid was prepared using the resin D solution. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(比較例4) 除了調製下述組成的塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。 水                                  36.80質量份 異丙醇                            37.29質量份 矽溶膠                              1.33質量份 (平均粒徑40nm的矽溶膠，固體成分濃度40質量%) 矽溶膠                              1.23質量份 (平均粒徑450nm的矽溶膠，固體成分濃度40質量%) 樹脂A溶液                     13.31質量份 (固體成分濃度25質量%) 樹脂E溶液                       5.99質量份 (固體成分濃度37質量%) 交聯劑P溶液                    3.47質量份 (固體成分濃度40質量%) 界面活性劑                       0.25質量份 (氟系，固體成分濃度10質量%) 高沸點溶媒                       0.34質量份 (Comparative Example 4) Except preparing the coating liquid of the following composition, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. Water 36.80 parts by mass Isopropyl alcohol 37.29 parts by mass Silica sol 1.33 parts by mass (Silica sol with an average particle diameter of 40 nm, solid content concentration of 40 mass %) Silica sol 1.23 parts by mass (Silica sol with an average particle size of 450 nm, solid content concentration of 40% by mass) Resin A solution 13.31 parts by mass (solid content concentration 25% by mass) Resin E solution 5.99 parts by mass (solid content concentration 37% by mass) Cross-linking agent P solution 3.47 parts by mass (solid content concentration 40% by mass) Surfactant 0.25 parts by mass (Fluorine-based, solid content concentration 10% by mass) High boiling point solvent 0.34 parts by mass

關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

(比較例5) 除了使用交聯劑T溶液來調製塗布液以外，與實施例1同樣地，得到易接著性聚酯薄膜。關於所得之易接著性聚酯薄膜的評價，與實施例1同樣地進行，其結果係如表1中記載。 (Comparative Example 5) Except having used the crosslinking agent T solution to prepare a coating liquid, it carried out similarly to Example 1, and obtained the easily adhesive polyester film. About the evaluation of the easily adhesive polyester film obtained, it carried out similarly to Example 1, and the result is as described in Table 1.

[表1] 樹脂 (水分 散體) 交聯劑 固體成分比率 (質量%) 粒子 I1640/I1410 霧度 (%) 硬塗材料 密著性(%) 樹脂 交聯劑 X Y (Y/X)×100 未高溫高濕放置 高溫高濕放置後 實施例1 Aw P 80 20 矽石 1.375 1.750 127 0.72 L 100 100 實施例2 Aw P 85 15 矽石 1.192 1.318 111 0.74 L 100 100 實施例3 Aw P 75 25 矽石 1.556 2.178 140 0.70 L 100 99 實施例4 Aw Q 80 20 矽石 1.342 1.697 126 0.69 L 100 97 實施例5 Aw R 80 20 矽石 1.396 1.736 124 0.80 L 98 96 實施例6 Aw S 80 20 矽石 1.382 1.762 127 0.66 L 99 99 實施例7 Bw P 80 20 矽石 1.383 1.744 126 0.73 L 99 98 實施例8 Cw P 80 20 矽石 1.413 1.777 126 0.73 L 99 99 實施例9 Aw P 80 20 氧化鋯/矽石 1.380 1.770 128 0.74 L 100 100 實施例10 Aw P 80 20 氧化鈦/矽石 1.368 1.745 128 0.76 L 100 100 實施例11 Aw P 80 20 氧化鋯/氧化鈦/矽石 1.379 1.812 131 0.74 L 100 100 實施例12 Aw P 80 20 矽石 1.386 1.872 135 0.77 M 100 100 實施例13 Aw P 80 20 矽石 1.366 1.719 126 0.69 N 100 99 比較例1 Aw P 90 10 矽石 0.833 0.888 107 0.72 L 50 0 比較例2 Aw P 57 43 矽石 2.215 3.734 169 0.73 L 100 0 比較例3 Dw P 80 20 矽石 2.030 2.122 105 0.72 L 37 0 比較例4 E/Aw P 80 20 矽石 0.928 1.965 212 0.70 L 100 0 比較例5 Aw T 80 20 矽石 1.352 2.846 211 0.71 L 98 0 固體成分比率係相對於樹脂與交聯劑的固體成分質量之和，以樹脂、交聯劑各自的固體成分質量之百分率表示。 [產業上利用之可能性] [Table 1] Resin (Aqueous Dispersion) cross-linking agent Solid content ratio (mass %) particle I1640/I1410 Haze(%) Hard coating material Adhesion (%) resin cross-linking agent X Y (Y/X)×100 Not placed in high temperature and high humidity After being placed in high temperature and high humidity Example 1 Aw P 80 20 silica 1.375 1.750 127 0.72 L 100 100 Example 2 Aw P 85 15 silica 1.192 1.318 111 0.74 L 100 100 Example 3 Aw P 75 25 silica 1.556 2.178 140 0.70 L 100 99 Example 4 Aw Q 80 20 silica 1.342 1.697 126 0.69 L 100 97 Example 5 Aw R 80 20 silica 1.396 1.736 124 0.80 L 98 96 Example 6 Aw S 80 20 silica 1.382 1.762 127 0.66 L 99 99 Example 7 Bw P 80 20 silica 1.383 1.744 126 0.73 L 99 98 Example 8 Cw P 80 20 silica 1.413 1.777 126 0.73 L 99 99 Example 9 Aw P 80 20 Zirconia/Silica 1.380 1.770 128 0.74 L 100 100 Example 10 Aw P 80 20 Titanium oxide/silica 1.368 1.745 128 0.76 L 100 100 Example 11 Aw P 80 20 Zirconia/Titanium/Silica 1.379 1.812 131 0.74 L 100 100 Example 12 Aw P 80 20 silica 1.386 1.872 135 0.77 M 100 100 Example 13 Aw P 80 20 silica 1.366 1.719 126 0.69 N 100 99 Comparative Example 1 Aw P 90 10 silica 0.833 0.888 107 0.72 L 50 0 Comparative Example 2 Aw P 57 43 silica 2.215 3.734 169 0.73 L 100 0 Comparative Example 3 Dw P 80 20 silica 2.030 2.122 105 0.72 L 37 0 Comparative Example 4 E/Aw P 80 20 silica 0.928 1.965 212 0.70 L 100 0 Comparative Example 5 Aw T 80 20 silica 1.352 2.846 211 0.71 L 98 0 The solid content ratio is expressed as a percentage of the solid content mass of each of the resin and the crosslinking agent with respect to the sum of the solid content mass of the resin and the crosslinking agent. [Possibility of Industrial Use]

