TWI360477B - Hard-coated film and optical functional film - Google Patents

Hard-coated film and optical functional film Download PDF

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TWI360477B
TWI360477B TW096118643A TW96118643A TWI360477B TW I360477 B TWI360477 B TW I360477B TW 096118643 A TW096118643 A TW 096118643A TW 96118643 A TW96118643 A TW 96118643A TW I360477 B TWI360477 B TW I360477B
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layer
film
phase
hard coating
adhesive
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TW200810924A (en
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Naoki Mizuno
Hideki Sugihara
Shigenori Iwade
Yasuhiro Nishino
Katsuhiko Nose
Toshitake Suzuki
Chikao Morishige
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Toyo Boseki
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Description

1360477 九、發明說明： 【發明所屬之技術領域】1360477 IX. Description of the invention: [Technical field to which the invention belongs]

本發明關於主要使用在顯示器用構件的硬被覆薄膜及 使用該薄膜的抗反射薄膜、光擴散片、稜鏡狀透鏡片、近 紅外線遮斷薄膜、透明導電性薄膜、防眩薄膜等的光學機 能性薄膜。詳而言之，關於含基材薄膜和無機微粒子的硬 被覆層，以及與其它光學機能層（硬被覆層、光擴散層、稜 鏡層、紅外線吸收層、透明導電層、防眩層等）之密接性優 異而且耐擦傷性優異的硬被覆薄膜，及使用其的光學機能 性薄膜。 【先前技術】 —般地，液晶顯示器（LCD)、電漿顯示器面板（PDP)等 的顯示器之構件所用的硬被覆薄膜，係經由接著性改質樹 脂層而積層熱塑性樹脂薄膜和硬被覆（HC)層。再者，顯示 器用光學機能薄膜通常係經由黏着劑層來貼合機能不同的 光學機能性薄膜而使用。然而，大型平面顯示器，在近年 的低價格化市場之要求係變大。因此，於顯示器用構件中 ，對在1片硬被覆薄膜上積層有其它光學機能層的複合薄 膜進行開發。例如，於液晶顯示器（LCD)中，可舉出於硬 被覆薄膜上，積層有防止外光的映入之抗反射層（AR層）、 用於光之聚光或擴散的稜鏡狀透鏡層、提高亮度的光擴散 層等光學機能層之光學用複合機能性薄膜》 於成爲硬被覆薄膜的基材之熱塑性樹脂薄膜中，使用 由聚對酞酸乙二酯（PET)、聚醯胺、丙烯酸、聚碳酸酯（PC)The present invention relates to a hard coating film mainly used for a member for a display, and an optical function of an antireflection film, a light diffusion sheet, a lenticular lens sheet, a near-infrared ray shielding film, a transparent conductive film, an anti-glare film, or the like using the film. Film. Specifically, the hard coating layer containing the base film and the inorganic fine particles, and other optical functional layers (hard coating layer, light diffusion layer, ruthenium layer, infrared absorbing layer, transparent conductive layer, antiglare layer, etc.) A hard coating film which is excellent in adhesion and excellent in scratch resistance, and an optical functional film using the same. [Prior Art] Generally, a hard coating film for a member of a display such as a liquid crystal display (LCD) or a plasma display panel (PDP) is laminated with a thermoplastic resin film and a hard coating (HC) via an adhesive modified resin layer. )Floor. Further, the optical functional film for a display is usually used by bonding an optical functional film having different functions via an adhesive layer. However, the demand for large flat panel displays in the low-priced market in recent years has grown. Therefore, in the member for display, a composite film in which another optical functional layer is laminated on one hard coating film has been developed. For example, in a liquid crystal display (LCD), an anti-reflection layer (AR layer) for preventing reflection of external light, and a lens layer for concentrating or diffusing light may be laminated on a hard coating film. An optical functional composite film for an optical functional layer such as a light-diffusing layer for improving brightness. In a thermoplastic resin film which is a substrate of a hard coating film, polyethylene terephthalate (PET), polyamine, Acrylic, polycarbonate (PC)

1360477 、三乙醯纖維素（TAC)、環狀聚烯烴等所成 於此等基材薄膜之中，特別地從優良的透明 性、耐藥品性之點來看，二軸配向聚酯薄膜 爲各種光學機能性薄膜的熱塑性樹脂薄膜。 一般地，於二軸配向聚酯薄膜或二軸配 般的二軸配向熱塑性薄膜的情況中，由於薄 結晶配向，故有缺乏與各種塗料、接著劑、 性之缺點。因此，於迄今的二軸配向熱塑性 ，有提案以各種方法來賦予易接著性的方法 又，於聚烯烴薄膜般之不具有極性基的 與各種塗料、接著劑、油墨等的密接性係非 提案在事前進行電暈放電處理、火焰處理等 化學處理後，對薄膜表面藉由各.種方法來觫 方法。 例如，一般已知藉由塗布法，將含薄膜 酸、聚胺甲酸酯、丙烯酸接枝聚酯等接著怕 著性改質層，設置於熱塑性樹脂薄膜的表1 性樹脂薄膜賦予易接著性的方法。於該塗冇 廣泛實施對於結晶配向結束前的熱塑性樹月! 或視需要地施予電暈放電處理後，將含有i 或樹脂經分散介質所分散的分散體之水性i 基材薄膜，使乾燥後，至少在一軸方向中β 熱處理，而完成熱塑性樹脂薄膜的結晶配向 線內塗覆法），或在熱塑性樹脂薄膜的製造老 的透明薄膜' 性、尺寸安定 係廣泛使用作 向聚醯胺薄膜 膜表面的高度 油墨等的密接 樹脂薄膜表面 〇 薄膜中，由於 常缺乏，故有 的物理處理或 予易接著性的 、聚酯、丙烯 改質樹脂的接 上，而對熱塑 法中，工業上 薄膜，直接地 述樹脂的溶液 布液，塗布到 伸，接著施予 之方法（所謂的 :，於該薄膜上 1360477 塗布水系或溶劑系的塗布液後，使乾燥之方法（所謂的離線 塗覆法）。1360477, triethylene fluorene cellulose (TAC), cyclic polyolefin, etc. are formed among these base film, especially from the viewpoint of excellent transparency and chemical resistance, the biaxial alignment polyester film is A thermoplastic resin film of various optical functional films. In general, in the case of a biaxially oriented polyester film or a biaxially oriented biaxially oriented thermoplastic film, there is a lack of various coatings, adhesives, and properties due to the thin crystal alignment. Therefore, there has been proposed a method of imparting easy adhesion by various methods in the biaxial alignment thermoplastics, and the adhesion to various coatings, adhesives, inks, etc., which does not have a polar group like a polyolefin film, is not proposed. After the chemical treatment such as corona discharge treatment or flame treatment is performed in advance, the surface of the film is subjected to various methods. For example, it is generally known that a film-like acid film, a polyurethane, a acryl-grafted polyester or the like is attached to a thermoplastic resin film to impart easy adhesion by a coating method. Methods. The thermoplastic resin layer before the end of the crystal alignment is widely applied to the coating; or, after the corona discharge treatment is optionally applied, the aqueous i-substrate film containing the dispersion of the i or the resin dispersed in the dispersion medium is dried. After that, at least in the axial direction, the β heat treatment is performed to complete the crystallographic alignment of the thermoplastic resin film, or the old transparent film of the thermoplastic resin film is used, and the dimensional stability is widely used as the polyimide film. The surface of the film is highly adhered to the surface of the resin film such as ink. Since it is often lacking, some physical treatments or adhesions of polyester and propylene-modified resins are attached, and in the thermoplastic process, industrial The upper film, directly the solution solution of the resin, applied to the stretching, and then applied (so-called: 1360477 on the film after coating the aqueous or solvent-based coating liquid, the method of drying (so-called off-line coating) Overlay).

LCD、PDP等的顯示器係年年往大型化及低成本化進展 ’於作爲其構件而使用的光學機能性薄膜之製程中，正在 進行提高生產速度。隨著如此的製程之高速化，在硬被覆 層、擴散層、稜鏡層般的機能層與基材薄膜之界面，由於 硬化收縮所伴隨的應力變成更容易發生。因此，爲了製造 顯示器，於將光學機能性薄膜切割成特定尺寸時，若在上 述界面的密接性不充分，則在端部特別會有容易剝離的問 題。該傾向在捲成圓筒狀的薄膜之大型化，或在製程中進 行生產速度的高速化時，切割時的衝撃所造成的界面剝離 之影響變成更顯著，以往的密接性水平係變成不足。 再者，爲了形成上述稜鏡層或擴散層等的機能層，所 使用的加工劑，從環境負荷的減低之點來看，不以有機溶 劑來稀釋，而直接將加工劑塗布在基材薄膜上的情況係多 的。因此，由於不能充分得到有機溶劑對接著性改質層的 潤濕改良效果，而要求更高的密接性》另一方面，於硬被 覆層般地重視平滑性之用途中，爲了降低加工劑的黏度以 得到良好的均平效果，以有機溶劑來稀釋的加工劑的情況 係多的。於此情況中，對於接著性改質基材薄膜的接著性 改質層，要求適度的耐溶劑性。 爲了提高機能層與基材薄膜之間的密接性，一般爲於 構成接著性改質層的樹脂中，使用玻璃轉移溫度低的樹脂 之方法。然而，於使用玻璃轉移溫度低的樹脂之情況中， 1360477 將接著性改質基材薄膜連續捲成圓筒狀，從圓筒狀薄膜捲 出薄膜時，防黏連性有降低的傾向。 又，近年來爲了低成本化，用於將硬被覆層或擴散層 等的機能層積層到基材薄膜的加工機係往大型化進展，作 爲基材薄膜而使用的易接著薄膜之圓筒直徑亦大型化。伴 隨著此，爲了防止圓筒的捲繞偏移，於高張力下捲取時， 於圓筒的捲繞芯部，爲了以高的壓力來壓接，而變成更容 易發生黏連。In the process of increasing the size and cost of the display, such as the LCD and the PDP, the production speed is being increased in the process of the optical functional film used as the member. With such a high speed of the process, the stress accompanying the hardening shrinkage becomes more likely to occur at the interface between the hard coating layer, the diffusion layer, the enamel-like functional layer and the base film. Therefore, in order to manufacture a display, when the optical functional film is cut into a specific size, if the adhesion at the above interface is insufficient, there is a problem that the end portion is particularly likely to be peeled off. When the film is rolled up into a cylindrical shape, or when the production speed is increased during the process, the influence of the interface peeling due to the squeezing at the time of dicing becomes more remarkable, and the conventional level of adhesion becomes insufficient. Further, in order to form the functional layer such as the ruthenium layer or the diffusion layer, the processing agent used is directly coated with the processing agent on the substrate film from the viewpoint of a reduction in environmental load, without being diluted with an organic solvent. There are many situations on it. Therefore, since the effect of improving the wetting of the adhesive layer by the organic solvent is not sufficiently obtained, higher adhesion is required. On the other hand, in order to reduce the smoothness of the hard coating layer, in order to reduce the processing agent The viscosity is good to obtain a good leveling effect, and the processing agent diluted with an organic solvent is often used. In this case, moderate solvent resistance is required for the adhesion-modifying layer of the adhesive-modified substrate film. In order to improve the adhesion between the functional layer and the base film, a resin having a low glass transition temperature is generally used for the resin constituting the adhesive reforming layer. However, in the case of using a resin having a low glass transition temperature, 1360477 continuously rolls the adhesive-modified substrate film into a cylindrical shape, and when the film is wound up from the cylindrical film, the blocking resistance tends to be lowered. In addition, in recent years, in order to reduce the cost, the processing machine for laminating the hard coat layer or the diffusion layer to the base film has been enlarged, and the diameter of the easy-to-adhere film used as the base film has been increased. It is also large. Accordingly, in order to prevent the winding deviation of the cylinder, when winding under high tension, the winding core portion of the cylinder is more likely to be adhered in order to be pressure-bonded under high pressure.

爲了提高防黏連性，一般採用對接著性改質基材薄膜 的表面賦予凹凸，而減小接觸面積的方法。爲了對薄膜表 面賦予凹凸，而使含於接著性改質層或基材薄膜中，一般 有增加無機粒子或有機粒子的含量之方法，或使用粒徑大 的粒子之方法。然而，由於一般市售可取得的粒子之折射 率係不同於接著性改質層中所用的樹脂之折射率，而且隨 著薄膜的拉伸處理，在粒子的周圍形成空隙，故此等方法 會發生薄膜的光線透過率降低下、霧度的上升等》特別地 ，降低光學機能性薄膜的基材薄膜所要求的透明性。即， 於以往的方法中，隨著製程的高速化或薄膜的圓筒直徑之 大型化而產生新問題，一面維持透明性，一面提高與機能 層的密接性或防黏連性係極困難的。 再者，近年來，光學機能性薄膜’以防止與導光板的 密接，提高透過率，或減低捲曲等爲目的，在基材薄膜的 兩面上設置硬被覆層的情況，或在稜鏡透鏡層或光擴散層 般的光學機能層之相反側之面亦積層硬被覆層的情況係變 (s) 1360477 多°特別地，硬被覆薄膜通常係使用熱硬化型樹脂或紫外 線硬化型樹脂般的電離輻射線硬化型樹脂，在熱塑性樹脂 薄膜上形成厚度爲3〜10 μιη的薄硬化塗膜（硬被覆層）。 然而，硬被覆層的厚度由於比基材薄膜還薄，故硬被 覆薄膜本身的硬度受到基材薄膜的影響，不會充分變高。 因此’爲了提高硬被覆層的耐擦傷性，有檢討在硬被覆層 中含有無機粒子》In order to improve the anti-blocking property, a method of imparting irregularities to the surface of the adhesive-modified substrate film to reduce the contact area is generally employed. In order to impart unevenness to the surface of the film and to be contained in the adhesive layer or the base film, a method of increasing the content of inorganic particles or organic particles or a method of using particles having a large particle size is generally employed. However, since the refractive index of the particles which are generally commercially available is different from the refractive index of the resin used in the adhesion modifying layer, and the voids are formed around the particles as the film is stretched, such methods may occur. In particular, the light transmittance of the film is lowered, the haze is increased, and the like, and the transparency required for the base film of the optical functional film is particularly lowered. In other words, in the conventional method, as the speed of the process is increased or the diameter of the cylinder of the film is increased, a new problem arises, and it is extremely difficult to improve the adhesion to the functional layer or the anti-blocking property while maintaining the transparency. . In addition, in recent years, the optical functional film has a hard coating layer on both surfaces of the base film for preventing the adhesion to the light guide plate, improving the transmittance, or reducing the curl, or the ruthenium lens layer. The surface of the opposite side of the optical functional layer such as the light-diffusing layer is also laminated with a hard coating layer. (s) 1360477. In particular, the hard-coated film is usually ionized using a thermosetting resin or an ultraviolet curing resin. A radiation-curable resin is formed into a thin hard coating film (hard coating layer) having a thickness of 3 to 10 μm on a thermoplastic resin film. However, since the thickness of the hard coating layer is thinner than the base film, the hardness of the hard coating film itself is affected by the base film and does not become sufficiently high. Therefore, in order to improve the scratch resistance of the hard coating layer, it is reviewed that inorganic particles are contained in the hard coating layer.

另一方面’於硬被覆層中含有無機粒子時，由於硬被 覆層中的硬化型樹脂之比率降低，故在接著性改質基材薄 膜的接著性改質層與硬被覆層之界面中之密接性會降低。 特別地’已知二軸配向聚酯薄膜與稜鏡透鏡或硬被覆 層等中所使用之以丙烯酸系樹脂當作主成分的塗覆劑之密 接性差。因此’於聚酯薄膜的表面，形成由聚胺甲酸酯等 所成的接著性改質層者係有各種提案（例如參照專利文獻1) 。然而，形成由聚胺甲酸酯所成的接著性改質層，雖然提 高與硬被覆層等的機能層之密接力，但是與基材即聚酯薄 膜的密接力不充分，結果在接著性改質層與機能層的界面 ’密接性係不充分。特別地，接著性改質層與含無機粒子 的硬被覆層之界面的密接性係顯著變差。專利文獻1:特 開平6-340049號公報。 又，有提案藉由線內塗覆法，在由二軸配向聚對酞酸 乙二酯所成的基體薄膜上，設置以共聚合聚酯與聚胺甲酸 酯當作主要構成成分的樹脂組成物層，以提高基材聚酯薄 膜與油墨等的機能層之密接性的方法（例如參照專利文獻2) 1360477 。具體地，於縱方向經一軸拉伸的聚酯薄膜上，塗布含有 共聚合聚酯和聚胺甲酸酯（ = 2 0/80 ;質量％)的水分散性塗布 液後，導引至拉幅機，使乾燥，進行橫向拉伸後，在220 °C熱定型以得到易接著性二軸配向聚酯薄膜。專利文獻2 :特公昭64-6025號公報On the other hand, when the inorganic particles are contained in the hard coating layer, the ratio of the curing resin in the hard coating layer is lowered, so that it is in the interface between the adhesion-modifying layer and the hard coating layer of the adhesive-modified base film. The adhesion will be reduced. In particular, it is known that the biaxially oriented polyester film is inferior in adhesion to a coating agent containing an acrylic resin as a main component used in a tantalum lens or a hard coating layer. Therefore, there are various proposals for forming an adhesive layer formed of a polyurethane or the like on the surface of the polyester film (see, for example, Patent Document 1). However, the adhesion-modifying layer formed of the polyurethane is formed to improve the adhesion to the functional layer such as the hard coating layer, but the adhesion to the polyester film as the substrate is insufficient, and as a result, the adhesion is improved. The interface between the modified layer and the functional layer is not sufficiently adhered. In particular, the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles is remarkably deteriorated. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 6-340049. Further, it has been proposed to provide a resin having a copolymerized polyester and a polyurethane as a main constituent component on a base film formed of biaxially aligned polyethylene terephthalate by an in-line coating method. The composition layer is a method for improving the adhesion between the base polyester film and the functional layer such as ink (see, for example, Patent Document 2) 1360477. Specifically, a water-dispersible coating liquid containing a copolymerized polyester and a polyurethane (=20/80; mass%) is applied onto a polyester film which is longitudinally stretched in the longitudinal direction, and then guided to pull. The web was dried, and after transverse stretching, it was heat-set at 220 ° C to obtain an easily bondable biaxially oriented polyester film. Patent Document 2: Japanese Patent Publication No. 64-6025

然而，於專利文獻2記載的方法中，雖然改善密接性 ，但是作爲近年來使用於光學機能性薄膜的基材薄膜所要 求的基材薄膜與硬被覆層或擴散層等之機能層，尤其接著 性改質層與含有無機粒子的硬被覆層之界面的密接性係不 充分。 本案申請人提出在由二軸配向聚對酞酸乙二酯所成的 基材薄膜上，設置共聚合聚酯與聚胺甲酸酯及加有適度粒 徑的無機粒子的樹脂組成物層，而且，可邊維持作爲光學 用基材薄膜的極重要特性之透明性，邊充分滿足市場要求 水平的密接性，且光學的缺點少的積層聚酯薄膜（例如參照 專利文獻3、4)。具體地，揭示於縱方向經一軸拉伸的聚 酯薄膜上，塗布含有共聚合聚酯、聚胺甲酸酯（ = 20/80;質 量％)及2種平均粒徑不同的矽石粒子、陰離子性界面活性 劑之水分散性塗布液後，導引至拉幅機，使乾燥，進行橫 向拉伸後，在240 °C熱定型而得之易接著性二軸配向聚酯 薄膜。 專利文獻3及4所得到的易接著性二軸配向聚酯薄膜 ，係具有優異的密接性及防黏連性、透明性，而且雜質異 、刮傷等的光學缺點係被大幅改善，爲滿足以往要求的特 -10- 1360477 性者。然而，如前述地，隨著近年來的低成本化、顯示器 的大畫面化，作爲光學機能性薄膜用的基材薄膜所要求的 基材薄膜與硬被覆層、擴散層、稜鏡層等機能層之密接性 、及對防黏連性的要求水平係年年有變嚴格的傾向。特別 地，對於接著性改質層與含無機粒子的硬被覆層之界面的 密接性而言，係不能充分滿足現在市場上所要求的品質。 專利文獻3 :特開平1 1 -32327 1號公報。專利文獻4 :特開 2000-246855 號公報。However, in the method described in Patent Document 2, although the adhesion is improved, the functional layer such as the base film and the hard coating layer or the diffusion layer which are required for the base film used in the optical functional film in recent years is particularly advanced. The adhesion between the modified layer and the hard coating layer containing the inorganic particles is insufficient. The applicant of the present invention proposed to provide a resin composition layer of a copolymerized polyester and a polyurethane and an inorganic particle having a moderate particle diameter on a substrate film formed by biaxially-aligned polyethylene terephthalate. In addition, a laminated polyester film which can sufficiently satisfy the adhesion at the market level and has few optical defects while maintaining the transparency of the extremely important characteristics of the optical base film (see, for example, Patent Documents 3 and 4). Specifically, it is disclosed on a polyester film which is stretched in the longitudinal direction by a single axis, and coated with a copolymerized polyester, a polyurethane (=20/80; mass%), and two kinds of vermiculite particles having different average particle diameters, After the water-dispersible coating liquid of the anionic surfactant, it is guided to a tenter, dried, and transversely stretched, and then heat-set at 240 ° C to obtain an easily bondable biaxially oriented polyester film. The easy-adhesive biaxial alignment polyester film obtained in Patent Documents 3 and 4 has excellent adhesion, anti-blocking property, and transparency, and optical defects such as impurities and scratches are greatly improved to satisfy Specially required by the previous -10- 1360477. However, as described above, with the reduction in cost in recent years and the large screen size of the display, the base film, the hard coat layer, the diffusion layer, the ruthenium layer and the like required for the base film for the optical functional film are required. The level of adhesion between the layers and the level of anti-blocking properties tend to be stricter year after year. In particular, the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles cannot sufficiently satisfy the quality required on the market today. Patent Document 3: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. Patent Document 4: JP-A-2000-246855.

又，本案申請人爲了改善密接性的均一性，而提出與 已減低塗布量的變動之易接著薄膜捲筒有關的發明（例如參 照專利文獻5)。於專利文獻5的實施例中記載：於縱方向 經一軸拉伸的聚酯薄膜上，塗布含共聚合聚酯和聚胺甲酸 酯（ = 50/50;質量％)、平均粒徑1.4 μπι的矽石粒子、及氟系 界面活性劑的水分散性塗布液後，藉由乾燥爐在120°C乾 燥後，進行橫拉伸，接著在220 °C進行熱定型處理而得之 易接著性二軸配向聚酯薄膜。所得到的薄膜捲筒係在整個 薄膜捲筒均勻地具有優異的密接性，可滿足市場的要求水 平。然而，對於接著性改質層與含無機粒子的硬被覆層之 界面的密接性而言，係不能充分満足。專利文獻5:特開 20 04-10669 號公報 又，以提高耐擦傷性爲目的，有提案在易接著聚對酞 酸乙二酯薄膜上，塗布對於100質量份的樹脂而言，含有 約40質量份的粒徑約50nm以下的矽石超微粒子之電離輻 射線硬化型硬被覆劑，以使乾厚度成爲約15μιη，經電子 -11- 1360477 線而硬化的硬被覆薄膜（例如參照專利文獻6)。然而，該 硬被覆薄膜雖然硬被覆層的硬度高、耐擦傷性優良，但是 對於接著性改質層與含無機粒子的硬被覆層之界面的密接 性而言，係不能充分滿足現在市場的要求品質。 專利文獻6:特開2000-112379號公報 另一方面，有提案於由共聚合聚酯與蜜胺交聯劑所成 的接著性改質層之易接著聚對酞酸乙二酯薄膜上，積層有Further, in order to improve the uniformity of the adhesion, the applicant of the present invention has proposed an invention relating to a film roll which has been reduced in the amount of coating which is easy to change (for example, refer to Patent Document 5). In the examples of Patent Document 5, it is described that a copolymerized polyester and a polyurethane (=50/50; mass%) are coated on a polyester film which is longitudinally stretched in the longitudinal direction, and an average particle diameter of 1.4 μm is applied. After the vermiculite particles and the water-dispersible coating liquid of the fluorine-based surfactant are dried in a drying oven at 120 ° C, the film is horizontally stretched, and then heat-set at 220 ° C to obtain an easy adhesion property. Biaxially oriented polyester film. The obtained film reel uniformly has excellent adhesion throughout the film reel to meet the market demand level. However, the adhesion to the interface between the adhesion-modifying layer and the hard coating layer containing the inorganic particles is not sufficiently sufficient. Further, in order to improve the scratch resistance, it is proposed to apply a coating on a polyethylene terephthalate film which is easy to apply, and it is coated for about 100 parts by mass of the resin. A hard coating film of an ionizing radiation hardening type hard coating agent of a vermiculite ultrafine particle having a particle diameter of about 50 nm or less, which has a dry thickness of about 15 μm and hardened by an electron-11-1360477 line (for example, refer to Patent Document 6) ). However, although the hard coating film has high hardness and excellent scratch resistance, the hard coating layer does not sufficiently satisfy the requirements of the current market for the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles. quality. Patent Document 6: JP-A-2000-112379. On the other hand, there is a proposal for an easy-to-peel polyethylene terephthalate film which is formed by a copolymerization layer of a copolymerized polyester and a melamine crosslinking agent. There are layers

不含有粒子的硬被覆層之硬被覆薄膜（例如參照專利文獻7) 。然而，該硬被覆薄膜在硬被覆層的密接性及硬被覆層的 硬度方面係不能充分滿足者。 專利文獻7:特開2004-160774號公報。 即，於先前技術中，雖然能維持高硬度，但不能得到 近年來所要求的耐高速切割之密接性，尤其與含無機粒子 的硬被覆層之優良密接性的硬被覆薄膜。 【發明內容】 發明所欲解決的問頴 本發明之目的係提供在接著性改質層與含無機粒子的 硬被覆層之界面的密接性高度優異且硬度高的硬被覆薄膜 ，以及使用其的光學機能性薄膜。 解決問題的手段 上述課題可藉由以下解決手段來達成。 即’本發明中的第1發明係一種硬被覆薄膜，其特徵 爲該硬被覆薄膜包含在熱塑性樹脂薄膜A的一面或兩面上 ’形成有含共聚合聚酯及聚胺甲酸酯的接著性改質層B之 -12- 1360477A hard coating film of a hard coating layer containing no particles (for example, see Patent Document 7). However, the hard coating film is not sufficiently satisfactory in terms of the adhesion of the hard coating layer and the hardness of the hard coating layer. Patent Document 7: JP-A-2004-160774. In other words, in the prior art, although high hardness can be maintained, a hard coating film which is excellent in adhesion to high-speed dicing which has been required in recent years, and which is excellent in adhesion to a hard coating layer containing inorganic particles, cannot be obtained. SUMMARY OF THE INVENTION The object of the present invention is to provide a hard coating film having high adhesion and high hardness at the interface between an adhesive layer and an inorganic particle-containing hard coating layer, and a hard coating film using the same Optical functional film. Means for Solving the Problem The above problems can be achieved by the following solutions. In other words, the first invention of the present invention is a hard coating film characterized in that the hard coating film comprises a "contact property of a copolymerizable polyester and a polyurethane on one or both sides of the thermoplastic resin film A. Modified layer B -12- 1360477

接著性改質基材薄膜，與在該薄膜的任一面之接著性改質 層B的表面上之含無機微粒子的硬被覆層C，所積層而成 的A/B/C或B/A/B/C之層構成，其中接著性改質層B具有 聚酯（PEs)相與聚胺甲酸酯（PU)相的微相分離構造或奈米相 分離構造，而且使用掃描型探針顯微鏡以相位測定模式來 觀察硬被覆薄膜的切削面時，在從接著性改質層B與硬被 覆層C的界面起到深度2 Onm爲止的範圍內，下述式（1)所 定義的接著性改質層B之聚胺甲酸酯相（在相位像顯示明 色相）的面積率係30%以上且60%以下。 PU相的面積率（％) = (PU相的面積/測定面積）χ100··· (1) 第2發明係一種硬被覆薄膜，其特徵爲該硬被覆薄膜 包含在熱塑性樹脂薄膜Α的一面或兩面上，形成有含共聚 合聚酯及聚胺甲酸酯的接著性改質層B之接著性改質基材 薄膜，與在該薄膜的任一面之接著性改質層B的表面上之 含無機微粒子的硬被覆層 C，所積層而成的 A/B/C或 B/A/B/C之層構成，其中接著性改質層B具有聚酯（PEs)相 與聚胺甲酸酯（PU)相的微相分離構造或奈米相分離構造， 而且使用掃描型探針顯微鏡以相位測定模式來觀察接著性 改質層B的表面時，下述（2)式所定義的接著性改質層B 之表面的聚酯相（在相位像顯示暗色相）的面積率在 5411^50111的範圍內係35%以上且低於9〇%。 PEs相的面積率（％) = (PEs相的面積/測定面積）χ1〇〇··_ (2) 第3發明係如第1或2發明所記載的硬被覆薄膜，其 中硬被覆層C中的無機微粒子之含量係20〜80質量％。 (S ) -13- 1360477 又，第4發明如第1或2發明所記載的硬被覆薄膜’ 其中於熱塑性樹脂薄膜中不含有或含有5 〇PPm以下的粒子 ，於接著性改質層中含有0.1〜20質量％的粒子。 第5發明係如第4發明所記載的硬被覆薄膜’其中粒 子係矽石粒子。Next, the modified base film and the hard-coated layer C containing inorganic fine particles on the surface of the adhesive layer B on either side of the film are laminated to form A/B/C or B/A/. Layer B/C composition in which the adhesion modifying layer B has a microphase separation structure or a nano phase separation structure of a polyester (PEs) phase and a polyurethane (PU) phase, and uses a scanning probe microscope When the cut surface of the hard coating film is observed in the phase measurement mode, the adhesion defined by the following formula (1) is within a range from the interface between the adhesion modifying layer B and the hard coating layer C to the depth of 2 Onm. The area ratio of the polyurethane phase of the modified layer B (the phase image shows a clear color phase) is 30% or more and 60% or less. Area ratio (%) of the PU phase = (area of the PU phase/measurement area) χ100 (1) The second invention is a hard coating film characterized in that the hard coating film is contained on one side of the thermoplastic resin film or On both sides, a film of an adhesive-modified substrate having an adhesive layer B containing a copolymerized polyester and a polyurethane is formed on the surface of the adhesive layer B on either side of the film. The hard coating layer C containing inorganic fine particles is composed of a layer of A/B/C or B/A/B/C laminated, wherein the adhesive modified layer B has a polyester (PEs) phase and a polyamic acid. In the microphase separation structure or the nano phase separation structure of the ester (PU) phase, when the surface of the adhesion modifying layer B is observed in the phase measurement mode using a scanning probe microscope, the following definition of (2) is followed. The area ratio of the polyester phase (the phase image showing the dark phase) on the surface of the modified layer B is 35% or more and less than 9% by weight in the range of 5411^50111. The area ratio (%) of the PEs phase = (area of the PEs phase/measurement area). The third invention is a hard coating film according to the first or second invention, wherein the hard coating layer C is The content of the inorganic fine particles is 20 to 80% by mass. (A) The hard-coated film of the first or second aspect of the present invention, wherein the thermoplastic resin film does not contain or contain particles of 5 〇 PPm or less, and is contained in the adhesive modified layer. 0.1 to 20% by mass of particles. According to a fifth aspect of the invention, the hard-coated film of the fourth aspect is the particle-based vermiculite particle.

第6發明係一種光學機能性薄膜，其爲在第1和2發 明所記載的硬被覆薄膜之與硬被覆層C的相反面上’積層 有從硬被覆層、光擴散層、稜鏡狀透鏡層、電磁波吸收層 、近紅外線遮斷層、透明導電層所選出的至少1層之光學 機能層。 第7發明係一種光學機能性薄膜，其爲在第1或2發 明所記載的硬被覆薄膜之硬被覆層C上，積層有抗反射層 或防污層的光學機能性薄膜。 發明的效果 本發明硬被覆薄膜具有當作熱塑性樹脂薄膜與硬被覆 層的中間層之在聚酯相和聚胺甲酸酯相具有特異的微相分 離構造或奈米相分離構造，於接著性改質層的切削面中， 與硬被覆層之界面附近的聚胺甲酸酯相之面積率係在特定 的範圍內。因此，即使積層含無機微粒子的硬被覆層，也 能一面維持高的硬度，一面提高與硬被覆層的密接性。再 者，與擴散層、稜鏡層等的光學機能層的密接性亦優良。 再者’藉由僅於接著性改質層中含有特定量的特定粒 徑之粒子’或在.接著性改質層的表面之聚酯相或聚胺甲酸 酯相中的任一相中，使粒子偏在化，則可一面維持高度的 -14- 1360477 透明性，一面改善防黏連性、處理性、耐刮性。因此，適 用於作爲要求高透明性的硬被覆薄膜或光學機能性薄膜。 特別地，於接著性改質層中含有矽石粒子時，由於可使矽 石粒子偏在於聚胺甲酸酯相中，故可彌補防黏連性差的聚 胺甲酸酯之缺點。 【實施方式】 實施發明的最隹形熊According to a sixth aspect of the invention, there is provided an optically functional film which is formed by laminating a hard coating layer, a light diffusion layer, and a crown lens on a surface opposite to the hard coating layer C of the hard coating film according to the first and second aspects of the invention. At least one optical function layer selected from the layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer. According to a seventh aspect of the invention, there is provided an optical functional film which is an optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coating layer C of the hard coating film according to the first or second aspect. Advantageous Effects of Invention The hard coating film of the present invention has a specific micro phase separation structure or a nano phase separation structure in a polyester phase and a polyurethane phase as an intermediate layer of a thermoplastic resin film and a hard coating layer, in the adhesion property. In the cutting surface of the modified layer, the area ratio of the polyurethane phase in the vicinity of the interface with the hard coating layer is within a specific range. Therefore, even if a hard coating layer containing inorganic fine particles is laminated, the adhesion to the hard coating layer can be improved while maintaining high hardness. Further, the adhesion to the optical functional layer such as the diffusion layer or the ruthenium layer is also excellent. Furthermore, 'by containing only a specific amount of particles of a specific particle size in the adhesive modifying layer alone' or in any of the polyester phase or the polyurethane phase of the surface of the adhesive modifying layer When the particles are biased, the transparency of the height of -14,360,477 can be maintained while improving the anti-blocking property, handling property, and scratch resistance. Therefore, it is suitable as a hard coating film or an optical functional film which requires high transparency. In particular, when the vermiculite particles are contained in the adhesive reforming layer, since the vermiculite particles are biased in the polyurethane phase, the disadvantage of the polyurethane having poor anti-blocking property can be compensated for. [Embodiment] The most scorpion bear implementing the invention

首先說明於本發明中，課題所記載的密接性與硬度之 於本發明的硬被覆薄膜中，密接性係意味對含無機微 粒子的硬被覆層，以膠帶重複10次棋盤格剝離試驗（100 個方格）後，硬被覆層與基材薄膜的接著性改質層之界面的 密接性。 於本發明中，將下式所定義的密接性爲80 %以上者當 作合格。較佳爲85%以上，特佳爲90%以上》 密接性（％)= (1-方格經剝離的個數/100個）χ100 又，於本發明所用的接著性改質基材薄膜中，密接性 係意味將溶劑稀釋型的光硬化型丙烯酸系樹脂經紫外線所 硬化的硬被覆層，形成在薄膜的接著性改質層上，以膠帶 重複10次棋盤格剝離試驗（100個方格）後，丙烯酸系硬被 覆層與薄膜的接著性改質層之界面的密接性。於本發明中 ，將下式所定義的密接性爲80%以上者當作合格。較佳爲 85%以上，特佳爲90%以上》 密接性（％)= (1-方格經剝離的個數/100個）xl〇〇 -15- 1360477 再者，本發明中所言的硬度係意味以根據JIS-K5400 的鉛筆硬度試驗所評價的「鉛筆硬度」。鉛筆硬度係爲對 於硬被覆薄膜的硬被覆層之表面，重複5次鉛筆硬度試驗 ’在任一試驗中皆看到傷痕等的外觀異常時，將該試驗所 使用的鉛筆之硬度當作鉛筆硬度。例如，使用3H的鉛筆 ，進行5次的試驗操作，若1次也沒有發生外觀異常的話 ，則將該材料的鉛筆硬度當作3H。First, in the present invention, the adhesion and hardness described in the subject are in the hard coating film of the present invention, and the adhesiveness means that the hard coating layer containing inorganic fine particles is repeated 10 times in a checkerboard peeling test (100 pieces) After the square, the adhesion between the hard coating layer and the interface of the adhesive layer of the base film is adhered. In the present invention, those having an adhesiveness as defined in the following formula of 80% or more are regarded as acceptable. Preferably, it is 85% or more, particularly preferably 90% or more." Adhesion (%) = (1 - number of peeled squares / 100) χ 100 Further, in the adhesive modified base film used in the present invention The adhesiveness means that a hard coating layer in which a solvent-diluted photocurable acrylic resin is cured by ultraviolet rays is formed on the adhesive modified layer of the film, and the checkerboard peeling test is repeated 10 times with a tape (100 squares). After that, the adhesion between the acrylic hard coating layer and the adhesive layer of the film is improved. In the present invention, those having an adhesiveness defined by the following formula of 80% or more are regarded as acceptable. Preferably, it is 85% or more, and particularly preferably 90% or more." Adhesion (%) = (1 - number of squares peeled off / 100) xl 〇〇 -15 - 1360477 Furthermore, what is stated in the present invention The hardness means "pencil hardness" evaluated in accordance with the pencil hardness test of JIS-K5400. The pencil hardness is the surface of the hard coating layer of the hard coating film, and the pencil hardness test is repeated five times. When the appearance of the flaw or the like is abnormal in any of the tests, the hardness of the pencil used in the test is regarded as the pencil hardness. For example, a pencil of 3H is used for five test operations, and if the appearance is not abnormal once, the pencil hardness of the material is regarded as 3H.

又，本發明所用的接著性改質基材薄膜之防黏連性， 係將2片的薄膜試料之接著性改質層以對向的方式作疊合 ，對其在 lkgf/cm2的壓力，於50°C ' 60%RH的氣氛下密 接24小時後，剝離，將其剝離狀態爲「接著性改質層沒 有轉移，而可輕鬆地剝離者」當作合格。 再者，本發明中的透明性高度優良之薄膜係意味霧度 爲1.5 %以下的薄膜。較佳的霧度係1.0%以下。 於本發明所用的接著性改質基材薄膜中，爲了得到優 良的密接性與防黏連性，重要地是在接著性改質層的表面 表現特異的微相分離構造或奈米相分離構造。再者，於本 發明的硬被覆薄膜，爲了亦提高接著性改質基材薄膜的接 著性改質層與含無機微粒子的硬被覆層之密接性，在接著 性改質層的表面，即在與硬被覆層的界面，重要的是表現 特異的微相分離構造或奈米相分離構造。 然而，於本發明的硬被覆薄膜中，接著性改質層B係 成爲熱塑性樹脂薄膜A與硬被覆層C的中間層》即，從硬 被覆薄膜的表面，無法觀察接著性改質層B的表面之相分 -16- (S ) 1360477 離構造。因此，於本發明中，將硬被覆薄膜切削，從其切 削面來觀察與硬被覆層的界面附近之接著性改質層的相分 離構造。 本發明中的接著性改質層之特異的相分離構造，係可 藉由選擇地採用接著性改質層形成用的塗布液之樹脂組成 、界面活性劑的種類和濃度、塗布量、接著性改質層的乾 燥條件、及熱定型條件等，控制它們而形成。Further, the anti-blocking property of the adhesive-modified substrate film used in the present invention is such that the adhesive layer of the two film samples is laminated in an opposing manner to a pressure of lkgf/cm2. After adhering for 24 hours in an atmosphere of 50 ° C '60% RH, the film was peeled off, and the peeled state was judged as "the adhesive layer was not transferred, and it was easily peeled off" as a pass. Further, the film having high transparency in the present invention means a film having a haze of 1.5 % or less. A preferred haze is 1.0% or less. In the adhesive modified base film used in the present invention, in order to obtain excellent adhesion and anti-blocking property, it is important to exhibit a specific micro phase separation structure or a nano phase separation structure on the surface of the adhesion modifying layer. . Further, in the hard coating film of the present invention, in order to improve the adhesion between the adhesion-modifying layer of the adhesive modified base film and the hard coating layer containing the inorganic fine particles, the surface of the adhesive modified layer is At the interface with the hard coating layer, it is important to express a specific microphase separation structure or a nano phase separation structure. However, in the hard coating film of the present invention, the adhesion-modifying layer B is an intermediate layer of the thermoplastic resin film A and the hard coating layer C, that is, from the surface of the hard coating film, the adhesive layer B cannot be observed. The phase of the surface is divided into -16- (S) 1360477 from the structure. Therefore, in the present invention, the hard coating film is cut, and the phase separation structure of the adhesion modifying layer in the vicinity of the interface with the hard coating layer is observed from the cut surface. In the specific phase separation structure of the adhesion-modifying layer in the present invention, the resin composition of the coating liquid for forming the adhesion-modifying layer, the type and concentration of the surfactant, the coating amount, and the adhesion property can be selectively used. Drying conditions of the modified layer, heat setting conditions, and the like are formed by controlling them.

首先，關於本發明所用的接著性改質基材薄膜之製造 方法，以聚對酞酸乙二酯（以下簡稱PET)作爲代表例來槪 要地說明，惟當然不受該代表例所限定。 於將實質上不含有粒子（此粒子之目的爲賦予易滑性）的 PET之九粒作充分真空乾燥後，供應給擠壓機，在280°C 熔融擠出成片狀，使冷卻固化以製作未配向PET片。此時 ，熔融樹脂係保持在約2 8 0 °C的任意場所，爲了去除樹脂 中所含有的雜質，進行高精度過濾。所得到的未配向片， 以經加熱到80〜120°C的輥在長度方向中作2.5〜5.0倍拉 伸，得到一軸配向PET薄膜。 然後，於一軸配向PET薄膜的一面或兩面上，塗布上 述共聚合聚酯及聚胺甲酸酯的水溶液。爲了塗布上述的水 性塗布液，例如可舉出逆輥塗覆法、凹槽輥塗覆法、吻塗 法、輥刷法、噴塗法、氣刀塗覆法、線桿塗覆法、管刮法 、含浸塗覆法及簾幕塗覆法等，此等方法可單獨或組合地 進行。 其次’以夾具抓住薄膜的端部，導引至已加熱到8〇 1360477 180 °C的熱風區中，乾燥後在寬度方向作2.5〜5.0倍的拉 伸。接著，導引至220〜24〇°C的熱處理區，進行1〜20秒 的熱處理，完成結晶配向。於該熱處理工程中，視需要亦 可在寬度方向或長度方向中施予1〜12 %的鬆驰處理。 首先’說明本發明所用的接著性改質基材薄膜之接著 性改質層的相分離構造。其次，詳細說明本發明的硬被覆 薄膜或光學機能性薄膜所用的原料及製造條件，亦包括用 於控制上述相分離構造的條件因子。First, the method for producing the adhesive-modified substrate film used in the present invention is exemplified by polyethylene terephthalate (hereinafter abbreviated as PET) as a representative example, but it is of course not limited by the representative example. The nine particles of PET which are substantially free of particles (the purpose of which is to impart slipperiness) are sufficiently vacuum-dried, supplied to an extruder, melt-extruded into a sheet at 280 ° C, and solidified by cooling. Make unaligned PET sheets. At this time, the molten resin is kept at any position of about 280 ° C, and high-precision filtration is performed in order to remove impurities contained in the resin. The obtained unaligned sheet was stretched by 2.5 to 5.0 times in the longitudinal direction by a roll heated to 80 to 120 ° C to obtain a one-axis oriented PET film. Then, an aqueous solution of the copolymerized polyester and polyurethane was applied to one or both sides of the one-axis alignment PET film. In order to apply the above aqueous coating liquid, for example, a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire rod coating method, and a tube scraping method are mentioned. The method, the impregnation coating method, the curtain coating method, etc., may be carried out singly or in combination. Next, grasp the end of the film with a jig and guide it to a hot air zone that has been heated to 8 〇 1360477 180 °C. After drying, it is stretched 2.5 to 5.0 times in the width direction. Next, it is guided to a heat treatment zone of 220 to 24 ° C for heat treatment for 1 to 20 seconds to complete the crystal alignment. In the heat treatment process, a relaxation treatment of 1 to 12% may be applied in the width direction or the length direction as needed. First, the phase separation structure of the adhesion-modifying layer of the adhesive-modified substrate film used in the present invention will be described. Next, the raw materials and production conditions for the hard coating film or the optical functional film of the present invention will be described in detail, and the condition factors for controlling the phase separation structure described above are also included.

(1)接著性改質層的相分離構造 於本發明中，接著性改質層係具有以共聚合聚酯當作 主成分的聚酯相（以下亦簡稱PEs相）、與以聚胺甲酸酯當 作主成分的聚胺甲酸酯相（以下亦簡稱PU相）之微相分離構 造或奈米相分離構造》 於本發明的硬被覆薄膜中，接著性改質層B的使用目 的係爲了改善含無機微粒子的硬被覆層與熱塑性樹脂薄膜 的密接性。再者，於上述硬被覆層之相反側的表面上，若 積層同樣的硬被覆層或其它光學機能層時，則亦可用於改 善這些層與熱塑性樹脂薄膜之密接性。 於本發明中，重要的特徵爲：接著性改質層B係在聚 酯（PEs)相和聚胺甲酸酯（PU)相中具有微相分離或奈米相分 離構造，而且使用掃描型探針顯微鏡以相位測定模式來觀 察硬被覆薄膜的切削面時，在從接著性改質層B與硬被覆 層C的界面起到深度2 0 nm爲止的範圍內，下式所定義的 接著性改質層B之聚胺甲酸酯相（在相位像顯示明色相）的 -18- 1360477 面積率（PU面積率）係30%以上60%以下。 PU相的面積率（％) = (PU相的面積/測定面積）χ100 再者，上述PU相的面積率係如以下地求得。 於以熱塑性樹脂薄膜/接著性改質層/硬被覆層當作構成 單位的本發明之硬被覆薄膜中，爲了算出中間層的接著性 改質層之PU相的面積率，必須要使埋沒在內部的接著性 改質層之表面露出。(1) Phase Separation Structure of Adhesive Modification Layer In the present invention, the adhesive modification layer has a polyester phase (hereinafter also referred to as PEs phase) having a copolymerized polyester as a main component, and a polyamine A microphase separation structure or a nano phase separation structure of a polyurethane phase (hereinafter also referred to as a PU phase) having an acid ester as a main component. In the hard coating film of the present invention, the purpose of use of the adhesion modifying layer B is In order to improve the adhesion between the hard coating layer containing inorganic fine particles and the thermoplastic resin film. Further, when the same hard coating layer or other optical functional layer is laminated on the surface on the opposite side of the hard coating layer, it is also possible to improve the adhesion between the layers and the thermoplastic resin film. In the present invention, an important feature is that the adhesion modifying layer B has a microphase separation or a nano phase separation structure in a polyester (PEs) phase and a polyurethane (PU) phase, and uses a scanning type. When the probe microscope observes the cut surface of the hard coating film in the phase measurement mode, the adhesion defined by the following formula is in the range from the interface between the adhesion modifying layer B and the hard coating layer C to a depth of 20 nm. The area ratio (PU area ratio) of the -18 to 1360477 of the polyurethane phase of the modified layer B (in the phase image showing the bright phase) is 30% or more and 60% or less. Area ratio (%) of PU phase = (area of PU phase / measurement area) χ 100 Further, the area ratio of the above PU phase was determined as follows. In the hard coating film of the present invention in which the thermoplastic resin film/adhesive modified layer/hard coating layer is used as a constituent unit, in order to calculate the area ratio of the PU phase of the adhesive layer of the intermediate layer, it is necessary to be buried in The surface of the internal adhesion modifying layer is exposed.

作爲使接著性改質層的表面露出之方法，適合採用表 面界面物性解析裝置（DAIPLA . WINTES株式會社製， SAICAS)，從斜方向來切削薄膜的方法。其次，使用掃描 型探針顯微鏡（SPM)，以相位測定模式（相模式）從接著性改 質層的相位像來觀察相分離構造，求得硬被覆層附近的PU 相之面積率。 於接著性改質層的切削面中，硬被覆層的界面附近之 聚胺甲酸酯相的面積率係有如下述的技術意義。 聚胺甲酸酯相的面積率若超過60%，則於接著性改質 基材薄膜的製造時，在接著性改質層的表面中，聚胺甲酸 酯相的比率會相對地變大，防黏連性降低的頻率會增加。 另一方面，若聚胺甲酸酯相的面積率未滿3 0%，則密接性 降低的頻率會增加。特別地，對於無溶劑型的硬被覆劑或 透鏡形成用樹脂而言，密接性降低會變顯著》 於與硬被覆層的界面附近之接著性改質層中，從防黏 連性之點來看，聚胺甲酸酯相的面積率之上限較佳係50% 。另一方面，從與硬被覆層或丙烯酸系樹脂所成的其它光 -19 - 1360477 學機能層的密接性之點來看，PU相的面積率之下限較佳係 3 5% »As a method of exposing the surface of the adhesion-modifying layer, a method of cutting a film from an oblique direction by using a surface interface physical property analyzer (DAICAS, manufactured by WINTES Co., Ltd.) is suitable. Next, using a scanning probe microscope (SPM), the phase separation structure was observed from the phase image of the adhesion-modifying layer in the phase measurement mode (phase mode), and the area ratio of the PU phase in the vicinity of the hard coating layer was obtained. In the cutting surface of the adhesive reforming layer, the area ratio of the polyurethane phase in the vicinity of the interface of the hard coating layer has the following technical meaning. When the area ratio of the polyurethane phase exceeds 60%, the ratio of the polyurethane phase becomes relatively large on the surface of the adhesive modified layer at the time of production of the adhesive modified base film. The frequency of anti-adhesion reduction will increase. On the other hand, if the area ratio of the polyurethane phase is less than 30%, the frequency at which the adhesion is lowered increases. In particular, in the solventless hard coating agent or the lens forming resin, the decrease in adhesion is remarkable. In the adhesion modifying layer in the vicinity of the interface with the hard coating layer, from the point of preventing blocking property It is preferable that the upper limit of the area ratio of the polyurethane phase is 50%. On the other hand, the lower limit of the area ratio of the PU phase is preferably 3 5% from the viewpoint of the adhesion of the other light -19 - 1360477 functional layer formed of the hard coating layer or the acrylic resin.

又’於積層硬被覆層之前，在接著性改質基材薄膜的 接著性改質層的表面中，觀察PEs相與PU相的微相分離 構造或奈米相分離構造。而且，藉由掃描型探針顯微鏡以 相位測定模式來觀察時，下式所定義的接著性改質層之表 面中，聚酯相（在相位像顯示暗色相）的面積率在5μιηχ5μηι 的範圍內係35 %以上且低於90%。再者，於本發明中，當 在熱塑性樹脂薄膜的兩面上設置接著性改質層時，任一接 著性改質層皆具有與上述同樣的聚酯相之面積率。 PEs相的面積率（％) = (PEs相的面積/測定面積）χ10〇 該接著性改質層的表面中之PEs相的面積率，係有如 下述的技術意義。若PEs相的面積率低於35%，則在接著 性改質層的表面中，聚胺甲酸酯相的面積率會相對地變大 ，防黏連性降低的頻率會增加。另一方面，若PEs相的面 積率爲90%以上，則密接性的降低頻率會增加。特別地， 對於無溶劑型的硬被覆劑而言，密接性的降低會變顯著。 於接著性改質層的表面中，PEs相的面積率之下限，從 防黏連性之點來看，較佳係40%，更佳係 45%，特佳係 5 0%。另一方面，於接著性改質層的表面中，PEs相的面 積率之上限，從與丙烯酸系樹脂所成的機能層之密接性的 點來看，較佳係8 5 %，更佳係8 0 %，特佳係7 5 %。 再者，於本發明中，接著性改質層的表面之相分離構 造的評價，係使用掃描型探針顯微鏡（SPM)的相位測定模 -20 - 1360477 式（相模式）。相模式係藉由通常動力模式（DFM模式；使用 SII奈米科技社製SPM時）的表面形態觀察，同時進行相位 延遲測定模式者》 茲簡單地說明以掃描型探針顯微鏡（SPM)的相位測定模 式（相模式）來測定接著性改質層的相分離構造之原理。Further, before the hard coat layer was laminated, the microphase separation structure or the nano phase separation structure of the PEs phase and the PU phase was observed on the surface of the subsequent reforming layer of the adhesive modified base film. Further, when observed by the scanning probe microscope in the phase measurement mode, the area ratio of the polyester phase (in the phase image showing the dark phase) in the surface of the adhesion-modifying layer defined by the following formula is in the range of 5 μm χ 5 μηι. It is more than 35% and less than 90%. Further, in the present invention, when the adhesion-modifying layer is provided on both surfaces of the thermoplastic resin film, any of the adhesion-modifying layers has an area ratio of the same polyester phase as described above. Area ratio (%) of the PEs phase = (area of the PEs phase/measured area) χ10 面积 The area ratio of the PEs phase in the surface of the adhesion-modifying layer is as follows. When the area ratio of the PEs phase is less than 35%, the area ratio of the polyurethane phase becomes relatively large on the surface of the adhesion modifying layer, and the frequency of preventing the blocking property increases. On the other hand, if the area ratio of the PEs phase is 90% or more, the frequency of decrease in adhesion will increase. In particular, in the case of a solventless hard coating agent, the decrease in adhesion is remarkable. In the surface of the adhesion modifying layer, the lower limit of the area ratio of the PEs phase is preferably 40%, more preferably 45%, and particularly preferably 50% from the viewpoint of blocking resistance. On the other hand, in the surface of the adhesion-modifying layer, the upper limit of the area ratio of the PEs phase is preferably 85 %, more preferably from the point of adhesion to the functional layer formed of the acrylic resin. 80%, especially good 75%. Further, in the present invention, the phase separation structure of the surface of the adhesion-modifying layer is evaluated by a phase measurement mode of the scanning probe microscope (SPM) -20 - 1360477 (phase mode). The phase mode is based on the surface morphology observation of the normal power mode (DFM mode; when SPM is manufactured by SII Nanotechnology Co., Ltd.), and the phase delay measurement mode is simultaneously described. The phase of the scanning probe microscope (SPM) is briefly explained. The measurement mode (phase mode) is used to determine the principle of the phase separation structure of the adhesion modifying layer.

於相模式中，檢測出讓DFM動作時的懸臂振動之相位 延遲。於DFM動作中，以使共振的懸臂之振動振幅成爲一 定的方式，控制探針·試料間的距離，測定形狀。此處， 將用於使懸臂振動的雙壓電晶片（壓電元件）振動之信號稱 爲「輸入信號j時，於相位測定模式中，與振動振幅同時 地檢測出對於該「輸入信號」而言，有效的懸臂之振動信 號的相位延遲。相位延遲係敏感地響應表面物性的影響， 愈軟的試料表面則延遲愈大。藉由將該相位延遲的大小作 影像化，則可觀察表面物性的分布（稱爲相位像或相像等） 。因此，於複數的物性不同之樹脂相存在於表面時，藉由 本測定法，可作相分離構造的評價。 但是，接著性改質層的相分離構造之評價，若爲掃描 型探針顯微鏡的表面物性分布評價模式，則在相位測定模 式以外，也可爲摩擦力測定模式或黏彈性測定模式等的其 它模式，最重要的是選擇可感度佳地評價相分離構造之觀 察模式。再者，於相位測定模式中，不僅可藉由接著性改 質層的黏彈性之差異來檢測出相位延遲，而且可藉由吸附 力的大小般之表面物性的差異來檢測出相位延遲。 而且，於觀察接著性改質層的切削面之相分離構造時 -21 -In the phase mode, the phase delay of the cantilever vibration when the DFM is operated is detected. In the DFM operation, the distance between the probe and the sample is controlled so that the vibration amplitude of the resonant cantilever is constant, and the shape is measured. Here, when the signal for vibrating the bimorph (piezoelectric element) that vibrates the cantilever is referred to as "input signal j, in the phase measurement mode, the "input signal" is detected simultaneously with the vibration amplitude. That is, the phase delay of the effective cantilever vibration signal. The phase delay is sensitive to the influence of surface physical properties, and the softer the surface of the sample is delayed. By visualizing the magnitude of the phase delay, the distribution of surface physical properties (referred to as phase image, phase, etc.) can be observed. Therefore, when a plurality of resin phases having different physical properties exist on the surface, the phase separation structure can be evaluated by the present measurement method. However, the evaluation of the phase separation structure of the adhesion-modifying layer may be a frictional force measurement mode or a viscoelasticity measurement mode other than the phase measurement mode in the case of the surface property distribution evaluation mode of the scanning probe microscope. Mode, the most important thing is to choose an observation mode that can evaluate the phase separation structure with good sensitivity. Further, in the phase measurement mode, not only the phase retardation can be detected by the difference in viscoelasticity of the adhesive layer, but also the phase retardation can be detected by the difference in surface physical properties such as the magnitude of the adsorption force. Moreover, when observing the phase separation structure of the cutting face of the adhesive reforming layer -21 -

1360477 ，爲了容易觀察相分離構造，較佳爲以S PIP軟 Metrology公司製，Version 4.1)來讀取相位像， 一化（Color Equalization)處理，增強對比。其理 述。 使用表面界面物性解析裝置（SAICAS)，從基 切削到硬被覆薄膜的內部時，對於切削方向而言 開接著性改質層的切削面之變形係困難的。又， 切削接著性改質層中所含有的無機粒子，故在無 周邊，切削時的傷害結果爲不能避免空隙的出現 此的切削，於表面露出的接著性改質層與熱塑性 或硬被覆層、其它機能層的界面中，與PEs成分 PU成分係成爲支配者。推測此係因爲從與PEs成 PU成分較容易受到變形之點，PEs成分的物性與 著性改質層的熱塑性樹脂薄膜之物性的差異小之 方向所切削的接著性改質層之厚度極薄之點來看 差異變小。 本發明中的接著性改質層之相分離構造，從 來看，係相當於微相分離構造或奈米相分離構造 明所用的接著性改質基材薄膜中，觀察接著性改 面（與硬被覆層的界面）之相位差像時，可瞭解具 的相分離構造。 於將PEs相看作具有長軸和短軸的連續構造 軸方向的寬度最大爲Ιμιη、長軸方向的長度超過 續構造當作主體。即，對於PEs相的全體面積而 體（Image 進行色均 由係如下 材薄膜側 ，完全避 由於無法 機粒子的 。藉由如 樹脂薄膜 比較下， 分比較下 鄰接於接 點，從斜 ，對比的 大小之點 。於本發 質層的表 有如下述 時，以短 1 μιη的連 言，具有 -22 - 1360477 上述連續構造的部分之面積係80%以上，較佳係85%以上 ，更佳係90%以上。又，不相當於上述定義中所記載的連 續構造，而分散成島狀的PEs相，雖然在接著性改質層的 內部具有連續構造，但末端亦出現在表面。1360477, in order to easily observe the phase separation structure, it is preferable to read a phase image, a color equalization process, and enhance contrast by SIPIP Soft Metrology, Version 4.1). Its rationale. When the surface interface physical property analysis device (SAICAS) is used, it is difficult to deform the cutting surface of the adhesion-modifying layer in the cutting direction from the base cutting to the inside of the hard coating film. Further, since the inorganic particles contained in the adhesive reforming layer are cut, the damage at the time of cutting is that the cutting of the void cannot be avoided as a result of the cutting, and the adhesive modified layer and the thermoplastic or hard coating layer exposed on the surface are formed. In the interface of other functional layers, it is the dominant component of the PU component of the PEs component. It is presumed that the thickness of the adhesive modified layer cut in the direction in which the physical properties of the PEs component and the physical properties of the thermoplastic resin film of the original modified layer are small are extremely thin because the PU component is more susceptible to deformation from the PE component. From the point of view, the difference becomes smaller. The phase-separated structure of the adhesion-modifying layer in the present invention is equivalent to a micro-phase separation structure or a nano-phase separation structure, and the adhesion-modified substrate film is observed. When the phase difference image of the interface of the coating layer is observed, the phase separation structure of the device can be understood. The PEs phase is regarded as a continuous structure having a long axis and a short axis. The width of the axis direction is at most Ιμιη, and the length in the long axis direction is longer than the continuous structure as the main body. That is, for the entire area of the PEs phase, the color of the image is based on the film side of the film, and it is completely avoided by the machine particles. By comparing with the resin film, it is adjacent to the contact point, and the skew is compared. The size of the hair layer is as follows. In the case of a short 1 μm, the area of the continuous structure having -22 - 1360477 is 80% or more, preferably 85% or more. More preferably, it is 90% or more. Further, it does not correspond to the continuous structure described in the above definition, and the PEs phase dispersed in the island shape has a continuous structure inside the adhesive reforming layer, but the end also appears on the surface.

就該PEs相的連續構造之大小而言，較佳爲短軸方向 的寬度最大係1 μιη，更佳係0.8μιη，更佳係〇.6μηι，特佳 係0.4 μπι。短軸方向的寬度之下限係沒有特別的限定，但 用於維持連續構造的最窄部分較佳係 0.01 μιη，特佳係 0.05 μιη。另一方面，就該PEs相的連續構造之大小而言， 長軸方向的長度較佳係超過1 μιη，更佳係1.5 μιη以上，尤 佳係2·0μιη以上，特佳係2.5μιη以上。 於本發明所用的接著性改質基材薄膜中，接著性改質 層的表面之相分離構造，亦可由第1圖所示的代表例得知 ，顯示自然界中所看不到的複雜構造，以一個含義來定義 相分離的形態係困難的。上述相分離構造亦可如以下地以 多方面的表現。 例如’若以上述相分離構造的形態當作模樣來表現， 則在文獻的記載中，係接近「樹枝狀構造」（「化學語大辭 典」，第226頁，昭和54年6月15日，三共出版（股）發 行）、「波紋狀構造」（「花樣」，第16 8·〜169頁、2002. Hi野薔薇（股）公司發行）、「迷彩調」。 如此的接著性改質層的表面之相分離構造，在聚合物 摻合物系統之形態學的領域中，類偶於以共連續構造表現 者。再者，亦可以共聚合聚酯與自交聯型聚胺甲酸酯相互 (S ) -23 - 1360477 纏繞而形成的相互網目侵入構造來表現。 又，於形態中，PEs相的自我相似性，亦可使用碎形次 元來定量表現。例如，如第3圖所示地，以掃描型探針顯 微鏡的相位測定模式來觀察接著性改質層的表面，在強調 明色相（聚胺甲酸酯相）與暗色相（聚酯相）的界面之輪廓的 相位像中，以明色相與暗色相的邊界線（界面的輪廓）之複 雜度當作指數，使用網格計數法，使用從上述界面的輪廓 所求得的碎形次元，可定量地表現。In terms of the size of the continuous structure of the PEs phase, the width in the short axis direction is preferably 1 μιη, more preferably 0.8 μηη, more preferably 66 μηι, and particularly preferably 0.4 μπι. The lower limit of the width in the short-axis direction is not particularly limited, but the narrowest portion for maintaining the continuous structure is preferably 0.01 μm, particularly preferably 0.05 μm. On the other hand, in terms of the size of the continuous structure of the PEs phase, the length in the long axis direction is preferably more than 1 μm, more preferably 1.5 μm or more, more preferably 2·0 μmη or more, and particularly preferably 2.5 μmη or more. In the adhesive modified base film used in the present invention, the phase separation structure of the surface of the adhesive modified layer can be obtained by the representative example shown in FIG. 1 and shows a complicated structure which is not visible in nature. Defining the phase separation morphology in one meaning is difficult. The phase separation structure described above can also be expressed in various aspects as follows. For example, if the form of the phase separation structure is expressed as a pattern, it is close to the "dendritic structure" in the description of the literature ("Chemical Dictionary", p. 226, June 15, 54, Showa, The three publications (shares), "corrugated structures" ("patterns", pages 16 8 ~ 169, 2002. Hi wild rose (shares) company issued), "camouflage tone." The phase separation structure of the surface of such an adhesion-modifying layer is, in the field of the morphology of the polymer blend system, the ones which are represented by a co-continuous structure. Further, it is also possible to express the mutual mesh intrusion structure formed by the copolymerization of the polyester and the self-crosslinking type polyurethane to each other (S) -23 - 1360477. Moreover, in the form, the self-similarity of the PEs phase can also be quantified using the fractal dimension. For example, as shown in Fig. 3, the surface of the adhesion modifying layer is observed by the phase measurement mode of the scanning probe microscope, and the bright phase (polyurethane phase) and the dark phase (polyester phase) are emphasized. In the phase image of the contour of the interface, the complexity of the boundary line of the bright phase and the dark phase (the contour of the interface) is used as an index, and the grid counting method is used, and the fractal dimension obtained from the contour of the interface is used. Can be expressed quantitatively.

單位面積的碎形（fractal)次元爲1時係意味直線（一次 元），2係意味實體面（二次元）。即，碎形次元愈接近2, 則意味構造愈緻密。另一方面，碎形次元愈接近1，則意 味愈稀疏的構造。 具體地，於接著性改質基材薄膜的接著性改質層之表 面上，在上述明色相（聚胺甲酸酯相）與暗色相（聚酯相）的 界面之輪廓經強調的相位像中，明色相與暗色相的邊界線（ 界面的輪廓）之碎形次元在5μηι><5μιη測定面積中較佳係 1.60〜1.95。上述碎形次元的上限更佳係 1.93，特佳係 1.90。另一方面，上述碎形次元的下限更佳係1.65，特佳 係 1.70 ° 例如，於第4圖所示的接著性改質層之表面中，明色 相（聚胺甲酸酯相）與暗色相（聚酯相）的邊界線（界面的輪廓） 之碎形次元分別是1.89和1.90。再者，第4圖顯示對於表 示本發明中的接著性改質層之表面的代表相分離構造的第 1圖之相位像，強調明色相與暗色相的界面之輪廓，明色 -24 - 1360477 相與暗色相的邊界線之圖。When the fractal dimension per unit area is 1, it means a straight line (primary element), and 2 means a solid surface (secondary element). That is, the closer the broken dimension is to 2, the more dense the structure is. On the other hand, the closer the fractal dimension is to 1, the more sparse the structure is. Specifically, on the surface of the adhesion modifying layer of the adhesive-modified substrate film, the contour image of the contour of the interface between the above-mentioned bright phase (polyurethane phase) and the dark phase (polyester phase) is emphasized. The fractal dimension of the boundary line (the outline of the interface) of the bright phase and the dark phase is preferably 1.60 to 1.95 in the measurement area of 5 μηι>5 μιη. The upper limit of the above fractal dimension is preferably 1.93, and the special grade is 1.90. On the other hand, the lower limit of the above-mentioned fractal dimension is more preferably 1.65, and particularly preferably 1.70 °. For example, in the surface of the adhesion modifying layer shown in Fig. 4, the bright phase (polyurethane phase) and the dark color The fractal dimensions of the boundary line (the contour of the interface) of the phase (polyester phase) are 1.89 and 1.90, respectively. Further, Fig. 4 is a view showing the phase image of the first figure representing the phase separation structure of the surface of the adhesion modifying layer in the present invention, emphasizing the contour of the interface between the bright phase and the dark phase, and the bright color - 24 - 1360477 A diagram of the boundary line between the phase and the dark phase.

於本發明中，爲了以最大限度來展現成爲接著性改質 層的原料之共聚合聚酯及聚胺甲酸酯所具有的機能，重要 的接著性改質層成爲微相分離構造或奈米相分離構造。因 爲若兩樹脂完全相溶，則兩樹脂的性質相抵，全體地不能 期待共聚合聚酯或聚胺甲酸酯的優異特性。於接著性改質 層中，作爲PEs相及PU相所可採取的其它相分離構造， 亦考慮PU相分散於PEs相內者，及PEs相分散於PU相內 的所謂複合形態，即顯示代表的海島構造。當然，該海島 構造在樹脂的非相溶狀態下，若增多一方的樹脂相，則另 —方必然變少，形成所謂的島。於本發明中若控制製造條 件，亦可成爲採取如此海島構造的分離相所成的接著性改 質層。 但是，若考慮用於形成島構造的樹脂相之大小的不均 勻或分布狀態的不均勻，則不能忽視島相的形狀、數目、 及分布狀態的影響。因此，亦顧慮構成海構造的樹脂之性 質的大影響。因此，茲認爲本發明的PEs相與PU相的相 分離構造，在形成互相絡合至每個角落的相分離構造方面 ’係有利於保持材料的均勻性。顯示PEs相和PU相的海 島構造之相分離構造，亦可被舉出當作本發明的代表態樣 之一個。 又，作爲本發明中的接著性改質層之其它相分離構造 ，亦可形成芯-殼構造。例如，PU相包圍PEs相的四周， 再以PEs相包圍包的構造。然而，爲了形成如此的芯-殻構 -25 - 1360477 造’需要非常高度的控制。又，由於採取該芯-殼構造，故 不能期待可顯示優良的材料行爲。In the present invention, in order to maximize the function of the copolymerized polyester and the polyurethane which are the raw materials of the adhesive reforming layer, the important adhesive reforming layer becomes a microphase separation structure or a nano phase. Phase separation structure. If the two resins are completely compatible, the properties of the two resins are offset, and the excellent properties of the copolymerized polyester or polyurethane are not expected as a whole. In the adhesive modification layer, other phase separation structures which can be taken as the PEs phase and the PU phase are also considered to be dispersed in the PEs phase, and the so-called composite morphology in which the PEs phase is dispersed in the PU phase, that is, the display representative Island structure. Of course, when the island structure is in an incompatible state of the resin, if one resin phase is added, the other side is inevitably reduced, and a so-called island is formed. In the present invention, if the manufacturing conditions are controlled, it may be an adhesive layer formed by a separate phase having such an island structure. However, considering the unevenness of the size of the resin phase for forming the island structure or the unevenness of the distribution state, the influence of the shape, the number, and the distribution state of the island phase cannot be ignored. Therefore, there is also a concern about the great influence of the properties of the resin constituting the sea structure. Therefore, it is considered that the phase separation structure of the PEs phase of the present invention and the PU phase is advantageous in maintaining the uniformity of the material in forming a phase separation structure which is mutually coupled to each corner. The phase separation structure showing the sea-island structure of the PEs phase and the PU phase can also be cited as one of the representative aspects of the present invention. Further, as another phase separation structure of the adhesion modifying layer in the present invention, a core-shell structure may be formed. For example, the PU phase surrounds the perimeter of the PEs phase, and the PEs phase surrounds the packet structure. However, in order to form such a core-shell structure - 25 - 1360477 requires a very high degree of control. Moreover, since the core-shell structure is adopted, it is not expected to exhibit excellent material behavior.

再者，作爲相分離構造的態樣，亦可採取PEs相與PU 相交互規則地並排之積層構造。然而，理想上爲各相係平 行地以約略等間隔地配置，但若的相的寬度變大，則在接 著性改質層的界面係難以均勻分佈PEs相和PU相》甚至 亦有影響接著性改質基材薄膜的品質之虞。藉由製造條件 的微妙疏遠，可一邊採取海島構造、芯-殼構造及積層構 造的形態，一邊成爲此等之混合存在型。但是，於接著性 改質層中’ PEs相與PU相具有一定的大小，其均勻地到處 混合存在，對於保持品質而言係重要的。 再者’ PEs相與PU相在接著性改質層在厚度方向中爲 2層的相分離構造，於本發明中係不宜的。因爲就本發明 而言，在接著性改質層的表面（與硬被覆層的界面），PEs 相與PU相以恰當的面積率作均勻分布，從本發明的作用 效果之點來看係重要的。 接著性改質層的表面或切削面中的相分離構造，具有 以共聚合聚酯當作主成分的聚酯相及以聚胺甲酸酯當作主 成分的聚胺甲酸酯相，各具不規則的形態。因此，此等樹 脂相係在接著性改質層的表面及內部，以不規則且緻密地 到處配置，形成複雜的排列構造。又，亦可爲對於一個樹 脂相的表面，使另一方的樹脂相以非相溶性的狀態侵入之 構造。而且，於第3圖中，黑色部分表示聚酯相，白色部 分表示聚胺甲酸酯相》 -26 -Furthermore, as a phase separation structure, a laminated structure in which the PEs phase and the PU phase are alternately arranged side by side may be employed. However, it is desirable that the phases are arranged at approximately equal intervals in parallel, but if the width of the phase becomes large, it is difficult to uniformly distribute the PEs phase and the PU phase at the interface of the adhesion modifying layer. The quality of the modified substrate film. By the subtle alienation of the manufacturing conditions, it is possible to adopt a sea-island structure, a core-shell structure, and a laminated structure, and to form such a mixed existence type. However, in the adhesive reforming layer, the 'PEs phase and the PU phase have a certain size, which is uniformly mixed everywhere, and is important for maintaining quality. Further, the phase separation structure in which the PEs phase and the PU phase are two layers in the thickness direction in the adhesive reforming layer is not preferable in the present invention. In the present invention, in the surface of the adhesion-modifying layer (the interface with the hard coating layer), the PEs phase and the PU phase are uniformly distributed at an appropriate area ratio, which is important from the viewpoint of the effect of the present invention. of. The phase separation structure in the surface of the modified layer or the cutting surface, having a polyester phase containing a copolymerized polyester as a main component and a polyurethane phase containing a polyurethane as a main component, each With an irregular shape. Therefore, these resin phases are arranged on the surface and inside of the adhesive reforming layer, and are arranged irregularly and densely to form a complicated alignment structure. Further, it may be a structure in which the other resin phase is infiltrated in a state in which the other resin phase is incompatible with respect to the surface of one resin phase. Further, in Fig. 3, the black portion indicates the polyester phase, and the white portion indicates the polyurethane phase -26 -

1360477 於接著性改質基材薄膜的接著性 於單位面積（例如5χ5μπ〇而言，在兩 而均勻排列時，一方的樹脂相之尺寸 —方的樹脂相之尺寸。因此，在樹脂 偏差。結果，兩樹脂相分離，變成難 列狀態，由於在接著性改質層的材質 上係不好的。 爲了使兩樹脂相產生相分離，且 態存在於接著性改質層中，較佳係使 軸方向的寬度最大爲Ιμπι、長軸方向 當然，於沒有高度要求品質的情況中 大爲6μιη左右之相對大的構造亦可能 的相分離構造，係可藉由選擇地採用 用的塗布液之樹脂組成、界面活性劑 量、塗布層的乾燥條件、及熱定型條 在接著性改質層中展現特異的微相分 構造。總之，如第1圖所示，接著性 相和聚胺甲酸酯相的相分離構造之態 發明的接著性改質基材薄膜之效果的 再者，詳細說明相分離構造的重I 於本發明所用的接著性改質基材 性改質層係以共聚合聚酯成分和聚胺 成分，而且以共聚合聚酯當作主成分 甲酸酯當作主成分的PU相成相分離 改質層之表面中，對 種樹脂相以分離狀態 若變大，則會限制另 相的存在中發生大的 以維持均勻的分散排 發生不均，品質管理 以均勻混合存在的狀 PEs相的形態成爲短 的長度爲Ιμηι以上。 ，短軸方向的寬度最 的。該連續相（PES相） 接著性改質層之形成 的種類和濃度、塗布 件等，控制它們，而 離構造或奈米相分離 i改質層的表面之聚酯 樣，係爲用於展現本 代表模型。 ί性。 薄膜中，較佳爲接著 甲酸酯成分當作樹脂 的PEs相係與以聚胺 :，各相具有連續構造 -27 - 1360477 。藉由使上述2種樹脂不均勻混合而成相分離，則對於由 熱塑性樹脂薄膜所成的基材薄膜而言，具有優異的密接性 且具有比較良好的耐溶劑性的共聚合聚酯，與耐溶劑性差 之對於硬被覆層或擴散層、丙烯酸系樹脂等許多樹脂而言 ，具有優良密接性的聚胺甲酸酯，係不會抵銷各自的特性 ，而能充分利用各樹脂的特長。1360477 The adhesion of the adhesive-modified substrate film to the unit area (for example, 5 χ 5 μπ〇, when the two are uniformly arranged, the size of one resin phase is the size of the resin phase. Therefore, the resin varies. The two resins are separated into a difficult state, which is not good in the material of the adhesive modifying layer. In order to cause phase separation between the two resin phases, and the state exists in the adhesive modifying layer, it is preferred to The width in the axial direction is at most Ιμπι, and the direction of the long axis. Of course, a phase separation structure having a relatively large structure of about 6 μm in the case where there is no high quality requirement is a resin which can be selectively used. The composition, the surfactant dose, the drying conditions of the coating layer, and the heat-set strip exhibit a specific micro-phase structure in the adhesive modifying layer. In summary, as shown in Figure 1, the adhesive phase and the polyurethane phase In the phase separation structure, the effect of the adhesion-modified substrate film of the invention will be described in detail, and the weight of the phase separation structure will be described in detail in the adhesion-modified substrate-modified layer used in the present invention. In the surface of the PU phase-forming reforming layer in which the polyester component and the polyamine component are copolymerized, and the copolymerized polyester is used as the main component formate as a main component, the phase of the resin phase is changed in a separated state. When the size is large, the occurrence of the other phase is limited to maintain a uniform dispersion, and the quality of the PEs phase in which the quality management is uniformly mixed becomes a short length of Ιμηι or more. The width in the short axis direction is the most The continuous phase (PES phase), the type and concentration of the formation of the modified layer, the coating member, etc., are controlled, and the polyester-like surface of the surface of the i-modified layer is separated from the structure or the nano phase. In the film, it is preferred that the PET phase is followed by the formate component as a resin and the polyamine: each phase has a continuous structure of -27 - 1360477. By making the above two resins When the phase separation is unevenly mixed, the base film formed of the thermoplastic resin film has excellent adhesion and has a relatively good solvent resistance. The copolymerized polyester is poor in solvent resistance. Many resin layer or a diffusion layer, an acrylic resin, the urethane polyamine having an excellent adhesion property, does not offset the characteristics of each system, but can take advantage of the respective strengths of the resin.

構成接著性改質層的聚酯相，較佳係由共聚合聚酯所 單獨構成，但是亦可含有0.01〜40質量％的聚胺甲酸酯。 再者，在聚酯相中也可含有0.001〜20質量％的粒子。又 ，於聚酯相中，界面活性劑亦可附著或含於上述樹脂中。 同樣地，聚胺甲酸酯相較佳係由聚胺甲酸酯所單獨構成， 可以含有上述共聚合聚酯中所記載程度之量的粒子、界面 活性劑等。特別地，於與聚胺甲酸酯的親和性高之粒子的 情況，在接著性改質層的形成過程中，可選擇地使在聚胺 甲酸酯相中比在聚酯相中更多偏在著。 一般地，於共聚合聚酯與聚胺甲酸酯的混合物所成的 組成物中，通常兩者係成爲化學均勻的材料，展現互相補 充彼此所具有的性質或機能的化學補足機能之情況係多的 。另一方面，就本發明之由聚酯相及聚胺甲酸酯相所成的 接著性改質層而言，如上述地聚酯相與聚胺甲酸酯相係物 理上各自成相分離，在樹脂相的存在中發生大的偏差，兩 樹脂相係分離，維持均勻分散排列的狀態之構造。各樹脂 所各自擁有性質，經由各樹脂相的表面，例如共聚合聚酯 分擔防黏連性的機能，聚胺甲酸酯分擔密接性的機能，各 -28- 1360477 自爲相分離狀態。譬如說，物理的補足機能之表現，其機 能或原理，正是先行技術中所完全不認識的新穎技術事項The polyester phase constituting the adhesive reforming layer is preferably composed of a copolymerized polyester alone, but may also contain 0.01 to 40% by mass of a polyurethane. Further, 0.001 to 20% by mass of particles may be contained in the polyester phase. Further, in the polyester phase, a surfactant may be attached or contained in the above resin. Similarly, the polyurethane phase is preferably composed of a polyurethane, and may contain particles, an surfactant, and the like in an amount as described in the above-mentioned copolymerized polyester. In particular, in the case of particles having a high affinity with the polyurethane, during the formation of the adhesion-modifying layer, it is optionally made more in the polyurethane phase than in the polyester phase. Be biased. In general, in a composition obtained by copolymerizing a mixture of a polyester and a polyurethane, usually both are chemically uniform materials, and the chemical replenishment function exhibiting each other's properties or functions is exhibited. Many. On the other hand, in the case of the adhesive modified layer of the polyester phase and the polyurethane phase of the present invention, the polyester phase and the polyurethane phase are physically separated as described above. In the presence of a resin phase, a large variation occurs, and the two resin phases are separated to maintain a structure in which the resin is uniformly dispersed. Each of the resins possesses properties, and the functions of the anti-blocking property are shared by the surfaces of the respective resin phases, for example, the copolymerized polyester, and the polyurethanes share the function of adhesion, and each of the -28-1360477 is self-separated. For example, the performance of physical supplemental functions, its function or principle, is a novel technical issue that is completely unknown in the prior art.

於本發明中，接著性改質層的相分離構造之詳細發生 機構係不明確。然而，藉由共聚合聚酯與聚胺甲酸酯的組 成比、水與醇的分散介質之比率、界面活性劑的種類、界 面活性劑中的不純物、水性塗布液的pH、塗布量等的塗布 液之材料構成或特性、乾燥及熱定型處理的時間、溫度、 風速的微妙條件之平衡，可在接著性改質層中展現特異的 微相分離構造或奈米相分離構造，此可由各實施例與比較 例的對比而容易理解。 再者，聚胺甲酸酯所具有的異氰酸基之反應開始溫度 亦有微妙的影響。此處所言的相分離構造，係指所謂的 PEs相與PU相的兩相保持物理的邊界，而非距離上分開， 邊界係沒有距離而接觸，在PEs相中共聚合聚酯係大多集 中偏置，在PU相中専門由聚胺甲酸酯所大多集中偏置， 兩層的邊界宛如附有明確的區別，在外觀上應可看到分離 的邊界。因此，於本發明的情況中，聚胺甲酸酯的異氰酸 基於該邊異亦有反應的可能性，顯示複雜的分離構造。 本發明所用的接著性改質基材薄膜，具有由PEs相與 PU相所成的接著性改質層，係指例如介於由熱塑性薄膜所 成的基材、硬被覆層或擴散層等的機能層之間存在，對所 謂的基材面與機能層面的兩面，達成同等作用的界面機能 之任務。如此，PEs相及PU相皆採取兩者分離的構造，In the present invention, the detailed mechanism of the phase separation structure of the adhesion modifying layer is not clear. However, the composition ratio of the copolymerized polyester to the polyurethane, the ratio of the dispersion medium of water to the alcohol, the type of the surfactant, the impurities in the surfactant, the pH of the aqueous coating liquid, the coating amount, and the like The material composition or characteristics of the coating liquid, the balance between the time and temperature of the drying and heat setting treatment, and the subtle conditions of the wind speed can exhibit a specific micro phase separation structure or a nano phase separation structure in the adhesion modifying layer. The examples are easily understood in comparison with the comparative examples. Further, the reaction initiation temperature of the isocyanate group of the polyurethane has a subtle influence. The phase separation structure referred to herein means that the so-called PEs phase and the two phases of the PU phase maintain physical boundaries, rather than being separated from each other, and the boundary system is not in contact with each other. In the PEs phase, the copolymerized polyester system is mostly concentrated. In the PU phase, the door is mostly offset by the polyurethane. The boundary of the two layers is clearly distinguished, and the separation boundary should be visible in appearance. Therefore, in the case of the present invention, the isocyanic acid of the polyurethane exhibits a complicated separation structure based on the possibility that the side also reacts. The adhesive modified base film used in the present invention has an adhesive modified layer formed of a PEs phase and a PU phase, and is, for example, a substrate, a hard coat layer or a diffusion layer formed of a thermoplastic film. There is a function between the functional layers to achieve the same function of the interface function on both sides of the so-called substrate surface and functional level. Thus, both the PEs phase and the PU phase adopt a separate structure.

(S -29- 1360477 PEs相的狀態係爲將本來所具有的共聚合聚酯之優異性質 ，對於接著性改質層的兩面（基材與接著性改質層的界面、 接著性改質層與硬被覆層等的機能層的界面），發擇最大限 度。即，PU相的狀態係將本來所具有的聚胺甲酸酯之優異 性質，對於兩面發揮最大限度。(S -29- 1360477 The state of the PEs phase is the excellent property of the copolymerized polyester originally possessed, and the both surfaces of the adhesive modified layer (the interface between the substrate and the adhesive modified layer, the subsequent modified layer) The interface with the functional layer such as the hard coating layer is selected to the maximum extent. That is, the state of the PU phase is to maximize the properties of the originally possessed polyurethane and to maximize both sides.

此係因爲在具有接著性改質層的接著性改質基材薄膜 中，接著性改質層的表面具有由PEs相及PU相所成的微 相分離構造或奈米相分離構造，故PEs相的共聚合聚酯露 出，以最大限度達成該共聚合聚酯的性質或機能，同樣地 ，PU相的聚胺甲酸酯露出，以最大限度達成該聚胺甲酸酯 本來所具有的性質或機能。因此，於接著性改質層的表面 ，若PEs相和PU相各自以特定的範圍分佈，則兩者樹脂 的性質或機能可發擇最大限度。此係因爲積層體的特有構 造，在基材與接著性改質層的界面、接著性改質層與機能 層的界面中，合理地作用。 再者，於本發明中，當在構成PEs相及PU相的樹脂組 成物中含有粒子時，例如可使矽石粒子偏在於PU相中。 推測此係因爲於表面能方面，PU相係比PEs相較接近矽石 粒子。使矽石粒子偏在於PU相中，則可提高聚胺甲酸酯 的短處，即防黏連性，而且可減少整個接著性改質層的粒 子含量，故爲有益於達成維持透明性的機能之構造。 同樣，若選擇表面能較接近共聚合聚酯的粒子，則暗 示可選擇地使粒子偏在於PEs相中。使粒子偏在於由PEs 相或PU相所相分離構造中的任一者係爲先行技術所不能 -30 - 1360477 預期的手法，可邊維持透明性邊高度改良滑性或黏連性。 因此，可增廣微相分、離構造或奈米相分離構造的材料設計 之應用範圍的點，在本發明中亦有有意義的。 (2)熱塑性樹脂薄膜This is because in the film of the adhesion-modified substrate having the adhesion-modifying layer, the surface of the adhesion-modifying layer has a microphase-separated structure or a nanophase-separated structure formed by the PEs phase and the PU phase, so PEs The phase copolymerized polyester is exposed to maximize the properties or functions of the copolymerized polyester. Similarly, the PU phase of the polyurethane is exposed to maximize the properties of the polyurethane. Or function. Therefore, on the surface of the adhesion modifying layer, if the PEs phase and the PU phase are each distributed in a specific range, the properties or functions of the two resins can be maximized. This is due to the unique structure of the laminate, which acts reasonably at the interface between the substrate and the adhesion modifying layer, and at the interface between the adhesion modifying layer and the functional layer. Further, in the present invention, when particles are contained in the resin composition constituting the PEs phase and the PU phase, for example, the vermiculite particles may be biased in the PU phase. It is speculated that this is because the PU phase is closer to the vermiculite particles than the PEs because of the surface energy. When the vermiculite particles are biased in the PU phase, the shortness of the polyurethane, that is, the anti-adhesion property, and the particle content of the entire adhesive reforming layer can be reduced, so that it is beneficial to achieve the function of maintaining transparency. Construction. Similarly, if a particle having a surface energy closer to the copolymerized polyester is selected, it is implicitly selected to bias the particle in the PEs phase. Any one of the structures in which the particles are separated by the PEs phase or the PU phase is not a prior art. -30 - 1360477 The desired method can improve the smoothness or adhesion while maintaining transparency. Therefore, the point of application of the material design which can augment the microphase, the off-structure or the nanophase separation structure is also significant in the present invention. (2) Thermoplastic resin film

作爲本發明所用的熱塑性樹脂薄膜，合適者是將熱塑 性樹脂經熔融擠出或溶液擠出所得之未配向片，按照需要 地，在長度方向或寬度方向的一軸方向作拉伸，或在二軸 方向中逐次二軸拉伸或同時二軸拉伸，施予熱定型處理而 成的二軸拉伸熱塑性樹脂薄膜》 又，熱塑性樹脂薄膜，在不損害本發明的目的之範圍 內，對於上述薄膜，亦可施予電暈放電處理、輝光放電處 理、火焰處理、紫外線照射處理 '電子線照射處理、臭氧 處理等的表面活性化處理。 本發明中所用的熱塑性樹脂薄膜之厚度係在30〜 300μιη的範圍內，可按照所使用的用途之規格來任意地決 定。上述熱塑性樹脂薄膜的厚度之上限較佳係250 μπι，特 佳係200 μιη。另一方面，薄膜厚度的下限較佳係50μιη，特 佳係75μιη。薄膜厚度若低於50μπι，則剛性或機械強度容 易變不足。另一方面，薄膜厚度若超過3 00 μιη，則由於薄 膜中所存在的雜質之絕對量增加，故成爲光學缺點的頻率 會變高。又，於將薄膜切斷成指定的寬度時之切割性亦變 差’製造成本變高。再者，由於剛性增強，將長條薄膜捲 繞成圓筒狀係容易變困難。 作爲熱塑性樹脂，可舉出聚乙烯（ΡΕ)、聚丙烯（ΡΡ)、聚 -31- 1360477 甲基戊烯（TPX)等的聚烯烴，聚對酞酸乙二酯（pet)、聚 2,6-萘二甲酸乙二酯（PEN)、聚對酞酸四亞甲酯（PTT)、聚 對酞酸丁二酯（PBT)等的聚酯樹脂，耐隆6、耐隆4、耐隆 66、耐隆12等的聚醯胺（PA)樹脂，聚醯亞胺（PI)、聚醯胺 醯亞胺（PAI)、聚醚颯（PES)、聚醚醚酮（PEEK)、聚碳酸酯 (PC)、聚芳酯（PAR)、丙酸纖維素、聚氯乙烯（PVC)、聚偏 二氯乙烯、聚乙烯醇（PVA)、聚醚醯亞胺（PEI)、聚苯硫醚The thermoplastic resin film used in the present invention is preferably an unaligned sheet obtained by melt-extruding or solution-extruding a thermoplastic resin, and stretching in one axial direction in the longitudinal direction or the width direction as needed, or in two axes. A biaxially stretched thermoplastic resin film which is subjected to heat setting treatment in the direction of secondary biaxial stretching or simultaneous biaxial stretching. Further, the thermoplastic resin film is, for the purpose of not impairing the object of the present invention, the film. Surface activation treatment such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, or the like may be applied. The thickness of the thermoplastic resin film used in the present invention is in the range of 30 to 300 μm, and can be arbitrarily determined in accordance with the specifications of the use. The upper limit of the thickness of the thermoplastic resin film is preferably 250 μm, and particularly preferably 200 μm. On the other hand, the lower limit of the film thickness is preferably 50 μm, particularly preferably 75 μm. If the film thickness is less than 50 μm, the rigidity or mechanical strength is liable to be insufficient. On the other hand, if the thickness of the film exceeds 300 μm, the absolute amount of impurities present in the film increases, so that the frequency of optical defects becomes high. Further, the cutting property is also deteriorated when the film is cut into a predetermined width, and the manufacturing cost is increased. Further, since the rigidity is increased, it is difficult to wind the long film into a cylindrical shape. Examples of the thermoplastic resin include polyolefins such as polyethylene (polypropylene), polypropylene (fluorene), poly-31-1360477 methylpentene (TPX), and polyethylene terephthalate (pet) and poly 2, Polyester resin such as 6-naphthalenedicarboxylate (PEN), polytetramethylene terephthalate (PTT), polybutylene terephthalate (PBT), Nylon 6, Nylon 4, Nylon 66. Polyamine (PA) resin such as london 12, polyimine (PI), polyamidoximine (PAI), polyether oxime (PES), polyetheretherketone (PEEK), polycarbonate Ester (PC), polyarylate (PAR), cellulose propionate, polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl alcohol (PVA), polyether phthalimide (PEI), polyphenylene sulfide

(PPS)、聚苯醚、聚苯乙烯（PS)、對排聚苯乙烯、原冰片烯 系聚合物等。又，此等聚合物可被單獨使用，亦可含有少 量的共聚合成分，也可摻合1種以上的其它熱塑性樹脂》 於此等熱塑性樹脂之中，較佳爲聚對酞酸乙二酯、聚 對酞酸丙二酯、聚2,6-萘二甲酸乙二酯、對排聚苯乙烯、 原冰片烯系聚合物、聚碳酸酯、聚芳酯等。又，如聚酯或 聚醯胺之具有極性官能基的樹脂，從與接著性改質層的密 接性之點來看，係較宜的。 其中，更佳爲聚對酞酸乙二酯、聚萘二甲酸-2,6-乙二 酯、聚對酞酸丁二酯、聚對酞酸丙二酯或以此等樹脂的構 成成分當作主成分的共聚物，特佳爲由聚對酞酸乙二酯所 形成的二軸配向薄膜。 例如，作爲用於形成熱塑性樹脂薄膜的樹脂，當使用 以聚對酞酸乙二酯當作基本骨架的聚酯共聚物時，較佳爲 共聚合成分的比率低於2 0莫耳％ »若在2 0莫耳％以上，則 薄膜強度、透明性、耐熱性會變差。作爲可當作共聚合成 分使用的二羧酸成分，可舉出己二酸、癸二酸等的脂肪族 -32-(PPS), polyphenylene ether, polystyrene (PS), aligned polystyrene, ortho-ene based polymer. Further, these polymers may be used singly, or may contain a small amount of a copolymerization component, or may be blended with one or more other thermoplastic resins. Among these thermoplastic resins, polyethylene terephthalate is preferred. , poly-p-propyl phthalate, polyethylene 2,6-naphthalenedicarboxylate, para-polystyrene, norbornene-based polymer, polycarbonate, polyarylate, and the like. Further, a resin having a polar functional group such as polyester or polyamine is preferred from the viewpoint of adhesion to the adhesion-modifying layer. Among them, more preferred are polyethylene terephthalate, polyethylene naphthalate-2,6-ethylene diester, polybutylene terephthalate, propylene terephthalate or the constituents of such resins. The copolymer as a main component is particularly preferably a biaxial alignment film formed of polyethylene terephthalate. For example, as a resin for forming a thermoplastic resin film, when a polyester copolymer having polyethylene terephthalate as a basic skeleton is used, it is preferred that the ratio of the copolymerization component is less than 20% by mole. When it is 20% by mole or more, the film strength, transparency, and heat resistance are deteriorated. Examples of the dicarboxylic acid component which can be used as a copolymerization component include an aliphatic group such as adipic acid or sebacic acid.