依本發明，可提供確保長期間或高溫高濕環境下的放置後之密著可靠性的易接著性聚酯薄膜，對於光學用途等的應用變得更容易。According to the present invention, it is possible to provide an easy-adhesive polyester film that ensures adhesion reliability after being left to stand for a long period of time or in a high-temperature and high-humidity environment, and the application to optical applications and the like becomes easier.

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Claims (4)

一種易接著性聚酯薄膜，其係在聚酯薄膜之至少一面上具有塗布層之易接著性聚酯薄膜，該塗布層係將包含具有多環芳香族骨架的聚酯與具有選自脂肪族、脂環族、雜環族的至少一個骨架的交聯劑之組成物硬化而成者，以傅立葉轉換型紅外光譜法(FT-IR)測定該塗布層之未與聚酯薄膜相接側之表面時，規定以歸屬於脲基的1640cm ^-1為波峰的吸收強度(I ₁₆₄₀)與以歸屬於聚酯之CH伸縮的1410cm ^-1為波峰的吸收強度(I ₁₄₁₀)之相對吸收強度比(I ₁₆₄₀/I ₁₄₁₀)時，滿足以下之關係； 評價製膜後的易接著性聚酯薄膜而得之相對吸收強度比(X)與評價80℃90%RH環境下放置24小時後的聚酯薄膜而得之相對吸收強度比(Y)滿足下述式(1)之關係； 110 ≦ (Y/X)×100 ≦ 140・・・(1)。 An easy-adhesive polyester film, which is an easy-adhesive polyester film with a coating layer on at least one side of the polyester film, the coating layer will comprise a polyester having a polycyclic aromatic skeleton and a polyester having a , The composition of the cross-linking agent with at least one skeleton of alicyclic and heterocyclic is hardened, and the side of the coating layer that is not in contact with the polyester film is measured by Fourier transform infrared spectroscopy (FT-IR). On the surface, the relative absorption intensity ratio (I ₁₆₄₀ ) of the absorption intensity at 1640 cm ^-1 attributed to the urea group as the peak and the absorption intensity at 1410 cm ^-1 attributable to the CH expansion of the polyester (I ₁₄₁₀ ) as the peak (I 1410 ) is defined ( When I ₁₆₄₀ /I ₁₄₁₀ ), the following relationship is satisfied; the relative absorption strength ratio (X) obtained by evaluating the easy-adhesive polyester film after film formation and evaluating the polyester after standing at 80°C and 90% RH for 24 hours The relative absorption intensity ratio (Y) obtained from the film satisfies the relationship of the following formula (1); 110≦(Y/X)×100≦140・・・(1). 如請求項1之易接著性聚酯薄膜，其中該具有多環芳香族骨架的聚酯為具有萘骨架的聚酯。The easily adhesive polyester film according to claim 1, wherein the polyester having a polycyclic aromatic skeleton is a polyester having a naphthalene skeleton. 如請求項1或2之易接著性聚酯薄膜，其中該具有選自脂肪族、脂環族、雜環族的至少一個骨架的交聯劑為具有選自脂肪族、脂環族、雜環族的至少一個骨架的異氰酸酯交聯劑。The easily adhesive polyester film according to claim 1 or 2, wherein the crosslinking agent having at least one skeleton selected from aliphatic, alicyclic and heterocyclic Isocyanate crosslinkers of at least one backbone of the family. 如請求項1至3中任一項記載之易接著性聚酯薄膜，其中在該塗布層表面上設置包含具有芳香族骨架的樹脂之硬塗層時，其密著性為95%以上。The easily adhesive polyester film according to any one of claims 1 to 3, wherein when a hard coat layer containing a resin having an aromatic skeleton is provided on the surface of the coating layer, the adhesion is 95% or more.