1360477 二羧酸，異酞酸、酞酸及2,6-萘二甲酸等的芳香族 ’偏苯三酸及均苯四酸等的多官能羧酸等。又，作 作共聚合成分使用的二醇成分，可舉出二乙二醇、 二醇、丙二醇及新戊二醇等的脂肪酸二醇；對二甲 等的芳香族二醇；1，4-環己烷二甲醇等的脂環族二 均分子量爲150〜20000的聚乙二醇等。 又，於上述熱塑性樹脂中，在不妨礙本發明的 範圍內，可以含有觸媒以外的各種添加劑。作爲添 例如可舉出無機粒子、耐熱性高分子粒子、鹼金屬 、鹼土類金屬化合物、磷化合物、抗靜電劑、紫外 劑、耐光劑、難燃劑、熱安定劑、抗氧化劑、膠化 、界面括性劑等。 上述粒子，從在熱塑性樹脂薄膜的製造時，捲 筒狀時或捲出時的處理性（滑性、行進性、黏連性、 所伴隨的空氣之脫空氣性等）之點來看，係用於賦予 面具有適度的表面凹凸。 作爲無機粒子，可舉出碳酸鈣、磷酸鈣、非晶 、結晶性的玻璃塡料、高嶺土、滑石、二氧化鈦、 、矽石-氧化鋁複合氧化物粒子、硫酸鋇、氟化鈣、 、沸石、硫化鉬、雲母等。又，作爲耐熱性高分子 可舉出交聯聚苯乙烯粒子、交聯丙烯酸系樹脂粒子 甲基丙烯酸甲酯系粒子、苯并胍胺.甲醛縮合物粒 胺•甲醛縮合物粒子、聚四氟乙烯粒子等。 於使用聚酯薄膜當作熱塑性樹脂薄膜時，在上 二羧酸 爲可當 1,4-丁 苯二醇 醇；平 效果之 加劑， 化合物 線吸收 防止劑 繞成圓 捲繞時 薄膜表 性矽石 氧化鋁 氟化鋰 粒子， 、交聯 子、蜜 述粒子 -33- 1360477 之中，矽石粒子由於可得到與聚酯樹脂之折射率比較接近 的高透明性，故最適合於強烈要求透明性的用途。另一方 面，於要求遮蔽性的用途中，氧化鈦般的白色顔料係合適 的。又，含於熱塑性樹脂薄膜中的粒子係可爲1種，也可 倂用數種。1360477 A polycarboxylic acid such as a dicarboxylic acid, an isophthalic acid, a citric acid or a 2,6-naphthalene dicarboxylic acid or the like, or a polyfunctional carboxylic acid such as trimesic acid or pyromellitic acid. Further, the diol component used as the copolymerization component may, for example, be a fatty acid diol such as diethylene glycol, diol, propylene glycol or neopentyl glycol; or an aromatic diol such as dimethyl; An alicyclic two-average molecular weight of cyclohexanedimethanol or the like of from 150 to 20,000, such as polyethylene glycol. Further, in the above thermoplastic resin, various additives other than the catalyst may be contained within the range not inhibiting the present invention. Examples of the additives include inorganic particles, heat-resistant polymer particles, alkali metals, alkaline earth metal compounds, phosphorus compounds, antistatic agents, ultraviolet agents, light stabilizers, flame retardants, heat stabilizers, antioxidants, gelatinization, and the like. Interface inclusions, etc. From the point of view of the handling property (slip property, ductility, adhesion, air deaeration of the air, etc.) at the time of roll-up or roll-out of the thermoplastic resin film, the particles are It is used to impart a moderate surface unevenness to the surface. Examples of the inorganic particles include calcium carbonate, calcium phosphate, amorphous, crystalline glass pigment, kaolin, talc, titanium oxide, vermiculite-alumina composite oxide particles, barium sulfate, calcium fluoride, and zeolite. Molybdenum sulfide, mica, etc. Further, examples of the heat resistant polymer include crosslinked polystyrene particles, crosslinked acrylic resin particles, methyl methacrylate particles, benzoguanamine, formaldehyde condensate, uramine, formaldehyde condensate particles, and polytetrafluoroethylene. Ethylene particles, etc. When a polyester film is used as the thermoplastic resin film, the upper dicarboxylic acid is 1,4-butylbenzene glycol; the flat effect additive, and the compound wire absorption preventing agent is wound into a circular winding film. Among the vermiculite aluminum fluoride lithium particles, crosslinkers, and mesa particles -33- 1360477, the vermiculite particles are most suitable for strong requirements because they have high transparency close to the refractive index of the polyester resin. The use of transparency. On the other hand, in the use of shielding properties, a titanium oxide-like white pigment is suitable. Further, the particles contained in the thermoplastic resin film may be one type or several types may be used.

就上述粒子的種類、平均粒徑、添加量而言，從透明 性與處理性的平衡之點來看，平均粒徑係0.01〜2μπι，薄 膜中的粒子含量係在0.01〜5.0質量％的範圍內，可依照薄 膜的用途來決定。又，使用於高度要求本發明所用的接著 性改質基材薄膜之透明性的用途時，在熱塑性樹脂薄膜中 ，較佳爲實質上不含有成爲降低透明性之原因的粒子，而 成爲在接著性改質層中含有粒子的構成。 上述「實質上不含有粒子」係意味，例如於無機粒子 的情況，以螢光X射線分析來定量無機元素時，其含量爲 5 0PPm以下，較佳爲i〇ppm以下，最佳爲在檢測極限以下 。此係因爲即使積極地在基材薄膜中不添加粒子，從外來 雜質而來的污染成分，原料樹脂或薄膜的製程中附著於生 產線或裝置的污垢之剝離，也會混入薄膜中。 又，本發明所使用的熱塑性樹脂薄膜之層構成係可爲 單層，也可成爲賦予單層所不能得到的機能之積層構造》 於積層構造時，共擠壓法係合適的。 以使用聚酯當作熱塑性樹脂薄膜的原料之情況當作代 表例，以下詳細說明基材薄膜的製造方法。 作爲薄膜原料所使用的聚酯九粒之固有黏度，較佳係 -34 -The type of the particles, the average particle diameter, and the amount of addition, the average particle diameter is 0.01 to 2 μm from the viewpoint of the balance between the transparency and the handleability, and the particle content in the film is in the range of 0.01 to 5.0% by mass. The inside can be determined according to the use of the film. Moreover, when it is used for the use which is highly required for the transparency of the adhesive-modified base film used in the present invention, it is preferable that the thermoplastic resin film does not substantially contain particles which cause deterioration of transparency, and The modified layer contains the composition of particles. The above-mentioned "substantially no particles" means that, for example, in the case of inorganic particles, when the inorganic element is quantified by fluorescent X-ray analysis, the content thereof is 50 ppm or less, preferably i 〇 ppm or less, and most preferably Below the limit. In this case, even if particles are not actively added to the base film, the contaminated components from the foreign matter, and the peeling of the dirt adhering to the production line or the device during the process of the raw resin or the film are mixed into the film. Further, the layer structure of the thermoplastic resin film used in the present invention may be a single layer or a laminated structure which imparts a function which cannot be obtained by a single layer. In the case of a laminated structure, a co-extrusion method is suitable. In the case where polyester is used as a raw material of a thermoplastic resin film, a method of producing a base film will be described in detail below. The inherent viscosity of the polyester nine particles used as the raw material of the film is preferably -34 -

1360477 在0.45〜〇_70dl/g的範圍內。固有黏度若低於 薄膜製造時變成容易經常發生斷裂。另一方面 若超過0.70dl/g，濾壓大幅上升，難以高精度 性容易降低。 又’於本發明的硬被覆薄膜或使用該薄膜 性薄膜中，較佳爲去除成爲光學缺點之原因的 酯中的雜質。爲了去除聚酯中的雜質，於熔融 將熔融樹脂在保持於約2 80 t的任意場所，進 濾。用於熔融樹脂之高精度過濾的濾材，係沒 定’但於不銹鋼燒結體的濾材時，以Si、Ti、 當作主成分的凝聚物及高熔點有機物的去除性 合適的。 用於熔融樹脂的高精度過濾之濾材的過濾 期過濾效率95%)，較佳係15μιη以下。濾材的 小若超過15μιη，則20μπι以上的雜質之去除係 分。使用過濾粒子大小（初期過濾效率9 5%)爲 的濾材來進行熔融樹脂的高精度過濾，雖然會 ，但爲了得到光學缺點少的薄膜，此係極重要 於熔融樹脂的擠出程序中，通過濾材的微 片狀熔融物的冷卻程序中雜質的周圍會進行結 配向程序中引起配向的不均一性，發生微小的 產生成爲透鏡狀態的地方。此處，若有透鏡 散射，以肉眼觀察時會看到比實際雜質還大 厚度差異，係可看做爲凸部的高度與凹部的 〇.45dl/g， ，固有黏度 過濾，生產 的光學機能 含於原料聚 擠出時際， 行高精度過 有特別的限 Sb、 Ge、 Cu 能優良者係 粒子大小（初 丨過濾粒子大 丨容易變不充 1 5 μιη以下 降低生產性 的。 細雜質，在 晶化，其在 t厚度差異， 丨光會折射或 '。該微小的 i度之差異， -35-1360477 is in the range of 0.45~〇_70dl/g. If the intrinsic viscosity is lower than when the film is produced, it becomes easy to break frequently. On the other hand, when it exceeds 0.70 dl/g, the filtration pressure is greatly increased, and it is difficult to reduce the high precision. Further, in the hard coating film of the present invention or the film-forming film, it is preferred to remove impurities in the ester which is a cause of optical defects. In order to remove impurities in the polyester, the molten resin is filtered at any place maintained at about 2 80 t. The filter medium for high-precision filtration of the molten resin is not required. However, in the case of the filter material of the stainless steel sintered body, the removal property of the aggregates of the Si and Ti as the main components and the high-melting organic substance is suitable. The filtration efficiency of the filter medium for high-precision filtration of the molten resin is 95% by filtration, preferably 15 μm or less. If the filter material is less than 15 μm, the removal factor of impurities of 20 μm or more is obtained. The filter material having a filtered particle size (initial filtration efficiency of 95%) is used for high-precision filtration of the molten resin. However, in order to obtain a film having few optical defects, this is extremely important in the extrusion process of the molten resin. In the cooling program of the microchip-like melt of the filter medium, the periphery of the impurities in the cooling process is subjected to the inhomogeneity of the alignment in the program, and a minute generation occurs in the lens state. Here, if there is lens scattering, it will be seen by the naked eye, and the difference in thickness is larger than the actual impurity. It can be regarded as the height of the convex portion and the 〇.45 dl/g of the concave portion, and the inherent viscosity is filtered, and the optical function of the production is produced. In the case of polycondensation of raw materials, there are special limits for Sb, Ge, and Cu. The particle size is excellent. (The primary filter particles are easily changed to less than 1 5 μηη to reduce productivity. Fine impurities , in crystallization, its difference in thickness t, twilight will refract or '. The difference between the tiny i degrees, -35-

1360477 若凸部的商度爲Im·01以上，與凸部鄰接的 0.5 μιη以上，則由於透鏡效果，即使大小爲 之物’肉眼也會看做爲50μιη以上的大小， 到ΙΟΟμιη以上的大之光學缺點的情形。 爲了得到高透明的薄膜，較佳爲在熱塑 不含有粒子，粒子含量愈少則透明性愈高， 致的光學缺點有成爲更鮮明的傾向。又，由 表面比薄的薄膜還難以驟冷，有進行結晶化 須在未配向片製造時對薄膜全體進行驟冷。 片冷卻的方法，合適者爲將熔融樹脂從模頭 片狀，而到旋轉的冷卻滾筒上，邊使片狀熔 的冷卻滾筒，邊作驟冷之方法。作爲將該未 面（爲與冷卻滾筒之接觸面的相反面）冷卻的 速氣流來冷卻的方法係有效的。 (3)接著性改質層 本發明所用的接著性改質基材薄膜，係 共聚合聚酯及聚胺甲酸酯的樹脂、含水及醇 界面活性劑當作主要構成成分的水性塗布液 在行進中的熱塑性樹脂薄膜之一面或兩面上 使塗布層（接著性改質層）乾燥的乾燥步驟， 軸方向中拉伸的伸步驟，再將經拉伸的塗布 處理的熱定型處理步驟，連續形成而得，以 相分離構造或奈米相分離構造的接著性改質 質基材薄膜。又，將從環氧系交聯劑、蜜胺 凹部之深度爲 20μιη的形狀 再者亦會有看 性樹脂薄膜中 微小的凹凸所 於厚的薄膜之 的傾向，故必 作爲將未配向 的狹縫部擠出 融物緊貼旋轉 配向片的空氣 方法，噴吹高 可經由將以含 的分散介質、 ，連續地塗布 之塗布步驟， 接著至少在一 薄膜作熱定型 製造設有具微 層之接著性改 系交聯劑、噚 -36 - 1360477 唑啉系交聯劑中所選出的至少一種交聯劑混入塗布液中， 進行熱處理，亦可在共聚合聚酯中形成交聯構造。 於該設有具微相分離構造或奈米相分離構造的接著性 改質層之接著性改質基材薄膜的製造方法中，上述共聚合 聚酯（PEs)與聚胺甲酸酯（PU)的質量比（PEs/PU)係30/70〜 70/30，較佳爲滿足下述（a)〜（f)的條件。又，於塗布液中 含有交聯劑的情況亦同樣。1360477 If the quotient of the convex portion is Im·01 or more, and 0.5 μm or more adjacent to the convex portion, the size of the object will be regarded as a size of 50 μm or more, even larger than ΙΟΟμιη. The case of optical defects. In order to obtain a highly transparent film, it is preferred that the thermoplastic does not contain particles, and the smaller the particle content, the higher the transparency, and the optical disadvantage tends to be more distinct. Further, it is difficult to rapidly cool the film having a relatively thin surface, and crystallization is required. The entire film is quenched when the unoriented sheet is produced. The method of cooling the sheet is preferably a method of quenching the molten resin from the die sheet to the rotating cooling drum while cooling the sheet-like cooling drum. It is effective as a method of cooling the velocity air which cools the unfaced surface (the opposite surface to the contact surface of the cooling drum). (3) Adhesive modified layer The adhesive modified base film used in the present invention is an aqueous coating liquid containing a copolymer of a polyester and a polyurethane resin, and an aqueous and alcoholic surfactant as a main constituent component. a drying step of drying the coating layer (adhesive modifying layer) on one or both sides of the advancing thermoplastic resin film, a stretching step in the axial direction, and a heat setting treatment step of the stretching coating treatment continuously A film of a contiguous modified base material having a phase separation structure or a nanophase separation structure is formed. In addition, since the depth of the epoxy-based crosslinking agent and the melamine concave portion is 20 μm, there is a tendency for the fine unevenness of the resin film to be thick in the film, so it is necessary to serve as an unaligned narrow. The method of extruding the melt from the air of the rotating alignment sheet, and the blowing is high, and the coating step is continuously applied by using the dispersion medium, and then at least one film is heat-set to manufacture the micro layer. At least one crosslinking agent selected from the crosslinking agent and the 噚-36 - 1360477 oxazoline crosslinking agent is mixed into the coating liquid to be heat-treated, and a crosslinked structure may be formed in the copolymerized polyester. In the method for producing an adhesive-modified substrate film provided with an adhesion-modifying layer having a microphase-separated structure or a nanophase-separated structure, the above-mentioned copolymerized polyester (PEs) and polyurethane (PU) The mass ratio (PEs/PU) is 30/70 to 70/30, and it is preferable to satisfy the following conditions (a) to (f). Further, the same applies to the case where the crosslinking agent is contained in the coating liquid.

U)從塗布液的塗布後到乾燥步驟的入口爲止，薄膜的 通過時間係少於2秒， (b) 於乾燥步驟中，在溫度120〜150°C歷0.1〜5秒， (c) 於乾燥步驟中，乾燥風的風速係30米/秒以上， (d) 熱定型處理步驟係連續地被區分爲數個熱定型區， 且各區係可獨立溫度控制地隔開，薄膜所通過的第1熱定 型區之溫度係190〜20(TC，設定於最高溫度的熱定型區之 溫度係210〜240 °C，從第1熱定型區的出口到設定於最高 溫度的熱定型區（而且於數個時，最近入口側的熱定型區） 爲止之薄膜的通過時間係1 0秒以下， (e) 對於塗布液而言非離子系界面活性劑或陽離子系界 面活性劑，配合0.0 1〜0 · 1 8質量％， (f) 接著性改質層的最終塗布量係0.005〜〇.20g/m2，而 且於上述接著性改質基材薄膜的製造中，更佳爲滿足下述 (g)〜（i)的條件： (g) 從塗布液的塗布後到乾燥步驟的入口爲止，薄膜的 通過時間係少於1.5秒， -37 - 1360477 (h) 於乾燥步驟中，在溫度130〜150 °C歷0.5〜3秒， (i) 於熱定型處理步驟中’設定於最高溫度的熱定型區 之溫度係225〜235 °C ’從第1熱定型區的出口到設定於最 高溫度的熱定型區（而且於數個時，最近入口側的熱定型區） 爲止，薄膜的通過時間係5秒以下。U) from the application of the coating liquid to the entrance of the drying step, the passage time of the film is less than 2 seconds, (b) in the drying step, at a temperature of 120 to 150 ° C for 0.1 to 5 seconds, (c) In the drying step, the wind speed of the drying wind is 30 m/sec or more, and (d) the heat setting process is continuously divided into a plurality of heat setting zones, and each zone can be independently temperature-controlledly separated, and the film passes through The temperature of the first heat setting zone is 190 to 20 (TC, the temperature of the heat setting zone set at the highest temperature is 210 to 240 ° C, from the outlet of the first heat setting zone to the heat setting zone set at the highest temperature (and In a few cases, the passage time of the film up to the heat-setting zone on the inlet side is 10 seconds or less, (e) the non-ionic surfactant or the cationic surfactant for the coating liquid, and 0.01 1 is added. 0 · 18% by mass, (f) The final coating amount of the subsequent modified layer is 0.005 to 20.20 g/m 2 , and more preferably satisfies the following in the production of the above-mentioned adhesive modified base film. Conditions of ~(i): (g) From the application of the coating liquid to the entrance of the drying step, the film The passage time is less than 1.5 seconds, -37 - 1360477 (h) in the drying step, at a temperature of 130 to 150 ° C for 0.5 to 3 seconds, (i) in the heat setting process step 'set to the highest temperature heat setting The temperature of the zone is 225 to 235 °C. 'From the outlet of the first heat setting zone to the heat setting zone set at the highest temperature (and at several times, the heat setting zone on the most recent inlet side), the film passage time is 5 Less than seconds.

又’於藉由上述線內塗覆法所積層的接著性改質層中 ，含有適當粒徑的微粒子，在接著性改質層的表面上形成 適切的凹凸，可賦予滑性、捲繞性、耐刮性。因此，不必 在熱塑性樹脂薄膜中含有微粒子，可保持高透明性。 於本發明所用的接著性改質基材薄膜中，接著性改質 層的表面之三次元中心面平均表面粗度（SRa)較佳係成.爲 0.002〜0.0 1 Ομηι的平滑者》SRa的上限，從透明性之點來 看，更佳係〇.〇〇80μιη，特佳係0.0060μιη。另一方面，SRa 的下限，從滑性或捲繞性等的處理性、耐刮性之點來看， 更佳係 〇.〇〇25μιη，特佳係 0.0030μιη。 接著性改質層的表面之SRa爲低於0.002μιη的平滑表 面係不宜的，因爲於將接著性改質基材薄膜捲繞成圓筒狀 時，防黏連性會降低，或於薄膜製造時或加工時，滑性或 捲繞性等的處理性、耐刮性會降低。另一方面，接著性改 質層的表面之SRa若超過0.010 μιη，則霧度上升，透明性 變差，故不適合作爲硬被覆薄膜或使用其的光學機能性薄 膜之基材薄膜。 於本發明所用的接著性改質基材薄膜中，接著性改質 層具有以下4個形態的構造特徴，可藉由如下述的手段來 -38- 1360477 獲得。 U)於聚酯相和聚胺甲酸酯相中微相分離或奈米相分離 ，它們具有特定的面積率， (b)接著性改質層的樹脂成分之組成比係可在表面和內 部變化， (Ο於接著性改質層中含有粒子時，粒子係偏在於聚酯 相或聚胺甲酸酯相中。Further, in the adhesion-modifying layer which is laminated by the above-described in-line coating method, fine particles having an appropriate particle diameter are formed, and appropriate irregularities are formed on the surface of the adhesion-modified layer to impart slip and winding properties. Scratch resistance. Therefore, it is not necessary to contain fine particles in the thermoplastic resin film, and high transparency can be maintained. In the adhesive modified base film used in the present invention, the three-dimensional center plane average surface roughness (SRa) of the surface of the adhesive modified layer is preferably set to be a smoother of 0.002 to 0.01 1 Ομηι "SRa" The upper limit, from the point of view of transparency, is better. 〇〇80μιη, especially good for 0.0060μιη. On the other hand, the lower limit of SRa is more preferably 〇〇25μιη, particularly preferably 0.0030μηη, from the viewpoints of handleability and scratch resistance such as slipperiness and winding property. It is not preferable that the surface of the modified layer has a smooth surface of less than 0.002 μm, because when the film of the adhesive modified substrate is wound into a cylindrical shape, the anti-blocking property is lowered, or the film is produced. At the time of processing or processing, handling properties such as slip properties and winding properties and scratch resistance are lowered. On the other hand, when the SRa of the surface of the adhesion-modifying layer exceeds 0.010 μm, the haze increases and the transparency deteriorates, so that it is not suitable as a base film of a hard coating film or an optical functional film using the same. In the adhesive modified base film used in the present invention, the adhesive modified layer has the following four structural features, which can be obtained by the following means -38-1360477. U) micro phase separation or nano phase separation in the polyester phase and the polyurethane phase, which have a specific area ratio, and (b) the composition ratio of the resin component of the adhesion modifying layer can be on the surface and inside Variation, (when the particles are contained in the adhesive layer, the particles are biased in the polyester phase or the polyurethane phase.

又’於接著性改質層的表面所觀察之以共聚合聚酯當 作主成分的聚酯相，較佳係具有寬度最大爲Ιμπι且長度超 過Ιμιη的連續構造，更佳爲共聚合聚酯相與聚胺甲酸酯相 具有共連續構造的構造。藉由在接著性改質層的表面之 PEs相的面積率之範圍內，具有以共聚合聚酯當作主成分 聚醋相之寬度最大爲Ιμιη、長度超過Ιμιη的微細連續構造 ，則可得到微觀均一的密接性。 於以共聚合聚酯當作主成分的聚酯相中，寬度最大超 過Ιμιη的地方所散佈於相分離構造，局部地對於硬被覆層 、擴散層、稜鏡層般的機能層，發生密接性差的地方。若 在接著性改質層的表面上存在有密接性差的地方，則以該 部分爲起點，會有巨觀的剝離連繫。爲了使上述聚酯相的 寬度成爲最大Ιμιη的微細連續構造，重要的是適宜選定從 橫拉伸區到達熱定型區的最高溫度爲止所需要的時間、熱 定型條件。特別地，於從橫拉伸區到達熱定型區的最高溫 度區爲止所需要的時間若過長，則接著性改質層的相分離 係過度進行，結果以共聚合聚酯當作主成分的聚酯相之寬 -39- 1360477 度最窄的地方，超過Ιμιη的地方係散佈著》製造接著性改 質基材薄膜時的具體熱定型條件係於後述。 爲了控制最終的接著性改質層之表面的相分離構造， 後述乾燥步驟中的溶劑蒸發速度及其後的加熱處理係極重 要的。藉由控制乾燥步驟中的溶劑蒸發速度，可在接著性 改質層的表面中，改變聚酯成分與聚胺甲酸酯成分的組成 比。Further, the polyester phase having the copolymerized polyester as a main component observed on the surface of the adhesion modifying layer preferably has a continuous structure having a width of at most Ιμπι and a length exceeding Ιμιη, more preferably a copolymerized polyester. The phase has a co-continuous structure with the polyurethane phase. By having a fine continuous structure in which the width of the polyvinyl acetate phase having the copolymerized polyester as the main component is Ιμιη and the length exceeds Ιμιη in the range of the area ratio of the PEs phase on the surface of the adhesive reforming layer, Microscopic uniformity of adhesion. In the polyester phase in which the copolymerized polyester is used as a main component, the portion having the largest width exceeding Ιμηη is dispersed in the phase separation structure, and the adhesion layer is hardly localized to the functional layer such as the hard coating layer, the diffusion layer, and the ruthenium layer. The place. If there is a place where the adhesion is poor on the surface of the adhesive reforming layer, there is a giant peeling connection starting from this portion. In order to make the width of the polyester phase to be a fine continuous structure of Ιμιη, it is important to appropriately select the time and heat setting conditions required from the transverse stretching zone to the maximum temperature of the heat setting zone. In particular, if the time required from the transverse stretching zone to the highest temperature zone of the heat setting zone is too long, the phase separation of the adhesion modifying layer is excessively performed, and as a result, the copolymerized polyester is used as a main component. The narrowest part of the polyester phase is -39 to 1360477 degrees, and the place where the Ιμιη is exceeded is scattered. The specific heat setting conditions for producing the adhesive modified base film are described later. In order to control the phase separation structure of the surface of the final adhesive reforming layer, the solvent evaporation rate in the drying step described later and the subsequent heat treatment are extremely important. By controlling the evaporation rate of the solvent in the drying step, the composition ratio of the polyester component to the polyurethane component can be changed in the surface of the adhesive modifying layer.

例如，使用水/異丙醇的混合溶劑時，在弱的乾燥條件 下，於乾燥後期過程殘留於表面的溶劑中，水的比率變多 。因此，比較親水性高的聚胺甲酸酯在接著性改質層的表 面中所存在的比率，與強的條件下使接著性改質層乾燥時 比較下，係變高。而且，即使變變塗布量，控制溶劑的蒸 發速度時，也不能得到同樣的效果，於增加塗布量時，乾 燥費時，於乾燥前不久存在塗布面的殘留溶劑中，水的比 率變多。即，於接著性改質層的表面中，與塗布量少時比 較下，聚胺甲酸酯成分的比率可能增高。 於拉伸步驟及熱定型處理步驟中，進行聚酯成分與聚 胺甲酸酯成分的相分離。然而，若任一方的樹脂開始熱交 聯，則各相的運動性大幅降低，抑制相分離的進行。即， 藉由控制拉伸步驟及熱定型處理步驟中加熱條件，可控制 相分離構造》 如上述，於乾燥步驟中控制聚酯/聚胺甲酸酯在接著性 改質層的表面附近之存在比率，於拉伸步驟、熱定型處理 步驟中控制相分離的進行，則可嚴密控制接著性改質層的 -40 - 1360477 表面相分離構造及各相在接著性改質層的表面附近之存在 比率。又，藉由控制接著性改質層中所含有的粒子之表面 能，則可選擇地使粒子偏在以共聚合聚酯當作主成分的聚 酯相或以聚胺甲酸酯當作主成分的聚胺甲酸酯相之任一方 中〇For example, when a mixed solvent of water/isopropyl alcohol is used, under a weak drying condition, the solvent remains in the solvent on the surface in the late drying stage, and the ratio of water becomes large. Therefore, the ratio of the more hydrophilic polyurethane having a higher hydrophilicity to the surface of the adhesive modifying layer is higher than that when the adhesive modifying layer is dried under strong conditions. Further, even when the coating amount is changed and the evaporation rate of the solvent is controlled, the same effect cannot be obtained. When the coating amount is increased, it takes a long time to dry, and the ratio of water in the residual solvent of the coated surface is increased shortly before drying. That is, in the surface of the adhesive reforming layer, the ratio of the polyurethane component may be increased as compared with the case where the coating amount is small. The phase separation of the polyester component and the polyurethane component is carried out in the stretching step and the heat setting treatment step. However, if either of the resins starts to thermally crosslink, the mobility of each phase is greatly lowered, and the progress of phase separation is suppressed. That is, by controlling the heating conditions in the stretching step and the heat setting treatment step, the phase separation structure can be controlled. As described above, the presence of the polyester/polyurethane in the vicinity of the surface of the adhesion modifying layer is controlled in the drying step. The ratio of the phase separation during the stretching step and the heat setting treatment step can strictly control the surface phase separation structure of the -4036047 surface of the adhesion modifying layer and the presence of each phase near the surface of the adhesion modifying layer. ratio. Further, by controlling the surface energy of the particles contained in the adhesive reforming layer, the particles are selectively biased to a polyester phase having a copolymerized polyester as a main component or a polyurethane as a main component. One of the polyurethane phases

接著性改質層含有共聚合聚酯及聚胺甲酸酯當作主要 的樹脂成分》以單獨的共聚合聚酯，雖然與聚酯系基材薄 膜的密接性充分，但是與含無機微粒子的硬被覆層之密接 性差。又，由於係比較脆的樹脂，故對於切割時的衝撃， 容易發生內聚破壞。 另一方面，以單獨的聚胺甲酸酯，雖然與含無機微粒 子的硬被覆層之密接性比較優良，但是與聚酯系基材薄膜 的密接性差。再者，於將接著性改質基材薄膜捲繞成圓筒 狀時，防黏連性差。因此，使用具有聚胺甲酸酯單獨系統 的接著性改質層之接著性改質基材薄膜所製造的硬被覆薄 膜或光學機能性薄膜，品位係顯著降低。爲了避免這樣的 問題，必須於接著性改質層中含有大量的粒子，含有粒徑 大的粒子，或增加粒子的含量。結果，由於薄膜的霧度上 升，特別是不適合當作透明性要求強的硬被覆薄膜或光學 機能性薄膜的基材薄膜。 (3-1)形成接著性改質層用的塗布液之調配步驟 於本發明中，接著性改質層係使用塗布法來形成。M 布液中所用的材料係樹脂及分散介質或溶劑。於本發日月巾 ，用於形成接著性改質層的塗布液，較佳係水性。又，於 -41 -The subsequent modified layer contains a copolymerized polyester and a polyurethane as a main resin component. The copolymerized polyester alone has sufficient adhesion to the polyester base film, but contains inorganic fine particles. The adhesion of the hard coating layer is poor. Further, since it is a relatively brittle resin, cohesive failure is likely to occur in the rinsing at the time of cutting. On the other hand, the individual polyurethanes are excellent in adhesion to the hard coating layer containing inorganic fine particles, but are inferior in adhesion to the polyester base film. Further, when the adhesive modified base film is wound into a cylindrical shape, the anti-blocking property is inferior. Therefore, the hard coat film or the optical functional film produced by using the adhesive modified base film of the adhesive modified layer of the polyurethane monolithic system has a markedly lowered grade. In order to avoid such a problem, it is necessary to contain a large amount of particles in the adhesive reforming layer, to contain particles having a large particle diameter, or to increase the content of the particles. As a result, since the haze of the film is increased, it is particularly unsuitable as a base film of a hard coating film or an optical functional film which is required to be transparent. (3-1) Preparation step of forming coating liquid for forming an adhesion-improving layer In the present invention, the adhesion-modifying layer is formed by a coating method. The material used in the M cloth liquid is a resin and a dispersion medium or a solvent. In the present invention, the coating liquid for forming the adhesive reforming layer is preferably aqueous. Also, at -41 -

1360477 本發明中，除了樹脂成分，亦倂用粒 爲較佳的實施形態。再者，視需要可 外線吸收劑、有機潤滑劑、抗菌劑、 劑。又，於塗布液中，爲了促進樹脂 添加觸媒，例如可以使用無機物質、 性物質、酸性物質及含金屬有機化合 。又，爲了調節水溶液的pH，可以添 質。塗布液係藉由在分散介質或溶劑 脂分散化或溶解，接著倂用界面活性 各種添加劑，稀釋到所欲的固體成分: 而且，爲了使塗布液的樹脂成分 了更去除粗大粒子凝聚物及製程內塵 對塗布液作精密過濾。 用於對塗布液作精密過濾的濾材 述性能即可，而沒有特別的限定，例 、網目型。用於對塗布液作精密過濾 具有上述性能且對塗布液沒有不良影 的限定，例如可爲不銹鋼、聚乙烯、 用於對塗布液作精密過濾的濾材 小（初期過濾效率：95%)爲25μιη以Τ 性能5μπι以下的濾材，特佳係過濾性 最佳爲組合使用過濾性能不同的過濾 濾粒子大小超過25 μιη的濾材時， 易不充分。因此，過濾未能去除的粗 子及界面活性劑者係 以使用抗靜電劑、紫 光氧化觸媒等的添加 的熱交聯反應，亦可 鹽類、有機物質、鹸 物等的各種化學物質 ;加鹼性物質或酸性物 中，於攪拌下，將樹 劑以及視需要選用的 濃度爲止而調製。 及粒子均勻分散，爲 埃等的雜質，較佳爲 之類型，只要具有上 如可爲單絲型、氈型 的濾材之材質，只要 » 響即可，而沒有特別 聚丙烯、耐隆等。 ，較佳係過濾粒子大 「的濾材，更佳係過濾 能Ιμηι以下的濾材。 器之方法。於使用過 t大凝聚物的去除係容 大凝聚物，由於塗布 -42- < S '； 1360477 乾燥後的一軸配向或二軸配向步驟的配向應力而擴大，看 到100 μιη以上的凝聚物，容易成爲光學缺點的原因。 以下詳細說明塗布液中所用的原料》 (a)樹脂1360477 In the present invention, in addition to the resin component, granules are also preferred embodiments. Further, an external absorbent, an organic lubricant, an antibacterial agent, or an agent may be used as needed. Further, in the coating liquid, in order to promote the addition of the catalyst to the resin, for example, an inorganic substance, a substance, an acidic substance, and a metal-containing compound may be used. Further, in order to adjust the pH of the aqueous solution, it may be added. The coating liquid is diluted or dissolved in a dispersion medium or a solvent grease, and then diluted with various interfacial active additives to dilute the desired solid component: Further, in order to make the resin component of the coating liquid remove coarse aggregates and processes The inner dust is precisely filtered by the coating liquid. The filter material for precisely filtering the coating liquid can be used without any particular limitation, such as a mesh type. It is used to precisely filter the coating liquid and has the above properties and has no adverse effect on the coating liquid. For example, it can be stainless steel or polyethylene, and the filter material for precision filtration of the coating liquid is small (initial filtration efficiency: 95%) is 25 μm. It is not easy to use a filter material with a performance of 5 μm or less. It is best to use a filter material with a filter filter particle size of more than 25 μm. Therefore, the crude cross-linking and the surfactant which are not removed by filtration are thermally cross-linked by the addition of an antistatic agent, a violet photocatalyst, or the like, and various chemical substances such as salts, organic substances, and sputum; An alkaline substance or an acid is added, and the mixture is prepared under stirring with a desired concentration of the tree. The particles are uniformly dispersed and are preferably impurities such as angstroms, and the like, as long as it has a material such as a monofilament type or a felt type filter material, as long as it is ringing, and there is no special polypropylene or diarrhea. Preferably, it is a filter medium having a large filter particle size, and more preferably a filter material having a filter capacity of ημηι or less. The method for removing the large aggregates using the large aggregate of t is due to coating -42- < S '; 1360477 Expanding the alignment stress in the one-axis alignment or the two-axis alignment step after drying, and seeing agglomerates of 100 μm or more easily causes optical defects. The following describes the raw materials used in the coating liquid. (a) Resin

於本發明中，作爲構成接著性改質層的樹脂，係使用 共聚合聚酯（PEs)及聚胺甲酸酯（PU)。於塗布液中，共聚合 聚酯（PEs)與聚胺甲酸酯（PU)的固體成分基準之質量比，較 佳係（PEs)/(PU) = 70/30 〜30/70，特佳係 60/40 〜40/60。再 者，構成接著性改質層的樹脂，除了上述共聚合聚酯與聚 胺甲酸酯，亦可倂用第3樹脂。又，也可倂用交聯劑。 而且，於本發明中，接著性改質層的表面之聚酯相的 面積率，與對於接著性改質層的樹脂成分而言，共聚合聚 酯的質量比，係如第6圖所示地，並沒有對應。於第6圖 中明確地顯示，對於接著性改質層的樹脂成分而言，共聚 合聚酯的質量比即使爲50%，接著性改質層的表面之PEs 表面分率也變化到30〜91%爲止。此暗示於接著性改質層 的表面與內部，共聚合聚酯與聚胺甲酸酯的構成比係不同 。即，此暗示係意味在接著性改質層的厚度方向中，可任 意地控制共聚合聚酯與聚胺甲酸酯的構成比》 又，藉由在接著性改質層中，使共聚合聚酯與聚胺甲 酸酯的比率在上述範圍內，則可使接著性改質層的表面之 硬度指數成爲3.0〜15.Onm。接著性改質層的表面之硬度 指數若低3 .Onm，則接著性改質層變脆。因此，於形成以 丙烯酸系樹脂當作構成成分的硬被覆層、擴散層、棱鏡層 -43 - 1360477 等機能層後，在高速切割成指定尺寸的加工步驟中，對於 高速切割時的剪斷力而言，變成難以得到充分的密接性。 又，接著性改質層的表面之硬度指數若超過15.0nm，則防 黏連性容易降低。再者，對基材薄膜的塗布性、密接性' 耐溶劑性有變不充分的傾向。In the present invention, as the resin constituting the adhesion modifying layer, a copolymerized polyester (PEs) and a polyurethane (PU) are used. In the coating liquid, the mass ratio of the solid content of the copolymerized polyester (PEs) to the polyurethane (PU) is preferably (PEs) / (PU) = 70 / 30 ~ 30 / 70, particularly good System 60/40 ~ 40/60. Further, the resin constituting the adhesion modifying layer may be a third resin in addition to the copolymerized polyester and the polyurethane. Further, a crosslinking agent can also be used. Further, in the present invention, the area ratio of the polyester phase on the surface of the adhesive modified layer and the resin component to the adhesive modified layer are as shown in Fig. 6 Ground, there is no correspondence. It is clearly shown in Fig. 6 that, for the resin component of the adhesive layer, the mass ratio of the copolymerized polyester is 50%, and the surface fraction of the surface of the adhesive layer is changed to 30~ 91% so far. This suggests that the composition and ratio of the copolymerized polyester to the polyurethane are different between the surface and the inside of the adhesion modifying layer. That is, this suggestion means that the composition ratio of the copolymerized polyester to the polyurethane can be arbitrarily controlled in the thickness direction of the adhesion-modifying layer, and the copolymerization is carried out in the adhesion-modifying layer. When the ratio of the polyester to the polyurethane is within the above range, the hardness index of the surface of the adhesive modified layer can be made 3.0 to 15. Onm. If the hardness index of the surface of the modified layer is lower by 3. Onm, the adhesive layer becomes brittle. Therefore, in the processing step of forming a hard coating layer, a diffusion layer, and a prism layer -43 - 1360477 which are made of an acrylic resin as a constituent component, the shearing force at the time of high-speed cutting is performed in a processing step of cutting at a high speed to a predetermined size. In this case, it becomes difficult to obtain sufficient adhesion. Further, when the hardness index of the surface of the adhesion-modifying layer exceeds 15.0 nm, the anti-blocking property is liable to lower. In addition, the coating property and the adhesion property of the base film tend to be insufficient.

於本發明中，水分散型共聚合聚酯成分與親水性聚胺 甲酸酯成分的相分離構造，茲推測係如以下地形成。以共 通的溶劑所混合的兩樹脂成分，係爲均勻分散或溶解在塗 布液內的狀態。於PET薄膜上塗布後，經由乾燥步驟的塗 布面，係爲不具有明確相分離構造的均一狀態。然後，藉 由拉伸步驟及熱定型處理步驟中的加熱處理，而表現相分 離構造。即，以共聚合聚酯當作主成分的相與以聚胺甲酸 酯當作主成分的相係分離。而且，茲認爲隨著相分離的進 行，具有較低表面能的共聚合聚酯成分於接著性改質層的 表面附近所存在的比率係變高。 (共聚合聚酯） 於本發明所用的接著性改質層中，所用的共聚合聚酯 較佳係以芳香族二羧酸成分、及當作二醇成分的乙二醇和 分枝二醇當作構成成分。作爲上述分枝二醇成分，例如可 舉出2,2-二甲基-1，3-丙二醇、2-甲基-2-乙基-1，3-丙二醇' 2-甲基-2-丁基-1,3-丙二醇、2-甲基-2-丙基-1，3-丙二醇、2-甲基-2-異丙基-1,3-丙二醇、2-甲基-2·正己基-1，3-丙二醇 、2,2·二乙基-1,3-丙二醇、2-乙基-2-正丁基-1，3-丙二醇、 2-乙基-2-正己基-1，3-丙二醇、2,2-二-正丁基-1，3-丙二醇 -44- 1360477 、2-正丁基-2-丙基-1，3-丙二醇、及2,2_二正己基- L3·丙二 醇等。 分枝二醇成分的莫耳比，對於全部二醇成分而言，下 限較佳係10莫耳％，特佳係2〇莫耳％。另一方面，上限較 佳係8 0莫耳°/。，尤佳係7 〇莫耳％、特佳係6 0莫耳％。又 ’視需要亦可倂用二乙二醇、丙二醇、丁二醇、己二醇或 1,4-環己烷二甲醇等。In the present invention, the phase-separated structure of the water-dispersed copolymerized polyester component and the hydrophilic polyurethane component is presumed to be formed as follows. The two resin components mixed in a common solvent are in a state of being uniformly dispersed or dissolved in the coating liquid. After coating on the PET film, the coating surface through the drying step is in a uniform state without a clear phase separation structure. Then, the phase separation structure is expressed by the heat treatment in the stretching step and the heat setting treatment step. Namely, a phase in which a copolymerized polyester is used as a main component is separated from a phase in which a polyurethane is used as a main component. Further, it is considered that as the phase separation proceeds, the ratio of the copolymerized polyester component having a lower surface energy existing in the vicinity of the surface of the adhesion modifying layer becomes higher. (Copolymerized Polyester) In the adhesive modifying layer used in the present invention, the copolymerized polyester used is preferably an aromatic dicarboxylic acid component, and an ethylene glycol and a branched glycol as a glycol component. As a constituent. Examples of the branched diol component include 2,2-dimethyl-1,3-propanediol and 2-methyl-2-ethyl-1,3-propanediol '2-methyl-2-butylene. -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2.n-hexyl -1,3-propanediol, 2,2·diethyl-1,3-propanediol, 2-ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1, 3-propanediol, 2,2-di-n-butyl-1,3-propanediol-44- 1360477, 2-n-butyl-2-propyl-1,3-propanediol, and 2,2-di-n-hexyl- L3·propylene glycol and the like. The molar ratio of the branched diol component is preferably 10 mol% for the entire diol component, and particularly preferably 2 mol%. On the other hand, the upper limit is better than 80%. , especially good 7 〇 Mo Er%, especially good 60 莫 mol%. Further, diethylene glycol, propylene glycol, butanediol, hexanediol or 1,4-cyclohexanedimethanol may be used as needed.

作爲芳香族二羧酸成分，最佳爲對酞酸及異酞酸。對 於全部二羧酸成分而言，若在10莫耳％以下的範圍內，則 亦可與添加其它芳香族二羧酸，尤其二苯基羧酸及2,6-萘 二甲酸等的芳香族二羧酸而使共聚合。 作爲本發明的接著性改質層之樹脂成分而使用的共聚 合聚酯，較佳係可水溶性或水分散的樹脂。因此，除了上 述二羧酸成分，爲了賦予聚酯具有水分散性，較佳爲亦使 用1〜1〇莫耳％之範圍的5-磺基異酞酸或其鹼金屬鹽，例 如可舉出磺基對酞酸、5-磺基異酞酸、4-磺基萘異酞酸-2,7-二羧酸及5-(4·磺基苯氧基）異酞酸或其鹼金屬鹽。 (聚胺甲酸酯） 接著性改質層中所用的聚胺甲酸酯，較佳係使用可水 溶性或水分散的樹脂。例如可舉出含封端型異氰酸基的樹 脂、末端異氰酸基經親水性基所封鎖（以下簡稱封閉）的熱 反應型水溶性胺甲酸酯等。 作爲上述異氰酸基的封閉化劑，可舉出亞硫酸氫鹽類 及含磺酸基的酚類、醇類、內醯胺類肟類、或活性亞甲基 (S ) -45 - 1360477As the aromatic dicarboxylic acid component, citric acid and isononanoic acid are most preferable. When all the dicarboxylic acid components are in the range of 10 mol% or less, aromatics such as diphenylcarboxylic acid and 2,6-naphthalene dicarboxylic acid may be added together with other aromatic dicarboxylic acids. The dicarboxylic acid is copolymerized. The copolymerized polyester used as the resin component of the adhesive modifying layer of the present invention is preferably a water-soluble or water-dispersible resin. Therefore, in addition to the above dicarboxylic acid component, in order to impart water dispersibility to the polyester, it is preferred to use 5-sulfoisodecanoic acid or an alkali metal salt thereof in the range of 1 to 1 mol%, for example, Sulfo-p-citric acid, 5-sulfoisodecanoic acid, 4-sulfonaphthoisophthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy)isodecanoic acid or alkali metal salts thereof . (Polyurethane) The polyurethane used in the subsequent modified layer is preferably a water-soluble or water-dispersible resin. For example, a resin containing a blocked isocyanate group and a thermally reactive water-soluble urethane having a terminal isocyanate group blocked by a hydrophilic group (hereinafter referred to as blocking) may, for example, be mentioned. Examples of the blocking agent for the above isocyanate group include hydrogen sulfites and sulfonic acid group-containing phenols, alcohols, decylamine steroids, or active methylene groups (S) -45 - 1360477

化合物類等。經封閉的異氰酸基係將胺甲酸酯預聚物親水 化或水溶化》藉由薄膜製造時的乾燥步驟或熱定型處理步 驟，給予上述樹脂熱能，由於封閉化劑從異氰酸基脫落， 故上述樹脂將混合在自交聯的網絡中之水分散性共聚合聚 酯作固定化，同時亦與上述樹脂的末端基等反應。塗布液 調整中的樹脂，由於親水性而耐水性差，但於塗布、乾燥 、熱定型及完成熱反應時，由於胺甲酸酯樹脂的親水基即 封閉化劑脫落，故得到耐水性良好的塗膜》 於上述封閉化劑之中，從於薄膜製造步驟中藉由熱處 理溫度、熱處理時間使封閉化劑從異氰酸基脫落之點、及 從工業上可取得之點來看，最佳爲亞硫酸氫鹽類。作爲上 述樹脂中所使用的胺甲酸酯預聚物之化學組成，可以爲（1) 分子內具有2個以上的活性氫原子之有機聚異氰酸酯，或 分子內至少具有2個活性氫原子的分子量爲200〜20,〇〇〇 的化合物，（2)分子內具有2個以上的異氰酸基之有機聚異 氰酸酯，或（3)使分子內具有至少2個活性氫原子的鏈延長 劑反應而得之具有末端異氰酸基的化合物。 作爲上述（1)的化合物，可舉出一般已知的在末端或分 子中含有2個以上的羥基、羧基、胺基或锍基者，作爲特 佳的化合物，可舉出聚醚多元醇及聚醚酯多元醇等。又， 作爲聚醚多元醇，例如可舉出環氧乙烷及環氧丙烷等環氧 烷類、或氧化苯乙烯及環氧氯丙烷等經聚合的化合物，或 進行此等的無規聚合、嵌段聚合或對多價醇的加成聚合而 得之化合物。 -46 - 1360477 作爲聚酯多元醇及聚醚酯多元醇，可舉出主要爲直鏈 狀或分枝狀的化合物。可由琥珀酸、己二酸、酞酸及馬來 酸酐等的多價飽和或不飽和羧酸、或該羧酸酐等與乙二醇 、二乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇及三羥甲 基丙烷等的多價飽和及不飽和醇類、比較低分子量的聚乙 二醇及聚丙烯二醇等的聚伸烷基醚二醇類、或此等醇類的 混合物之縮合反應而得。Compounds and the like. The blocked isocyanate group hydrophilizes or hydrolyzes the urethane prepolymer. The thermal energy of the above resin is given by a drying step or a heat setting treatment step in the production of a film, since the blocking agent is derived from an isocyanate group. Since the resin is detached, the above-mentioned resin is immobilized by mixing the water-dispersible copolymerized polyester in the self-crosslinking network, and also reacts with the terminal group or the like of the above resin. The resin in the coating liquid adjustment is poor in water resistance due to hydrophilicity. However, when coating, drying, heat setting, and completion of thermal reaction, the hydrophilic agent of the urethane resin, that is, the blocking agent, is detached, so that a coating having good water resistance is obtained. Membrane is the best in the above-mentioned blocking agent, from the point of the heat treatment temperature and the heat treatment time in which the blocking agent is detached from the isocyanate group and the industrially obtainable point. Bisulfites. The chemical composition of the urethane prepolymer used in the above resin may be (1) an organic polyisocyanate having two or more active hydrogen atoms in the molecule, or a molecular weight having at least two active hydrogen atoms in the molecule. a compound of 200 to 20, ruthenium, (2) an organic polyisocyanate having two or more isocyanato groups in the molecule, or (3) a chain extender having at least two active hydrogen atoms in the molecule; A compound having a terminal isocyanate group is obtained. The compound (1) may, for example, be a generally known compound having two or more hydroxyl groups, carboxyl groups, amine groups or sulfhydryl groups in the terminal or molecule. Preferred examples of the compound include polyether polyols and Polyether ester polyols and the like. In addition, examples of the polyether polyol include alkylene oxides such as ethylene oxide and propylene oxide, and polymerized compounds such as styrene oxide and epichlorohydrin, or random polymerizations thereof. A compound obtained by block polymerization or addition polymerization of a polyvalent alcohol. -46 - 1360477 As the polyester polyol and the polyether ester polyol, a compound which is mainly linear or branched is mentioned. a polyvalent saturated or unsaturated carboxylic acid such as succinic acid, adipic acid, citric acid or maleic anhydride, or the like, and ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl Polyvalent alkyl ether glycols such as polyvalent saturated and unsaturated alcohols such as diol, 1,6-hexanediol and trimethylolpropane, and relatively low molecular weight polyethylene glycol and polypropylene glycol Or a condensation reaction of a mixture of such alcohols.

再者，作爲聚酯多元醇，可舉出由內酯及羥酸所得之 聚酯類。又，作爲聚醚酯多元醇，可使用在預先製造的聚 酯類中，附加環氧乙烷或環氧丙烷等而得之聚醚酯類。 作爲上述（2)的有機聚異氰酸酯’可舉出伸甲苯基二異 氰酸酯的異構物類，4,4-二苯基甲烷二異氰酸酯等的芳香 族二異氰酸酯類，苯二甲基二異氰酸酯等的芳香族脂肪族 二異氰酸酯類，異佛爾酮二異氰酸酯及4,4-二環己基甲烷 二異氰酸酯等的脂環狀二異氰酸酯類、六亞甲基二異氰酸 酯及2，2,4·三甲基六亞甲基二異氰酸酯等的脂肪族二異氰 酸酯類，或此等化合物以單一或複數地預先附有三羥甲基 丙烷等的聚異氰酸酯類。 作爲上述（3)的具有至少2個活性氫的鏈延長劑’可舉 出乙二醇、二乙二醇、1,4-丁二醇、及1，6-己二醇等的二 醇類，甘油、三羥甲基丙烷、及季戊四醇等的多價醇類， 伸乙二胺、六亞甲二胺、及哌畊等的二胺類，單乙醇胺及 二乙醇胺等的胺基醇類，硫二乙二醇等_硫二甘醇類，或水 -47 - 1360477 爲了合成胺甲酸酯預聚物，通常藉由使用上述鏈延長 劑的一段式或多段式異氰酸酯加成聚合方法，在150 °C以 下，較佳在70〜12(TC的溫度，使反應5分鐘至數小時。 異氰酸基對於活性氫原子的比，若爲1以上則可自由地選 擇，惟必須在所得到的胺甲酸酯預聚物中，使游離的異氰 酸基殘留。再者，游離的異氰酸基之含量若爲10質量％以 下，考慮封閉化後的胺甲酸酯聚合物水溶液之安定性，則 較佳爲7質量％以下。Further, examples of the polyester polyol include polyesters obtained from lactones and hydroxy acids. Further, as the polyether ester polyol, a polyether ester obtained by adding ethylene oxide or propylene oxide to a polyester produced in advance can be used. Examples of the organic polyisocyanate of the above (2) include isomers of tolyl diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, and benzodimethyl diisocyanate. Aliphatic diisocyanates such as aromatic aliphatic diisocyanates, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and 2,2,4·trimethyl An aliphatic diisocyanate such as hexamethylene diisocyanate or a polyisocyanate such as trimethylolpropane is preliminarily attached to the compound in a single or plural form. Examples of the chain extender having at least two active hydrogens in the above (3) include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol. , polyvalent alcohols such as glycerin, trimethylolpropane, and pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine, and piperazine, and amine alcohols such as monoethanolamine and diethanolamine. Sulfur diethylene glycol or the like - thiodiglycol, or water -47 - 1360477 In order to synthesize a urethane prepolymer, usually by a one-stage or multi-stage isocyanate addition polymerization method using the above chain extender, 150 ° C or less, preferably 70 to 12 (TC temperature, the reaction for 5 minutes to several hours. The ratio of isocyanate groups to active hydrogen atoms, if it is 1 or more, can be freely selected, but must be obtained In the urethane prepolymer, the free isocyanate group remains. Further, if the content of the free isocyanate group is 10% by mass or less, the blocked aqueous solution of the urethane polymer is considered. The stability is preferably 7% by mass or less.

所得到的上述胺甲酸酯預聚物，較佳係使用亞硫酸氫 鹽來進行封閉化。與亞硫酸氫鹽混合，約5分鐘〜1小時 ，邊充分攪拌邊進行反應。反應溫度較佳係60°C以下。然 後，以水稀釋成適當濃度，當作熱反應型水溶性胺甲酸酯 組成物。於使用該組成物時，調製成適當的濃度及黏度， 但通常若加熱到80〜20(TC左右，封閉劑的亞硫酸氫鹽會 解離，爲了再生活性的異氰酸基，使藉由預聚物之分子內 或分子間所發生的加成聚合反應，生成聚胺甲酸酯聚合物 ，或具有對其它官能基發生加成的性質。 作爲上述說明的含有封閉型異氰酸基的樹脂（B)之1例 ，第一工業製藥（股）製的商品名稱ELASTRON係爲代表例 。ELASTRON係經亞硫酸氫鈉封閉異氰酸基者，在分子末 端具有強力的親水性，由於胺甲醯基磺酸酯基的存在，而 成爲水溶性。 (b)溶劑 於本發明中，溶劑係不僅爲溶解樹脂的液體，而且亦 -48- 1360477 廣義地包括用於將樹脂分散成粒子狀的分散介質。爲了實 施本發明，可以使用有機溶劑、水性溶劑等的各種溶劑。 用於塗布液的溶劑，較佳係爲水與乙醇、異丙醇、苯 甲醇等的醇類，以佔全部塗布液的比例在30〜50質量％的 範圍內作混合而成的混合液。再者，若低於1 〇質量％，則 在可能溶解的範圍內，亦可混合醇類以外的有機溶劑。但 是|於塗布液中，醇類與其它有機溶劑的合計係低於50 質量％。The obtained urethane prepolymer obtained is preferably blocked by using hydrogen sulfite. The reaction is carried out by mixing with bisulfite for about 5 minutes to 1 hour while stirring well. The reaction temperature is preferably 60 ° C or lower. It is then diluted with water to an appropriate concentration to serve as a thermally reactive water-soluble urethane composition. When the composition is used, it is prepared to an appropriate concentration and viscosity, but usually if heated to 80 to 20 (about TC, the bisulfite of the blocking agent will dissociate, in order to regenerate the active isocyanate group, by pre- Addition polymerization reaction occurring in or between molecules of a polymer to form a polyurethane polymer or having an additive property to other functional groups. The above-described resin containing a blocked isocyanate group In the case of (B), the trade name ELASTRON of the first industrial pharmaceutical company is a representative example. ELASTRON is a kind of strong hydrophilicity at the molecular end by blocking the isocyanate group with sodium hydrogen sulfite. The presence of a mercaptosulfonate group becomes water-soluble. (b) Solvent In the present invention, the solvent is not only a liquid in which a resin is dissolved, but also -48-1360477 broadly includes a dispersion for dispersing the resin into particles. In order to carry out the present invention, various solvents such as an organic solvent and an aqueous solvent can be used. The solvent used for the coating liquid is preferably an alcohol such as water and ethanol, isopropanol or benzyl alcohol. When the ratio of the liquid is in the range of 30 to 50% by mass, the organic solvent other than the alcohol may be mixed in a range in which it is likely to be dissolved. The total amount of the alcohol and other organic solvents in the coating liquid is less than 50% by mass.

有機溶劑的添加量，對於全部溶劑而言若低於50質量 %時，則在塗布乾燥時提高乾燥性，而且與水單獨的情況 比較下，具有提高塗布層的外觀之優點。有機溶劑的添加 量，對於全部溶劑而言若爲50質量％以上時，溶劑的蒸發 速度變快，塗布中塗布液容易發生濃度變化。結果，由於 塗布液的黏度上升，塗布性降低，有發生塗布膜的外觀不 良之情況。再者，由於有機溶劑的揮發，火災等的危險性 亦變高。又，有機溶劑的添加量，對於全部溶劑而言，若 低於3 0質量％，則相對地水之比率係增加，親水性高的胺 甲酸酯成分係在接著性改質層的表面附近偏析。結果，接 著性改質層的表面之PEs相的面積率，或接著性改質層的 切削面中與硬被覆層的界面附近之PU相的面積率難以成 爲在恰當的範圍內。 (c)塗布液的pH調整 本發明中用於形成接著性改質層的塗布液，較佳pH係 在5以上且低於8的範圍內。塗布液的pH若低於5，則接 -49 - 1360477When the amount of the organic solvent added is less than 50% by mass based on the total amount of the solvent, the drying property is improved during coating and drying, and the appearance of the coating layer is improved as compared with the case of water alone. When the amount of the organic solvent is 50% by mass or more in all the solvents, the evaporation rate of the solvent is increased, and the coating liquid is likely to change in concentration during coating. As a result, the viscosity of the coating liquid rises, the coatability is lowered, and the appearance of the coating film may be poor. Further, the risk of fire or the like is also increased due to volatilization of the organic solvent. In addition, when the amount of the organic solvent is less than 30% by mass, the ratio of the relative water is increased, and the highly hydrophilic urethane component is in the vicinity of the surface of the adhesive modified layer. Segregation. As a result, the area ratio of the PEs phase on the surface of the adhesion-modifying layer or the area ratio of the PU phase in the vicinity of the interface with the hard coating layer in the cutting surface of the adhesion-modifying layer is unlikely to be in an appropriate range. (c) pH adjustment of the coating liquid The coating liquid for forming the adhesion modifying layer in the present invention preferably has a pH of 5 or more and less than 8. If the pH of the coating liquid is lower than 5, then -49 - 1360477

著性改質層的表面之PEs相的面積率變大，或接著性改質 層的切削面中與硬被覆層的界面附近之PU相的面積率變 小，密接性有變差的傾向。另一方面，塗布液的pH若爲8 以上，則隨著粒子的種類而發生顯著的凝聚，霧度上升， 透明性變差，故係不宜的。作爲pH調整劑，只要不對密 接性、防黏連性 '塗覆性有不良影響，或可忽視地而沒有 特別的限定。例如，於提高pH時，可以使用碳酸氫鈉或 碳酸鈉，於降低pH時，可以使用醋酸等。 (d)界面活性劑的併用 於將上述水性塗布液塗布在熱塑性樹脂薄膜的表面時 ，爲了提高對該薄膜的潤濕性，均勻地塗布塗布液，通常 使用界面活性劑。於本發明中，除了其以外，作爲控制接 著性改質層的表面或內部的相分離構造的手段之一，可以 使用界面活性劑。 界面活性劑，只要能得到良好的塗布性，而且在接著 性改質層的表面或內部可得到適當的相分離構造即可，其 種類係沒有特別的限定。於界面活性劑之中，以微量添加 能得到良好塗布性的氟系界面活性劑係較佳的。 再者，爲了接著性改質層的表面之PEs相的面積率、 或接著性改質層的切削面中與硬被覆層的界面附近之PU 相的面積率在恰當的範圍內，較佳爲對於塗布液而言，配 合0.01〜0.18質量％的陽離子系界面活性劑或非離子系界 面活性劑。 於使用陰離子性界面活性劑時，有提高與上述所示的The area ratio of the PEs phase on the surface of the modified layer is increased, or the area ratio of the PU phase in the vicinity of the interface between the cutting surface of the adhesive modified layer and the hard coating layer is small, and the adhesion tends to be deteriorated. On the other hand, when the pH of the coating liquid is 8 or more, significant aggregation occurs depending on the type of the particles, and the haze is increased, and the transparency is deteriorated, which is not preferable. The pH adjuster is not particularly limited as long as it does not adversely affect the adhesion and the anti-blocking property. For example, when the pH is raised, sodium hydrogencarbonate or sodium carbonate can be used, and when the pH is lowered, acetic acid or the like can be used. (d) When the above-mentioned aqueous coating liquid is applied to the surface of the thermoplastic resin film in combination, the coating liquid is uniformly applied in order to improve the wettability of the film, and a surfactant is usually used. In the present invention, in addition to the above, a surfactant may be used as one of means for controlling the phase separation structure of the surface or the inside of the adhesion-modifying layer. The surfactant is not particularly limited as long as it can obtain good coatability and an appropriate phase separation structure can be obtained on the surface or inside of the adhesive reforming layer. Among the surfactants, a fluorine-based surfactant which is excellent in applicability is preferably added in a small amount. Further, it is preferable that the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the PU phase in the vicinity of the interface between the hard coating layer and the cutting surface of the adhesion modifying layer is within an appropriate range. The coating liquid is blended with 0.01 to 0.18 mass% of a cationic surfactant or a nonionic surfactant. When an anionic surfactant is used, there is an improvement as shown above.

-50 - 1360477-50 - 1360477

共聚合聚酯及聚胺甲酸酯之相溶性的情況，難以得到本發 明所規定的相分離構造。界面活性劑的添加量，可在不妨 礙與硬被覆層或擴散層等的機能層之密接性，能得到良好 的塗布性之範圍內，作適當的選擇。例如，於氟系界面活 性劑的情況，合適者爲對於純水而言從臨界微胞濃度到其 30倍以下。於臨界微胞濃度的30倍以上，由於塗布液中 所含有的粒子變成容易凝聚，所得到的積層薄膜之霧度上 升’特別是在作爲光學機能性薄膜的基材薄膜係不宜的。 又，界面活性劑成分係滲出接著性改質層的表面，亦會對 密接性有不利影響。另一方面，於臨界微胞濃度以下，係 得不到良好的塗布性。又，接著性改質層的表面之PEs相 的面積率，或接著性改質層的切削面中與硬被覆層的界面 附近之PU相的面積率係難以控制在恰當的範圍內。 (界面活性劑的精製） 本發明中所用的界面活性劑，較佳係使用精製者。上 市的界面活性劑一般大多含有微量的不純物。特別地，不 純物的聚乙二醇之含量會妨礙良好的相分離構造之獲得。 爲了防止它，較佳爲進行從界面活性劑去除不純物的前處 理，使用精製的界面活性劑。 作爲去除不純物的前處理步驟，只要不使界面活性劑 變質，可去除不純物的方法即可，而沒有特別的限定。例 如，可舉出如下的方法。 例如，至少將界面活性劑和聚乙二醇溶解於可溶解的 有機溶劑中，在低溫靜置，使主成分的界面活性劑作飽和When the compatibility of the polyester and the polyurethane is copolymerized, it is difficult to obtain the phase separation structure defined in the present invention. The amount of the surfactant to be added can be appropriately selected within a range in which good adhesion to a functional layer such as a hard coating layer or a diffusion layer is not impaired, and good coating properties can be obtained. For example, in the case of a fluorine-based surfactant, it is suitable for pure water from a critical microcell concentration to 30 times or less. 30 times or more of the critical cell concentration, the particles contained in the coating liquid become easily aggregated, and the haze of the obtained laminated film rises, which is particularly unsuitable as a base film which is an optical functional film. Further, the surfactant component oozes out of the surface of the adhesive modifying layer, which also adversely affects the adhesion. On the other hand, below the critical microcell concentration, good coatability is not obtained. Further, the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the PU phase in the vicinity of the interface with the hard coating layer on the cutting surface of the adhesion modifying layer is difficult to control within an appropriate range. (Refining of Surfactant) The surfactant used in the present invention is preferably a purified one. Most of the surfactants listed on the market generally contain trace amounts of impurities. In particular, the amount of polyethylene glycol in the impureness prevents the acquisition of a good phase separation structure. In order to prevent this, it is preferred to carry out the pretreatment for removing impurities from the surfactant, and to use a refined surfactant. As a pretreatment step for removing impurities, a method of removing impurities may be carried out without deteriorating the surfactant, and is not particularly limited. For example, the following methods can be mentioned. For example, at least the surfactant and polyethylene glycol are dissolved in a soluble organic solvent, and allowed to stand at a low temperature to saturate the main component surfactant.

(.S -51- 1360477 沈降，接著過濾，取出純度經提高的界面活性劑之方法° 於全氟烷基環氧乙烷加成物系界面活性劑的情況，在異丙 醇中於30°C的溫浴上加熱溶解，於〇°C靜置24小時後’ 過濾取出沈殿物，可得到純度經提高的界面活性劑。 (e)粒子(.S -51 - 1360477 Settling, followed by filtration, removal of the improved surfactant by the method of ° perfluoroalkyl oxirane adduct surfactant, in isopropanol at 30 ° The C bath was heated and dissolved, and after standing at 〇 ° C for 24 hours, the precipitate was removed by filtration, and a surfactant having improved purity was obtained. (e) Particles

接著性改質基材薄膜的霧度係1.5%以下，但於高度要 求透明性的用途中，較佳爲使用一種用硬被覆薄膜或該薄 膜的光學機能性薄膜。上述霧度更佳係1.0%以下。霧度若 超過1.5%，則在使用薄膜於LCD用的透鏡薄膜或背光用 基材薄膜等時，畫面的鮮明度會降低，故係不宜的。 爲了使接著性改質基材薄膜的霧度成爲1.5%以下，較 佳爲在熱塑性樹脂薄膜中不含有.粒子。於熱塑性樹脂薄膜 中不含有粒子時，爲了改善耐刮性或捲繞成圓筒狀時或捲 出時的處理性（滑性、行進性、黏連性、捲繞時所伴隨的空 氣之脫空氣性等），較佳爲於接著性改質層中含有特定量之 適當大小的粒子，在接著性改質層的表面上形成適度的凹 凸。 作爲粒子，較佳爲與共聚合聚酯或聚胺甲酸酯的親和 性高之粒子，較佳爲對於該兩者而言，親和性在任一相中 有偏在的程度差異。藉由使粒子局於存在於相分離的樹脂 之一方，粒子適度地聚集，以比較少的粒子添加，即霧度 不會大幅上升地，可得到優良的防黏連性。 作爲接著性改質層中所含有的粒子，可舉出碳酸鈣、 磷酸鈣、非晶性矽石、結晶性的玻璃塡料、高嶺土、滑石、 -52 - 1360477 二氧化鈦、氧化鋁、矽石一氧化鋁複合氧化物粒子、硫酸 鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲母等的無機粒子、 交聯聚苯乙烯粒子、交聯丙烯酸系樹脂粒子、交聯甲基丙 烯酸甲酯系粒子、苯并胍胺•甲醛縮合物粒子、蜜胺·甲 醛縮合物粒子、聚四氟乙烯粒子等的耐熱性高分子粒子。 於此等粒子之中，從以下之點來看，較佳爲矽石粒子The haze of the subsequently modified base film is 1.5% or less. However, in applications where transparency is required, it is preferred to use an optically functional film using a hard coating film or the film. The above haze is preferably 1.0% or less. When the haze is more than 1.5%, when the film is used for a lens film for LCD or a base film for a backlight, the sharpness of the screen is lowered, which is not preferable. In order to make the haze of the adhesive modified base film 1.5% or less, it is preferred that the thermoplastic resin film does not contain particles. When the thermoplastic resin film does not contain particles, the handleability (slip property, travelability, adhesion, and air entanglement accompanying winding) is improved in order to improve scratch resistance or to be wound into a cylindrical shape or to be wound up. It is preferable to contain a specific amount of particles of a suitable amount in the adhesive reforming layer, and to form moderate irregularities on the surface of the adhesive modified layer. The particles are preferably particles having a high affinity with the copolymerized polyester or polyurethane, and it is preferred that the affinity differs in any of the phases. By causing the particles to be present in one of the phase-separated resins, the particles are moderately aggregated, and relatively small particles are added, i.e., the haze does not rise significantly, and excellent anti-blocking property can be obtained. Examples of the particles contained in the adhesive layer include calcium carbonate, calcium phosphate, amorphous vermiculite, crystalline glass pigment, kaolin, talc, -52 - 1360477 titanium dioxide, aluminum oxide, and vermiculite. Inorganic particles such as alumina composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, and crosslinked methyl methacrylate Heat-resistant polymer particles such as particles, benzoguanamine/formaldehyde condensate particles, melamine-formaldehyde condensate particles, and polytetrafluoroethylene particles. Among these particles, from the following points, it is preferable that the particles are meteorite particles.

第1有利點爲：由於與接著性改質層的樹脂成分之折 射率比較接近，故容易得到高透明的薄膜。第2有利點爲 :矽石粒子具有偏在於經相分離的聚胺甲酸酯相中之特徵 ，可補充接著性改質層的表面上所存在的聚胺甲酸酯相之 防黏連性差的聚胺甲酸酯形樹脂之固有性質。茲認爲此係 因爲矽石粒子與聚胺甲酸酯的表面能係比共聚合聚酯更接 近，親和性高。 又，粒子的形狀係沒有特別的限定，但從賦予易滑性 之點來看，較佳爲接近球狀的粒子》 接著性改質層中的粒子含量，對於接著性改質層而言 ，較佳爲20質量％以下，更佳爲15質量％以下，特佳爲 10質量％以下。接著性改質層中的粒子含量若超過20質量 %，則透明性變差，薄膜的密接性亦容易變不足。另一方 面，粒子含量的下限，對於接著性改質層而言，較佳爲 〇. 1質量％，更佳爲1質量％，特佳爲3質量％。 又，於接著性改質層中中，亦可含有2種以上的平均 粒徑不同的粒子。 C S ) -53- 1360477 再者，亦可以含有同種類粒子的不同平均粒徑者。於 任一情況中，粒子的平均粒徑及總含量若在上述範圍內即 可。於塗布上述塗布液時，爲了去除塗布液中的粒子之粗 大凝聚物，較佳爲配置濾材*以在塗布前不久將塗布液精 密過濾。The first advantage is that a film having a high transparency is easily obtained because the refractive index of the resin component of the adhesive layer is relatively close. The second advantage is that the vermiculite particles are characterized by being biased in the phase-separated polyurethane phase, which can complement the adhesion prevention property of the polyurethane phase present on the surface of the adhesive modifying layer. The inherent properties of the polyurethane resin. It is considered that this is because the surface energy of vermiculite particles and polyurethane is closer than that of copolymerized polyester, and the affinity is high. Further, the shape of the particles is not particularly limited, but from the viewpoint of imparting slipperiness, it is preferable that the particle content in the next modified particle layer is the particle content in the subsequent modified layer. It is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the content of the particles in the modified layer is more than 20% by mass, the transparency is deteriorated, and the adhesion of the film is likely to be insufficient. On the other hand, the lower limit of the particle content is preferably 0.1% by mass, more preferably 1% by mass, particularly preferably 3% by mass, for the adhesion modifying layer. Further, in the adhesive reforming layer, two or more kinds of particles having different average particle diameters may be contained. C S ) -53- 1360477 Furthermore, it is also possible to contain different average particle diameters of the same type of particles. In either case, the average particle diameter and the total content of the particles are within the above ranges. When the coating liquid is applied, in order to remove coarse aggregates of particles in the coating liquid, it is preferred to dispose the filter medium* to precisely filter the coating liquid shortly before coating.

又，粒子的平均粒徑較佳爲20〜150nm，更佳爲40〜 60nm。平均粒徑若低於20nm，則難以得到充分的防黏連 性，而且耐刮性有變差的傾向。另一方面，粒子的平均粒 徑若超過150nm，則霧度上升，而且粒子容易脫落，故係 不宜的。 於本發明，於僅平均粒徑爲20〜150nm的粒子A時， 有得不到充分的防黏連性及耐刮性之情況。因此，爲了更 提高防黏連性及耐刮性，較佳爲更少量倂用平均粒徑大的 粒子B。平均粒徑大的粒子B之平均粒徑較佳係160〜 lOOOnm，特佳係200〜800nm。粒子 B的平均粒徑若低於 16 Onm，則耐刮性、滑性、捲繞性會變差。另—方面，粒 子B的平均粒徑若超過1〇 〇0nm，則霧度有變高的傾向》 又，粒子B較佳係一次粒子所凝聚的凝聚體粒子，使用凝 聚狀態下的平均粒徑與一次粒子的平均粒徑之比爲4倍以 上的粒子，從耐刮性之點來看係較佳的。 於使用2種粒子時，例如接著性改質層中的粒子a(平 均粒徑：20〜150nm)與粒子B(平均粒徑：160〜lOOOnm)的 含量比（P1/P2)係成爲5〜30，而且粒子B的含量，對於接 著性改質層的固體成分而言，係〇_1〜1質量％。藉由將2Further, the average particle diameter of the particles is preferably from 20 to 150 nm, more preferably from 40 to 60 nm. When the average particle diameter is less than 20 nm, it is difficult to obtain sufficient anti-blocking property, and the scratch resistance tends to be deteriorated. On the other hand, when the average particle diameter of the particles exceeds 150 nm, the haze increases, and the particles are liable to fall off, which is not preferable. In the present invention, when only the particles A having an average particle diameter of 20 to 150 nm are obtained, sufficient anti-blocking properties and scratch resistance are not obtained. Therefore, in order to further improve the anti-blocking property and the scratch resistance, it is preferred to use a smaller amount of the particles B having a larger average particle diameter. The average particle diameter of the particles B having a large average particle diameter is preferably 160 to 100 nm, and particularly preferably 200 to 800 nm. When the average particle diameter of the particles B is less than 16 Onm, the scratch resistance, the sliding property, and the winding property are deteriorated. On the other hand, when the average particle diameter of the particles B exceeds 1 〇〇 0 nm, the haze tends to be high. Further, the particles B are preferably aggregated particles in which primary particles are aggregated, and the average particle diameter in agglomerated state is used. The particles having a ratio of the average particle diameter of the primary particles of 4 or more are preferable from the viewpoint of scratch resistance. When two kinds of particles are used, for example, the content ratio (P1/P2) of the particles a (average particle diameter: 20 to 150 nm) and the particles B (average particle diameter: 160 to 100 nm) in the adhesion-modifying layer is 5~ 30. Further, the content of the particles B is 〇_1 to 1% by mass based on the solid content of the adhesion-modifying layer. By 2

-54- 1360477 種特定粒徑的粒子之含量控制在上述範圍內’將接著性改 質層的表面之三次元中心面平均表面粗度恰當化，使透明 性與處理性或防黏連性並存係較宜的。對於接著性改質層 而言，粒子B的含量若超過1質量％，則霧度有變顯著上 升的傾向。 上述粒子的平均一次粒徑及平均粒徑的測定係藉由下 述方法來進行。-54- 1360477 The content of particles of a specific particle size is controlled within the above range. 'The average surface roughness of the three-dimensional center plane of the surface of the adhesion-modifying layer is appropriately adjusted, so that transparency and handling or anti-blocking property coexist. It is more suitable. When the content of the particles B exceeds 1% by mass, the haze tends to increase remarkably. The measurement of the average primary particle diameter and the average particle diameter of the above particles was carried out by the following method.

以電子顯微鏡來拍攝粒子的照片，在最小粒子1個的 大小成爲2〜5mm的倍率下，測定300〜500個粒子的最大 直徑，以其平均値當作平均一次粒徑或平均粒徑。又，於 求出積層薄膜的接著性改質層中之粒子的平均粒徑時，使 用透射型電子顯微鏡（TEM)，以倍率12萬倍來拍攝積層薄 膜的截面，可求得接著性改質層的截面中所存在的粒子之 最大直徑。凝聚體所成的粒子B之平均粒徑，係使用光學 顯微鏡以200倍的倍率來拍攝300〜5 00個積層薄膜的接 著性改質層之截面，測定其最大直徑。 ⑴交聯劑 如攜帶式電話、PDA、移動型電腦般，在屋外使用資訊 終端的機會係增多。再者，如汽車導航等所用的觸控面板 般，在夏天使用於高溫的車內之材料亦增多。因此，要求 在如此高溫、高濕的嚴苛環境下，品質變化少的硬被覆薄 膜，即耐濕熱密接性優異的薄膜係爲如此用途所要求者。 於如此的用途中，使用本發明的硬被覆薄膜時，爲了 提高接著性改質層的耐濕熱性，在塗布液中添加交聯劑， -55- 1360477 藉由進行以下熱處理’形成含有具交聯構造的樹脂之接著 性改質層。作爲交聯劑’使用從環氧系交聯劑、蜜胺系交 聯劑、噚唑啉系交聯劑中所選出的至少一種。可邊考慮與 塗布液中所使用的共聚合聚酯樹脂之親和性、及接著性改 質層中所要求的耐濕熱密接性，邊選定交聯劑。The photograph of the particles was taken with an electron microscope, and the maximum diameter of 300 to 500 particles was measured at a magnification of 2 to 5 mm of the smallest particles, and the average 値 was regarded as the average primary particle diameter or the average particle diameter. Further, when the average particle diameter of the particles in the adhesion-modified layer of the laminated film is determined, a cross section of the laminated film is imaged at a magnification of 120,000 times using a transmission electron microscope (TEM), and the adhesion is improved. The largest diameter of the particles present in the cross section of the layer. The average particle diameter of the particles B formed by the aggregates was taken by a light microscope at a magnification of 200 times to take a cross section of the adhesive modified layer of 300 to 500 sheets of the laminated film, and the maximum diameter thereof was measured. (1) Cross-linking agents Like mobile phones, PDAs, and mobile computers, the opportunities for using information terminals outside the home are increasing. Furthermore, as in touch panels used in car navigation and the like, materials used in high-temperature cars in summer are also increasing. Therefore, it is required that a hard coating film having a small change in quality in a severe environment of such high temperature and high humidity, that is, a film excellent in moisture and heat adhesion is required for such use. In such a use, when the hard coating film of the present invention is used, in order to improve the moist heat resistance of the adhesive reforming layer, a crosslinking agent is added to the coating liquid, and -55-1360477 is formed by the following heat treatment. An adhesive modification layer of a resin of a joint structure. As the crosslinking agent, at least one selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, and an oxazoline crosslinking agent is used. The crosslinking agent can be selected in consideration of the affinity with the copolymerized polyester resin used in the coating liquid and the moisture-resistant heat adhesion required in the adhesive layer.

特別地，於要求高度耐濕熱密接性時，上述交聯劑中 較佳爲環氧系交聯劑或蜜胺系交聯劑。作爲環氧系交聯劑 ，並沒有特別的限定，例如NAGASE化成工業公司製的水 溶性環氧交聯劑（Deconal 系列；EX-521、EX-512、EX-421 、EX-8 10、EX-81 1、EX-8 51等）可當作市售品取得。作爲 蜜胺系交聯劑，例如住友化學公司製Sumitex系列（M-3、 MK、M-6、MC等）或三和化學公司製甲基化蜜胺樹脂（MW-22、MX-706等）可當作市售品取得。又，作爲噚唑啉系交 聯劑，曰本觸媒公司製Epocros系列（WS-700)、新中村化 學工業公司製NX Linker FX等可當作市售品取得。 上述交聯劑，對於接著性改質層中的共聚合聚酯樹脂 與交聯劑之合計量（1〇〇質量°/〇而言，較佳係以5〜40質量 %、更佳係以1 〇〜3 0質量％含於接著性改質層形成用塗布 液中。交聯劑的含量若超過40質量％，則接著性改質層變 脆，於從丙烯酸酯系樹脂來形成硬被覆層或擴散層等的機 能層後，在加工程序中，有不能充分得到儘量耐高速切割 的密接性之情況。另一方面，交聯劑的含量若低於5質量 %，則會難以得到近年來所要求的耐久性。而且，於塗布 液中，爲了促進交聯，視需要亦可添加觸媒。 -56- 1360477 (3-2)塗布步驟In particular, when high moisture and heat resistance is required, the above crosslinking agent is preferably an epoxy crosslinking agent or a melamine crosslinking agent. The epoxy-based crosslinking agent is not particularly limited. For example, a water-soluble epoxy crosslinking agent manufactured by NAGASE Chemical Industry Co., Ltd. (Deconal series; EX-521, EX-512, EX-421, EX-8 10, EX) -81 1, EX-8 51, etc.) can be obtained as a commercial product. As a melamine-based crosslinking agent, for example, Sumitex series (M-3, MK, M-6, MC, etc.) manufactured by Sumitomo Chemical Co., Ltd. or methylated melamine resin (MW-22, MX-706, etc.) manufactured by Sanwa Chemical Co., Ltd. ) can be obtained as a commercial product. Further, as an oxazoline-based crosslinking agent, Epocros series (WS-700) manufactured by Sakamoto Co., Ltd., and NX Linker FX manufactured by Shin-Nakamura Chemical Co., Ltd. can be obtained as commercial products. The crosslinking agent is preferably a total of 5 to 40% by mass, more preferably 5 to 40% by mass, based on the total amount of the copolymerized polyester resin and the crosslinking agent in the adhesion modifying layer. 1% to 30% by mass is contained in the coating liquid for forming an adhesive layer. When the content of the crosslinking agent exceeds 40% by mass, the adhesive layer becomes brittle and forms a hard coating from the acrylate resin. After the functional layer such as the layer or the diffusion layer, in the processing procedure, the adhesion to the high-speed cutting is not sufficiently obtained. On the other hand, if the content of the crosslinking agent is less than 5% by mass, it is difficult to obtain a recent year. In order to promote crosslinking, a catalyst may be added as needed in the coating liquid. -56- 1360477 (3-2) Coating step

塗布上述水性塗布液的步驟，較佳係在該薄膜的製造 步驟中塗布的線內塗覆法。更佳爲在結晶配向完成之前， 塗布在基材薄膜上。水性塗布液中的固體成分濃度，較佳 係3 0質量％以下，特佳係1 0質量％以下。固體成分濃度的 下限較佳係1質量％，更佳係3質量％，特佳係5質量％。 於該水性塗布液的塗布量下，以該水性塗布液所塗布的薄 膜’爲了配向及熱定型，而導入拉幅機，於該處被加熱， 藉由熱交聯反應形成安定的被膜，成爲聚酯系積層薄膜。 (塗布量） 未乾燥時的塗布量（以下簡稱濕塗布量），較佳係2g/m2 以上且低於1 〇g/m2。濕塗布量若低於2g/m2，則爲了得到 所設計的乾塗布量（最終接著性改質層的塗布量），必須提 高塗布液的固體成分濃度。若提高塗布液的固體成分濃度 ，則塗布液的黏度會變高，而容易發生筋狀的塗布不均。 另一方面’濕塗布量若爲10g/m2以上，則容易受到乾燥爐 內的乾燥風之影響’容易發生塗布不均。再者，爲了防止 塵埃的附著之缺點，較佳係在乾淨度爲5000以下等級的 環境下來塗布塗布液。 又，最終的接著性改質層之塗布量（薄膜每單位面積的 固體成分質量）較佳係控制在0.005〜〇.20g/m2。於先前技 術中，塗布量若低於〇_〇5g/m2，則難以得到充分的密接性 。然而，由於接著性改質層具有特定的相分離構造，故塗 布量即使低於0.〇5g/m2，也以得到對於機能層和基材具有 -57 - 1360477 優良密接性的積層薄膜。塗布量若低於0.005g/m2，則 接性變不充分。又，於塗布量低於0.05g/m2時，所使用 粒子較佳係使用平均粒徑爲6Onm以下的粒子。粒子的 均粒徑若超過60nm，則在接著性基材薄膜的製造時或加 時，粒子變成容易從接著性改質層脫落。於粒子偏在於 琴甲酸酯柑中時，塗布量若爲0.00 5 g/m2以上，則粒子 以脫落。另一方面，塗布量若超過0.2 0 g/m2，則偏析在 著性改質層的表面的聚胺甲酸酯成分會變多，防黏連性The step of applying the above aqueous coating liquid is preferably an in-line coating method applied in the production step of the film. More preferably, it is coated on the substrate film before the crystallization alignment is completed. The solid content concentration in the aqueous coating liquid is preferably 30% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the solid content concentration is preferably 1% by mass, more preferably 3% by mass, and particularly preferably 5% by mass. At a coating amount of the aqueous coating liquid, the film coated with the aqueous coating liquid is introduced into a tenter for alignment and heat setting, and is heated there to form a stable film by thermal crosslinking reaction. Polyester laminated film. (Coating amount) The coating amount at the time of drying (hereinafter referred to as wet coating amount) is preferably 2 g/m 2 or more and less than 1 〇 g/m 2 . When the wet coating amount is less than 2 g/m2, in order to obtain a designed dry coating amount (coating amount of the final adhesive reforming layer), it is necessary to increase the solid content concentration of the coating liquid. When the solid content concentration of the coating liquid is increased, the viscosity of the coating liquid is increased, and uneven coating unevenness is likely to occur. On the other hand, when the wet coating amount is 10 g/m2 or more, it is likely to be affected by the dry wind in the drying furnace, and coating unevenness is likely to occur. Further, in order to prevent the adhesion of dust, it is preferred to apply the coating liquid in an environment having a cleanliness level of 5,000 or less. Further, the coating amount of the final adhesive reforming layer (solid content per unit area of the film) is preferably controlled to 0.005 to 20.20 g/m2. In the prior art, if the coating amount is less than 〇_〇5 g/m2, it is difficult to obtain sufficient adhesion. However, since the adhesive reforming layer has a specific phase-separated structure, even if the coating amount is less than 0.5 g/m2, a laminated film having excellent adhesion to the functional layer and the substrate of -57 to 1360477 is obtained. When the coating amount is less than 0.005 g/m2, the connectivity is insufficient. Further, when the coating amount is less than 0.05 g/m2, it is preferred to use particles having an average particle diameter of 6 Onm or less. When the average particle diameter of the particles exceeds 60 nm, the particles become easily detached from the adhesive reforming layer at the time of production or addition of the adhesive base film. When the particles are in the citric acid citrus, the coating amount is 0.005 g/m2 or more, and the particles are detached. On the other hand, when the coating amount exceeds 0.20 g/m2, the amount of the polyurethane component segregated on the surface of the modified layer becomes large, and the blocking property is improved.

又，接著性改質層的厚度，係可藉由切片機來切斷 著性改質層的截面，以電子顯微鏡來觀察而測定。於接 性改質層柔軟時，切斷時會有變形。爲了簡便，塗布量 爲已知，則可從接著性改質層的密度來換算厚度。例如 於接著性改質層的密度爲lg/cm3時，塗布量若爲lg/m2 則厚度相當於1 μηι »接著性改質層的密度、係可藉由從 成接著性改質層的樹脂、粒子的種類來求出各自材料的 度，使各材料的密度乘以材料的質量比，求得其和，以 測接著性改質層的厚度。 (3-3)乾燥步驟 於接著性改質基材薄膜的製造方法中，在熱塑性樹 薄膜上塗布塗布液後，使薄塗布的塗膜被乾燥。一般地 在塗布塗布液後，使塗膜乾燥時，利用拉幅機的預熱區 乾燥的情況係多的》於該情況下，雖然亦依賴於製膜設 的大小、薄膜的行進速度，但是一般從塗布到乾燥開始 密 的 平 工 聚 難 接 會 接 著 若 構 密 推 脂 使 備 爲 -58- (S ) 1360477 止的時間係至少5秒左右。期間，塗布液的溶劑之水與醇 的平衡崩潰，親水性高的聚胺甲酸酯成分變成容易偏析在 接著性改質層的表面。因此，於最後所得到的接著性改質 基材薄膜中，接著性改質層的表面之PEs相的面積率，或 接著性改質層的切削面中與硬被覆層的界面附近之PU相Further, the thickness of the adhesive modified layer can be measured by observing the cross section of the modified layer by a microtome and observing it with an electron microscope. When the interface is soft, it will be deformed when it is cut. For the sake of simplicity, the coating amount is known, and the thickness can be converted from the density of the adhesive layer. For example, when the density of the adhesive modifying layer is lg/cm3, the coating amount is lg/m2, and the thickness is equivalent to 1 μm. The density of the adhesive layer is changed by the resin from the adhesive layer. The type of the particles is used to determine the degree of each material, and the density of each material is multiplied by the mass ratio of the material, and the sum is obtained to measure the thickness of the adhesive layer. (3-3) Drying step In the method for producing an adhesive-modified substrate film, the coating liquid is applied onto the thermoplastic resin film, and then the thin coating film is dried. Generally, when the coating film is applied, when the coating film is dried, the preheating zone of the tenter is used for drying. In this case, although depending on the size of the film formation and the traveling speed of the film, Generally, it is generally difficult to connect from the application to the drying, and then the time to prepare the grease to be -58-(S) 1360477 is at least about 5 seconds. During this period, the balance of water and alcohol in the solvent of the coating liquid collapses, and the highly hydrophilic polyurethane component becomes easily segregated on the surface of the subsequent modified layer. Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer in the cut surface of the subsequent modified layer

的面積率係難以控制在恰當的範圍內。於本發明中，將專 用於塗膜之乾燥的乾燥爐（板式乾燥機）配置在儘量接近塗 布裝置的薄膜進行方向出口，將塗布液塗布在聚酯薄膜後 ，立刻使乾燥係爲重點。 於乾燥爐內中，吹到塗布面的乾燥風之溫度較佳係120 °C以上且低於150°C。又，風速較佳係30m/秒以上。更佳 的乾燥溫度係130°C以上且低於150°C。於該乾燥溫度低 於120°C或風速低於30m/秒未時，乾燥速度變慢。塗布液 之溶劑的水與醇之平衡會崩潰，相對地水的比率容易增加 。因此，親水性高的聚胺甲酸酯成分會偏析在接著性改質 層的表面。因此，於最終所得到的接著性改質基材薄膜中 ，接著性改質層的表面之PEs相的面積率，或接著性改質 層的切削面中與硬被覆層的界面附近之PU相的面積率係 難以控制在恰當的範圍內。另一方面，乾燥溫度若在150 °C以上，則熱塑性樹脂薄膜變成容易發生結晶化，橫拉伸 時發生斷裂的頻率會增加。 又，於上述乾燥爐中，較佳爲邊將溫度維持在120°C以 上且低於1 50°C，邊乾燥0.1〜5秒。乾燥時間更佳係〇.5 〜3秒。乾燥時間若低於Ο · 1秒，則塗膜的乾燥變不充分 -59 - 1360477 ，於通過從乾燥步驟到橫拉伸步驟之間所配置的輥時，該 輥變成容易被乾燥不充分的塗布面所污染。另一方面，乾 燥時間若超過5秒，則熱塑性樹脂薄膜變成容易發生結晶 化，橫拉伸時發生斷裂的頻率i增加。The area ratio is difficult to control within the proper range. In the present invention, a drying oven (plate dryer) dedicated to the drying of a coating film is placed in a direction exit as close as possible to the film of the coating device, and after the coating liquid is applied to the polyester film, the drying system is immediately focused. In the drying furnace, the temperature of the dry wind blown to the coated surface is preferably 120 ° C or more and less than 150 ° C. Further, the wind speed is preferably 30 m/sec or more. More preferably, the drying temperature is 130 ° C or more and less than 150 ° C. When the drying temperature is lower than 120 ° C or the wind speed is lower than 30 m / sec, the drying speed becomes slow. The balance of water and alcohol in the solvent of the coating liquid collapses, and the ratio of water is relatively increased. Therefore, the highly hydrophilic polyurethane component is segregated on the surface of the adhesive reforming layer. Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer on the cut surface of the adhesive modified layer The area ratio is difficult to control within the proper range. On the other hand, when the drying temperature is 150 °C or higher, the thermoplastic resin film is liable to be crystallized, and the frequency of occurrence of cracking during lateral stretching increases. Further, in the above drying furnace, it is preferred to dry the mixture while maintaining the temperature at 120 ° C or higher and lower than 150 ° C for 0.1 to 5 seconds. The drying time is better. The system is 〇5~3 seconds. If the drying time is less than Ο1 sec, the drying of the coating film becomes insufficient -59 - 1360477, and the roller becomes insufficiently dried when passing through the roller disposed between the drying step and the lateral stretching step. Contaminated by the coated surface. On the other hand, when the drying time exceeds 5 seconds, the thermoplastic resin film is liable to be crystallized, and the frequency i at which fracture occurs during transverse stretching increases.

藉由上述乾燥爐，在120 °C以上且低於150 °C的溫度將 塗膜乾燥後，較佳爲立刻將具有接著性改質層的接著性改 質基材薄膜冷卻到室溫附近爲止。於上述接著性改質基材 薄膜的表面溫度在100 °C以上的高溫照樣地取出乾燥爐， 使接著性改質基材薄膜接觸室溫附近的輥時，由於薄膜的 收縮而變成容易發生傷痕。 乾燥爐內的風速若爲通常的3 0m/秒以上，則由於在乾 燥爐內強的乾燥風吹打未乾燥狀態的塗布面，變成容易發 生乾燥斑紋。然而，於本發明中，藉由將與所噴吹的風量 同量或其以上的風量排氣到乾燥爐外，則可能在3 0m/秒以 上的風速進行。又，亦重要的是該排氣風係流向與塗布機 的相反側，以防止塗布機的排氣風對塗布面發生斑紋。 重要的是從塗布後起到進行乾燥爐內爲止，薄膜的通 過時間係少於2秒，較佳係少於1 . 5秒。從塗布到進行乾 燥爐內的時間若爲2秒以上，則期間塗布液的溶劑之水與 醇的平衡崩潰，親水性高的聚胺甲酸酯成分變成容易偏析 在接著性改質層的表面。因此，於最後所得到的接著性改 質基材薄膜中，接著性改質層的表面之PEs相的面積率， 或接著性改質層的切削面中與硬被覆層的界面附近之PU 相的面積率係難以控制在恰當的範圍內。 -60 - 1360477 爲了將從塗布後起到進入乾燥爐爲止的薄膜之通過時 間維持在少於2秒，必須選擇適宜的薄膜行進速度，但較 佳爲使塗布機和乾燥爐入口儘可能接近。再者，於乾燥爐 中，爲了防止來自乾燥風的塵埃之混入，較佳爲使用經 HEP A過濾器所乾淨化的空氣。此時所用的HEPA過濾器 較佳係使用具有能阻擋95%以上之標稱過濾精度0.5μηι以 上的塵埃之性能的過濾器。After drying the coating film at a temperature of 120 ° C or higher and lower than 150 ° C in the drying oven, it is preferred to immediately cool the adhesive-modified substrate film having the adhesion modifying layer to near room temperature. . When the surface temperature of the adhesive-modified substrate film is taken out at a high temperature of 100 ° C or higher, the drying furnace is taken out, and when the adhesive-modified substrate film is brought into contact with a roll near room temperature, the film is likely to be scratched due to shrinkage of the film. . When the wind speed in the drying furnace is usually 30 m/sec or more, the dry surface of the drying oven blows the coated surface in an undried state, and drying streaks are likely to occur. However, in the present invention, by exhausting an air volume of the same amount or more as that of the blown air volume to the outside of the drying furnace, it is possible to perform at a wind speed of 30 m/sec or more. Further, it is also important that the exhaust air flows toward the opposite side of the coater to prevent the exhaust air of the coater from being streaked on the coated surface. It is important that the passage time of the film is from less than 2 seconds, preferably less than 1.5 seconds, from the time of application to the drying of the furnace. When the time from application to drying in the drying furnace is 2 seconds or longer, the balance of water and alcohol in the solvent of the coating liquid collapses, and the highly hydrophilic polyurethane component becomes easily segregated on the surface of the adhesive reforming layer. . Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer on the cut surface of the adhesive modified layer The area ratio is difficult to control within the proper range. -60 - 1360477 In order to maintain the passage time of the film from the time of application to the drying oven to less than 2 seconds, it is necessary to select a suitable film traveling speed, but it is preferable to make the coater and the drying furnace inlet as close as possible. Further, in the drying furnace, in order to prevent the incorporation of dust from the dry air, it is preferable to use air cleaned by the HEP A filter. The HEPA filter used at this time preferably uses a filter having a property of blocking dust of more than 95% of the nominal filtration accuracy of 0.5 μm or more.

乾燥步驟較佳係依順序改變乾燥溫度及乾燥時間的條 件，即由所謂分割成2〜8區的乾燥區所構成。特佳爲採 用分割成3〜6區的多段乾燥裝置。例如’於將塗布液塗 布在一軸配向熱塑性樹脂薄膜的一面或兩面’藉由塗布機 正上方配置的多段乾燥爐來乾燥時，下述的方法係合適的 例如，於以4階段進行乾燥時，在劃分爲4個乾燥區 的乾燥爐中進行乾燥。例如，第1乾燥區係在溫度125〜 140 °C進行0.1〜4秒的乾燥，第2乾燥區係在溫度55〜 1〇〇 °C進行0.1〜4秒的乾燥’第3乾燥區係在溫度35〜55 。(：進行0.1〜4秒的乾燥’第4乾燥區係在溫度25〜3 5°C 進行0.1〜4秒的乾燥之方法。 上述乾燥條件的數値範圍係隨著塗布液的固體成分濃 度而有稍微的變動，不受上述代表的條件所限定。再者’ 重要的是於進行熱風乾燥時’風量在各階段中亦有變化。 例如，以下般的方法係較佳的。 於第1乾燥區中，將乾燥風的風速設定在20〜5 〇111/秒 -61-The drying step is preferably carried out by sequentially changing the conditions of the drying temperature and the drying time, i.e., by a drying zone which is divided into 2 to 8 zones. It is particularly preferable to use a multi-stage drying device which is divided into 3 to 6 zones. For example, when the coating liquid is applied to one side or both sides of a one-axis oriented thermoplastic resin film to be dried by a multi-stage drying furnace disposed directly above the coater, the following method is suitable, for example, when drying in four stages, Drying was carried out in a drying oven divided into 4 drying zones. For example, the first drying zone is dried at a temperature of 125 to 140 ° C for 0.1 to 4 seconds, and the second drying zone is dried at a temperature of 55 to 1 ° C for 0.1 to 4 seconds. Temperature 35~55. (: drying for 0.1 to 4 seconds) The fourth drying zone is a method of drying at a temperature of 25 to 3 5 ° C for 0.1 to 4 seconds. The range of the drying conditions is in accordance with the solid content concentration of the coating liquid. There is a slight variation, which is not limited by the conditions of the above-mentioned representative. It is also important that 'the air volume is also changed in each stage during hot air drying. For example, the following method is preferred. In the zone, set the wind speed of the dry wind to 20~5 〇111/sec-61-

1360477 ，將乾燥風的給氣風量設定在100〜150m/秒，將劫 設定在150〜200m3/秒。從第2乾燥區到第4乾燥 ，將給氣風量設定在60〜140m/秒，將排氣風量 100〜180m/秒。於任一乾燥區中，皆設定不使乾燥 塗布機側，接著以夾具來抓住薄膜的端部，導引 100〜140°C、風速10〜20m/秒的熱風區，在寬度戈 〜6倍的拉伸。 又，亦可邊將溫度維持在120°C至150°C，邊在 秒，較佳在0.5秒至低於3秒的時間中，適當調整 度及總乾燥時間。該乾燥步驟中各段（區）的決定， 慮分散液的濃度、塗布量、所塗布行進的薄膜之行 、熱風的溫度、風速、風量等諸條件，在製造現場 宜、恰當値。 (3-4)熱定型處理步驟 於接著性改質基材薄膜的製造方法中，設計榜 驟、熱定型處理步驟、冷卻步驟，連續劃分成10 ’而且各區係可獨立地溫度控制地被分隔，且各逼 生劇烈的溫度變化。特別地，於從橫拉伸區後半至 最高溫度設定區中，藉由階段地升溫，可抑制毗舞 之劇烈溫度變化。於本發明中，當製造在接著性泛 表面或內部具有特異的相分離構造之接著性改質差 時’於乾燥步驟或熱定型處理步驟中，溫度控制 要的。又，爲了在構成接著性改質層的樹脂中形技 造，熱定型處理步驟中的溫度係非常重要的，該涵 氣風量 區爲止 設定在 風流到 至溫度 向作2 0· 1 〜5 乾燥溫 係可考 進速度 決定適 :拉伸步 〜30區 [間不發 I熱定型 ;的區間 :質層的 丨材薄膜 ;尤其重 :交聯構 L度對交 -62 - 1360477 聯反應速度有大的影響。 以下，詳細說明其之實施態樣。 如前述地，於熱定型處理步驟中，熱處理條件係影響 接著性改質層的相分離狀態。即，適當地設定熱定型處理 步驟中的最高溫度、到達上述最高溫度所需要的時間、及 從接著性改質層的相分離開始顯著進行的溫度到熱定型處 理步驟中到達最高溫度所需要的時間係重要的。1360477, set the air supply air volume of the dry wind to 100~150m/sec, and set the robbery to 150~200m3/sec. From the second drying zone to the fourth drying, the amount of the supplied air is set to 60 to 140 m/sec, and the exhaust air volume is 100 to 180 m/sec. In any drying zone, it is set not to dry the coater side, then grasp the end of the film with a clamp, and guide the hot air zone of 100~140 ° C, wind speed 10~20 m / sec, in the width Ge ~ 6 Stretching times. Further, it is also possible to maintain the temperature at 120 ° C to 150 ° C while adjusting the degree and total drying time in seconds, preferably from 0.5 seconds to less than 3 seconds. The determination of each stage (zone) in the drying step is such that the concentration of the dispersion, the amount of coating, the course of the film to be coated, the temperature of the hot air, the wind speed, the air volume, and the like are appropriate at the manufacturing site. (3-4) Heat setting processing step In the manufacturing method of the adhesive modified base film, the design step, the heat setting processing step, and the cooling step are successively divided into 10 ' and each zone can be independently temperature-controlled Separated, and each forced a drastic temperature change. In particular, in the second half of the transverse stretching zone to the highest temperature setting zone, the temperature rise in the stage can suppress the severe temperature change of the Vish. In the present invention, when manufacturing an adhesion modification having a specific phase separation structure on the adhesive surface or inside, the temperature is controlled in the drying step or the heat setting treatment step. Further, in order to form a technique in the resin constituting the adhesion modifying layer, the temperature in the heat setting treatment step is very important, and the condensing air volume region is set to be dried at a flow rate of 2 0 1 to 5 The temperature can be determined by the speed: stretching step ~ 30 zone [without heat setting]; interval: the coffin film of the layer; especially heavy: cross-linking L degree to cross -62 - 1360477 Have a big impact. Hereinafter, the implementation thereof will be described in detail. As described above, in the heat setting treatment step, the heat treatment conditions affect the phase separation state of the subsequent reforming layer. That is, it is necessary to appropriately set the maximum temperature in the heat setting treatment step, the time required to reach the above maximum temperature, and the temperature required to proceed from the phase separation of the subsequent reforming layer to the maximum temperature in the heat setting treatment step. Time is important.

於熱定型處理步驟中，各熱定型區的溫度係隨著構成 熱塑性樹脂薄膜的樹脂之種類而有若干的不同，但亦在 100〜260 °c的溫度範圍內適宜地設定。以下，舉出代表的 熱塑性樹脂’即聚對酞酸乙二酯，當作熱塑性樹脂薄膜來 說明。 熱定型處理步驟的最高溫度較佳係控制在210〜240t ，更佳的下限係22 5 °C，上限係23 5 °C。一般地，熱定型 處理的初期階段係在210〜24(TC之比較高的溫度作熱定型 ’隨著成爲後段，在100〜200 °C依順序下溫度的情況係多 的。 於熱定型處理步驟中，最高溫度若低於210。(：，則在接 著性改質層中形成微相分離構造或奈米相分離構造係困難 的。因此’難以充分得到近年來所要求的基材與機能層之 密接性’以便耐得住高速·切割時的衝撃，不會在界面剝離 。再者’所得到的接著性改質基材薄膜之熱收縮率變大， 故係不宜的。 又’於熱定型處理步驟中，最高溫度若超過24〇〇c，則 -63 - 1360477In the heat setting treatment step, the temperature of each heat setting zone varies somewhat depending on the kind of the resin constituting the thermoplastic resin film, but is also suitably set in the temperature range of 100 to 260 °C. Hereinafter, a representative thermoplastic resin, i.e., polyethylene terephthalate, will be described as a thermoplastic resin film. The maximum temperature of the heat setting treatment step is preferably controlled at 210 to 240 t, the lower limit is 22 5 ° C, and the upper limit is 23 5 ° C. Generally, the initial stage of the heat setting treatment is in the range of 210 to 24 (the relatively high temperature of the TC is set for heat setting), and the temperature is increased in the order of 100 to 200 ° C in the subsequent stage. In the step, the maximum temperature is less than 210. (:, it is difficult to form a micro phase separation structure or a nano phase separation structure in the adhesion modifying layer. Therefore, it is difficult to sufficiently obtain the substrate and function required in recent years. The adhesiveness of the layer is such that it can withstand high-speed and high-cutting at the time of cutting, and does not peel off at the interface. Further, the heat-shrinkage rate of the obtained adhesive-modified base film becomes large, which is not preferable. In the heat setting process, if the maximum temperature exceeds 24〇〇c, then -63 - 1360477

接著性改質層的表面之PEs表面分率變大，對於硬被覆層 、擴散層、稜鏡層、紫外線硬化型油墨所印刷的印刷層等 機能層之密接性變成容易降低。再者，由於從接著性改質 層的相分離開始顯著進行的溫度至達到熱定型處理步驟的 最高溫度所需要的時間變長，故以共聚合聚酯當作主成分 的聚酯相之最細的地方之寬度超過Ιμιη的地方係成散佈的 狀態。結果，局部地對於硬被覆層、擴散層' 稜鏡層、紫 外線硬化型油墨所印刷的印刷層等的機能層，發生密接性 差的地方，與以該部分爲起點之巨觀的剝離有關。 從接著性改質層的相分離開始顯著進行的溫度至達到 熱定型處理步驟的最高溫度所需要的時間，具體地較佳係 如以下地設定。 於本發明中，從接著性改質層的相分離開始顯著進行 的溫度設定區至達到熱定型處理步驟的最高溫度設定區入 口爲止，薄膜的通過時間較佳係3秒以上且少於20秒， 特佳係4秒以上且少於1 5秒。 上述通過時間若少於3秒，則用於展現本發明所規定 的相分離構造之時間會有不足的情況。另一方面，上述通 過時間若爲20秒以上，則相分離係過度進行，以共聚合 聚酯當作主成分的相之最細的地方之寬度超過Ιμιη的地方 係容易成爲散佈的狀態。結果，局部地對於硬被覆層、擴 散層、稜鏡層、紫外線硬化型油墨所印刷的印刷層等的機 能層，發生密接性差的地方，與以該部分爲起點之巨觀的 剝離有關》 < S ) -64- 1360477 於本發明中，接著性改質層的相分離開始顯著進行的 溫度，於本發明的實施例中所顯示的塗布液之組成的範圍 內，推測約20(TC。然而，由於該溫度當然係隨著接著性 改質層的樹脂成分而不同，故不受該溫度所限定的。 茲更具體說明熱定型處理步驟。Further, the surface area of the PEs on the surface of the modified layer is increased, and the adhesion between the functional layer such as the hard coating layer, the diffusion layer, the ruthenium layer, and the printing layer printed by the ultraviolet curable ink is easily lowered. Further, since the time required from the temperature at which the phase separation of the adhesion-modifying layer starts to proceed to the maximum temperature at which the heat-setting treatment step is reached becomes long, the polyester phase having the copolymerized polyester as a main component is the most The area where the width of the thin part is more than Ιμιη is in a state of being scattered. As a result, the functional layer such as the hard coating layer, the diffusion layer '稜鏡 layer, and the printed layer printed on the ultraviolet curable ink is partially inferior in adhesion to the macroscopic coating starting from the portion. The time required from the temperature at which the phase separation of the adhesive reforming layer proceeds significantly to the maximum temperature at which the heat setting treatment step is reached is specifically preferably set as follows. In the present invention, the passage time of the film is preferably from 3 seconds or more and less than 20 seconds from the temperature setting region where the phase separation of the adhesive reforming layer is significantly performed to the entrance of the highest temperature setting region of the heat setting treatment step. , Very good for more than 4 seconds and less than 15 seconds. If the passage time is less than 3 seconds, the time for exhibiting the phase separation structure defined by the present invention may be insufficient. On the other hand, when the passage time is 20 seconds or more, the phase separation system is excessively performed, and the portion where the width of the finest portion in which the copolymerized polyester is used as the main component exceeds Ιμηη is likely to be dispersed. As a result, in a functional layer such as a hard coating layer, a diffusion layer, a ruthenium layer, or a printing layer printed with an ultraviolet curable ink, a place where adhesion is inferior is caused, and the peeling of the macroscopic view starting from the part is related to the < S) -64 - 1360477 In the present invention, the temperature at which the phase separation of the adhesion-modifying layer starts to proceed remarkably is estimated to be about 20 (TC) within the range of the composition of the coating liquid shown in the examples of the present invention. However, since this temperature is of course different depending on the resin component of the adhesive reforming layer, it is not limited by this temperature. The heat setting treatment step will be more specifically described.

一般地，橫拉伸步驟、熱定型處理步驟、冷卻步驟， 爲了抑制鄰接的各區之劇烈溫度變化，在拉幅機內分割成 10〜30區，各區被獨立地溫度控制。特別地，較佳爲於從 橫拉伸區的後半到熱定型處理步驟的最高溫度所設定的區 中，各區的溫度係對於薄膜進行方向而言以階段地升溫， 使各熱定型區間不會發生劇烈的溫度變化。 於本發明中，在從相分離開始顯著進行的溫度設定區 到熱定型處理步驟的最高溫度設定區入口爲止之薄膜通過 時間，以快速且均一地升溫係重要的。爲了快速地上升溫 度’提高各熱定型區中的熱傳導效率之方法，例如提高對 薄膜噴吹的熱風之風速之方法係有效。然而，於該方法中 ’由於一般容易發生溫度不均，故在接著性改質層的相分 離狀態會發生不均，或在熱定型區內稍微附著於裝置內的 寡聚物等雜質會飛揚，所飛揚的雜質會附著於薄膜，而與 光學缺點有關。 另一方面，風速若過低，則得不到充分的升溫速度》 因此’於本發明中，風速較佳爲l〇m/秒以上且低於20m/ 秒°爲了快速且均一地將積層薄膜升溫，將用於噴吹熱風 的噴嘴之間隔以500mm以下之比較短的間隔作配置的手段 (S ) -65- 1360477 係有效的。於將用於噴吹熱風的噴嘴之間隔配置成500mm 以下時，例如將噴嘴間隔配置成3 00mm、3 50mm、400mm 時，設備維護上係變成不利的，但爲了完成本發明係重要 的。相當於一段的每1區之噴嘴個數若爲6〜12個左右’ 則其個數係考慮噴嘴間隔、通風量' 通風時間的狀態來決 定。再者，本發明中所記載的風速，係意味面對熱風吹出 的噴嘴出口之薄膜表面的風速，使用熱式風速計（日本 ΚΑΝΟΜΑΧ製風速計6161型）來測定者。Generally, the transverse stretching step, the heat setting treatment step, and the cooling step are divided into 10 to 30 zones in the tenter to suppress the severe temperature change of the adjacent zones, and the zones are independently temperature controlled. In particular, it is preferred that in the region set from the second half of the transverse stretching zone to the highest temperature of the heat setting treatment step, the temperature of each zone is gradually increased in temperature for the direction of the film, so that the heat setting zones are not Intense temperature changes can occur. In the present invention, it is important to rapidly and uniformly heat up the film passage time from the temperature setting region which is significantly performed from the phase separation to the entrance of the highest temperature setting region of the heat setting treatment step. In order to rapidly increase the degree of temperature rise to improve the heat transfer efficiency in each heat setting zone, for example, a method of increasing the wind speed of the hot air blown by the film is effective. However, in this method, since temperature unevenness is generally likely to occur, unevenness may occur in the phase separation state of the adhesive reforming layer, or impurities such as oligomers slightly attached to the device in the heat setting zone may fly. The flying impurities will adhere to the film and are related to optical defects. On the other hand, if the wind speed is too low, a sufficient temperature increase rate cannot be obtained. Therefore, in the present invention, the wind speed is preferably l〇m/sec or more and less than 20 m/sec. In order to quickly and uniformly laminate the film. The means for raising the temperature of the nozzle for blowing hot air at a relatively short interval of 500 mm or less is effective (S) -65 - 1360477. When the interval between the nozzles for blowing hot air is set to 500 mm or less, for example, when the nozzle intervals are arranged to be 300 mm, 3 50 mm, or 400 mm, the maintenance of the equipment becomes unfavorable, but it is important to complete the present invention. When the number of nozzles per zone corresponding to one section is about 6 to 12, the number of nozzles is determined in consideration of the nozzle interval and the ventilation amount of the ventilation time. In addition, the wind speed described in the present invention means that the wind speed of the surface of the film at the nozzle outlet which is blown by the hot air is measured by a thermal anemometer (Model No. 6161 manufactured by Nippon Co., Ltd.).

茲顯示於製造接著性改質基材薄膜時，熱定型處理步 驟的較佳一實施態樣。 上述熱定型處理步驟係連續劃分成複數的熱定型區， 而且各區係可獨立溫度控制地被分隔。熱定型區係分割成 2〜10段的熱定型區以連續排列的步驟，較佳爲分割成4 〜8段的步驟，藉由以該多段所分割的熱定型區，來作接 著性改質基材薄膜的溫度控制管理係較宜的。 例如，可舉出於具有接著性改質層的聚酯薄膜之情況 ，使依順序連續通過如下述所分割成6段的熱定型區，使 各階段具有微妙的溫度差異來進行熱定型處理，修剪薄膜 兩端部沒有被塗覆的部分之方法。就上述熱定型處理溫度 而言，第1熱定型區係200 °C，第2熱定型區係225。(：， 第3熱定型區係230°C，第4熱定型區係230°C，第5熱 定型區係210°C，第6熱定型區係17〇。(：，第7熱定型區 係120 °C。又，於第6熱定型區中在寬度方向進行3 %的鬆 驰處理。 -66 - 1360477 上述階段係相當於1個熱定型區。如此的各段之熱定 型區的溫度，較佳爲具有微妙的溫度差，即具有5〜40°C 左右的溫度差。該溫度差的設定係考慮具有接著性改質層 的熱塑性樹脂薄膜之行進速度、風量、及接著性改質層的 厚度等諸要因來任意決定。A preferred embodiment of the heat setting treatment step is shown in the manufacture of an adhesive modified substrate film. The heat setting treatment step described above is continuously divided into a plurality of heat setting zones, and each zone can be separated independently of temperature control. The heat-fixing zone is divided into 2 to 10 segments of heat-setting zones to be continuously arranged, preferably divided into 4 to 8 segments, and the heat-fixing zone divided by the plurality of segments is used for the subsequent modification. The temperature control management of the substrate film is preferred. For example, in the case of a polyester film having an adhesion-modifying layer, heat-setting treatment can be carried out by continuously passing through a heat-setting zone divided into six stages as follows, so that each stage has a subtle temperature difference. A method of trimming portions of the film that are not coated at both ends. In the heat setting treatment temperature, the first heat setting zone is 200 °C, and the second heat setting zone is 225. (:, the third heat-set zone is 230 ° C, the fourth heat-set zone is 230 ° C, the fifth heat-set zone is 210 ° C, and the sixth heat-set zone is 17 〇. (:, the 7th heat-set zone It is 120 ° C. In addition, in the 6th heat setting zone, 3% relaxation treatment is performed in the width direction. -66 - 1360477 The above stage is equivalent to one heat setting zone. The temperature of the heat setting zone of each segment Preferably, it has a subtle temperature difference, that is, a temperature difference of about 5 to 40° C. The temperature difference is set in consideration of the traveling speed, the air volume, and the adhesion modification of the thermoplastic resin film having the adhesion modifying layer. The thickness of the layer and other factors are arbitrarily determined.

於用作爲透鏡薄膜或擴散板等的光學機能性薄膜之基 材薄膜時，薄膜厚度係ΙΟΟμηι以上的比較厚之薄膜，通常 薄膜長度係至少l〇〇〇m以上，有時以捲繞成2000m以上的 圓筒狀之形態，供應給用於積層稜鏡層或擴散層的加工步 驟。 於本發明中’接著性改質層的表面之PEs相（在相位像 中顯示暗色相）的面積率，或接著性改質層的切削面中與硬 被覆層的界面附近之PU相的面積率（在相位像中顯示明色 相），於在薄膜的長度方向中以1 〇〇m間隔來測定時，它們 的長度方向之面積率的最大値與最小値的差較佳係丨5%以 下，更佳係以下。藉由使它們的長度方向之面積率的 最大値與最小値的差成爲1 5%以下，可得到具有安定的密 接性和防黏連性之接著性改質基材薄膜捲筒。 爲了將它們的長度方向之面積率的最大値與最小値的 差控制在1 5%以下，於連續地製造本發明所用的長條狀接 著性改質基材薄膜輥捲筒時，重要的是將塗布條件、乾燥 條件等、及熱定型條件等的製膜條件保持一定。然而，塗 布液所用的混合溶劑之比率特別容易變動，將該混合溶劑 的比率保持-定的工夫，在減小薄膜捲筒之長度方向中表 -67 - 1360477 面的PEs相的面積率或切削面的pu相之面積率的變動方 面，係重要的。例如，藉由以下所示的手段，可將接著性 改質層之表面的PEs相之面積率或切削面的PU相之面積 率的變動幅度控制在1 5%以下》再者，將混合溶劑的比率 保持一定之手段，係不限於下述方法。When a base film of an optical functional film such as a lens film or a diffusion plate is used, a film having a film thickness of ΙΟΟμηι or more is usually at least l〇〇〇m or more, and may be wound into 2000 m. The above cylindrical form is supplied to a processing step for laminating the tantalum layer or the diffusion layer. In the present invention, the area ratio of the PEs phase (the dark phase in the phase image) on the surface of the adhesion modifying layer, or the area of the PU phase in the vicinity of the interface with the hard coating layer in the cutting surface of the adhesion modifying layer. The ratio (the color phase is displayed in the phase image) is preferably 5% or less of the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction when measured at intervals of 1 μm in the longitudinal direction of the film. , better below. By setting the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction thereof to be 15% or less, a pressure-sensitive adhesive base film roll having stable adhesion and anti-blocking property can be obtained. In order to control the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction thereof to be less than 1 5%, it is important to continuously manufacture the long-length adhesive-modified substrate film roll used in the present invention. The film forming conditions such as coating conditions, drying conditions, and heat setting conditions are kept constant. However, the ratio of the mixed solvent used for the coating liquid is particularly liable to vary, and the ratio of the mixed solvent is maintained for a predetermined period of time, and the area ratio of the PEs phase of the surface of the -67 - 1360477 surface is reduced in the length direction of the film roll or cutting. It is important to change the area ratio of the pu phase of the surface. For example, the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the PU phase of the cutting surface can be controlled to be less than 1 5% by the means described below. The means for maintaining the ratio is not limited to the following method.

對於塗布液的接盤（第7圖的11)之容量而言，加大循 環用槽（第7圖的13)的容量係有效於使混合溶劑的濃度比 安定化。具體地，如第7圖所示地，以塗布液的接盤之容 量爲1時，循環用槽的容量比較佳爲10以上，特佳爲50 以上。容量比（循環用槽的容量/塗布液的接盤之容量）低於 1 0，即循環用槽的容量過小時，混合溶劑的濃度比之變動 容易變大。 再者，以循環用槽的容量爲1時，調配用槽（第7圖的 14)的容量之比較佳爲10以上，特佳爲20以上。藉此，於 從調配用槽將塗布液供應給循環用槽時，循環用槽的容量 在運轉時可經常保持一定》 又，提高塗布裝置中的塗布輥之精度（真圓度與圓筒度） ，從在薄膜捲筒的長度方向中減低接著性改質層的塗布厚 度不均之點來看，亦有效的。再者，從於薄膜捲筒的長度 方向中，減小接著性改質層的表面之PEs相的面積率或切 削面的PU相的面積率之變動所伴隨著的特性變動之點來 看，亦有效的》 上述塗布輥的真圓度係如JIS B 0621所示地’爲使用 記錄式真圓度測定器所決定的最小區域法’以二個同心圓 -68- 1360477 的各半徑之差所表示的指標。再者，輥的真圓度之單位係 mm。又，塗布輥的圓筒度係將在底盤上置有該輥的附測微 器之台在軸線方向移動，以圓筒上面碰觸測定器的狀態下 ，在經過全長的種種測定平面中實施測定，以此時讀數之 最大差的1/2來表示的指標。而且，圓筒度的單位係mm。 於本發明中，藉由提高輥精度（真圓度與圓筒度），可減 低長度方向的塗布層之厚度的變動。具體地，輥精度（真圓 度與圓筒度）較佳爲低於5/1000mm。With respect to the capacity of the coating liquid (11 in Fig. 7), the capacity of the circulation groove (13 in Fig. 7) is increased to stabilize the concentration ratio of the mixed solvent. Specifically, as shown in Fig. 7, when the capacity of the coating liquid is 1, the capacity of the circulation tank is preferably 10 or more, and particularly preferably 50 or more. The capacity ratio (the capacity of the circulation tank/the capacity of the coating liquid) is less than 10, that is, the capacity of the circulation tank is too small, and the concentration of the mixed solvent tends to become large. In addition, when the capacity of the circulation tank is 1, the capacity of the preparation tank (14 of Fig. 7) is preferably 10 or more, and particularly preferably 20 or more. Therefore, when the coating liquid is supplied from the mixing tank to the circulation tank, the capacity of the circulation tank can be kept constant during operation, and the accuracy of the coating roller in the coating device is improved (roundness and cylindricality). It is also effective from the viewpoint of reducing the coating thickness unevenness of the adhesive reforming layer in the longitudinal direction of the film roll. Further, from the viewpoint of the change in the area ratio of the PEs phase on the surface of the adhesive reforming layer or the variation in the area ratio of the PU phase on the cutting surface in the longitudinal direction of the film roll, Also effective" The roundness of the above-mentioned coating roller is the difference between the radii of two concentric circles -68 - 1360477 as shown in JIS B 0621 'the minimum area method determined by using the recording roundness tester' The indicator indicated. Furthermore, the unit of roundness of the roll is mm. Further, the cylindricality of the application roller moves the stage of the micrometer on which the roller is placed on the chassis in the axial direction, and is carried out in various measurement planes over the entire length in a state where the cylinder is in contact with the measuring device. The indicator is expressed as 1/2 of the maximum difference of the reading at this time. Moreover, the unit of the cylinder is mm. In the present invention, by increasing the roller precision (roundness and cylindricality), the variation in the thickness of the coating layer in the longitudinal direction can be reduced. Specifically, the roller precision (true roundness and cylindricality) is preferably less than 5/1000 mm.

又，於塗布塗布液時，藉由使逆塗布機的各輥之表面 加工度成爲0.3S以下，且使塗布輥及計量輥的精度（真圓 度與圓筒度）成爲低於5/1 000mm且2/1000mm以上，則可 以壓制濕塗布量的變動，而且亦可以壓制塗膜的厚度變動 。較佳可以使用塗布輥及計量輥的精度（真圓度與圓筒度） 爲3/ 1 000mm的塗布輥。 再者，藉由使薄膜的張力成爲4000〜1 0000N/原版寬度 (原版寬度係1〜2m)，而保持工業規模的薄膜之平面性， 使塗布液的轉印量成爲均勻。而且，薄膜的張力係隨著薄 膜的厚度而不同，藉由對比較薄的薄膜施加比較低的張力 ，可以保持平面性。 薄膜的張力若超過1 0000N/原版寬度，則薄膜會變形或 斷裂。另一方面，薄膜的張力若低於4000N/原版寬度，則 塗布時的薄膜之平面性會變不充分，或薄膜會發生蛇行》 結果，塗布液的轉印量在薄膜的長度方向會成爲不均勻， 由於薄膜的濕塗布量之大變動，塗布層的厚度亦有大的變 -69 - 1360477 動。In addition, when the coating liquid is applied, the surface working degree of each roll of the reverse coater is 0.3 S or less, and the accuracy (roundness and cylindricality) of the coating roll and the measuring roll are made lower than 5/1. When the thickness is 000 mm and 2/1000 mm or more, the variation of the wet coating amount can be suppressed, and the thickness variation of the coating film can also be suppressed. It is preferable to use a coating roller having a precision (roundness and cylindricality) of the coating roller and the metering roller of 3/1000 mm. Further, by setting the tension of the film to 4000 to 10,000 N/original width (the original width is 1 to 2 m), the planarity of the film on an industrial scale is maintained, and the amount of transfer of the coating liquid is made uniform. Moreover, the tension of the film varies depending on the thickness of the film, and flatness can be maintained by applying a relatively low tension to a relatively thin film. If the tension of the film exceeds 1 0000 N/original width, the film may be deformed or broken. On the other hand, if the tension of the film is less than 4000 N/original width, the planarity of the film at the time of coating may become insufficient, or the film may be serpentine. The transfer amount of the coating liquid will become no in the longitudinal direction of the film. Uniform, due to large changes in the wet coating amount of the film, the thickness of the coating layer also changed greatly -69 - 1360477.

又，爲了在薄膜輥的寬度方向中將接著性改質層的表 面之PEs相或切削面的PU相之面積率的變動（最大値與最 小値的差）控制在10%以下，對於薄膜輥的寬度方向而言’ 減小塗布層的厚度變動係重要的。因此，提高塗布時的寬 度方向之平面性係有效的。具體地，於逆輥之塗布後，立 刻使用夾輥（第7圖的16)僅抓住薄膜的兩端面。藉由在夾 輥抓住薄膜的兩端部，則可以工業規模地提高薄膜的寬度 方向之平面性，使薄膜的寬度方向之濕塗布量安定化。藉 此，可減低薄膜輥的寬度方向中塗布層的厚度之變動。於 夾輥不抓住薄膜的兩端部時，薄膜的寬度方向及長度方向 的濕塗布量會大變動，塗布層的厚度變動亦更大。 (4)硬被覆層及其它光學機能層 本發明的硬被覆薄膜係爲於熱塑性樹脂薄膜A的一面 或兩面上，積層形成有含共聚合聚酯及聚胺甲酸酯的接著 性改質層B之接著性改質基材薄膜，及在該薄膜的接著性 改質層B之一面上含有無機微粒子的硬被覆層C，而成之 含A/B/C或B/A/B/C的層構成之硬被覆薄膜。作爲構成硬 被覆層的硬化型樹脂，較佳係電離輻射線硬化型樹脂，作 爲電離輻射線硬化型樹脂，例如可舉出下述的樹脂。 電離輻射線硬化型樹脂，較佳係具有丙烯酸酯系官能 基的樹脂，特佳係聚酯丙烯酸酯或胺甲酸酯丙烯酸酯。聚 酯丙烯酸酯係由聚酯系多元醇的寡聚物之丙烯酸酯或甲基 丙烯酸酯（以下亦有丙烯酸酯及/或甲基丙烯酸酯記載爲（甲 -70 - 1360477 基）丙烯酸酯的情況）、或其混合物所構成。又，胺甲酸酯（ 甲基）丙烯酸酯係由多元醇化合物與二異氰酸酯化合物所成 的寡聚物經（甲基）丙烯酸酯化而構成。 作爲構成（甲基）丙烯酸酯的單體，可舉出（甲基）丙烯酸 甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丁酯、（甲基）丙烯 酸2-乙基己酯、（甲基）丙烯酸甲氧基乙酯、（甲基）丙烯酸 丁氧基乙酯、（甲基）丙烯酸苯酯。Moreover, in order to control the fluctuation of the area ratio (maximum 値 and minimum )) of the PEs phase of the surface of the adhesive reforming layer or the PU phase of the cutting surface in the width direction of the film roll, the film roll is controlled to 10% or less. In terms of the width direction, it is important to reduce the thickness variation of the coating layer. Therefore, it is effective to improve the planarity in the width direction at the time of coating. Specifically, after the application of the reverse roll, the nip rolls (16 of Fig. 7) were used for the purpose of grasping only the both end faces of the film. By grasping both end portions of the film by the nip rolls, the flatness in the width direction of the film can be improved on an industrial scale, and the wet coating amount in the width direction of the film can be stabilized. Thereby, the variation in the thickness of the coating layer in the width direction of the film roll can be reduced. When the nip rolls do not grasp the both end portions of the film, the wet coating amount in the width direction and the longitudinal direction of the film greatly fluctuates, and the thickness variation of the coating layer is also larger. (4) Hard coating layer and other optical functional layer The hard coating film of the present invention is formed by laminating a modified layer containing a copolymerized polyester and a polyurethane on one or both sides of the thermoplastic resin film A. a B-bonding modified base film and a hard coating layer C containing inorganic fine particles on one side of the adhesive modified layer B of the film, and comprising A/B/C or B/A/B/C The layer constitutes a hard coated film. The curable resin constituting the hard coating layer is preferably an ionizing radiation curable resin, and examples of the ionizing radiation curable resin include the following resins. The ionizing radiation curable resin is preferably a resin having an acrylate functional group, and particularly preferably a polyester acrylate or a urethane acrylate. Polyester acrylate is an acrylate or methacrylate of an oligomer of a polyester-based polyol (hereinafter, acrylate and/or methacrylate is also described as (A-70 - 1360477) acrylate) ), or a mixture thereof. Further, the urethane (meth) acrylate is composed of an oligomer of a polyol compound and a diisocyanate compound, which is (meth) acrylated. Examples of the monomer constituting the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. And methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and phenyl (meth)acrylate.

又，於必須更提高硬被覆層的硬度時，較佳爲倂用多 官能單體。例如，作爲多官能單體，可舉出三羥甲基丙烷 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、季戊四醇三 (甲基）丙烯酸酯、二季戊四醇六（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》 作爲聚酯系多元醇的寡聚物，可舉出己二酸與二醇（乙 二醇、聚乙二醇、丙二醇、聚丙烯二醇、丁二醇、聚丁二 醇等）或三醇（甘油、三羥甲基丙烷等）、癸二酸與二醇和三 醇的縮合生成物之聚己二酸酯多元醇、或聚癸二酸酯多元 醇。又，上述脂肪族的二羧酸之一部分或全部可被其它有 機酸所取代。例如，可以使用異酞酸、對酞酸、或酞酸酌: 當作提高硬被覆層的硬度之成分。 於將硬被覆劑塗布在基材薄膜的接著性改質層之表@ 上時，爲了提高均平性，視需要亦可使用稀釋劑來稀釋。 作爲稀釋劑，可舉出苯、甲苯、二甲苯等的芳香族烴、S 烷、庚烷、辛烷、壬烷、癸烷等的脂肪族烴、甲基乙基_ -71- 1360477 、二乙基酮、二異丙基酮等的酮等。可適當地選擇稀釋劑 的配合量，以使成爲恰當的黏度。 作爲硬被覆層c中所含有的無機微粒子，例如可舉出 非晶性矽石、結晶性的玻璃塡料、矽石、氧化锆、二氧化 鈦、氧化鋁等的無機氧化物、矽石-氧化鋁複合氧化物粒子 、碳酸鎂 '氫氧化鋁、硫酸鋇、碳酸鈣、磷酸鈣、高嶺土 、滑石、硫酸鋇、氟化鈣、氟化鋰、沸石 '硫化鉬、雲母Further, when it is necessary to further increase the hardness of the hard coating layer, it is preferred to use a polyfunctional monomer. For example, examples of the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, and diethylene glycol di( Methyl) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate Ester: Examples of the oligomer of the polyester-based polyol include adipic acid and a diol (ethylene glycol, polyethylene glycol, propylene glycol, polypropylene diol, butylene glycol, polytetramethylene glycol, etc.) or A polyadipate polyol or a polysebacate polyol which is a condensation product of a triol (glycerin, trimethylolpropane, etc.), a sebacic acid and a diol and a triol. Further, part or all of the above aliphatic dicarboxylic acid may be substituted by another organic acid. For example, isophthalic acid, citric acid, or citric acid may be used as a component for increasing the hardness of the hard coating layer. When the hard coating agent is applied to the surface of the adhesive modifying layer of the base film, in order to improve the leveling property, it may be diluted with a diluent as needed. Examples of the diluent include an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as S-alkane, heptane, octane, decane or decane, and methylethyl _71- 1360477 and A ketone such as ethyl ketone or diisopropyl ketone. The amount of the diluent can be appropriately selected so as to be an appropriate viscosity. Examples of the inorganic fine particles contained in the hard coating layer c include amorphous vermiculite, crystalline glass tantalum, vermiculite, zirconia, titania, alumina, and the like, and vermiculite-alumina. Composite oxide particles, magnesium carbonate 'aluminum hydroxide, barium sulfate, calcium carbonate, calcium phosphate, kaolin, talc, barium sulfate, calcium fluoride, lithium fluoride, zeolite 'molybdenum sulfide, mica

於硬被覆層c的表面上，積層由高折射率層/低折射率 層、或高折射率層/中折射率層/低折射率層所構成的抗反 射層時，使硬被覆層C高折射率化，則可以從抗反射層中 省略高折射率層。結果，可以減低成本。爲了提高硬被覆 層C的折射率，在硬被覆層中含有折射率高的無機微粒子 係有效的。作爲折射率高的無機微粒子，例如可舉出氧化 鉻、氧化鈦。 於硬被覆層中，無機微粒子的含量爲20質量％以上、 80質量％以下係重要的。無機微粒子的含量若低於20質量 %，則耐擦傷性不足。另一方面，無機微粒子的含量若超 過80質量％ ’則透明性有降低的傾向。又，無機微粒子的 平均粒徑’從透明性之點來看，較佳係5〜l〇〇nm。然而， 這樣平均粒徑小的無機微粒子係容易凝聚而不安定的。因 此，爲了提高無機微粒子的分散安定性，較佳爲對無機微 粒子的表面賦予光感應性基’提高與硬化型樹脂的親和性 -72- 1360477 如此之含有無機微粒子的硬被覆劑係可由市售品取得 。例如’可舉出JSR株式會社製的紫外線硬化型樹脂 (Desolite ； Z7400A、Z7410A、Z7400B、Z7410B、Z7400C 、Z7410C 、 Z7410D 、 Z7410E 、 Z7501 、 Z7503 、 Z7521 、 Z7527)。On the surface of the hard coating layer c, when the antireflection layer composed of the high refractive index layer/low refractive index layer or the high refractive index layer/medium refractive index layer/low refractive index layer is laminated, the hard coating layer C is made high. When the refractive index is increased, the high refractive index layer can be omitted from the antireflection layer. As a result, the cost can be reduced. In order to increase the refractive index of the hard coating layer C, it is effective to contain inorganic fine particles having a high refractive index in the hard coating layer. Examples of the inorganic fine particles having a high refractive index include chromium oxide and titanium oxide. In the hard coating layer, it is important that the content of the inorganic fine particles is 20% by mass or more and 80% by mass or less. When the content of the inorganic fine particles is less than 20% by mass, the scratch resistance is insufficient. On the other hand, when the content of the inorganic fine particles exceeds 80% by mass, the transparency tends to be lowered. Further, the average particle diameter ' of the inorganic fine particles is preferably from 5 to 10 nm from the viewpoint of transparency. However, such inorganic fine particles having a small average particle diameter are easily aggregated and are not stable. Therefore, in order to improve the dispersion stability of the inorganic fine particles, it is preferred to impart a photo-sensitive group to the surface of the inorganic fine particles to improve the affinity with the curable resin. -72 - 1360477 Such a hard coating agent containing inorganic fine particles is commercially available. Product acquisition. For example, an ultraviolet curable resin (Desolite; Z7400A, Z7410A, Z7400B, Z7410B, Z7400C, Z7410C, Z7410D, Z7410E, Z7501, Z7503, Z7521, Z7527) manufactured by JSR Corporation can be cited.

電離輻射線硬化型樹脂係藉由紫外線或電子線照射而 硬化。於照射紫外線時，使用超高壓水銀燈、高壓水銀燈 、低壓水銀燈、碳弧、金屬鹵化物，在100〜400nm的波 長範圍，較佳在 200〜400nm的波長範圍，以 100〜 3 0 00m J/m2的能量來照射紫外線。又，於照射電子線時， 使用掃描型或簾幕型電子線加速器，照射具有加速電壓 lOOOkeV以下，較佳100〜300keV的能量，且l〇〇nm以下 的波長範圍之電子線。 硬被覆層的厚度係在0.1〜30 μιη的範圍內，可見需用 途來決定，更佳爲1〜15 μηι。硬被覆層的厚度若在上述範 圍內，則硬被覆層的表面硬度高，不易損傷。再者，硬被 覆層不易變脆，將硬被覆薄膜彎曲時，硬被覆層中不產生 裂紋。 以下本發明中所記載的光學機能性薄膜’係於本發明 的硬被覆薄膜之硬被覆層C的相反面或其上’積層光學機 能層的薄膜，有下述2個實施形態。 (a)於硬被覆層C的相反面，積層有從硬被覆層、光擴 散層、稜鏡狀透鏡層、電磁波吸收層、近紅外線遮斷層、 透明導電層所選出的至少1層之光學機能層的光學機能性 < S ) -73 - 1360477 薄膜。 (b)於硬被覆層C之上’積層有抗反射層或防污層的光 學機能性薄膜》 以下說明使用透鏡層當作光學機能層的透鏡薄膜、使 用光擴散層的光擴散薄膜當作代表例。 (透鏡薄膜）The ionizing radiation-curable resin is cured by irradiation with ultraviolet rays or electron beams. When irradiating ultraviolet rays, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide is used in a wavelength range of 100 to 400 nm, preferably in a wavelength range of 200 to 400 nm, to 100 to 300 m J/m 2 . The energy to illuminate the ultraviolet light. Further, when irradiating the electron beam, an electron beam having an acceleration voltage of 100 keV or less, preferably 100 to 300 keV, and a wavelength range of 10 nm or less is irradiated using a scanning type or a curtain type electron beam accelerator. The thickness of the hard coating layer is in the range of 0.1 to 30 μm, which can be determined by the use, and more preferably 1 to 15 μm. When the thickness of the hard coating layer is within the above range, the surface hardness of the hard coating layer is high and it is not easily damaged. Further, the hard coating layer is less likely to be brittle, and when the hard coating film is bent, cracks do not occur in the hard coating layer. The optical functional film described in the present invention is a film which is formed on the opposite surface of the hard coating layer C of the hard coating film of the present invention or on the optical layer of the laminated optical function layer, and has the following two embodiments. (a) On the opposite side of the hard coating layer C, an optical function of at least one layer selected from the hard coating layer, the light diffusion layer, the scorpion lens layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer is laminated. The optical function of the layer <S) -73 - 1360477 film. (b) An optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coating layer C. Hereinafter, a lens film using a lens layer as an optical function layer and a light diffusion film using a light diffusion layer are used as Representative example. (lens film)

稜鏡透鏡薄膜或菲涅耳透鏡薄膜，係由在具有以共聚 合聚酯及聚胺甲酸酯當作主要構成成分的接著性改質層之 接著性改質基材薄膜的一面上，積層含有無機微粒子的電 離輻射線硬化型硬被覆層，在相反面上積層稜鏡透鏡層或 菲涅耳透鏡層而構成》亦有將透鏡薄膜稱爲透鏡片的情況 ，但本發明中的薄膜亦包括片。 其次，說明構成稜鏡透鏡層的活性能量線硬化樹脂成 分0 作爲活性能量線硬化樹脂成分，自由基可聚合的單體 或寡聚物中的至少1種係決定所製造的透鏡片之性能，可 依照目的之透鏡薄膜的性能來適當選擇。 樹脂成分係單獨地或組合2種以上來使用自由基可聚 合單體或寡聚物。特別地，若使用2種以上的樹脂，則可 以給予透鏡薄膜所要求的機械強度、耐衝撃性、耐熱性、 表面硬度、耐藥品性。又，作爲自由基聚合性官能基，藉 由對於組成物而言使用60質量份以上的具有丙烯醯基或 甲基丙烯醯基的化合物，於照射活性能量線時，部分地共 聚合，瞬間不流動化。因此，於形成透鏡層時，由於對流 -74 - 1360477 所致的光學畸變係變少。A 稜鏡 lens film or a Fresnel lens film is laminated on one side of a film of an adhesive-modified substrate having an adhesion-modifying layer containing a copolymer of polyester and polyurethane as a main constituent component. The ionizing radiation-hardening type hard coating layer containing inorganic fine particles is formed by laminating a ruthenium lens layer or a Fresnel lens layer on the opposite surface. The lens film is also referred to as a lens sheet, but the film in the present invention is also Includes tablets. Next, the active energy ray-curable resin component 0 constituting the 稜鏡 lens layer will be described as an active energy ray-curable resin component, and at least one of the radical polymerizable monomers or oligomers determines the performance of the manufactured lens sheet. It can be suitably selected according to the performance of the lens film for the purpose. The resin component is used singly or in combination of two or more kinds, and a radical polymerizable monomer or oligomer is used. In particular, when two or more kinds of resins are used, the mechanical strength, the impact resistance, the heat resistance, the surface hardness, and the chemical resistance required for the lens film can be imparted. In addition, as the radical polymerizable functional group, 60 parts by mass or more of a compound having an acryloyl group or a methacrylium group is used as a component, and when the active energy ray is irradiated, it is partially copolymerized, and it is not instantaneous. Fluidization. Therefore, when the lens layer is formed, the optical distortion due to convection -74 - 1360477 is reduced.

作爲樹脂成分，可舉出由脂肪族、脂環族、芳香族系 的一元醇或多元醇與丙烯酸酸或甲基丙烯酸的縮合反應所 得到的酯型（甲基）丙烯酸酯，分子內具有2個以上的異氰 酸基之異氰酸酯化合物與含有羥基或硫醇基的（甲基）丙烯 酸酯之胺甲酸酯化反應所得到的胺甲酸酯聚（甲基）丙烯酸 酯，或分子內具有至少2個環氧基的化合物與丙烯酸酸或 甲基丙烯酸之縮水甘油基閉環反應所得到的環氧聚（甲基） 丙烯酸酯，飽和或不飽和多價羧酸、多價醇、及（甲基）丙 烯酸酸之縮合反應所得到的聚酯（甲基）丙烯酸酯等之（甲基 )丙烯醯基官能性單體、寡聚物，或苯乙烯、氯苯乙烯、溴 苯乙烯、二溴苯乙烯、二乙烯基苯等的乙烯系化合物、二 乙二醇雙烯丙基碳酸酯、酞酸二烯丙酯、聯苯基二烯丙酯 等的（甲基）烯丙基化合物。 以下顯示較佳的具體例子。下述各種樹脂成分係可被 單獨使用，亦可以組合2種以上來使用。又，稜鏡透鏡或 菲涅耳透鏡用樹脂係可取得市售品。例如，可舉出JSR公 司製的 UV 硬化型樹脂（Desolite; Z9590、Z9502)。 (a) 脂肪族單（甲基）丙烯酸酯 (甲基）丙烯酸甲酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸 羥乙酯、（甲基）丙烯酸羥丙酯， (b) 脂環族單（甲基）丙烯酸酯 (甲基）丙烯酸環己酯、（甲基）丙烯酸二環戊酯、（甲基） 丙烯二環戊烯酸酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯 -75 - 1360477 酸冰片酯 (C)芳香族單（甲基）丙烯酸酯The resin component may, for example, be an ester type (meth) acrylate obtained by a condensation reaction of an aliphatic, alicyclic or aromatic monohydric alcohol or a polyhydric alcohol with an acryl acid or methacrylic acid, and has 2 in the molecule. a urethane poly(meth) acrylate obtained by the esterification reaction of one or more isocyanate-based isocyanate compounds with a hydroxyl group or a thiol group-containing (meth) acrylate, or has an intramolecular An epoxy poly(meth) acrylate obtained by ring-closing reaction of at least two epoxy-based compounds with a glycidyl group of acrylic acid or methacrylic acid, a saturated or unsaturated polyvalent carboxylic acid, a polyvalent alcohol, and (a) (meth)acryloyl-functional monomer, oligomer, or styrene, chlorostyrene, bromostyrene, dibromide such as polyester (meth) acrylate obtained by condensation reaction of acrylic acid A (meth)allyl compound such as a vinyl compound such as styrene or divinylbenzene, diethylene glycol bisallyl carbonate, diallyl phthalate or biphenyl diallyl. Preferred specific examples are shown below. The various resin components described below may be used singly or in combination of two or more. Further, a commercially available product is available as a resin for a 稜鏡 lens or a Fresnel lens. For example, a UV curable resin (Desolite; Z9590, Z9502) manufactured by JSR Corporation can be mentioned. (a) Aliphatic mono (meth) acrylate (methyl methacrylate), butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (b) Cyclomono-mono (meth) acrylate cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) propylene dicyclopentenoate, isobornyl (meth) acrylate, ( Methyl) propylene-75 - 1360477 acid borneol ester (C) aromatic mono (meth) acrylate

(甲基）丙烯酸苯酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸 苯氧基乙酯、（甲基）丙烯酸苯氧基-2-甲基乙酯、（甲基）丙 烯酸3-苯氧基-2-羥丙酯、（甲基）丙烯酸2-苯基苯酯、（甲 基）丙烯酸2-苯基苯氧基乙酯、（甲基）丙烯酸4-苯基苯氧基 £酯、（甲基）丙烯酸2-苯基苯基-2-甲氧基乙酯、（甲基）丙 烯酸2-萘酯、（甲基）丙烯酸2·溴苯酯、（甲基）丙烯酸4-溴 苯酯、（甲基）丙烯酸2,4-二溴苯酯、（甲基）丙烯酸2,4,6-三 溴苯酯、（甲基）丙烯酸苯硫基乙酯、（甲基）丙烯酸苯硫基 乙氧基乙酯， (d)芳香族骨架的酯二（甲基）丙烯酸酯 雙（4 一（甲基）丙烯醯氧基乙氧基苯基）甲烷、雙（4-(甲基） 丙烯醯氧基二乙氧基苯基）甲烷、2,2-雙（4 一（甲基）丙烯醯 氧基乙氧基苯基）丙烷、2，2-雙（4-(甲基）丙烯醯氧基二乙氧 基苯基）丙烷、2,2-雙（4-(甲基）丙烯醯氧基五乙氧基苯基） 丙烷、2,2-雙（4·(甲基）丙烯醯氧基丙氧基苯基）丙烷、2，2-雙（4-(甲基）丙烯醯氧基二丙氧基苯基）丙烷、2,2-雙（4-(甲 基）丙烯醯氧基乙氧基-3,5-二溴苯基）丙烷、2,2-雙（4-(甲基） 丙烯醯氧基二乙氧基-3,5·二溴苯基）丙烷、2，2-雙（4-(甲基） 丙烯醯氧基五乙氧基-3,5-二溴苯基）丙烷、雙（4-(甲基）丙 烯醯氧基乙氧基苯基）碾、雙（4-(甲基）丙烯醯氧基二乙氧基 苯基）颯、雙（4-(甲基）丙烯醯基硫苯基）硫化物、雙（4_(甲 基）丙烯醯氧基乙基硫苯基）硫化物等， -16- (S ) 1360477 (e)脂環族骨架的酯二（甲基）丙烯酸酯 雙（4-(甲基）丙烯醯氧基環己基）甲烷、雙（4-(甲基）丙烯 醯氧基乙氧基環己基）甲烷、雙（4-(甲基）丙烯醯氧基二乙氧 基環己基）甲烷、雙（4-(甲基）丙烯醯氧基環己基）丙烷、雙 (4-(甲基）丙烯醯氧基乙氧基環己基）丙烷、雙（4-(甲基）丙 烯醯氧基二乙氧基環己基）丙烷、二環戊烷二（甲基）丙烯酸 酯， (f)脂肪族骨架的酯二（甲基）丙烯酸酯Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, 3-(meth)acrylate Phenoxy-2-hydroxypropyl ester, 2-phenylphenyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxy (meth)acrylate Ester, 2-phenylphenyl-2-methoxyethyl (meth)acrylate, 2-naphthyl (meth)acrylate, 2·bromophenyl (meth)acrylate, 4-(meth)acrylate Bromophenyl ester, 2,4-dibromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, phenylthioethyl (meth)acrylate, (meth)acrylic acid Phenylthioethoxyethyl ester, (d) Aromatic backbone ester di(meth)acrylate bis(4-(methyl)propenyloxyethoxyphenyl)methane, bis(4-(A) Acryloxydiethoxyphenyl)methane, 2,2-bis(4-(methyl)propenyloxyethoxyphenyl)propane, 2,2-bis(4-(methyl) ) propylene decyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl) Propylene decyloxypentaethoxyphenyl)propane, 2,2-bis(4.(methyl)propenyloxypropoxyphenyl)propane, 2,2-bis(4-(methyl) Propylene decyloxydipropoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxyethoxy-3,5-dibromophenyl)propane, 2,2-dual ( 4-(Methyl)propenyloxydiethoxy-3,5·dibromophenyl)propane, 2,2-bis(4-(methyl)propenyloxypentaethoxy-3,5 -dibromophenyl)propane, bis(4-(methyl)propenyloxyethoxyphenyl) milled, bis(4-(methyl)propenyloxydiethoxyphenyl)anthracene, double (4-(Methyl)propenylthiophenyl) sulfide, bis(4-(methyl)propenyloxyethylthiophenyl) sulfide, etc., -16- (S) 1360477 (e) alicyclic Group of esters of di(meth)acrylate bis(4-(methyl)propenyloxycyclohexyl)methane, bis(4-(methyl)propenyloxyethoxycyclohexyl)methane, bis ( 4-(Methyl)propenyloxydiethoxycyclohexyl)methane, bis(4-(methyl)propenyloxycyclohexyl)propane, bis(4-(methyl)propene oxime Ethoxycyclohexyl)propane, bis(4-(methyl)propenyloxydiethoxycyclohexyl)propane, dicyclopentane di(meth)acrylate, (f) ester of aliphatic backbone (meth) acrylate

乙二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯 、三乙二醇二（甲基）丙烯酸酯、聚乙二醇（η =4〜15)二（甲 基）丙烯酸酯、丙二醇二（甲基）丙烯酸酯 '三丙二醇二（甲 基）丙烯酸酯、聚丙二醇（η=4〜15)二（甲基）丙烯酸酯、 1，4-丁二醇二（甲基）丙烯酸酯、聚丁二醇（η =2〜15)二（甲 基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、羥基三甲基乙 酸新戊二醇酯的二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙 烯酸酯、1，9·壬二醇二（甲基）丙烯酸酯， (g)多官能性（甲基）丙烯酸酯 三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇三（甲基）丙 烯酸酯、季戊四醇四（甲基）丙烯酸酯 '二三羥甲基丙烷四（ 甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯， (h)胺甲酸酯聚（甲基）丙烯酸酯 三（異氰酸基己基）異氰尿酸酯、異佛爾酮二異氰酸酯、 雙（4 異氰酸基環己基）甲烷、1，3·雙（異氰酸基甲基）環己 烷、間苯二甲基二異氰酸酯、2，4-伸甲苯基二異氰酸酯、 -77 - 1360477 2,6-伸甲苯基二異氰酸酯等的聚異氰酸酯化合物與（甲基） 丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸 2-羥丁酯、（甲基）丙烯酸4-羥丁酯般之含羥基的（甲基）丙 烯酸酯之反應生成物， (i)環氧聚（甲基）丙烯酸酯Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (η=4~15) di(methyl) Acrylate, propylene glycol di(meth)acrylate 'tripropylene glycol di(meth)acrylate, polypropylene glycol (η=4~15) di(meth)acrylate, 1,4-butanediol di(a) Acrylate, polybutanediol (η = 2~15) di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol ester Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, (g) polyfunctional (meth)acrylate trishydroxyl Propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Ester, (h) urethane poly(meth) acrylate tris(isocyanatohexyl)isocyanurate, isophorone II Cyanate ester, bis(4isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, m-xylylene diisocyanate, 2,4-tolyl diisocyanate -77 - 1360477 2,6-polyisocyanate compound such as tolyl diisocyanate and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy(meth)acrylate Reaction product of a hydroxy group-containing (meth) acrylate such as butyl acrylate or 4-hydroxybutyl (meth) acrylate, (i) epoxy poly(meth) acrylate

2,2-雙（4-縮水甘油氧基環己基）丙烷、2,2-雙（4-縮水甘 油氧基苯基）丙烷、雙酚A二縮水甘油醚、雙酚F二縮水 甘油醚、雙酚S二縮水甘油醚、四溴雙酚A二縮水甘油醚 、四溴雙酚S二縮水甘油醚般之環氧化合物與（甲基）丙烯 酸酸的反應物， (j)聚酯聚（甲基）丙烯酸酯 馬來酸、富馬酸、駄酸、或琥珀酸中至少1種與乙二 醇、丙二醇、丁二醇、三羥甲基丙烷、或季戊四醇中至少 1種、與甲基丙烯酸或丙烯酸酸的反應物， 作爲活性能量線感應觸媒，更佳爲主要對波長200〜 4 OOnm的活性能量線感應而發生自由基源者。作爲具體例 子，可舉出苯偶姻、苯偶姻單甲基醚、苯偶姻異丙基醚、 乙偶姻、苄偶醯、二苯甲酮、對甲氧基二苯甲酮、二乙氧 基苯乙酮、苄基二甲基縮酮、2,2-二乙氧基苯乙酮、1-羥 基環己基苯基酮、甲基苯基乙醛酸酯、乙基苯基乙醛酸酯 * 、2 -羥基-2·甲基-1-苯基丙烷-1-酮等的羰基化合物、四甲 基秋蘭姆單硫化物、四甲基秋籣姆二硫化物等的硫化合物 、2，4,6-三甲基苯甲醯基二苯基膦氧化物等的醯基膦氧化 物。此等可以1種或2種以上的混合系來使用。於此等之 -78 - 1360477 中’更佳爲二苯甲酮、苯偶姻異丙基醚、甲基苯基乙醛酸 酯、1-羥基環己基苯基酮、苄基二甲基縮酮、2，4,6-三甲基 苯甲醯基二苯基膦氧化物。 活性能量線感應觸媒的含量，對於100質量份的樹脂 成分之合計量而言，係0.005〜5質量份，更佳係〇.〇2〜2 質量份。2,2-bis(4-glycidoxycyclohexyl)propane, 2,2-bis(4-glycidoxyphenyl)propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, a reaction of bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S diglycidyl ether epoxy compound with (meth)acrylic acid, (j) polyester poly( At least one of methyl methacrylate, fumaric acid, citric acid, or succinic acid and at least one of ethylene glycol, propylene glycol, butanediol, trimethylolpropane, or pentaerythritol, and methyl The reactant of acrylic acid or acrylic acid is used as an active energy ray-sensing catalyst, and is preferably a radical source mainly induced by an active energy ray having a wavelength of 200 to 400 nm. Specific examples thereof include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl oxime, benzophenone, p-methoxybenzophenone, and the like. Ethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethyl phenyl b Sulfur such as carbonyl compound such as aldehyde ester* or 2-hydroxy-2-methyl-1-phenylpropan-1-one, sulfuric acid such as tetramethylthiuram monosulfide or tetramethyl colchim disulfide A fluorenylphosphine oxide such as a compound or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. These may be used in combination of one type or two or more types. In this -78 - 1360477, 'better is benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl condensate Ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. The content of the active energy ray-sensing catalyst is 0.005 to 5 parts by mass, more preferably 〜2 to 2 parts by mass, based on 100 parts by mass of the total of the resin components.

又’於透鏡層中，在不損害透鏡的機能之範圍內，亦 可以配合各種添加劑，例如抗氧化劑、耐熱安定劑、耐候 安定劑、紫外線吸收劑、黃變防止劑、有機的易滑劑、顔 料、染料、藍化劑、有機或無機的微粒子、塡充劑、抗靜 電劑、界面活性劑、均平劑、核劑、擴散劑等。 於接著性改質基材薄膜的接著性改質層之表面上，積 層以上述活性線硬化型樹脂當作透鏡層的構成成分之方法 ’係視所要求的特性或用途來選擇各種方法。例如，使用 將該樹脂以切割成稜鏡狀的桿來塗布之方法，或使該樹脂 流入成爲稜鏡狀等透鏡層之形狀的模具內，重疊於接著性 改質基材薄膜的接著性改質層之表面的方法。 再者，活性線係意味紫外線、電子線、放射線（α線、β 線、γ線等）等之能使丙烯酸系的乙烯基聚合之電磁波。實 用上’紫外線係簡便的。作爲紫外線源，例如使用紫外線 螢光燈、低壓水銀燈、高壓水銀燈、超高壓水銀燈、氙燈 、碳弧燈。又，電子線方式之裝置必須在高價的惰性氣體 下操作，但從可以不含有光聚合引發劑或光增感劑等之點 來看係有利的。 -79- 1360477 透鏡層的厚度係可依照透鏡薄膜之目的或透鏡單位的 形狀來任意選擇。一般地，透鏡層的厚度較佳爲0.1〜5mm ，更佳爲0.2〜3mm»透鏡層的厚度若比0.1mm還薄，則 有得不到作爲透鏡層之效果的傾向。另一方面，透鏡層的 厚度若比5mm還厚，則在亮度方面有變不足的傾向。 又，透鏡單位的間距亦依照透鏡薄膜之目的或透鏡單 位的形狀來任意選擇》—般地，各透鏡層的中心間距離較 佳爲0.03〜0.5mm，更佳爲0.05〜0.3mm。Moreover, in the lens layer, various additives such as an antioxidant, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, a yellowing preventive agent, an organic slip agent, and the like may be blended in a range that does not impair the function of the lens. Pigments, dyes, blueants, organic or inorganic microparticles, chelating agents, antistatic agents, surfactants, leveling agents, nucleating agents, diffusing agents, and the like. On the surface of the adhesion-improving layer of the adhesive-modified substrate film, a method of laminating the active-ray-curable resin as a constituent component of the lens layer is selected. Various methods are selected depending on the desired characteristics or use. For example, a method of applying the resin to a rod cut into a crucible shape, or a method of causing the resin to flow into a mold having a shape of a lens layer such as a dome shape, and superimposing the adhesion property of the adhesive-modified substrate film The method of the surface of the layer. Further, the active line means an electromagnetic wave capable of polymerizing an acrylic vinyl group such as an ultraviolet ray, an electron beam, or a radiation (α line, β line, γ line, or the like). Practically, the UV system is simple. As the ultraviolet source, for example, an ultraviolet ray lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp are used. Further, the electron beam type device must be operated under an expensive inert gas, but it is advantageous in that it does not contain a photopolymerization initiator or a photosensitizer. -79- 1360477 The thickness of the lens layer can be arbitrarily selected in accordance with the purpose of the lens film or the shape of the lens unit. In general, the thickness of the lens layer is preferably 0.1 to 5 mm, more preferably 0.2 to 3 mm. ● If the thickness of the lens layer is thinner than 0.1 mm, the effect as a lens layer tends not to be obtained. On the other hand, if the thickness of the lens layer is thicker than 5 mm, the brightness tends to be insufficient. Further, the pitch of the lens unit is arbitrarily selected in accordance with the purpose of the lens film or the shape of the lens unit. Generally, the distance between the centers of the lens layers is preferably from 0.03 to 0.5 mm, more preferably from 0.05 to 0.3 mm.

特別地，積層有稜鏡狀的透鏡層之稜鏡狀透鏡薄膜， 從亮度、形成的容易性之點來看係較宜的《又，稜鏡的頂 角較佳爲80〜150度，更佳爲85〜130度。 (光擴散薄膜） 於本發明中，光擴散薄膜，係由在具有共聚合聚酯及 聚胺甲酸酯當作主要構成成分的接著性改質層之接著性改 質基材薄膜的一面上，積層含有無機微粒子的電離輻射線 硬化型硬被覆層，在相反面上積層擴散層而構成。亦有將 光擴散薄膜稱爲光擴散片的情況，但本發明中的薄膜亦包 括片。 光擴散層係由含有黏結劑樹脂和光擴散劑的組成物所 構成。作爲上述樹脂，合適者爲具有光學透明性的樹脂^ 例如，可舉出丙烯酸系樹脂、聚酯樹脂、聚氯乙烯、聚胺 甲酸酯、聚矽氧樹脂。該樹脂例如是三菱螺縈株式會社以 「Dianal系列」的商品名所市售者。 又，作爲光擴散劑所使用的粒子，合適考爲透明粒子 -80- 1360477 ’例如可舉出聚矽氧樹脂粒子、丙烯酸樹脂粒子、耐隆樹 脂粒子、胺甲酸酯樹脂粒子、苯乙烯樹脂粒子、聚乙烯樹 脂粒子、矽石粒子、聚酯樹脂粒子。此等粒子可被單獨使 用’亦可以2種以上倂用。又，上述微粒子之表面或全體 亦可被交聯。對於樹脂而言，粒子的混合比，從邊確保光 透過率邊得到充分的光擴散性之觀點來看，對於100質量 份的樹脂而言，其較佳爲5〜150質量份。In particular, a dome-shaped lens film in which a lens layer having a braided shape is laminated is preferable from the viewpoint of brightness and ease of formation. Further, the apex angle of the crucible is preferably 80 to 150 degrees. Good for 85~130 degrees. (Light-diffusing film) In the present invention, the light-diffusing film is formed on one side of the adhesive-modified substrate film of the adhesive-modified layer having a copolymerized polyester and a polyurethane as a main constituent component. An ionizing radiation-hardening type hard coating layer containing inorganic fine particles is laminated, and a diffusion layer is laminated on the opposite surface. There is also a case where the light-diffusing film is referred to as a light-diffusing sheet, but the film in the present invention also includes a sheet. The light diffusion layer is composed of a composition containing a binder resin and a light diffusing agent. As the resin, a resin having optical transparency is suitably used, and examples thereof include an acrylic resin, a polyester resin, a polyvinyl chloride, a polyurethane, and a polyoxymethylene resin. This resin is, for example, marketed by Mitsubishi Snail Co., Ltd. under the trade name "Dianal Series". Moreover, as a particle used for a light-diffusion agent, it is suitable as transparent particle -80-1360477', and a polyphthalate resin particle, an acryl resin particle, a lon-resistant resin particle, a urethane resin particle, and a styrene resin are mentioned, for example. Particles, polyethylene resin particles, vermiculite particles, and polyester resin particles. These particles may be used singly or in combination of two or more. Further, the surface or the entirety of the above fine particles may be crosslinked. In the resin, the mixing ratio of the particles is preferably from 5 to 150 parts by mass based on 100 parts by mass of the resin from the viewpoint of obtaining sufficient light diffusibility while ensuring light transmittance.

又，上述粒子的平均粒徑通常爲1〜70 μιη，較佳爲5〜 5 〇 μιη。即，粒子的平均粒徑若在上述範圍外，則光透過率 與光擴散性的平衡會崩潰，有不能提高正面亮度之虞。再 者，於使用球狀粒子作粒子時，各球狀粒子係當作1種透 鏡來作用，可具有更有效的光擴散效果。特別地，真球狀 粒子係有效的。真球狀粒子，例如是日本觸媒株式會社以 Epo star的商品名所販售的真球狀矽石粒子。 下述顯示光擴散薄膜的代表性製造方法。 藉由習知的塗布方法，將黏結劑樹脂、溶劑、粒子以 特定的比例混合、分散而成的塗布液，塗布在接著性改質 基材薄膜的接著性改質層（用於積層硬被覆層的表面之相反 面）之表面上。接著，藉由自然乾燥、熱風加熱乾燥等的乾 燥方法來使塗布層乾燥硬化，以在接著性基材薄膜的表面 上形成光擴散層。 塗布液的較佳調配方法係如下述。 首先，將黏結劑樹脂以特定的比例溶解在溶劑中。於 該溶解液中，可使粒子與視需要選用的其它副成分以特定 -81 - 1360477 的比例來分散，以調製混合分散液。此時，調整混合分散 液的黏度，以使在1〜500泊的範圍內。再者，液的黏度 可使用布魯克菲爾德黏度計（B形黏度計）來測定。 其次，於接著性改質基材薄膜的接著性改質層之表面 上，塗布上述塗布液及使乾燥。塗布液的塗布方法係依照 溶液的黏度或目的之塗布層的厚度來選擇。例如，作爲塗 布方法，可舉出逗點導引法、輥塗法、浸漬法、刀塗法、 簾流法、噴塗法、旋塗法、層壓法。Further, the average particle diameter of the particles is usually from 1 to 70 μm, preferably from 5 to 5 μm. In other words, if the average particle diameter of the particles is outside the above range, the balance between the light transmittance and the light diffusibility may collapse, and the front luminance may not be increased. Further, when spherical particles are used as the particles, each of the spherical particles functions as one type of lens, and a more effective light diffusion effect can be obtained. In particular, true spherical particles are effective. The true spherical particles are, for example, true spherical vermiculite particles sold by Nippon Shokubai Co., Ltd. under the trade name of Epo star. A representative production method of the light-diffusing film is shown below. A coating liquid obtained by mixing and dispersing a binder resin, a solvent, and particles in a specific ratio by a conventional coating method is applied to an adhesive modified layer of an adhesive modified base film (for laminated hard coating) On the opposite side of the surface of the layer). Then, the coating layer is dried and cured by a drying method such as natural drying or hot air drying to form a light diffusion layer on the surface of the adhesive base film. A preferred method of formulating the coating liquid is as follows. First, the binder resin is dissolved in a solvent in a specific ratio. In the solution, the particles may be dispersed in a ratio of -81 - 1360477, optionally with other optional components, to prepare a mixed dispersion. At this time, the viscosity of the mixed dispersion was adjusted so as to be in the range of 1 to 500 poise. Further, the viscosity of the liquid can be measured using a Brookfield viscometer (B-shaped viscometer). Next, the coating liquid was applied to the surface of the adhesive modified layer of the adhesive modified base film and dried. The coating method of the coating liquid is selected in accordance with the viscosity of the solution or the thickness of the coating layer to be used. For example, as a coating method, a comma guiding method, a roll coating method, a dipping method, a knife coating method, a curtain flow method, a spray coating method, a spin coating method, and a lamination method can be given.

再者，接著性改質基材薄膜的厚度，從用途或作業性 之點來看，較佳爲50〜200 μηι。又，光擴散層的厚度較佳 爲2〜30μιη。又，溶劑例如是甲苯、甲基乙基酮、二甲苯 、環己烷、醋酸乙酯。 而且，對於黏結劑樹脂而言，溶劑的混合比係依照塗 布方法或作業性、溶劑的種類等來適宜設定，但對於100 質量份的黏結劑樹脂而言，較佳爲50〜500質量份的溶劑 又，對於粒子而言，溶劑的混合比係依照塗布方法或 作業性、溶劑的種類等，對於1〇〇質量份的粒子而言，將 溶劑適宜設定在20〜5 00質量份的範圍內。更佳爲對於 100質量份的粒子而言，溶劑係50〜3 00質量份。即，對 於粒子而言，溶劑的混合比若在上述範圍內，則對於粒子 而言，溶劑的量係成爲使樹脂軟化的恰當量。 再者，作爲上述光擴散層的副成分，例如可以含有單 獨或二種以上的異氰酸酯化合物、環氧樹脂、羥甲基化蜜 -82 - 1360477 胺樹脂、羥甲基化尿素樹脂、金屬鹽、金屬氫氧化物等的 交聯劑、胍衍生物、含磷酸陰離子活性劑、磺酸類、四級 銨鹽、吡啶鍚鹽、咪唑啉衍生物、嗎啉衍生物、聚氧化乙 烯-烷基酚、烷基醯胺醚、山梨糖醇酐脂肪酸酯等的抗靜電 劑、矽烷偶合劑。 實施例Further, the thickness of the adhesive-modified substrate film is preferably from 50 to 200 μm from the viewpoint of use or workability. Further, the thickness of the light diffusion layer is preferably 2 to 30 μm. Further, the solvent is, for example, toluene, methyl ethyl ketone, xylene, cyclohexane or ethyl acetate. In addition, the mixing ratio of the solvent is appropriately set in accordance with the coating method, the workability, the type of the solvent, and the like, but it is preferably 50 to 500 parts by mass for 100 parts by mass of the binder resin. In the case of the particles, the mixing ratio of the solvent is preferably in the range of 20 to 500 parts by mass based on the coating method, the workability, the type of the solvent, etc., for the particles of 1 part by mass. . More preferably, the solvent is 50 to 30,000 parts by mass for 100 parts by mass of the particles. In other words, when the mixing ratio of the solvent is within the above range, the amount of the solvent in the particles is an appropriate amount to soften the resin. Further, as an accessory component of the light-diffusing layer, for example, an isocyanate compound, an epoxy resin, a methylolated honey-82-1360477 amine resin, a methylolated urea resin, a metal salt, or the like may be contained. Crosslinking agent such as metal hydroxide, hydrazine derivative, phosphoric acid anionic active agent, sulfonic acid, quaternary ammonium salt, pyridinium salt, imidazoline derivative, morpholine derivative, polyoxyethylene-alkylphenol, An antistatic agent such as an alkylamine or a sorbitan fatty acid ester or a decane coupling agent. Example

接著，關於本發明的硬被覆薄膜及使用其的光學機能 性薄膜，使用實施例和比較例來說明，惟本發明當然不受 此等實施例所限定。又，實施例中所記載的接著性改質基 材薄膜、硬被覆薄膜、光學機能性薄膜之物性或特性，係 使用下述方法來評價。 (1)接著性改質層的相分離構造 (1-1)接著性改質基材薄膜的接著性改質層之表面 (1-1-1)相位像的觀察 接著性改質層的表面中接著性改質層的相分離構造之 評價，係使用掃描型探針顯微鏡（SII奈米科技公司製， SPI3 8 00N系列/SPA300)，以相位測定模式（相模式）來進行 。於相位像中，相位延遲愈大則表現愈明亮，相反地相位 延遲愈小則表現愈黑暗。相位延遲小係意味與其它相比較 下，係硬的或吸附力比較小。於本發明所用的接著性改質 基材薄膜之接著性改質層中，暗色相係聚酯相，明色相係 聚胺甲酸酯相。 掃描型探針顯微鏡的相位測定模式之測定原理，係記載 於 SII 奈米科技公司的網址(http://www.siint.com/technologv/ -83- 1360477 probe_applications.html)「1-2.應用（模式別）」中 Phase 欄 的「1 .SPM的相位測定」之PDF檔案中。Next, the hard coating film of the present invention and an optical functional film using the same will be described using examples and comparative examples, but the present invention is of course not limited to the examples. Further, the physical properties or properties of the adhesive modified base film, the hard coated film, and the optical functional film described in the examples were evaluated by the following methods. (1) Phase separation structure of the adhesion modifying layer (1-1) Surface of the adhesion modifying layer of the adhesive modified base film (1-1-1) Observation of the phase image Surface of the modified layer The evaluation of the phase separation structure of the intermediate-adapted modified layer was carried out in a phase measurement mode (phase mode) using a scanning probe microscope (SPI3 8 00N series/SPA300, manufactured by SII Nanotech Co., Ltd.). In the phase image, the larger the phase retardation, the brighter the performance, and the smaller the phase retardation, the darker the performance. A small phase delay means that the system is hard or has a relatively small adsorption force compared to others. In the adhesive modifying layer of the adhesive modified base film used in the present invention, the dark phase is a polyester phase and the bright phase is a polyurethane phase. The measurement principle of the phase measurement mode of the scanning probe microscope is described in the website of SII Nano Technology Co., Ltd. (http://www.siint.com/technologv/ -83- 1360477 probe_applications.html) "1-2. Application In the PDF file of "1. SPM Phase Measurement" in the Phase column of "Mode".

用於測定的懸臂，主要係使用 DF3(彈簧常數：約 1.6N/m)，爲了防止由於探針污染而造成感度及分解能力的 降低，經常使用新品。掃描器係使用FS-20A。又，相位像 觀察係以分解能力5 1 2 X 5 1 2畫素以上來進行，觀察視野係 5μιηχ5μιη。測定時的懸臂之振幅衰減率或掃描査速度、掃 描頻率等的測定參數，係設定於實施線性掃描、感度最高 且分解能力良好之可觀察的條件。 (1-1·2)聚酯相的面積率之測定 (a)影像解析 以影像處理軟體）（Adobe製Photoshop 7.0版）來讀取所 得到的相模式影像（位元映像形式，512x512畫素），以影像 大小成爲205mmx205mm的方式顯示在顯示器上（參照第1 .圖）。接著，藉由同軟體的鉛筆工具（主要直徑：3px)，在 明色相與暗色相的邊界，描繪黑色線以使兩相之邊界明確（ 參照第2圖）。再者，使用同軟體的塗滿工具，將暗色相塗 成黑色，將明色相塗成白色，以分爲2値化（參照第3圖） 。此時，以畫面上的大小，判斷明色相內之直徑2mm以下 的暗色部，係爲偏在於明色相的粒子，塗滿白色。例如， 於使用矽石粒子時，確認如此之偏在於明色相者。 將此2値化的影像，以同軟體，將亮度（黑、白）當作橫 軸，將度數當作縱軸，以條帶圖來表示，求得黑色部（聚酯 相）的面積率，當作接著性改質基材薄膜的接著性改質層之 -84- 1360477 表面中聚酯相的面積率。 (b)紙重量法 接著性改質層的表面中聚酯相的面積率之測定，除了 使用影像解析法，亦可以使用紙重量法。測定手續係如下 述。The cantilever used for the measurement mainly uses DF3 (spring constant: about 1.6 N/m), and new products are often used in order to prevent the sensitivity and decomposition ability from being lowered due to probe contamination. The scanner uses the FS-20A. Further, the phase image observation system was performed with a decomposition ability of 5 1 2 X 5 1 2 pixels or more, and the observation field of view was 5 μm η 5 μιη. The measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency at the time of measurement are set to observable conditions in which linear scanning is performed, sensitivity is the highest, and decomposition ability is good. (1-1·2) Measurement of area ratio of polyester phase (a) Image analysis Image processing software (Adobe Photoshop 7.0) was used to read the obtained phase mode image (bit image format, 512x512 pixels) ), displayed on the display in such a manner that the image size is 205 mm x 205 mm (refer to Fig. 1). Next, the black line is drawn at the boundary between the bright phase and the dark phase by the pencil tool of the same software (main diameter: 3px) to make the boundary between the two phases clear (refer to Fig. 2). Furthermore, using the coating tool of the same software, the dark phase is painted black, and the bright phase is painted white to be divided into two (see Fig. 3). At this time, the dark portion having a diameter of 2 mm or less in the bright phase is judged by the size on the screen, and the particles are partially colored in the bright phase and are coated with white. For example, when using vermiculite particles, it is confirmed that such a bias is in the bright phase. The image of the two sides is represented by the same software, the brightness (black and white) is taken as the horizontal axis, and the degree is regarded as the vertical axis, and is represented by a strip chart, and the area ratio of the black portion (polyester phase) is obtained. , as the adhesion modifying layer of the adhesive modified base film - 84 - 1360477 The area ratio of the polyester phase in the surface. (b) Paper gravimetric method The area ratio of the polyester phase in the surface of the next modified layer was measured by using a paper weight method in addition to image analysis. The measurement procedure is as follows.

將所得到的相模式影像以位元映像形式的數位影像作 保存β接著，將該影像以印表機（Xerox製，DocuPrint C830)印刷輸出到 A4版上質紙。對於所輸出的影像 (200mmx200mm)，於5 0 0勒克司之照明下的明亮室內，目 視確認影像內的明色相與暗色相之.邊界，以4 B鉛筆使明 確。此時，明色相內所存在的直徑Ο.ίμιη以下的暗色部， 係被確認爲在明色相中所偏在的含於接著性改質層中的粒 子。因此，在明色相與其內部的暗色部之邊界不描線，使 該暗色部含於明色相中。然後，用切刀在明色相與暗色相 已明確的邊界線上切開而分割。接著，測定明色相（聚胺甲 酸酯相）和暗色相（聚酯相）的紙之質量，以％的單位來求得 對於明色相和暗色相的紙之總質量而言，暗色相（聚酯相） 的質量之比率，以其當作接著性改質層的表面中聚酯相的 面積率， (c)聚酯相的面積率之變動幅度（最大値與最小値的差） (c-1)薄膜捲筒的長度方向 將長度l〇〇〇m以上、寬度50mm以上的接著性改質基 材薄膜所成的捲筒捲出》對於該薄膜的長度方向（MD)，在 下述的地方測定上述接著性改質層的表面中聚酯相（在相位 -85 - 1360477 像顯示暗色相）的面積率。接著，於各地方，求得接著性改 質層的表面中聚酯相的面積率。再者，從它們的面積率求 得最大値與最小値的差。 接著性改質層的表面中聚酯相的面積率之測定，係將 薄膜物性安定的穩定區域之一端當作第1端部，將另一端 當作第2端部，在第1端部的內側2m以下進行第1次測 定’在第2端部的內側2m以下進行最終測定，而且從第1 次的測定地方起每隔1 00m進行測定。The obtained phase mode image was stored as a digital image in the form of a bit map. Then, the image was printed on a printer (DocuPrint C830, manufactured by Xerox) and printed on A4 paper. For the output image (200mm x 200mm), in the bright room under the illumination of 500 lux, visually confirm the boundary between the bright and dark colors in the image, and make it clear with a 4 B pencil. At this time, the dark portion having a diameter of Ο.ίμιη or less present in the bright phase was confirmed to be a particle contained in the adhesion modifying layer which was biased in the bright phase. Therefore, no line is drawn at the boundary between the bright phase and the dark portion inside, so that the dark portion is contained in the bright phase. Then, use a cutter to cut and divide the boundary between the bright phase and the dark phase. Next, the mass of the paper of the bright phase (polyurethane phase) and the dark phase (polyester phase) was measured, and the dark phase was obtained in units of % for the total mass of the paper of the bright phase and the dark phase ( The ratio of the mass of the polyester phase to the area ratio of the polyester phase in the surface of the adhesive modified layer, and (c) the variation range of the area ratio of the polyester phase (the difference between the maximum 値 and the minimum )) ( C-1) The roll of the adhesive-modified base film having a length of l〇〇〇m or more and a width of 50 mm or more in the longitudinal direction of the film roll. For the longitudinal direction (MD) of the film, the following The area ratio of the polyester phase (in the phase -85 - 1360477 image showing the dark phase) in the surface of the above-mentioned adhesion modifying layer was measured. Next, the area ratio of the polyester phase in the surface of the adhesion-modifying layer was determined in each place. Furthermore, the difference between the maximum 値 and the minimum 求 is obtained from their area ratios. The area ratio of the polyester phase in the surface of the modified layer is determined by using one end of the stable region of the physical stability of the film as the first end and the other end as the second end, and at the first end. The first measurement was performed on the inside 2 m or less. The final measurement was performed at 2 m or less inside the second end portion, and the measurement was performed every 100 m from the first measurement position.

(c-2)薄膜捲筒的寬度方向 將長度1000m以上、寬度50mm以上的接著性改質基 材薄膜捲筒捲出，對於該薄膜的寬度方向（TD)，將薄膜在 寬度方向作4等份。接著，於各自的中央部，測定接著性 改質層的表面之聚酯相（在相位像顯示暗色相）的面積率。 接著，求得寬度方向的接著性改質層之表面中聚酯相的面 積率之最大値與最小値的差。該測定係可藉由在將薄膜的 寬度方向切割成小幅尺寸之前的大輥來進行》 (1-2)與硬被覆薄膜中的接著性改質層成傾斜的切削面 於本發明的硬被覆薄膜中，接著性改質層B係爲熱塑 。性樹脂薄膜A與硬被覆層C的中間層。因此，於接著性改 質層B與硬被覆層C的界面（接著性改質基材薄膜中的接 著性改質層之表面）中，直接觀察樹脂的相分離構造係困難 的。因此，本案發明人們發現，可在厚度方向切削硬被覆 薄膜，從該切削面來測定接著性改質層之厚度方向中樹脂 的相分離構造。又，由於接著性改質層的厚度通常係薄的 -86- 1360477 ，故從接著性改質層的切削面係難以觀察樹脂的相分離構 造。 因此，對於厚度方向而言，以斜地且淺的角度來切削 硬被覆薄膜。結果可擴大接著性改質層的厚度方向之觀察 面積。藉此技術，於接著性改質層B與硬被覆層C的界面 附近，可觀察構成接著性改質層的樹脂之相分離構造。(c-2) The film of the adhesive-modified base film having a length of 1000 m or more and a width of 50 mm or more is wound up in the width direction of the film roll, and the film is made into 4 in the width direction in the width direction (TD) of the film. Share. Next, the area ratio of the polyester phase (the dark phase in the phase image) of the surface of the adhesive reforming layer was measured at the respective center portions. Next, the difference between the maximum 値 and the minimum 面 of the area ratio of the polyester phase in the surface of the adhesion-modifying layer in the width direction was determined. The measurement can be carried out by the large roll before cutting the width direction of the film into a small size. (1-2) The hardened surface of the present invention is inclined with the cut surface of the adhesive layer in the hard coated film. In the film, the adhesion modifying layer B is thermoplastic. An intermediate layer of the resin film A and the hard coating layer C. Therefore, it is difficult to directly observe the phase separation structure of the resin in the interface between the adhesion-modifying layer B and the hard coating layer C (the surface of the adhesion-modifying layer in the adhesive-modified substrate film). Therefore, the inventors of the present invention have found that the hard coating film can be cut in the thickness direction, and the phase separation structure of the resin in the thickness direction of the adhesion modifying layer can be measured from the cutting surface. Further, since the thickness of the adhesive reforming layer is usually -86 to 1360477, it is difficult to observe the phase separation structure of the resin from the cutting surface of the adhesive reforming layer. Therefore, for the thickness direction, the hard coating film is cut at an obliquely shallow angle. As a result, the observation area in the thickness direction of the adhesive reforming layer can be enlarged. According to this technique, the phase separation structure of the resin constituting the adhesion modifying layer can be observed in the vicinity of the interface between the adhesion modifying layer B and the hard coating layer C.

以下，詳細說明評價用試料的製作方法，及與硬被覆 層C的界面附近之接著性改質層的切削面中聚胺甲酸酯相 的面積率之評價方法。 (1-2-1)切削試料之作成 本發明的硬被覆薄膜，以熱塑性樹脂薄膜當作Α，以 接著性改質層當作Β，以硬被覆層當作C時，係爲含有 A/B/C或B/A/B/C之層構成的積層體。又，對於使用該硬 被覆薄膜的光學機能性薄膜，以其它光學機能層當作D時 ，於含有D(亦含C)/B/A/B/C的層構成之積層體。 即硬被覆薄膜或光學機能性薄膜中，從熱塑性樹脂薄 膜A或光學機能層D的表面，使用切削裝置1(SA1CAS DN20-S型），在下述所示的條件下，從斜方向來切削。當 刀刀達到指定的深度時，按壓稱爲”切入限度”的按鈕，以 進行一定深度的切削。又，於所切削的熱塑性樹脂薄膜爲 厚的情況中，較佳爲在同樣的場所進行數次的切削。 (a) 切削手段：鑽石刀（前角：40度） (b) 水平方向的刀刃之移動速度：3000nm/s (Ο垂直方向的刀刃之移動速度：200nm/sHereinafter, a method for producing the sample for evaluation and a method for evaluating the area ratio of the polyurethane phase in the cut surface of the adhesive layer adjacent to the interface with the hard coating layer C will be described in detail. (1-2-1) Cutting specimens The hard coating film of the invention has a thermoplastic resin film as a crucible, an adhesive layer as a crucible, and a hard coating layer as a C, which contains A/ A layered body composed of layers of B/C or B/A/B/C. Further, in the optical functional film using the hard coating film, when another optical functional layer is used as D, it is a laminate comprising a layer of D (including C)/B/A/B/C. In the hard coating film or the optical functional film, the surface of the thermoplastic resin film A or the optical function layer D was cut from the oblique direction using the cutting device 1 (SA1CAS DN20-S type) under the conditions shown below. When the knife reaches the specified depth, press a button called "cut-in limit" to perform cutting at a certain depth. Further, in the case where the thermoplastic resin film to be cut is thick, it is preferable to perform cutting several times in the same place. (a) Cutting means: Diamond knife (front angle: 40 degrees) (b) Moving speed of the blade in the horizontal direction: 3000 nm/s (Ο Moving speed of the blade in the vertical direction: 200 nm/s

< S -87 - 1360477 再者，上述“指定的深度”係意味切削熱塑性樹脂薄膜 的大部分，但沒有到達接著性改質層的深度。又，”切入限 度”係意味使垂直方向的刀刃之移動速度成爲零，僅進行水 平方向的切削。 接著，對同一地方，使用切削裝置2(SAICAS NN-04型） ，在下述所示的條件，從斜方向來進行高精度的切削，以 製作切削試料。 (d) 切削手段：鑽石刀（前角：40度）<S - 87 - 1360477 Further, the above "designated depth" means that most of the thermoplastic resin film is cut, but the depth of the adhesive modified layer is not reached. Further, the "cutting limit" means that the moving speed of the blade in the vertical direction is zero, and only the cutting in the horizontal direction is performed. Then, using the cutting device 2 (SAICAS NN-04 type) in the same place, high-precision cutting was performed from the oblique direction under the conditions described below to prepare a cutting sample. (d) Cutting means: diamond knife (front angle: 40 degrees)

(e) 水平方向的刀刃之移動速度：5 00nm/s ⑴垂直方向的刀刃之移動速度：20nm/s 再者，上述切削條件係爲用於切削本發明中所記載的 實施例及比較例所得到的硬被覆薄膜之代表條件。按照試 料而定，使用三次元切削工具的三次元切削方法亦有效的 。又，鑽石刀的刀刃寬度通常係lmm，但0.3 mm亦爲有效 的情況。於本發明所記載的實施例和比較例中，使用刀刃 的寬度爲1mm的鑽石刀。 因此，硬被覆薄膜的各層之材料種類，當與本發明中 所記載的實施例及比較例所使用的材料不同時，較佳爲進 行預備試驗，決定恰當的切削條件。 又，於光學機能層D(亦含硬被覆層C)的表面來進行切 削時，依照光學機能層的物性’在切削時有必須加熱或冷 卻的情形。加熱或冷卻係可以使用低溫、高溫氣體噴吹裝 置（TTFC-L型，DAIPLA.WINTES株式會社製）。加熱或冷 卻時的溫度或氣體流量，係可依照切削面的狀態來適宜調 -88- 1360477 整。 (1-2-2)相位像的觀察(e) Movement speed of the blade in the horizontal direction: 500 nm/s (1) Movement speed of the blade in the vertical direction: 20 nm/s Further, the above cutting conditions are used for cutting the examples and comparative examples described in the present invention. Representative conditions for the resulting hard coated film. The three-dimensional cutting method using a three-dimensional cutting tool is also effective depending on the sample. Also, the blade width of a diamond knife is usually 1 mm, but 0.3 mm is also effective. In the examples and comparative examples described in the present invention, a diamond blade having a blade width of 1 mm was used. Therefore, when the material type of each layer of the hard coating film is different from the materials used in the examples and comparative examples described in the present invention, it is preferable to carry out preliminary tests to determine appropriate cutting conditions. Further, when cutting is performed on the surface of the optical function layer D (including the hard coating layer C), the physical properties of the optical functional layer must be heated or cooled during cutting. For the heating or cooling, a low-temperature, high-temperature gas injection device (TTFC-L type, manufactured by DAIPLA.WINTES Co., Ltd.) can be used. The temperature or gas flow rate during heating or cooling can be adjusted to -88-1360477 according to the state of the cutting surface. (1-2-2) Observation of phase image

於所得到的切削試料之切削面中，接著性改質層B的 樹脂之相分離構造，使用上述掃描型探針顯微鏡（SPM)， 藉由相位測定模式（相模式）所得到的相位像，來觀察接著 性改質層B的樹脂之相分離構造。相模式通常係與藉由動 力模式（DFM模式；用SII奈米科技社製SPM的情況）之形 態觀察的同時，所進行的相位延遲測定模式。於接著性改 質層B的切削面之相位像中，暗色相係聚酯相，明色相係 聚胺甲酸酯相。 用於測定的懸臂，主要係使用 DF3(彈簧常數：約 1·6Ν/ιη)，爲了防止由於探針污染而造成感度及分解能力的 降低，經常使用新品。掃描器係使用FS-100A。又，相位 像的觀察視野係3μιη><3μιη。測定時的懸臂之振幅衰減率或 掃描速度、掃描頻率等的測定參數，係設定於實施線性掃 描、感度最高且分解能力良好之可觀察的條件。 (1-2-3)聚胺甲酸酯相的面積率之測定 申請文件中所附的圖面亦包含以彩色影像所表示的圖 面，但爲以電子檔申請的關係，將彩色影像以JPEG的檔 案形式作保存，以灰階來表示。又，爲了防止畫質的劣化 ，黑白的影像亦以JPEG的檔案形式作保存，以灰階來表 示。 (a)相位像的讀取 使用SPIP軟體（Image Metrology公司製，4.2.5版），以 -89 - 1360477 彩色讀取所得到的相位像。 (b) 相分離構造的對比之強調（參照第8圖） 接著，藉由該軟體，進行色均一化（Color Equalization) 處理’以使相分離構造成爲容易可見的方式，強調對比。 (c) 相分離構造的觀察範圍之確定（參照第9圖）In the cutting surface of the obtained cutting sample, the phase separation structure of the resin of the subsequent modified layer B, the phase image obtained by the phase measurement mode (phase mode) using the scanning probe microscope (SPM), The phase separation structure of the resin of the adhesive layer B was observed. The phase mode is usually a phase delay measurement mode that is performed while observing the state of the power mode (DFM mode; SPM by SII Nanotechnology Co., Ltd.). In the phase image of the cut surface of the adhesive layer B, the dark phase is a polyester phase and the bright phase is a polyurethane phase. The cantilever used for the measurement mainly uses DF3 (spring constant: about 1.6 Ν/ιη), and new products are often used in order to prevent the sensitivity and decomposition ability from being lowered due to probe contamination. The scanner uses the FS-100A. Further, the observation field of the phase image is 3 μηη >< 3 μιη. The measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency at the time of measurement are set to observable conditions in which linear scanning is performed, sensitivity is high, and decomposition ability is good. (1-2-3) Determination of the area ratio of the polyurethane phase The image attached to the application document also includes the image indicated by the color image, but for the relationship of the electronic file application, the color image is The JPEG file format is saved in grayscale. Also, in order to prevent deterioration of image quality, black and white images are also stored in JPEG file format and expressed in grayscale. (a) Reading of phase image The phase image obtained was read in color from -89 - 1360477 using SPIP software (manufactured by Image Metrology, Inc., version 4.2.5). (b) Emphasis on the contrast of the phase separation structure (refer to Fig. 8) Next, the color equalization process is performed by the software to make the phase separation structure easy to see, and the contrast is emphasized. (c) Determination of the observation range of the phase separation structure (refer to Figure 9)

複製已進行色均一化處理的相位像，貼在簡報軟體 (Microsoft Power point 2002)的畫面。接著，在接著性改 質層B與硬被覆層C的界面（B/C)，畫紅線20。此時，界 面不鮮明時，則調整對比。 再者，從該界面（B/C)朝向接著性改質層B，在垂直方 向中的20nm之深度位置’平行地複製顯示上述界面的紅 線，作貼上（第9圖的線21)。 再者’於製作切削試料時，從斜方向來切削積層體。 因此，於上述所示的切削條件中，從上述界面朝向接著性 改質層B，在深度20nm的位置，係於第9圖中相當於與 界面距離5 00nm的位置^ 如此作，以此等2條紅線所包圍的範圍，即從界面 (B/C)到接著性改質層B之深度2 0nm爲止的範圍，當作觀 察接著性改質層B的切削面中樹脂的相分離構造之範圍。 (d)相分離構造的影像處理 將第8圖的影像以JPEG的檔案形式來保存，貼於影像 處理軟體（Adobe製Photoshop 6.0.1版）之畫面，閾値係以 128的黑白二階調來表示（參照第10.圖）。 接著，將第10圖的影像貼到簡報軟體（Microsoft -90- 1360477Copy the phase image that has been subjected to color uniformization and paste it on the screen of the presentation software (Microsoft Power Point 2002). Next, a red line 20 is drawn at the interface (B/C) between the adhesive layer B and the hard coating layer C. At this time, when the interface is not clear, adjust the contrast. Further, from the interface (B/C) toward the adhesive reforming layer B, the red line of the interface is reproduced in parallel at a depth position of 20 nm in the vertical direction, and is pasted (line 21 of Fig. 9). Further, when the cutting sample is produced, the laminated body is cut from the oblique direction. Therefore, in the above-described cutting conditions, from the interface toward the adhesion-modifying layer B, the position at the depth of 20 nm corresponds to the position of the interface distance of 00 nm in the ninth figure, and so on. The range surrounded by the two red lines, that is, the range from the interface (B/C) to the depth of the adhesion modifying layer B of 20 nm, is used as the phase separation structure of the resin in the cutting surface of the adhesion modifying layer B. range. (d) Image processing of the phase separation structure The image of Fig. 8 is stored as a JPEG file and attached to the image processing software (Photoshop 6.0.1 version of Adobe). The threshold is represented by a black and white second-order tone of 128. (Refer to Figure 10.). Next, paste the image of Figure 10 into the presentation software (Microsoft -90-1360477

Powerpoint 2002)的畫面。然而，與第9圖的影像重疊，在 第10圖的影像上，表示第9圖所記載的2條紅線（2 0、 21)(參照第11圖）》Powerpoint 2002) screen. However, overlapping with the image of Fig. 9, the two red lines (20, 21) shown in Fig. 9 are shown on the image of Fig. 10 (refer to Fig. 11).

在影像處理軟體（Adobe製Photoshop 6.0.1版）的畫面 上顯示將該第11圖的影像'。再者，使用筆刷工具將接著 性改質層B以外的部分塗滿紅色（參照第12圖）。使用同一 軟體，將白、黑、紅的3倍化影像，以亮度（黑、白）當作 橫軸，以度數當作縱軸，藉由條帶圖來表示。 再者，於第12圖所示的接著性改質層B之相位像中， 黑色部意味聚酯相和粒子，白色部意味聚胺甲酸酯相。從 接著性改質層B與硬被覆層C的界面到深度20nm爲止的 範圍之切削面中，接著性改質層B的聚胺甲酸酯相（白色 部）之面積率係藉由下式來算出。而且，下式的右邊之“測 定面積”係意味第11圖的相位像之線20(界面B/C)與線21 所包圍的範圍。 聚胺甲酸酯相的面積率（％) = (白色部的面積/測定面積 )χ 1 00 (2) 聚酯相的寬度最小超過Ιμιη的地方之有無 於上述相模式影像中，關於不同的測定地方的10地方 ，於以共聚合聚酯當作主成分的聚酯相中，調査短軸方向 的寬度最細地方超過Ιμιη者的有無。 (3) 相分離構造的碎形次元 使用上述掃描型探針顯微鏡（SII奈米科技製，SPI3 8 00N 系統/SP A3 00)，將由相位測定模式（相模式）所得到的相模 -91 - 1360477The image of the 11th image is displayed on the screen of the image processing software (Photoshop 6.0.1 of Adobe). Further, a portion other than the adhesive reforming layer B is painted with red using a brush tool (refer to Fig. 12). Use the same software to convert white, black, and red 3x images with brightness (black and white) as the horizontal axis and degrees as the vertical axis, represented by the strip chart. Further, in the phase image of the adhesion-modifying layer B shown in Fig. 12, the black portion means a polyester phase and particles, and the white portion means a polyurethane phase. The area ratio of the polyurethane phase (white portion) of the adhesive modified layer B from the interface between the interface of the adhesion-modified layer B and the hard coating layer C to the depth of 20 nm is determined by the following formula To calculate. Further, the "measured area" on the right side of the following equation means the range surrounded by the line 20 (interface B/C) of the phase diagram 11 and the line 21. Area ratio (%) of the polyurethane phase = (area of white portion / area of measurement) χ 1 00 (2) Where the width of the polyester phase is the smallest at least Ιμιη in the above phase mode image, In the polyester phase in which the copolymerized polyester was used as the main component, it was investigated in the place where the width of the short-axis direction was the smallest, and the presence or absence of the Ιμιη was investigated. (3) Fractal Dimension of Phase Separation Structure Using the above-described scanning probe microscope (SII Nanotechnology, SPI3 8 00N system / SP A3 00), the phase mode obtained by the phase measurement mode (phase mode) -91 - 1360477

式影像（位元映像形式，5 1 2 χ 5 1 2畫素）讀入影像處理軟體 (Adobe 製 Photoshop 7.0)，以影像大小成爲 205mmx205mm 的方式在顯示器上顯示（參照第1圖）。接著，藉由同軟體 的鉛筆工具（主要直徑：3 ρχ)，在明色相與暗色相的邊界， 描繪黑色線以使兩相的邊界明確（參照第2圖）。此時，畫 面上的大小之明色相內的直徑2mm以下的暗色部，經判斷 係爲偏在於明色相的粒子，畫邊界線的操作係不對該部分 進行。例如，於使用矽石粒子時，可確認如此之偏在於明 將邊界線經明確化的影像以位元映像形式影像作保存 ，藉由網格計數法來進行碎形次元解析，將所得到的碎形 次元數値當作表示相分離的邊界線之複雜度的指數。於網 格計數法的解析中，使用影像解析軟體（AT-Image3.2版）。 具體地，於影像解析軟體（AT-Image 3.2版）上打開所保存 的位元映像影像，根據手冊上的影像取出，進行亮度條帶 圖的二値化處理（參照第6圖）。而且，二値化時的閥値係 8。對於經二値化處理的影像，根據手冊上的影像計測來 選擇碎形次元，求得碎形次元。此時，於最小平方的碎形 次元之計算中，使用一邊長度6畫素至63畫素的網格之 計數結果。 再者，網格計數法的碎形次元之解析係爲習知的方法 ，於次元解析中所使用的其它影像解析軟體或程式，只要 能充分得到解析結果的再現性，則亦可使用其它同功能的 軟體。其它軟體例如可舉出「獨立行政法人農業技術硏究 -92- 1360477 機構畜產草地硏究所製碎形解析系統3.33版」、「Digital B e i n g K i d s公司製P 〇 p I m a g i n g 3.4 0版j等的影像解析軟 體。 (4)硬被覆相C中的無機微粒子之平均粒徑The image (bit image format, 5 1 2 χ 5 1 2 pixels) is read into the image processing software (Adobe Photoshop 7.0) and displayed on the display so that the image size is 205 mm x 205 mm (see Fig. 1). Next, the black line is drawn at the boundary between the bright phase and the dark phase by the pencil tool (main diameter: 3 ρ χ) of the same software to make the boundary of the two phases clear (see Fig. 2). At this time, the dark portion having a diameter of 2 mm or less in the bright phase of the size on the screen is judged to be a particle having a bright phase, and the operation line for drawing the boundary line is not performed on the portion. For example, when using vermiculite particles, it can be confirmed that the image is clearly preserved in the image of the bit map, and the fractal method is used to perform the fractal analysis. The fractal dimension 値 is used as an index representing the complexity of the phase boundary of the phase separation. In the analysis of the grid counting method, the image analysis software (AT-Image version 3.2) is used. Specifically, the stored bitmap image is opened on the image analysis software (AT-Image version 3.2), and the luminance strip image is binarized according to the image taken in the manual (see Fig. 6). Moreover, the valve system is the second. For the binarized image, select the fractal dimension according to the image measurement in the manual to obtain the fractal dimension. At this time, in the calculation of the least square fractal element, the counting result of the grid of 6 pixels to 63 pixels on one side is used. Furthermore, the analysis of the fractal dimension of the grid counting method is a conventional method, and other image analysis software or programs used in the dimensional analysis can be used as long as the reproducibility of the analysis result can be sufficiently obtained. Functional software. Other softwares include, for example, "Independent Administrative Corporation Agricultural Technology Research -92- 1360477 Institutional Livestock Grassland Research Institute's Fragment Analysis System 3.33" and "Digital B eing K ids P 〇p I maging 3.4 0 Edition j Image analysis software such as (4) Average particle size of inorganic particles in hard-coated phase C

將硬被覆薄膜的試料埋設於可見光硬化型樹脂（例如環 氧樹脂）中，在室溫放置使硬化。接著，使用安裝有鑽石刀 的超薄切片機來製作超薄切片，藉由四氧化釕來染。對於 該經染色的超薄切片，使用透射型電子顯微鏡（日本電子公 司製TEM2010)，觀察硬被覆層C的截面，拍攝照片。再 者，照片的放大倍率係按照所觀察的無機粒子之粒徑，在 10,000〜100，0 00倍的範圍內適宜設定。而且，於本發明的 實施例1中，將放大倍率當作80,000倍（加速電壓200kv) 。從該照片求得硬被覆層C中的無機微粒子之數基準的平 均粒徑。 (5)霧度 根據JISK7136，使用霧度計（日本電色製NDH2 00 0)， 在薄膜試料的不同3個地方測定霧度，使用其平均値。 (6)防黏連性 將2片接著性改質基材薄膜的接著性改質層各自重疊 。接著，對其施加lkgf/cm2的壓力，在50°C、60%RH的 氣氛下24小時以使密接。然後，在經密接的2片接著性 改質基材薄膜之接著性改質層與接著性改質層的界面作剝 離，以下述基準來判斷剝離狀態》 〇：接著性改質層沒有轉移，可輕鬆地剝離 -93- 1360477 △:發生剝離音，接著性改質層部分地轉移到對手面 X: 2片薄膜固着而不能剝離，即使剝離基材聚酯薄膜也 裂開 (7)接著性改質層的硬度指數 於接著性改質基材薄膜的接著性改質層之表面上，使The sample of the hard coating film is embedded in a visible light-curable resin (for example, an epoxy resin), and is allowed to stand at room temperature to be cured. Next, an ultrathin section was prepared using an ultramicrotome equipped with a diamond knife, and dyed by osmium tetroxide. For the dyed ultrathin section, a cross section of the hard coating layer C was observed using a transmission electron microscope (TEM 2010 manufactured by JEOL Ltd.), and photographs were taken. Further, the magnification of the photograph is suitably set in the range of 10,000 to 100,000 times in accordance with the particle diameter of the inorganic particles observed. Further, in the first embodiment of the present invention, the magnification is regarded as 80,000 times (acceleration voltage 200 kv). From this photograph, the average particle diameter on the basis of the number of inorganic fine particles in the hard coating layer C was determined. (5) Haze According to JIS K7136, a haze meter (NDH2 00 0 made by Nippon Denshoku Co., Ltd.) was used, and the haze was measured at three different places of the film sample, and the average enthalpy was used. (6) Anti-blocking property The adhesive modifying layers of the two sheets of the adhesive-modified substrate film were each overlapped. Subsequently, a pressure of lkgf/cm2 was applied thereto, and the mixture was allowed to adhere for 24 hours in an atmosphere of 50 ° C and 60% RH. Then, the interface between the adhesion-modifying layer and the adhesion-modifying layer of the two sheets of the adhesive-attached substrate film which were adhered to each other was peeled off, and the peeling state was judged based on the following criteria: 〇: The adhesive layer was not transferred, Can be easily peeled off -93- 1360477 △: Peeling sound occurs, and then the modified layer is partially transferred to the hand surface X: 2 sheets of film are fixed without peeling, even if the base film is peeled off (7) Adhesive The hardness index of the modified layer is on the surface of the adhesive modifying layer of the adhesive-modified substrate film,

用表面性測定器（新東亞化學製HEIDON14)來弄痕。於此 情況下，作爲用於弄傷的針，使用前端附有半徑75μιη的 藍寶石之純正針。針的行進速度係150mm/分鐘，加重係 5 gf。 對於接著性改質層經弄傷的表面形狀，使用三次元非 接觸表面形狀計測裝置（MICROMAP製Micromap 5 5 0)，於 下述條件下測定，表示成輪廓模式數據。代表例係顯示於 第5圖中。由所得到的傷痕之形狀數據，在30個地方測 定毗鄰的凸與凹之高低差，求得它們的平均値，當作接著 性改質層的硬度指數。此時，判斷高度爲3 Onm以上的突 起係爲起因於接著性改質層或熱塑性樹脂薄膜中所含有的 粒子之突起，將其從測定數據去除。又，高度爲Inm以下 的突起，由於雜訊的影響，故同樣地從測定數據去除。 (測定條件） •輪廓模式：波形模式 •物鏡：1〇倍 .解像度：1 60 x 1 60畫素 .測定長：2 0 7.1 n m (8)與硬被覆層的密接性 -94- 1360477 (8-1)接著性改質層B與硬被覆層C的密接性A surface measuring instrument (HEIDON 14 manufactured by New East Asia Chemical Co., Ltd.) was used for the marking. In this case, as a needle for injury, a pure needle having a sapphire having a radius of 75 μm at the tip end is used. The speed of the needle was 150 mm/min and the weight was 5 gf. The surface shape of the adhesion-modified layer was measured using a three-dimensional non-contact surface shape measuring device (Micromap 550 manufactured by MICROMAP) under the following conditions, and expressed as outline pattern data. A representative example is shown in Figure 5. From the shape data of the obtained flaws, the height difference between the adjacent convex and concave portions was measured at 30 places, and their average enthalpy was obtained as the hardness index of the adhesive modified layer. In this case, the protrusion having a height of 3 Onm or more is determined to be a protrusion caused by the particles contained in the adhesive modification layer or the thermoplastic resin film, and is removed from the measurement data. Further, the protrusions having a height of less than Inm are similarly removed from the measurement data due to the influence of noise. (Measurement conditions) • Contour mode: Waveform mode • Objective lens: 1〇. Resolution: 1 60 x 1 60 pixels. Measurement length: 2 0 7.1 nm (8) Adhesion to hard coating layer -94 - 1360477 (8 -1) Adhesion between the adhesive layer B and the hard coating layer C

於黏貼有雙面膠帶的厚度5mm之玻璃板上，黏貼實施 例及比較例所得到的硬被覆薄膜或光學機能性薄膜之與硬 被覆層C的相反面。接著，使用間隙間隔2mm的刀片導 引器，弄出貫通硬被覆層C與接著性改質層B且到達熱塑 性樹脂薄膜A的100個方格狀之刀傷。接著，將膠帶 (NICHBAN製405號；24mm寬）黏貼在方格狀的刀傷面。 黏貼時藉由橡皮擦來按壓界面中所殘留的空氣，以使完全 密接後，強勢地垂直撕下膠帶。再同樣地重新貼上新的膠 帶，同樣強勢地垂直撕下膠帶。該膠帶的撕下操作係合計 重複10次，藉由下式目視求得密接性。再者，1個方格內 有部分剝離者亦包含在已剝離的個數內。 密接性（％)= (1-方格經剝離的個數/100個）χ100 (8-2)接著性改質基材薄膜的評價 形成由溶劑稀釋型與無溶劑型的2種光硬化型丙烯酸 系樹脂所成且不含有粒子的硬被覆層，依照上述方法來評 價硬被覆層與接著性改質層B的密接性。用於評價接著性 改質基材薄膜與硬被覆層之密接性的試料，係依照下述方 法來製作。 (a)與由溶劑稀釋型的光硬化型丙烯酸系樹脂所構成的硬被 覆層之密接性 於薄膜試料的接著性改質層B之表面，藉由線桿來塗 布由 50質量份的硬被覆劑（大日精化製 Seikabeam EXF01MB))、25質量份的甲苯、25質量份的甲基乙基酮所 -95 - 1360477 良好攪拌而成的塗布劑，在70°C乾燥1分鐘以去除溶劑後 ，以高壓水銀燈在200mJ/cm2、照射距離15cm、行進速度 5 m/分鐘的條件下，得到具有厚度3 μπι的硬被覆層之硬被 覆薄膜。 (b)與由無溶劑型的光硬化型丙烯酸系樹脂所構成的硬被覆 層之密接性On the glass plate having a thickness of 5 mm to which a double-sided tape was adhered, the opposite surface of the hard coating film C or the optical functional film obtained in the examples and the comparative examples was adhered to the hard coating layer C. Next, using a blade guide having a gap of 2 mm, 100 square-shaped blade wounds penetrating the hard coating layer C and the adhesion-modifying layer B and reaching the thermoplastic resin film A were produced. Next, the tape (No. 405 made by NICHAN); 24 mm wide was attached to the square-shaped blade. When pasting, the air remaining in the interface is pressed by the eraser so that the tape is strongly and vertically peeled off after the close contact. The new tape is reapplied in the same way, and the tape is also peeled off vertically. The tearing operation of the tape was repeated 10 times in total, and the adhesion was visually determined by the following formula. Furthermore, some of the peelers in one square are also included in the number of stripped. Adhesiveness (%) = (1-number of 1-part peeled/100) χ100 (8-2) Evaluation of adhesive-modified base film Two types of light-curing type which are solvent-diluted and solvent-free The hard coating layer formed of the acrylic resin and containing no particles was evaluated for the adhesion between the hard coating layer and the adhesion-modifying layer B in accordance with the above method. The sample for evaluating the adhesion between the adhesive-modified substrate film and the hard coating layer was produced in the following manner. (a) Adhesion to a hard coating layer composed of a solvent-diluted photocurable acrylic resin to the surface of the adhesive-modified layer B of the film sample, and 50 parts by mass of hard coating was applied by a wire rod Agent (Seikabeam EXF01MB manufactured by Daisei Seiki Co., Ltd.), 25 parts by mass of toluene, and 25 parts by mass of methyl ethyl ketone -95 - 1360477. The coating agent was stirred well at 70 ° C for 1 minute to remove the solvent. A hard coating film having a hard coating layer having a thickness of 3 μm was obtained under the conditions of a high pressure mercury lamp at 200 mJ/cm 2 , an irradiation distance of 15 cm, and a traveling speed of 5 m/min. (b) Adhesion to a hard coating layer composed of a solvent-free photocurable acrylic resin

於保持乾淨的厚度5 mm之玻璃板上，載置約5克硬被 覆劑（大日精化製Seikabeam EXF01(B))，以薄膜試料的接 著性改質層之表面與硬被覆劑成接觸的方式作重疊，從薄 膜試料之上，藉由寬度l〇cm、直徑4cm的手動式荷重橡 膠輥，以擴展硬被覆劑的方式來壓接。接著，從薄膜面側 ，以高壓水銀燈在5 00mJ/cm2、照射距離15cm、行進速度 5m/分鐘的條件下，照射紫外線，而使硬被覆層硬化。然 後，從玻璃板剝離具有硬被覆層的薄膜試料，得到硬被覆 薄膜。 (9)鉛筆硬度 根據JIS-K5400，藉由鉛筆硬度試驗來測定硬被覆層C 的表面。於鉛筆硬度試驗中，重複進行5次試驗’於所有 的試驗中，若在硬被覆層C的表面沒有看到傷痕等的外觀 異常時，則以該試驗時所使用的鉛筆之硬度當作鉛筆硬度 。例如，使用3 Η的鉛筆，進行5次試驗，於所有試驗中 若沒有發生外觀異常，則該材料的鉛筆硬度係至少3 Η。於 本評價中，將3Η以上當作〇，將2Η以下當作X。 (實施例1) -96 - 1360477 (i)塗布液的調配 依照以下方法來調製本發明中所用的塗布液。 將對酞酸二甲酯（95質量份）、異酞酸二甲酯（9 5質量份）Approximately 5 g of a hard coating agent (Seikabeam EXF01 (B) manufactured by Daisei Seiki Co., Ltd.) was placed on a glass plate having a thickness of 5 mm, and the surface of the adhesive layer of the film sample was brought into contact with the hard coating agent. The method was overlapped, and a manual load-bearing rubber roller having a width of 1 cm and a diameter of 4 cm was used to press the film by expanding the hard coating agent from the film sample. Next, the hard coating layer was cured by irradiating ultraviolet rays from the film surface side under the conditions of a high-pressure mercury lamp at 500 mJ/cm 2 , an irradiation distance of 15 cm, and a traveling speed of 5 m/min. Then, the film sample having the hard coating layer was peeled off from the glass plate to obtain a hard coating film. (9) Pencil hardness The surface of the hard coating layer C was measured by a pencil hardness test in accordance with JIS-K5400. In the pencil hardness test, the test was repeated five times. In all the tests, if the appearance of the scratch or the like was not observed on the surface of the hard coating layer C, the hardness of the pencil used in the test was regarded as a pencil. hardness. For example, using a 3 铅笔 pencil for 5 tests, the pencil hardness of the material is at least 3 若 if no appearance abnormality occurs in all tests. In this evaluation, 3Η or more is regarded as 〇, and 2Η is regarded as X. (Example 1) -96 - 1360477 (i) Preparation of coating liquid The coating liquid used in the present invention was prepared in accordance with the following method. Dimethyl phthalate (95 parts by mass), dimethyl isononanoate (95 parts by mass)

、乙二醇（35質量份）、新戊二醇（145質量份）、醋酸鋅（〇·1 質量份）及三氧化銻（0.1質量份）投入反應容器內，在180 °C費3小時進行酯交換反應。接著，添加磺基異酞酸5-鈉 (6.0質量份），在240°C費1小時進行酯化反應後，在250 °C的減壓下（10〜0.2mmHg)，費2小時間進行聚縮合反應 ，得到數量平均分子量爲1 9,500、軟化點爲60°C的共聚合 聚醋。 將7.5質量份的所得到之共聚合聚酯（A)的30質量％的 水分散液、11.3質量份的含有亞硫酸氫鈉所封閉的異氰酸 基之自交聯型聚胺甲酸酯（B)的20質量％的水溶液（第一工 業製藥製ELASTRON H-3)、0.3質量份的ELASTRON用觸 媒（第一工業製藥製Cat64)、39.8質量份的水及37.4質量 份的異丙醇分別混合。再者，添加0.6質量份的氟系非離 子型界面活性劑（大日本油墨化學工業製、Megafac F142D) 的1 0質量％水溶液、2.3質量份當作粒子A的膠態矽石（日 產化學工業製Snowtex OL ;平均粒徑40nm)之20質量％水 分散液、0.5質量份當作粒子B的乾式法矽石（日本Arosil 製Arosil 0X50 ;平均粒徑200nm，平均一次粒徑40nm)之 3.5質量％水分散液。接著，用5質量％的碳酸氫鈉水溶液 將塗布液的pH調整至6.2，以過濾粒子尺寸（初期過濾效 率：95%)爲ΙΟμηι的氈型聚丙烯製過濾器來精密過濾，調 -97 - 1360477 製塗布液A。而且，上述界面活性劑係使用下述方法所前 處理者。Ethylene glycol (35 parts by mass), neopentyl glycol (145 parts by mass), zinc acetate (〇·1 parts by mass), and antimony trioxide (0.1 parts by mass) were placed in a reaction vessel and charged at 180 ° C for 3 hours. The transesterification reaction is carried out. Next, 5-sulfoisophthalic acid 5-sodium (6.0 parts by mass) was added, and the esterification reaction was carried out at 240 ° C for 1 hour, and then under reduced pressure (10 to 0.2 mmHg) at 250 ° C for 2 hours. The polycondensation reaction gave a copolymerized polyester having a number average molecular weight of 1,900 and a softening point of 60 °C. 7.5 parts by mass of a 30% by mass aqueous dispersion of the obtained copolymerized polyester (A), and 11.3 parts by mass of a self-crosslinking type polyurethane of isocyanate blocked with sodium hydrogen sulfite (B) 20% by mass aqueous solution (ELASTRON H-3 manufactured by Dai-ichi Pharmaceutical Co., Ltd.), 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 39.8 parts by mass of water, and 37.4 parts by mass of isopropylidene The alcohols were mixed separately. Further, 0.6 parts by mass of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals, Megafac F142D) of 10% by mass of an aqueous solution and 2.3 parts by mass of colloidal vermiculite as a particle A were added (Nissan Chemical Industry) 20% by mass aqueous dispersion of Snowtex OL; average particle size 40 nm), 0.5 mass part of dry vermiculite as particle B (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) % aqueous dispersion. Next, the pH of the coating liquid was adjusted to 6.2 with a 5% by mass aqueous solution of sodium hydrogencarbonate, and the filter was prepared by filtering a particle size (initial filtration efficiency: 95%) of a felt-type polypropylene filter of ΙΟμηι. 1360477 Coating liquid A. Further, the above surfactant is a pretreated person using the following method.

於上述界面括性劑中添加異丙醇（IP A)，在30°C的溫浴 上加熱溶解，以製作1 5質量％的界面活性劑之IPA溶液。 以定量爐紙（ADVANTECH東洋製N 〇 · 5 C )來過濾該溶液， 去除溶液中的不溶份及塵土。於過濾上述溶液後，將該溶 液置入已密閉的玻璃容器內，在0°C的冷凍庫內靜置24小 時。經過24小時後，使用上述定量濾紙，抽吸過濾含有 所析出的固體之溶液。將濾紙上的固體作真空乾燥，得到 固體，以水稀釋成10質量％水溶液，用當作已前處理的界 面活性劑* 再者，對於上述前處理所得到的界面活性劑，以甲醇 當作展開液，以TLC塗布過的塑膠片（Merck製矽凝膠60) 來分析。試料斑點係藉由碘蒸氣進行著色，結果確認沒有 檢測出相當於聚乙二醇的斑點。 (2)接著性改質基材薄膜的製造 對於作爲原料聚合物之不含有粒子的固有黏度爲 〇.62dl/g之聚對酞酸乙二酯（PET)樹脂九粒，在135°C作6 小時減壓乾燥（ITorr)。接著，將乾燥後的PET樹脂九粒供 應給擠壓機，在約285 °C熔融擠出成片狀，於表面溫度保 持20°C的金屬輥上驟冷固化，得到流延薄膜。此時，作爲 用於去除熔融樹脂中的雜質之濾材，使用過濾粒子尺寸（初 期過濾效率：95%)爲15 μπι的不銹鋼製燒結濾材。 以經加熱的輥群及紅外線加熱器，將所得到的流延薄Isopropyl alcohol (IP A) was added to the above-mentioned interface-containing compound, and the solution was heated and dissolved in a warm bath at 30 ° C to prepare an IPA solution of 15% by mass of a surfactant. The solution was filtered using a quantitative furnace paper (ADVANTECH Toyo N 5 · C) to remove insoluble matter and dust from the solution. After filtering the solution, the solution was placed in a closed glass container and allowed to stand in a freezer at 0 ° C for 24 hours. After 24 hours, the above-mentioned quantitative filter paper was used, and a solution containing the precipitated solid was suction-filtered. The solid on the filter paper was vacuum dried to obtain a solid, which was diluted with water to a 10% by mass aqueous solution, and used as a pretreated surfactant*. Further, the surfactant obtained by the above pretreatment was treated with methanol. The developing solution was analyzed by TLC-coated plastic tablets (Merck 矽 gel 60). The sample spots were colored by iodine vapor, and as a result, it was confirmed that no spots corresponding to polyethylene glycol were detected. (2) Production of adhesively modified base film: For the raw material polymer, the particles having no intrinsic viscosity of 62.62 dl/g of polyethylene terephthalate (PET) resin containing no particles were produced at 135 ° C. Dry under reduced pressure (ITorr) for 6 hours. Next, nine pieces of the dried PET resin were supplied to an extruder, melt-extruded into a sheet at about 285 ° C, and quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C to obtain a cast film. At this time, as a filter medium for removing impurities in the molten resin, a sintered stainless steel filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used. The resulting cast thinner is obtained by a heated roller group and an infrared heater

(S -98- 1360477 膜加熱到95°C，然後藉由具有周速差的輥群在長度方向中 拉伸3 .5倍，以得到一軸配向PET薄膜。接著，以過濾粒 子尺寸（初期過濾效率：95%) 10 μιη的氈型聚丙烯製濾材對 上述塗布液Α進行精密過濾，藉由逆輥法塗布在一軸配向 PET薄膜的一面上。而且，此時塗布機的塗布輥及計量輥 係使用經超硬鍍鉻加工所製作的表面爲0.2S以下且真圓度 與圓筒度爲3/1000mm的輥。(S-98-1360477 The film was heated to 95 ° C, and then stretched by 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis aligned PET film. Next, the particle size was filtered (initial filtration) Efficiency: 95%) 10 μm of a felt-type polypropylene filter material, which is precisely filtered by the coating liquid, and coated on one side of the one-axis alignment PET film by a reverse roll method. Moreover, the coating roller and the metering roll of the coater at this time A roll having a surface of 0.2 S or less and a roundness and a cylindricalness of 3/1000 mm produced by superhard chrome plating was used.

然後，於塗布機正上方所配置的劃分爲4區的乾燥爐 中’在第1區（135°C歷1.0秒）、第2區（65°C歷2.2秒）、 第3區（40 °C歷1.8秒）、第4區（30 °C歷1.8秒）將塗布面乾 燥。又，塗布量係使最終的固體成分量成爲0.08 g/m2。從 薄膜的塗布起到乾燥爐入口爲止，薄膜的通過時間係0.8 秒。又，此時，設定第1區的乾燥風之風速爲30m/秒，乾 燥風的給氣風量爲130m3/秒，排氣風量爲170m3/秒，從第 2區到第 4區爲止的給氣風量爲lOOm3/秒，排氣風量爲 15 0m3/秒，不使乾燥風流到塗布機側。再者，薄膜的張力 係7000N/原版，於從塗布起到乾燥爐入口爲止之間，以夾 輥抓住薄膜的兩端部，而且於此時的塗布中，塗布液的接 盤之容量與循環用槽的容量及調配用槽的容量之比，係使 用具有以下關係的塗布裝置。 (a) 塗布液的接盤之容量與循環用槽的容量比=1/50 (b) 循環用槽的容量與調配用槽的容量比=1/4 0 接著，邊以夾具來抓住薄膜的端部，邊導引至溫度120 °C、風速1 5m/秒的熱風區中，在寬度方向中作4.3倍拉伸 (S ) -99 - 1360477Then, in the drying furnace divided into 4 zones disposed directly above the coater, 'in the first zone (135 ° C for 1.0 seconds), the second zone (65 ° C for 2.2 seconds), the third zone (40 °) The coated surface was dried in the fourth zone (C., 1.8 seconds). Further, the coating amount was such that the final solid content was 0.08 g/m2. The film passage time was 0.8 seconds from the application of the film to the entrance of the drying furnace. Further, at this time, the wind speed of the dry air in the first zone is set to 30 m/sec, the air supply air volume of the dry air is 130 m 3 /sec, the exhaust air volume is 170 m 3 /sec, and the air supply from the second zone to the fourth zone is given. The air volume is lOOm3/sec, and the exhaust air volume is 150 m3/sec, so that the dry air does not flow to the coater side. Further, the tension of the film is 7000 N/original, and the both ends of the film are grasped by the nip rolls from the application to the entrance of the drying furnace, and the capacity of the coating liquid is applied during the coating at this time. The ratio of the capacity of the circulation tank to the capacity of the preparation tank is a coating apparatus having the following relationship. (a) The ratio of the capacity of the coating liquid to the capacity of the circulation tank = 1/50 (b) The ratio of the capacity of the circulation tank to the capacity of the mixing tank = 1/4 0 Next, grasp the film with a jig The end is guided to a hot air zone with a temperature of 120 °C and a wind speed of 15 m/s, and is stretched 4.3 times in the width direction (S) -99 - 1360477

。然後，將寬度方向經拉伸的寬度保持原狀，依順序連續 通過第1熱定型區（溫度：200°C )、第2熱定型區（溫度： 225 °C)、第3熱定型區（溫度：230 °C)、第4熱定型區（溫 度：230°C)、第5熱定型區（溫度：210°C)、第6熱定型區 (溫度：170°C)、第7熱定型區（溫度：120°C)。再者，在 第6熱定型區中於寬度方向進行3 %的鬆弛處理。接著，修 剪薄膜兩端部沒有被塗覆的部分，捲繞於捲繞裝置，再將 其在寬度方向切割成4等份，得到寬度1 0 00mm、薄膜長 度1000m、薄膜厚度125μιη的接著性改質聚酯薄膜之捲筒 。再者，熱定型區中的熱風之風速皆是15m/秒，通過時間 在各區皆是4.5秒，吹出熱風的噴嘴間隔係3 50mm，每1 區的噴嘴個數係8個》 表4中顯示接著性改質基材薄膜的物性及特性。又， 表5中顯示於所得到的接著性改質聚酯薄膜之捲筒的長度 方向及寬度方向中，接著性改質層的表面之聚酯相的面積 率之最大値、最小値，霧度之最大値、最小値，對於硬被 覆層而言密接性之最大値、最小値。而且，關於防黏連性 ，在全部測定點皆是〇。 (3)硬被覆薄膜的製造 其次，藉由下述方法，於上述接著性改質基材薄膜的 接著性改質層B之表面上，在一面積層含有無機微粒子的 硬被覆層C，以得到硬被覆薄膜。 作爲用於形成硬被覆層的塗布液，準備以紫外線硬化 型丙烯酸酯單體、氧化锆超微粒子、甲基乙基酮當作主成 -100- 1360477 分的有機/無機混合系硬被覆劑（JSR公司製Desolite Z7410B;固體成分濃度：50質量％)。以乾厚度成爲8μιη 的方式，將該硬被覆劑塗布在接著性改質基材薄膜的接著 性改質層Β之表面，於40°C乾燥1分鐘。 接著，用高壓水銀燈，在1 〇〇〇mJ/cm2的條件下，照射 紫外線，使樹脂硬化，而形成硬被覆層C。. Then, the width in the width direction is maintained as it is, and the first heat setting zone (temperature: 200 ° C), the second heat setting zone (temperature: 225 ° C), and the third heat setting zone (temperature) are continuously passed in this order. : 230 ° C), 4th heat setting zone (temperature: 230 ° C), 5th heat setting zone (temperature: 210 ° C), 6th heat setting zone (temperature: 170 ° C), 7th heat setting zone (Temperature: 120 ° C). Further, 3% relaxation treatment was performed in the width direction in the sixth heat setting zone. Next, the uncoated portions at both ends of the film were trimmed, wound around a winding device, and then cut into 4 equal portions in the width direction to obtain an adhesive change of a width of 100 mm, a film length of 1000 m, and a film thickness of 125 μm. A roll of polyester film. Furthermore, the wind speed of the hot air in the heat setting zone is 15 m/sec, the passage time is 4.5 seconds in each zone, the nozzle spacing of the hot air is 3 50 mm, and the number of nozzles per zone is 8). The physical properties and characteristics of the adhesive-modified substrate film are shown. Further, in Table 5, in the longitudinal direction and the width direction of the obtained roll of the adhesive modified polyester film, the area ratio of the polyester phase on the surface of the adhesive modified layer was the maximum 値, minimum 値, and fog. The maximum 値 and minimum 度, the maximum 値 and minimum 密 of the hard coating. Moreover, regarding the anti-blocking property, it is 〇 at all measurement points. (3) Production of Hard Coating Film Next, a hard coating layer C containing inorganic fine particles in one area layer is obtained on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film by the following method. Hard coated film. As a coating liquid for forming a hard coating layer, an organic/inorganic hybrid hard coating agent having an ultraviolet curable acrylate monomer, zirconia ultrafine particles, and methyl ethyl ketone as a main component -100 to 1360477 minutes is prepared ( Desolite Z7410B manufactured by JSR Co., Ltd.; solid content concentration: 50% by mass). The hard coating agent was applied onto the surface of the adhesive modified layer of the adhesive modified base film so as to have a dry thickness of 8 μm, and dried at 40 ° C for 1 minute. Next, a high-pressure mercury lamp was irradiated with ultraviolet rays under conditions of 1 〇〇〇mJ/cm 2 to cure the resin to form a hard coating layer C.

於所得到的硬被覆層中，平均粒徑l〇nm的氧化锆超微 粒子之含量，對於1〇〇質量份的丙烯酸酯樹脂而言’係31 質量份。 (實施例2) 除了於實施例1中，作爲塗布液用的界面活性劑，使 用與實施例1同樣的方法所前處理的氟系陽離子型界面活 性劑（NEOS公司製Ftergent 3 10)的10質量％水溶液，變更 爲塗布液B以外，藉由與實施例1同樣的方法，得到接著 性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例3) 除了於實施例1的熱定型處理步驟中，將各熱定型區 的溫度設定爲第1熱定型區係190 °C，第2熱定型區係 20 5 °C，第3熱定型區係220 °C，第4熱定型區係220 °C以 外，藉由與實施例1同樣的方法，得到接著性改質聚酯薄In the obtained hard coating layer, the content of the zirconia ultrafine particles having an average particle diameter of 10 nm was 31 parts by mass for 1 part by mass of the acrylate resin. (Example 2) In the first embodiment, as the surfactant for the coating liquid, a fluorine-based cationic surfactant (Ftergent 3 10 manufactured by NEOS Co., Ltd.) pretreated in the same manner as in Example 1 was used. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the mass % aqueous solution was changed to the coating liquid B. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 3) In the heat setting treatment step of Example 1, the temperature of each heat setting zone was set to 190 ° C in the first heat setting zone, and the second heat setting zone was 20 5 ° C, the third heat. By the same method as in Example 1 except that the setting zone was 220 ° C and the fourth heat setting zone was 220 ° C, the adhesive modified polyester was obtained.

-101- < S ) 1360477 其次’於上述接著性改質基材薄膜的接著性改質層B 之表面上’與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例4) 除了於實施例1中’將塗布液中的共聚合聚酯與聚胺 甲酸酯的質量比變更爲60/4 0，變更爲下述的塗布液c以 外，藉由與實施例1同樣的方法，得到接著性改質聚酯薄 膜。-101- <S) 1360477 Next, 'on the surface of the adhesion-modifying layer B of the above-mentioned adhesive-modified base film', in the same manner as in Example 1, the hard coating layer C containing inorganic fine particles in one area layer, To obtain a hard coated film. (Example 4) In the same manner as in the first embodiment, the mass ratio of the copolymerized polyester to the polyurethane in the coating liquid was changed to 60/40, and the coating liquid c was changed to the following coating liquid c. In the same manner as in Example 1, an adhesive modified polyester film was obtained.

(塗布液C的調配） 將9.0質量份的實施例1所用的共聚合聚酯（A)之30質 量％水分散液、9.0質量份的實施例1所用的聚胺甲酸酯（B) 之2Ό質量％水溶液、0.3質量份的ELASTRON用觸媒（第 一工業製藥製Cat64)、40.6質量份的水、及37,3質量份的 異丙醇分別混合。再者，添加0.6質量份的實施例1所使 用的界面活性劑水溶液、2.3質量份當作粒子A的膠態矽 石（日產化學工業製S no wt ex OL;平均粒徑40 nm)之20質 量％水分散液、〇.5質量份當作粒子B的乾式法矽石（日本 Arosil製 Arosil 0X50;平均粒徑200nm，平均一次粒徑 40nm)之3.5質量％水分散液，用5質量％的碳酸氫鈉水溶 液粒子來調整pH，依順序使通過過濾性能5μιη和Ιμηι的 過濾器，而成爲塗布液C。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作’在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 -102 - 1360477 (實施例5) 除了於實施例1中’將塗布液中的共聚合聚酯與聚胺 甲酸酯的質量比變更爲40/60 ’變更爲下述的塗布液D以 外，藉由與實施例1同樣方法’得到接著性改質聚酯薄膜 (塗布液D的調配）(Preparation of Coating Liquid C) 9.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and 9.0 parts by mass of the polyurethane (B) used in Example 1 2% by mass aqueous solution, 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 40.6 parts by mass of water, and 37,3 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of the aqueous surfactant solution used in Example 1 and 2.3 parts by mass of colloidal vermiculite (Sno wt ex OL manufactured by Nissan Chemical Industries; average particle diameter 40 nm) of 20 parts by mass were added. 5% by mass aqueous dispersion, 5% by mass of dry-type vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) of 3.5% by mass aqueous dispersion, 5% by mass The sodium hydrogencarbonate aqueous solution particles were used to adjust the pH, and the filter having a filtration performance of 5 μm and Ιμηι was passed in order to form a coating liquid C. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was formed in the same manner as in Example 1 to obtain a hard coating film. -102 - 1360477 (Example 5) In addition to the coating liquid D described below, the mass ratio of the copolymerized polyester to the polyurethane in the coating liquid was changed to 40/60' in the first embodiment, An adhesive modified polyester film (formulation of coating liquid D) was obtained by the same method as in Example 1.

將6.0質量份的實施例1所用的共聚合聚酯（A)之30質 量％水分散液、1 3 · 5質量份的實施例1所用的聚胺甲酸酯 (B)之20質量％水溶液、0.3質量份的ELASTRON用觸媒（ 第一工業製藥製Cat64)、38.9質量份的水、及37.5質量份 的異丙醇分別混合。再者’添加〇 · 6質量份的實施例1所 用的界面活性劑之1〇質量％水溶液、2.3質量份當作粒子 A的膠態矽石（日產化學工業製Snowtex OL :平均粒徑 4 0nm)之20質量％水分散液、0.5質量份當作粒子B的乾 式法矽石（日本 Arosil製 Arosil 0X50;平均粒徑200nm, 平均一次粒徑40nm)之3.5質量％水分散液，用5質量％碳 酸氫鈉水溶液將pH調整至6.2，依順序使通過過濾性能 5μηι和Ιμιη的過爐器，而成爲塗布液D» 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例6) 除了於實施例1中，使塗布量成爲最終的固體成分量 係0.12g/m2以外，藉由與實施例1同樣的方法，得到接著 -103- 1360477 性改質聚酯薄膜。 其次’於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例7) 除了於實施例1中，將塗布液中的界面活性劑之配合 量變更爲〇.〇3質量％，及使用下述的塗布液E以外，藉由 與實施例1同樣的方法，得到接著性改質聚酯薄膜。6.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and 13.5% by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1. 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 38.9 parts by mass of water, and 37.5 parts by mass of isopropyl alcohol were separately mixed. In addition, 6 parts by mass of the 1% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of the colloidal vermiculite as the particle A (Nissan Chemical Industry, Snowtex OL: average particle diameter 40 nm) 20% by mass aqueous dispersion, 0.5 parts by mass of dry vermiculite as a particle B (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm), 3.5 mass% aqueous dispersion, with 5 masses The sodium hydrogencarbonate aqueous solution was adjusted to a pH of 6.2, and passed through a furnace having a filtration performance of 5 μm and Ιμηη in order to form a coating liquid D», followed by an adhesion-modified layer of the above-mentioned adhesive modified base film. On the surface, in the same manner as in Example 1, a hard coating layer C containing inorganic fine particles in one area layer was obtained to obtain a hard coating film. (Example 6) A modified polyester film of -103-1360477 was obtained in the same manner as in Example 1 except that the coating amount was changed to a final solid content of 0.12 g/m2. . Next, on the surface of the adhesion-modifying layer B of the above-mentioned adhesive-modified base film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 7) In the same manner as in Example 1, except that the amount of the surfactant in the coating liquid was changed to 3% by mass, and the coating liquid E described below was used. In the method, an adhesive modified polyester film was obtained.

(塗布液E的調配） 於實施例1的塗布液之調配中，將氟系非離子型界面 活性劑（大日本油墨化學工業製Megafac F142D)的10質量 %水溶液變更爲0.3質量份，將水變更爲38.2質量份，及 將異丙醇變更爲39.3質量份。 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例8) 除了於實施例1中，將塗布液中的界面活性劑之配合 量變更爲〇.1〇質量％，及使用下述的塗布液F以外，藉由 與實施例1同樣的方法，得到接著性改質聚酯薄膜。 (塗布液F的調配） 於實施例1的塗布液之調配中，將氟系非離子型界面 活性劑（大日本油墨化學工業製Megafac F142D)的10質量 %水溶液變更爲1.0質量份，將水變更爲37.5質量份，及 -104- 1360477 異丙醇變更爲39.3質量份。 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例9)(Preparation of the coating liquid E) In the preparation of the coating liquid of the first embodiment, a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 0.3 parts by mass, and water was added. It was changed to 38.2 parts by mass, and isopropyl alcohol was changed to 39.3 parts by mass. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 8) In the same manner as in Example 1, except that the amount of the surfactant in the coating liquid was changed to 0.1% by mass, and the coating liquid F described below was used. In the method, an adhesive modified polyester film was obtained. (Preparation of the coating liquid F) In the preparation of the coating liquid of the first embodiment, a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 1.0 part by mass, and water was added. Changed to 37.5 parts by mass, and -104-1360477 isopropyl alcohol was changed to 39.3 parts by mass. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 9)

除了於實施例1中，將從塗布起到乾燥爐入口爲止的 薄膜通過時間變更爲0.7秒間，將乾燥時間變更爲0.8秒 ，以及將熱定型處理步驟中各區的通過時間變更爲3.5秒 ，將薄膜厚度變更爲ΙΟΟμιη以外，藉由實施例1同樣的方 法，得到接著性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例10) 除了於實施例1中，將從塗布起到乾燥爐入口爲止的 薄膜通過時間變更爲1 · 〇秒間，將乾燥時間變更爲1 . 9秒 ，以及將熱定型處理步驟中各區的通過時間變更爲6.6秒 ，將薄膜厚度變更爲188μιη以外，藉由與實施例1同樣的 方法，得到接著性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例1 1) 除了於實施例1中，用5質量％的碳酸鈉水溶液將塗布 -105 - 1360477 液的pH調整至7·9,變更爲塗布液G以外，藉由與實施例 1同樣的方法，得到接著性改質聚酯薄膜。 其次’於上述接著性改質基材薄膜的接著性改質層B 之表面上’與實施例1同樣地作’在一面積層含有無機微 粒子的硬.被覆層C，以得到硬被覆薄膜。 (實施例12)In addition to the first embodiment, the film passage time from the application to the drying furnace inlet was changed to 0.7 seconds, the drying time was changed to 0.8 seconds, and the passage time of each zone in the heat setting treatment step was changed to 3.5 seconds. An adhesive modified polyester film was obtained by the same method as in Example 1 except that the film thickness was changed to ΙΟΟμηη. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 10) In the first embodiment, the film passage time from the application to the drying furnace inlet was changed to 1 · 〇 second, the drying time was changed to 1.9 seconds, and each of the heat setting treatment steps was performed. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the film passage time was changed to 6.6 seconds and the film thickness was changed to 188 μm. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 1 1) In the same manner as in Example 1, except that the pH of the coating -105 - 1360477 solution was adjusted to 7.9 by using a 5% by mass aqueous solution of sodium carbonate, and changed to the coating liquid G. The method of obtaining an adhesive modified polyester film. Then, the hard coating layer C containing inorganic fine particles in one area layer was formed in the same manner as in Example 1 to obtain a hard coating film on the surface of the adhesion-modifying layer B of the adhesive-modified base film. (Embodiment 12)

除了於實施例1中’於一軸配向聚酯薄膜的兩面上塗 布接著性改質層B以外，藉由與實施例丨同樣的方法，得 到接著性改質聚酯薄膜。而且，從對薄膜的塗布起到乾燥 爐入口爲止的薄膜通過時間，在一面係0.8秒，在相反面 係1.0秒》 於上述接著性改質基材薄膜上，隔著接著性改質層B， 在兩面積層硬被覆層C，以得到硬被覆薄膜。而且，硬被 覆層c的形成方法係如下。 於上述接著性改質基材薄膜的接著性改質層B之一表 面上’將實施例1所使用之含無機粒子的硬被覆劑，以硬 化後的膜厚成爲3μιη的方式，用美亞桿來塗布，在40 °C 使乾燥60秒。再者，照射3 00mJ/cm2的紫外線，使樹脂硬 化，在一面形成硬被覆層C。 其次’在其相反面的接著性改質層B之表面上，亦將 與上述同樣的硬被覆劑，以硬化後的膜厚成爲3 μιη的方式 ，以美亞桿來塗布，在401使乾燥60秒。再者，照射 500mJ/cm2的紫外線，使樹脂硬化，而在另—面亦形成硬 被覆層C。 -106- 1360477 (實施例13) 除了於實施例1中，使用不進行界面活性劑的前處理 之塗布液Η以外，藉由與實施例1同樣的方法，得到接著 性改質聚酯薄膜。 於所得到的接著性改質聚酯薄膜之接著性改質層的表 面中，掃描型探針顯微鏡（SPM)的聚酯相與聚胺甲酸酯相 之相分離構造，雖然可辨別，但是稍微不明確。An adhesive modified polyester film was obtained in the same manner as in Example 除了 except that the adhesive modified layer B was applied to both surfaces of the one-axis alignment polyester film in Example 1. Further, the film passage time from the application of the film to the entrance of the drying furnace was performed for 0.8 seconds on one side and 1.0 second on the opposite side, on the adhesive-modified substrate film, via the adhesive modification layer B. The hard coating layer C is applied to the two-layer layer to obtain a hard coating film. Further, the method of forming the hard coating layer c is as follows. On the surface of one of the adhesive modifying layers B of the adhesive-modified substrate film, the inorganic coating-containing hard coating agent used in Example 1 was used to have a film thickness of 3 μm after curing. To coat, dry at 40 °C for 60 seconds. Further, ultraviolet rays of 300 mJ/cm2 were irradiated to harden the resin, and a hard coating layer C was formed on one surface. Next, on the surface of the adhesive layer B on the opposite side, the same hard coating agent as described above was coated with a meyer bar so that the film thickness after hardening was 3 μm, and dried at 401. second. Further, ultraviolet rays of 500 mJ/cm2 were irradiated to harden the resin, and a hard coating layer C was formed on the other surface. -106- 1360477 (Example 13) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that in Example 1, a coating liquid which was not subjected to the pretreatment of the surfactant. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase of the scanning probe microscope (SPM) and the polyurethane phase is discernible, although it is discernable. Slightly unclear.

其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，藉由與實施例1同樣地作，在一面積層含有無 機微粒子的硬被覆層C，以得到硬被覆薄膜。 於所得到的硬被覆薄膜的切削面之接著性改質層Β中 ，聚酯相與聚胺甲酸酯相的相分離構造亦與上述同樣地， 稍微不明確。 (實施例14) 除了於實施例1中，將塗布液的分散介質（水/ΙΡΑ)之質 量比變更爲50/50，使用下述塗布液I以外’藉由與實施 例1同樣的方法，得到接著性改質聚酯薄膜。 (塗布液I的調配） 於實施例1的塗布液之調配中，將7_5質量份的實施例 i所用的共聚合聚酯之30質量％水分散液、11.3質量份的 實施例1所用的聚胺甲酸酯之20質量％水溶液、0.3質量 份的ELASTRON用觸媒（第一工業製藥製Cat64)、30.4質 量份的水、及46.8質量份的異丙醇分別混合。再者’添加 0.6質量份的實施例1所用的界面活性劑之1〇質量％水溶 < S ) -107- 1360477 液' 2.3質量份當作粒子A的膠態矽石（日產化學工業製 Snowtex OL;平均粒徑40nm)之20質量％水分散液、0.5 質量份當作粒子 B的乾式法矽石（日本 Arosil製 Arosil 0X50;平均粒徑200nm，平均一次粒徑40nm)之3.5質量 %水分散液。接著，用5質量％碳酸氫鈉水溶液將pH調整 至6.2，依順序使通過過濾性能5μπι和Ιμιη的過濾器，而 成爲塗布液I 。Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. In the adhesion modifying layer of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase is also slightly unclear as described above. (Example 14) In the same manner as in Example 1, except that the mass ratio of the dispersion medium (water/enthalpy) of the coating liquid was changed to 50/50 in the first embodiment, the same method as in Example 1 was used. An adhesive modified polyester film was obtained. (Preparation of Coating Liquid I) In the preparation of the coating liquid of Example 1, 7 to 5 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester used in Example i, and 11.3 parts by mass of the polymerization used in Example 1 were used. A 20% by mass aqueous solution of urethane, 0.3 parts by mass of a catalyst for ELASTRON (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 30.4 parts by mass of water, and 46.8 parts by mass of isopropyl alcohol were separately mixed. Further, '0.6 parts by mass of the surfactant used in Example 1 was added, and 1% by mass of water-soluble <S) -107-1360477 liquid '2.3 parts by mass of colloidal vermiculite as particle A (Snowtex manufactured by Nissan Chemical Industry Co., Ltd.) 20% by mass aqueous dispersion of OL; average particle diameter: 40 nm), and 0.5 mass% of water of dry-type vermiculite (Arosil 0X50, manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) as particles B Dispersions. Subsequently, the pH was adjusted to 6.2 with a 5 mass% aqueous sodium hydrogencarbonate solution, and a filter having a filtration performance of 5 μm and Ιμηη was passed in order to obtain a coating liquid I.

其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例15) 除了於實施例1中，以醋酸將塗布液的pH變更爲4.6 ，使用塗布液J以外，藉由與實施例1同樣的方法，得到 厚度爲125μιη的接著性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例16) 除了於實施例1中，將聚胺甲酸酯（Β)變更爲下述的聚 胺甲酸酯，使用塗布液Κ以外，與實施例1同樣地作，得 到接著性改質聚酯薄膜。聚胺甲酸酯係藉由下述方法來獲 得。 (聚胺甲酸酯的調製） 混合93質量份的由己二酸//1,6-己二醇/新戊二醇（莫耳 • 10 8- 1360477 比：4//3/2)的組成所成聚酯二醇（〇HV; lll.Seq/ton，AV: l.leq/t ο η)、22質量份的苯二甲基二異氰酸酯，在氮氣流 下，使在95〜100 °C反應1小時’得到胺甲酸酯預聚物 (NCO/OH比：1.50，游離異氰酸基：理論値3.29質量％， 實測値3_16質量％)。Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 15) An adhesive modified polyester having a thickness of 125 μm was obtained by the same method as in Example 1 except that the pH of the coating liquid was changed to 4.6 with acetic acid in Example 1. film. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 16) In the same manner as in Example 1, except that the polyurethane was changed to the following polyurethane in Example 1, and the coating liquid was used, the adhesion was changed. Polyester film. Polyurethane is obtained by the following method. (Preparation of polyurethane) 93 parts by mass of adipic acid//1,6-hexanediol/neopentyl glycol (mole • 10 8- 1360477 ratio: 4//3/2) The resulting polyester diol (〇HV; lll.Seq/ton, AV: l.leq/t ο η), 22 parts by mass of phenyldimethyl diisocyanate, reacted at 95 to 100 ° C under a nitrogen stream The urethane prepolymer was obtained in 1 hour (NCO/OH ratio: 1.50, free isocyanate group: theoretical 値 3.29 mass%, measured 値 3-16 mass%).

將所得到的胺甲酸酯預聚物冷卻到60 °C爲止，添加4.5 質量份的甲乙酮肟，使在6 0 °C反應50分鐘’得到含有1.3 質量％的游離異氰酸酯且部分封閉化的胺甲酸酯預聚物。 接著，將上述胺甲酸酯預聚物冷卻到55 °C爲止’添加9質 量份的異丙醇與140質量份的甲醇所成的混合溶劑’使均 勻混合。接著，添加9.3質量份的50質量％之亞硫酸氫鈉 水溶液及5.4質量份的N-甲基牛磺酸的30質量％水溶液， 進行激烈攪拌。約30分後開始出現水溶性，2小時後，游 離的亞硫酸氫鈉成爲大致約零，反應結束。於其中加入水 ，得到白濁且黏稠的20質量％水溶液。 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例1) (1)塗布液L的調配 .混合33.7質量份的對酞酸二甲酯、20.0質量份的異酞 酸二甲酯、9.1質量份的磺基二甲基異酞酸5·鈉、40.0質 量份的乙二醇、1〇_〇質量份的二乙二醇、0.049質量份的 醋酸鈣·1水鹽，在200〜230 °C進行酯交換直到理論量的 -109 - 1360477 甲醇蒸餾出爲止。接著，添加0.0 9質量份的正磷酸，於減 壓下在280°C聚合，得到共聚合聚酯。 混合192質量份的從烯丙醇出發的環氧乙烷之聚醚經 焦亞硫酸鈉所磺化的含磺酸基之聚醚（S03含量：8.3質量％， 聚環氧乙烷含量：83質量％)、1013質量份的聚四亞甲基 己二酸酯（數量平均分子量：2,250)、248質量份以雙酚A 開始的聚環氧丙烷聚醚（數量平均分子量：55 0)，在真空下 於l〇〇°C脫水》The obtained urethane prepolymer was cooled to 60 ° C, 4.5 parts by mass of methyl ethyl ketone oxime was added, and reacted at 60 ° C for 50 minutes to obtain an amine containing 1.3% by mass of free isocyanate and partially blocked. Formate prepolymer. Next, the above urethane prepolymer was cooled to 55 ° C, and a mixed solvent of 9 parts by mass of isopropyl alcohol and 140 parts by mass of methanol was added to uniformly mix. Next, 9.3 parts by mass of a 50% by mass aqueous sodium hydrogensulfite solution and 5.4 parts by mass of a 30% by mass aqueous solution of N-methyltaurine were added, followed by vigorous stirring. Water solubility began to occur after about 30 minutes, and after 2 hours, the free sodium hydrogen sulfite became approximately zero and the reaction was completed. Water was added thereto to obtain a white turbid and viscous 20% by mass aqueous solution. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 1) (1) Preparation of coating liquid L. Mixing 33.7 parts by mass of dimethyl perruthenate, 20.0 parts by mass of dimethyl isononanoate, and 9.1 parts by mass of sulfodimethylisodecanoic acid 5 · Sodium, 40.0 parts by mass of ethylene glycol, 1 part by mass of diethylene glycol, 0.049 parts by mass of calcium acetate · 1 water salt, transesterified at 200 to 230 ° C until the theoretical amount of -109 - 1360477 Methanol is distilled off. Next, 0.09 parts by mass of orthophosphoric acid was added and polymerized at 280 ° C under reduced pressure to obtain a copolymerized polyester. Mixing 192 parts by mass of a polyether of ethylene oxide derived from allyl alcohol with a sulfonic acid group-containing polyether sulfonated with sodium metabisulfite (S03 content: 8.3% by mass, polyethylene oxide content: 83% by mass) ), 1013 parts by mass of polytetramethylene adipate (number average molecular weight: 2,250), 248 parts by mass of polypropylene oxide polyether (number average molecular weight: 55 0) starting from bisphenol A, under vacuum Dehydration at l〇〇°C

使該混合物成爲7〇°C，於其中加入178質量份的異佛 爾酮二異氰酸酯與244份的六亞甲基·1，6-二異氰酸酯之混 合物，接著在8CTC至90°C的範圍內攪拌生成混合物直到 異氰酸酯含量成爲5.6質量％。將此預聚物冷卻到60 °C， 依順序添加56質量份的由3莫耳的六亞甲基二異氰酸酯 與1莫耳的水所得到的縮二脲聚異氰酸酯及175質量份由 異佛爾酮二胺與丙酮所得到的雙克米胺，得到聚胺甲酸酯 水分散液。 將上述共聚合聚酯及聚胺甲酸酯水分散液各以固體成 分計成20質量份、80質量份地配合，調製固體成分濃度 10質量％的水分散液，當作塗布液L。而且，於塗布液中 ’不配合粒子及界面活性劑。 (2)接著性改質基材薄膜的製造 對於作爲原料聚合物之不含有粒子的固有黏度爲 〇.66dl/g的聚對酞酸乙二酯樹脂九粒，在135〇c作6小時 減壓乾燥（ITorr)後，供應給擠壓機，在約285 T：熔融擠出 -110- 1360477 成片狀，於表面溫度保持60°C的金屬輥上驟冷固化，得到 流延薄膜。此時，作爲與實施例1同樣之用於去除熔融樹 脂的雜質之濾材，使用過濾粒子尺寸（初期過濾效率：95%) 爲15 μηι的不銹鋼製燒結濾材。The mixture was brought to 7 ° C, and a mixture of 178 parts by mass of isophorone diisocyanate and 244 parts of hexamethylene·1,6-diisocyanate was added thereto, followed by 8 CTC to 90 ° C. The mixture was stirred to give an isocyanate content of 5.6% by mass. The prepolymer was cooled to 60 ° C, and 56 parts by mass of a biuret polyisocyanate obtained from 3 mol of hexamethylene diisocyanate and 1 mol of water and 175 parts by weight of a different Buddha were sequentially added. The bis-maleamine obtained from ketone diamine and acetone gives a polyurethane aqueous dispersion. Each of the above-mentioned copolymerized polyester and polyurethane aqueous dispersion was blended in an amount of 20 parts by mass and 80 parts by mass in terms of a solid content, and an aqueous dispersion having a solid concentration of 10% by mass was prepared to obtain a coating liquid L. Further, the particles and the surfactant were not blended in the coating liquid. (2) Production of adhesively modified base film: For the raw material polymer, the intrinsic viscosity of the raw material polymer was 〇.66 dl/g of polyethylene terephthalate resin, which was not contained in the raw material polymer, and was reduced at 135 〇c for 6 hours. After press drying (ITorr), it was supplied to an extruder at a temperature of about 285 T: melt extrusion -110 - 1360477, and was rapidly solidified on a metal roll having a surface temperature of 60 ° C to obtain a cast film. In this case, a stainless steel sintered filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used as the filter medium for removing impurities of the molten resin in the same manner as in the first embodiment.

接著，以經加熱的輥群及紅外線加熱器，將該流延薄 膜加熱到95°C，然後藉由具有周速差的輥群在長度方向中 拉伸3.5倍，得到一軸配向PET薄膜。接著，以過濾粒子 尺寸（初期過濾效率：95%) ΙΟμιη的氈型聚丙烯製濾材對上 述塗布液L進行精密過濾，藉由逆輥法塗布在一軸配向 PET薄膜的一面上。接著，以夾具來抓住薄膜的端部，導 入經加熱到110 °C的熱風區中，使乾燥後，在寬度方向中 拉伸3.5倍。此時拉幅機內的風速係15m/秒，乾燥時間係 2〇秒。從薄膜塗布起到拉幅機入口爲止的時間係10.0秒 。又，塗布量係使最終的固體成分量成爲0.15 g/m2。 接著，將寬度方向經拉伸的薄膜之寬度保持原狀，依 順序連續通過第1熱定型區（2 0 0°C )、第2熱定型區（205 °C ) 、第3熱定型區及第4熱定型區（210 °C)、第5熱定型區 (215°C)、第6熱定型區（220°C)、第7熱定型區（170°C)。 再者，於第7熱定型區中在寬度方向進行3 %的鬆弛處理後 ，修剪薄膜兩端部沒有被塗覆的部分，得到厚度125 μιη的 接著性改質聚酯薄膜。又，熱定型區中的熱風之風速皆是 15m/秒，通過時間在各區皆是4.5秒，吹出熱風的噴嘴間 隔係700mm間隔，每1區的噴嘴個數係4個。 於所得到的接著性改質聚酯薄膜的接著性改質層之表 -111- 1360477 面中，共聚合聚酯與聚胺甲酸酯的相分離構造係不明確。 (3)硬被覆薄膜的製造 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例2) (1) 塗布液Μ的調配Next, the cast film was heated to 95 °C by a heated roll group and an infrared heater, and then stretched by 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis aligned PET film. Then, the coating liquid L was finely filtered by a felt-type polypropylene filter material having a particle size of filtration (initial filtration efficiency: 95%) ,μηη, and coated on one surface of the one-axis alignment PET film by a reverse roll method. Next, the end portion of the film was grasped with a jig, and introduced into a hot air region heated to 110 ° C to be stretched 3.5 times in the width direction after drying. At this time, the wind speed in the tenter is 15 m/sec, and the drying time is 2 sec. The time from the application of the film to the entrance of the tenter was 10.0 seconds. Further, the coating amount was such that the final solid content was 0.15 g/m2. Next, the width of the film stretched in the width direction is maintained as it is, and sequentially passes through the first heat setting zone (200 ° C), the second heat setting zone (205 ° C), the third heat setting zone, and the 4 heat setting zone (210 °C), 5th heat setting zone (215 °C), 6th heat setting zone (220 °C), 7th heat setting zone (170 °C). Further, after 3% relaxation treatment in the width direction in the seventh heat setting zone, the uncoated portions at both end portions of the film were trimmed to obtain a subsequent modified polyester film having a thickness of 125 μm. Further, the wind speed of the hot air in the heat setting zone was 15 m/sec, the passage time was 4.5 seconds in each zone, and the nozzle interval of the hot air was 700 mm, and the number of nozzles per zone was four. The phase separation structure of the copolymerized polyester and the polyurethane is not clear in the surface of the adhesive modified layer of the obtained adhesive modified polyester film -111-1360477. (3) Production of Hard Coating Film Next, on the surface of the adhesion-modified layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer is formed in the same manner as in Example 1. To obtain a hard coated film. (Comparative Example 2) (1) Preparation of coating liquid helium

將3.0質量份的實施例1所用的共聚合聚酯（Α)的30質 量％水分散液、18.0質量份的實施例1所用的聚胺甲酸酯 (Β)之20質量％水溶液、〇_3質量份ELASTRON用觸媒（第 一工業製藥製Cat6 4)、70.7質量份的水、及4.7質量份的 異丙醇分別混合。再者，添加0.6質量份當作界面活性劑 的十二基苯磺酸之10質量％水溶液、2.3質量份當作粒子 A的膠態较石（日產化學工業製 Snowtex OL;平均粒徑 40nm)之20質量％水分散液、0.5質量份當作粒子B的乾 式法矽石（日本 Arosil製 Arosil 0X50;平均粒徑 200nm， 平均一次粒徑40nrn)之3.5質量％水分散液，以成爲塗布液 Μ。塗布液Μ的pH由於沒有進行pH調整，故係4.8。 (2) 接著性改質基材薄膜的製造 對於作爲原料聚合物之不含有實施例1所用的粒子之 固有黏度爲〇.62dl/g的聚對酞酸乙二醋樹脂九粒，在135 °(：作ό小時減壓乾燥（iTorr)後，供應給擠壓機，在約285 °C熔融擠出成片狀，於表面溫度保持20t的金屬輥上驟冷 固化’得到流延薄膜。此時，作爲用於去除熔融樹脂的雜3.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, 18.0 parts by mass of a 20% by mass aqueous solution of the polyurethane used in Example 1, 〇_ 3 parts by mass of ELASTRON were mixed with a catalyst (Cat6 4 manufactured by Daiichi Kogyo Co., Ltd.), 70.7 parts by mass of water, and 4.7 parts by mass of isopropyl alcohol. Further, 0.6 parts by mass of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid as a surfactant and 2.3 parts by mass of a colloidal stone as a particle A (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) were added. 20% by mass aqueous dispersion, 0.5 parts by mass of dry-type vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nrn) as a particle B, and a 3.5% by mass aqueous dispersion to form a coating liquid Hey. The pH of the coating liquid was 4.8 because the pH was not adjusted. (2) Production of a Substituted Modified Substrate Film For a raw material polymer, the particles having the intrinsic viscosity of 62.62 dl/g which does not contain the particles used in Example 1 are nine pieces of polyethylene terephthalate resin at 135 °. (: After drying under reduced pressure (iTorr), it was supplied to an extruder, melt extruded into a sheet at about 285 ° C, and rapidly solidified on a metal roll having a surface temperature of 20 t to obtain a cast film. When used as a mist for removing molten resin

1360477 質之濾材，使用過濾粒子尺寸（初期過效 15 μιη的不銹鋼製燒結濾材。 以經加熱的輥群及紅外線加熱器，將 膜加熱到95°C，然後藉由具有周速差的輥 拉伸3.5倍，得到一軸配向PET薄膜。接 尺寸（初期過濾效率：95%)10μιη的氈型聚 述塗布液Μ進行精密過濾，藉由逆輥法 PET薄膜的一面上。 接著，邊以夾具抓住薄膜的端部，邊3 °C的熱風區中，使塗布面乾燥後，在寬度 倍。此時拉幅機內的風速係15m/秒，乾燥 從塗布起到拉幅機入口爲止的時間係10.0 係使最終的固體成分量成爲〇.l〇g/m2。再 處理步驟中的溫度而言，第1熱定型區係 定型區係210°C，第3熱定型區係220°C 係22 5 °C，第5熱定型區係23 0 °C，第6聚 ，第7熱定型區係240 °C，而且寬度方向 處理，以外係藉由與比較例1同樣的方法 爲125 μιη的接著性改質聚酯薄膜。 於所得到的接著性改質聚酯薄膜的接 面中，不能觀察聚酯相與聚胺甲酸酯相的^ (3)硬被覆薄膜的製造 接著，於上述接著性改質基材薄膜的 之表面上，與實施例1同樣地作，在一面 -113- |效率：95%)爲 所得到的流延薄 群在長度方向中 著，以過濾粒子 丙烯製濾材對上 塗布在一軸配向 寥入經加熱到80 方向中拉伸4.0 時間係2 0秒。 秒。又，塗布量 者，就各熱定型 2〇〇°C，第 2 熱 ，第4熱定型區 i定型區係23 5 °C 係沒有進行鬆弛 ，得到薄膜厚度 著性改質層之表 泪分離構造。 接著性改質層B 積層含有無機微 (S ) 1360477 粒子的硬被覆層c’以得到硬被覆薄膜。 於所得到的硬被覆薄膜之切削面的接著性改質層B中 ，聚酯相與聚胺甲酸酯相的相分離構造亦與上述同樣地不 能觀察》 (比較例3) (1) 塗布液N的調配1360477 Quality filter material, using filter particle size (initial effect of 15 μιη stainless steel sintered filter material. With heated roller group and infrared heater, the film is heated to 95 ° C, and then pulled by a roller with a peripheral speed difference The film was stretched 3.5 times to obtain a one-axis oriented PET film. The size (initial filtration efficiency: 95%) 10 μm of the felt-type coating liquid was precisely filtered by the reverse roll method on one side of the PET film. At the end of the film, in the hot air zone at 3 °C, the coated surface is dried and then multiplied by the width. At this time, the wind speed in the tenter is 15 m/sec, and the time from drying to the tenter entrance is dried. Line 10.0 is such that the final solid content is 〇.l〇g/m2. The temperature in the reprocessing step is 210 ° C for the first heat-set zone and 220 ° C for the third heat-set zone. 22 5 °C, the 5th heat-set zone is 23 0 °C, the 6th heat, the 7th heat-set zone is 240 °C, and the width direction is treated, and the other method is 125 μm by the same method as Comparative Example 1. Subsequent modification of the polyester film. The obtained adhesive modified polyester film In the joint, the production of the (3) hard coating film in which the polyester phase and the polyurethane phase were not observed was carried out in the same manner as in Example 1 on the surface of the above-mentioned adhesive modified base film. On one side -113- | efficiency: 95%), the obtained cast thin group is in the longitudinal direction, and the filter particle propylene filter material is coated on the upper side, and the upper side is twisted in the direction of heating to 80. 20 seconds. second. In addition, in the case of the coating amount, the heat is set at 2 ° C, the second heat, and the fourth heat-set region i is defined in the 23 ° C system without relaxation, and the tear separation of the film thickness-changing layer is obtained. structure. Next, the modified layer B was laminated to contain a hard coating layer c' of inorganic micro (S) 1360477 particles to obtain a hard coating film. In the adhesion-modified layer B of the cut surface of the obtained hard-coated film, the phase separation structure of the polyester phase and the polyurethane phase was also observed in the same manner as described above (Comparative Example 3) (1) Coating Liquid N blending

將7.5質量份的實施例1所用的共聚合聚酯（A)之30質 量％水分散液、11.3質量份的實施例1所用的聚胺甲酸酯 (B)之20質量％水溶液、0.3質量份的ELASTRON用觸媒（ 第一工業製藥製Cat6 4)、40.5質量份的水及39.5質量份的 異丙醇分別混合。再者，添加0.6質量份的未經前處理的 氟系非離子界面活性劑（大日本油墨化學工業製Megafac F142D)之10質量％水溶液，不使用粒子B，添加0.03質 量份當作粒子 A的凝聚體矽石（富士 SILYSIA化學製 Sylysia —3 10;平均粒徑1.4μιη)之3.5質量％水分散液，以 成爲塗布液Ν。而且，不進行塗布液Ν的pH調整》塗布 液N的pH係4.6» (2) 接著性改質基材薄膜的製造 將對於作爲原料聚合物之不含有實施例1所用的粒子 之固有黏度爲0.62dl/g的聚對酞酸乙二酯樹脂九粒供應給 擠壓機，在約285 °C熔融擠出成片狀，於表面溫度保持20 °C的金屬輥上驟冷固化，得到流延薄膜》此時，作爲用於 去除熔融樹脂的雜質之濾材，使用過濾粒子尺寸（初期過濾 效率：95%)爲15 μιη的不銹鋼製燒結濾材。 -114- 1360477 以經加熱的輥群及紅外線加熱器，將所得到的流延薄 膜加熱到95°C，然後藉由具有周速差的輥群在長度方向中 拉伸3.5倍，得到一軸配向PET薄膜。接著，以過濾粒子 尺寸（初期過濾效率：95%)10μιη的氈型聚丙烯製濾材對上 述塗布液L進行精密過濾，藉由逆輥法塗布在一軸配向 PET薄膜的一面上。7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, 11.3 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat6 4 manufactured by Daiichi Kogyo Co., Ltd.), 40.5 parts by mass of water, and 39.5 parts by mass of isopropyl alcohol. Further, 0.6 parts by mass of a 10% by mass aqueous solution of a non-pretreated fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was added, and 0.03 parts by mass was added as the particle A without using the particle B. A 3.5% by mass aqueous dispersion of agglomerated vermiculite (Sylysia - 3 10; average particle size 1.4 μιη, manufactured by Fuji SILYSIA Chemical Co., Ltd.) was used as a coating liquid. Further, the pH of the coating liquid is not adjusted. The pH of the coating liquid N is 4.6» (2) The production of the subsequently modified base film is such that the intrinsic viscosity of the particles used as the raw material polymer in the first embodiment is The 0.62 dl/g polyethylene terephthalate resin was supplied to an extruder, melt extruded into a sheet at about 285 ° C, and quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C to obtain a stream. In the case of the filter material for removing impurities of the molten resin, a sintered filter material made of stainless steel having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used. -114- 1360477 The obtained cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis alignment PET film. Then, the coating liquid L was finely filtered with a filter medium having a filter particle size (initial filtration efficiency: 95%) of 10 μm, and coated on one surface of the one-side alignment PET film by a reverse roll method.

塗布後，導引至乾燥爐，在溫度120 °C乾燥3.2秒。又 ，塗布量係使最終的固體成分量成爲〇.〇8 g/m2。從塗布起 到拉幅機入口爲止，薄膜的通過時間係3.2秒，乾燥爐的 第1區之風速係15m/秒，第2區至第4區的風速，與實施 例1同樣地，使乾燥風的給氣風量在第1乾燥區至第4乾 燥區皆係7〇m3/秒，排氣風係從乾燥爐前後的自然排氣。After coating, it was guided to a drying oven and dried at a temperature of 120 ° C for 3.2 seconds. Further, the coating amount was such that the final solid content was 〇.〇8 g/m2. The film passage time was 3.2 seconds from the application to the tenter inlet, the wind speed of the first zone of the drying furnace was 15 m/sec, and the wind speeds of the second zone to the fourth zone were dried in the same manner as in Example 1. The air supply air volume of the wind is 7〇m3/sec in the first to fourth drying zones, and the exhaust air is naturally exhausted from the front and rear of the drying furnace.

接著，除了使橫拉伸倍率爲4.0倍以外，藉由與實施例 1同樣的方法作橫拉伸，藉由與比較例1同樣的方法來熱 定型，進行寬度方向的鬆弛處理，得到薄膜厚度爲125 μηι 的接著性改質聚酯薄膜。於所得到的接著性改質聚酯薄膜 的接著性改質層之表面中，聚酯相與聚胺甲酸酯相的相分 離構造係不能觀察。 (3)硬被覆薄膜的製造 接著，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 於所得到的硬被覆薄膜的切削面之接著性改質層Β中 ，聚酯相與聚胺甲酸酯相的相分離構造亦與上述同樣地不 -115- 1360477 能觀察。 (比較例4 ) 除了於實施例1中，使從塗布液A塗布在薄膜後到乾 燥爐入口爲止的薄膜通過時間成爲3.2秒以外，藉由與實 施例1同樣的方法，得到薄膜厚度爲125 μιη的接著性改質 聚酯薄膜。Then, the film was subjected to transverse stretching in the same manner as in Example 1 except that the transverse stretching ratio was 4.0 times, and the film was heat-set by the same method as in Comparative Example 1, and relaxed in the width direction to obtain a film thickness. It is an adhesive modified polyester film of 125 μηι. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not observed. (3) Production of Hard Coating Film Next, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer is formed in the same manner as in Example 1. To obtain a hard coated film. In the adhesion modifying layer of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase was also observed in the same manner as described above without using -115-1360477. (Comparative Example 4) In the same manner as in Example 1, except that the film passage time from the application of the coating liquid A to the entrance of the drying furnace was 3.2 seconds, the film thickness was 125. An adhesive modified polyester film of μιη.

其次’於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例5) 將3.0質量份的實施例1所用的共聚合聚酯（Α)之30質 量％水分散液、18.0質量份的實施例1所用的聚胺甲酸酯 (Β)之20質量％水溶液、〇.3質量份的ELASTRON用觸媒（ 第一工業製藥製Cat64)、37.3質量份的水、及37.8質量份 的異丙醇分別混合。再者，添加0.6質量份的實施例1所 用的界面活性劑之1 0.質量％水溶液、2.3質量份當作粒子 A的膠態矽石（日產化學工業製、SnowtexOL ;平均粒徑 4〇nm)之20質量％水分散液、0.5質量份當作粒子B的乾 式法矽石（日本 Arosil製 Arosil 0X50;平均粒徑 200nm， 平均一次粒徑40nm)之3.5質量％水分散液，用5質量％碳 酸氫鈉水溶液將pH調整至6.2，以成爲塗布液0。除了作 爲塗布液，使用上述塗布液Ο以外，藉由與實施例1同樣 的方法，得到薄膜厚度爲125 μιη的接著性改質聚酯薄膜。 接著，於上述接著性改質基材薄膜的接著性改質層Β (S ) -116- 1360477 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層c，以得到硬被覆薄膜。 (比較例6)Then, on the surface of the adhesive-modified layer Β of the above-mentioned adhesive-modified base film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 5) 3.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, and 18.0 parts by mass of a 20% by mass of the polyurethane used in Example 1 The % aqueous solution, 〇.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 37.3 parts by mass of water, and 37.8 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of the 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of colloidal vermiculite which is used as the particle A were added (Nissan Chemical Industry, Snowtex OL; average particle diameter 4 〇 nm) 20% by mass aqueous dispersion, 0.5 parts by mass of dry vermiculite as a particle B (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm), 3.5 mass% aqueous dispersion, with 5 masses The sodium hydrogencarbonate aqueous solution was adjusted to pH 6.2 to become a coating liquid 0. An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the coating liquid was used as the coating liquid. Next, on the surface of the adhesive modified layer S(S)-116-1360477 of the adhesive-modified base film, in the same manner as in Example 1, the hard coating layer c containing inorganic fine particles in one area layer was used. A hard coated film was obtained. (Comparative Example 6)

將12.0質量份的實施例1所用的共聚合聚酯（A)之30 質量％水分散液、4.5質量份之實施例1所用的聚胺甲酸酯 (B)之20質量％水溶液、0.3質量份的ELASTRON用觸媒（ 第一工業製藥製Cat6 4)、42.3質量份的水及37.2質量份的 異丙醇分別混合，再添加0.6質量份的實施例1所用的界 面活性劑之10質量％水溶液、2.3質量份當作粒子A的膠 態矽石（日產化學工業製、SnowtexOL;平均粒徑4 0nm)之 20質量％水分散.液、0.5質量份當作粒子B的乾式法矽石（ 日本 Arosil製 Arosil 0X50 ;平均粒徑200nm，平均一次 粒徑4〇nm)之3.5質量％水分散液，用5質量％碳酸氫鈉水 溶液將pH調整至6.2，以成爲塗布液P。除了作爲塗布液 ，使用上述塗布液P以外，藉由與實施例1同樣的方法， 得到薄膜厚度爲125 μιη的接著性改質聚酯薄膜。 接著，於上述接著性改質基材薄膜的接著性改質層Β 之表面上’與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例7) 除了於實施例1中，就各熱定型處理步驟中的溫度而 言’使第1熱定型區爲1901，第2熱定型區爲195 °C, 從第3熱定型區至第5熱定型區爲20(rc以外，藉由與實 施例1同樣的方法，得到薄膜厚度爲125 μηι的接著性改質 (S ) -117- 1360477 聚酯薄膜。於所得到的接著性改質聚酯薄膜的接著性改質 層之表面中，聚酯相與聚胺甲酸酯相的相分離構造係不能 觀察。 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。12.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, 4.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat6 4 manufactured by Daiichi Kogyo Co., Ltd.), 42.3 parts by mass of water, and 37.2 parts by mass of isopropyl alcohol, and further added with 0.6 parts by mass of 10% by mass of the surfactant used in Example 1. Aqueous solution, 2.3 parts by mass of colloidal vermiculite (made by Nissan Chemical Industry Co., Ltd., Snowtex OL; average particle diameter 40 nm), 20% by mass of water dispersion liquid, 0.5 parts by mass of dry method vermiculite as particle B ( A water dispersion of 3.5% by mass of Arosil manufactured by Arosil, Japan, having an average particle diameter of 200 nm and an average primary particle diameter of 4 〇 nm, was adjusted to pH 6.2 with a 5% by mass aqueous sodium hydrogencarbonate solution to obtain a coating liquid P. An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the coating liquid P was used as the coating liquid. Then, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 7) Except that in Example 1, the temperature in each heat setting treatment step was set to 1901 for the first heat setting zone and 195 °C for the second heat setting zone, from the third heat setting zone to In the same manner as in Example 1 except that the fifth heat-setting zone was 20 (r), an adhesive film of (S)-117-1360477 polyester film having a film thickness of 125 μm was obtained. In the surface of the adhesion modifying layer of the polyester film, the phase separation structure of the polyester phase and the polyurethane phase cannot be observed. Next, the adhesion modifying layer B of the above-mentioned adhesive modified substrate film On the surface, in the same manner as in Example 1, a hard coating layer C containing inorganic fine particles in one area layer was obtained to obtain a hard coating film.

於所得到的硬被覆薄膜的切削面之接著性改質層B中 ，聚酯相與聚胺甲酸酯相的相分離構造亦與上述同樣地不 能觀察。 (比較例8) 除了於實施例1中，使乾燥爐內的風速成爲15m/秒以 外，藉由與實施例1同樣的方法，得到薄膜厚度爲125 μιη 的接著性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地，在一面積層含有無機微粒 子的硬被覆層C，以得到硬被覆薄膜。 (比較例9) 除了於實施例1中，塗布量係使最終的固體成分量成 爲0.20g/m2以外’藉由與實施例1的同樣的方法，得到薄 膜厚度125 μιη的接著性改質聚酯薄膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例1〇) -118- 1360477 除了於實施例1中’使用塗布液之pH經5質量％的碳 酸鈉水溶液調整爲9.0的塗布液Q以外，藉由與實施例1 同樣的方法’得到薄膜厚度爲125 μιη的接著性改質聚酯薄 膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例1 1)In the adhesion-modifying layer B of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase was also not observed in the same manner as described above. (Comparative Example 8) An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the wind speed in the drying furnace was changed to 15 m/sec. Then, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 9) In the same manner as in Example 1 except that the amount of the final solid content was 0.20 g/m 2 in the first embodiment, an adhesive modification of a film thickness of 125 μm was obtained. Ester film. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 1) -118-1360477 In the same manner as in Example 1, except that the coating liquid Q having a pH of the coating liquid adjusted to 9.0 by a 5% by mass aqueous sodium carbonate solution was used in Example 1 An adhesive modified polyester film having a film thickness of 125 μm. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 1 1)

除了於實施例1中，在塗布液中不配合界面括性劑， 而使用所調整的塗布液R以外，藉由與實施例1同樣的方 法，得到薄膜厚度爲125μπι的接著性改質聚酯薄膜。 接著，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例17)In the same manner as in Example 1, except that the interface coating agent was not used in the coating liquid, an adhesive modified polyester having a film thickness of 125 μm was obtained in the same manner as in Example 1. film. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 17)

將7.5質量份的實施例1所用的共聚合聚酯（Α)之30質 量％水分散液、11.3質量份的實施例1所用的聚胺甲酸酯 (Β)之20質量％水溶液、0.3質量份的ELASTRON用觸媒（ 第一工業製藥製Cat 64)、40·5質量份的水及39.5質量份的 異丙醇分別混合。再者，添加〇·6質量份的實施例1所用 的界面活性劑之1 〇質量％水溶液、4.3質量份當作粒子A 的凝聚體矽石（富士 SILYSIA化學製Sylysia 310;平均粒 徑1·4μιη)之3.5質量％水分散液，用5質量％的碳酸氫鈉 水溶液粒子將pH調整至6.2 ’依順序使通過過濾性能5μιη7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, 11.3 parts by mass of a 20% by mass aqueous solution of the polyurethane used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat 64 manufactured by Daiichi Kogyo Co., Ltd.), 40.5 parts by mass of water, and 39.5 parts by mass of isopropyl alcohol. Further, 6 parts by mass of the surfactant 1% by mass aqueous solution of the surfactant used in Example 1 and 4.3 parts by mass of the aggregated vermiculite as the particle A (Fuly SILYSIA Chemical Sylysia 310; average particle diameter 1·) were added. 4μιη) of a 3.5% by mass aqueous dispersion, adjusted to pH 6.2 with a 5 mass% aqueous solution of sodium bicarbonate, in order to pass filtration performance 5μιη

< S -119- 1360477 和Ιμιη的過濾器，而成爲塗布液S。再者，於塗布液不配 合粒子B。除了使用上述塗布液S以外，藉由與實施例1 同樣的方法，得到薄膜厚度爲125μιη的接著性改質聚酯薄 膜。 其次，於上述接著性改質基材薄膜的接著性改質層Β 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例12)< S-119-1360477 and Ιμιη filters become the coating liquid S. Further, the coating liquid does not contain the particles B. An adhesive modified polyester film having a film thickness of 125 μm was obtained by the same method as in Example 1 except that the above-mentioned coating liquid S was used. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 12)

除了於實施例1中，僅使塗布液中的界面活性劑量以 固體成分計爲0.60質量％，使用所調配的塗布液τ以外， 藉由與實施例1同樣的方法，得到薄膜厚度爲125μιη的接 著性改質聚酯薄膜。 其次’於上述接著性改質基材薄膜的接著性改質層Β 之表面上’與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例18) 除了於實施例1中’就各熱定型處理步驟中的溫度而 言，使第1熱定型區爲200 °c ’第2熱定型區爲210。(：， 第3熱定型區爲215 °C ’第4熱定型區爲220。(：，第5熱 定型區爲225 °C ’第6熱定型區爲230。(：，第7熱定型區 爲170 °C，在第7熱定型區中於寬度方向進行3 %的鬆弛處 理以外’藉由與實施例1同樣的方法，修剪薄膜兩端部沒 有被塗覆的部分’得到薄膜厚度爲的接著性改質聚 酯薄膜。 -120- 1360477 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作’在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 (比較例13)In the same manner as in Example 1, except that the amount of the interface active agent in the coating liquid was 0.60% by mass in terms of the solid content, the film thickness was 125 μm in the same manner as in Example 1 except that the coating liquid τ was used. The polyester film is then modified. Then, in the same manner as in the first embodiment, the hard coating layer C containing inorganic fine particles was formed in the same manner as in the first embodiment to obtain a hard coating film. (Embodiment 18) Except that in the first embodiment, the temperature in each heat setting treatment step was such that the first heat setting zone was 200 °c' and the second heat setting zone was 210. (:, the third heat setting zone is 215 °C 'The fourth heat setting zone is 220. (:, the fifth heat setting zone is 225 °C 'the sixth heat setting zone is 230. (:, the 7th heat setting zone In the same manner as in Example 1, except for the 3% relaxation treatment in the width direction of the seventh heat-setting zone at 170 ° C, the portion of the film which was not coated at both ends was trimmed to obtain a film thickness of Next, the polyester film was modified. -120-1360477 Next, on the surface of the adhesion-modifying layer B of the above-mentioned adhesive-modified base film, in the same manner as in Example 1, it was described as 'hard of inorganic particles in one area layer. The coating layer C was applied to obtain a hard coating film. (Comparative Example 13)

除了於實施例1中’將7·5質量份的實施例1所用的共 聚合聚醋（A)之30質量％水分散液、丨1·3質量份的實施例 1所用的聚胺甲酸酯（B)之20質量％水溶液，〇·3質量份的 ELASTRON用觸媒（第一工業製藥製Cat64)、5 1.0質量份 的水及26.2質量份的異丙醇分別混合。再者，添加〇.6質 量份的實施例1所用的界面活性劑之1 0質量％水溶液、 2.3質量份當作粒子 A的膠態矽石（日產化學工業製 Snowtex OL;平均粒徑40nm)之20質量％水分散液、0.5 質量份當作粒子 B的乾式法矽石（曰本 Arosil製 Arosil 0X50;平均粒徑200nm，平均一次粒徑40nm)之3.5質量 %水分散液，用5質量％碳酸氫鈉水溶液將pH調整至6.2 ，而使用塗布液U以外，藉由與實施例1同樣的方法，得 到接著性改質聚酯薄膜。 接著，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜》 (比較例14) 除了於實施例1，當作硬被覆劑，使用不含有無機微粒 子的由溶劑稀釋型之光硬化型丙烯酸酯系樹脂所構成的硬 被覆層（大日精化株式會社製Seikabeam EXF-01B)以外， -121- 1360477 藉由與實施例1同樣的方法，在一面上積層不含有無機微 粒子的硬被覆層，得到硬被覆薄膜。 所得到的硬被覆薄膜，雖然硬被覆層與接著性改質層 的密接性優良，但硬度降低，而且捲曲亦變大。 (實施例19)In the same manner as in Example 1, '7.5 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and 1.3 parts by mass of the polycarbamic acid used in Example 1 A 20% by mass aqueous solution of the ester (B), 3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 5 1.0 parts by mass of water, and 26.2 parts by mass of isopropyl alcohol were separately mixed. Further, 6 parts by mass of the 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of colloidal vermiculite as Particle A (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) were added. 20% by mass aqueous dispersion, 0.5 parts by mass of dry-type vermiculite as a particle B (Arosil 0X50 manufactured by Arosil; average particle diameter: 200 nm, average primary particle diameter: 40 nm), 3.5 mass% aqueous dispersion, with 5 masses The pH of the sodium hydrogencarbonate aqueous solution was adjusted to 6.2, and an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid U was used. Then, on the surface of the adhesion-modified layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. Example 14) A hard coating layer made of a solvent-diluted photocurable acrylate-based resin containing no inorganic fine particles was used as the hard coating material in the first embodiment (Seikabeam EXF-01B, manufactured by Daisei Seika Co., Ltd.) In addition, in the same manner as in Example 1, a hard coating layer containing no inorganic fine particles was laminated on one surface to obtain a hard coating film. In the obtained hard coating film, although the adhesion between the hard coating layer and the adhesive modified layer is excellent, the hardness is lowered and the curl is also increased. (Embodiment 19)

除了於實施例1的塗布液之調配中，代替氟系非離子 型界面活性劑（大日本油墨化學工業製Megafac F142D)的 1 0質量％水溶液，使用氟系非離子型界面活性劑（大日本油 墨化學工業製Megafac F444)的5質量％水溶液，使用塗布 液V以外，藉由與實施例1同樣的方法，得到接著性改質 聚酯薄膜。接著，於上述接著性改質基材薄膜的接著性改 質層B之表面上，與實施例1同樣地作，在一面積層含有 無機微粒子的硬被覆層C，以得到硬被覆薄膜。 (實施例20)In addition to the 10% by mass aqueous solution of the fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.), a fluorine-based nonionic surfactant (large Japan) was used in addition to the coating liquid of the first embodiment. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid V was used in a 5% by mass aqueous solution of Megafac F444. Then, on the surface of the adhesive-modified layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Embodiment 20)

除了於實施例1中，於一軸配向聚酯薄膜的兩面上塗 布接著性改質層B以外，藉由與實施例1同樣的方法，得 到接著性改質聚酯薄膜。再者，從對薄膜的塗布起到乾燥 爐入口爲止，薄膜的通過時間在一面係0.8秒，在相反面 係1 · 〇秒。 於上述接著性改質基材薄膜上，隔著接著性改質層B， 在一面積層硬被覆層C，在另一面積層稜鏡透鏡片層D， 得到稜鏡透鏡薄膜。 首先，說明硬被覆層C的形成方法。 於上述接著性改質基材薄膜的接著性改質層B之一表 -122- < S ) 1360477 面上，將實施例1所使用之含有無機粒子的硬被覆劑，以 硬化後的膜厚成爲3 μιη的方式，用美亞桿來塗布，在40 °C使乾燥60秒。再者，照射300mJ/cm2的紫外線，使樹脂 硬化，在一面形成硬被覆層C。 其次，說明稜鏡透鏡層D的形成方法。 於切削有間距爲〇.〇5mm、頂角爲90。的稜鏡形狀之反 型的成形模具內’注入紫外線硬化型樹脂液（JSR株式會社An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer B was applied to both surfaces of the one-axis alignment polyester film in Example 1. Further, from the application of the film to the entrance of the drying furnace, the passage time of the film was 0.8 seconds on one side and 1 〇 second on the opposite side. On the above-mentioned adhesive modified base film, a ruthenium lens film was obtained by hard coating layer C in one area layer and lenticular lens layer D in another area layer via the adhesive layer B. First, a method of forming the hard coating layer C will be described. The hard coating agent containing the inorganic particles used in Example 1 on the surface of the adhesive-modified layer B of the adhesive-modified substrate film, which is one of the surface-122- <S) 1360477, is a cured film. The thickness is 3 μm, coated with a Meyer rod, and dried at 40 ° C for 60 seconds. Further, ultraviolet rays of 300 mJ/cm 2 were irradiated to cure the resin, and a hard coating layer C was formed on one surface. Next, a method of forming the pupil lens layer D will be described. The cutting has a pitch of 〇.〇5 mm and an apex angle of 90. Injecting ultraviolet curable resin liquid into the molding die of the reverse shape of the crucible shape (JSR Corporation

製Desolite Z9590)後，在與上述硬被覆層c相反的接著性 改質層B之表面上’重疊上述成形模具。接著，從硬被覆 層C側，藉由紫外線燈（輸出：6.4kw)，照射80w/cm的紫 外線，使樹脂硬化後，剝離以形成稜鏡透鏡層。 (實施例21)After Desolite Z9590), the above-mentioned molding die was superposed on the surface of the adhesion-modifying layer B opposite to the above-mentioned hard coating layer c. Next, from the side of the hard coating layer C, an ultraviolet ray of 80 w/cm was irradiated with an ultraviolet lamp (output: 6.4 kW) to cure the resin, and then peeled off to form a ruthenium lens layer. (Example 21)

除了於實施例1中，於一軸配向聚酯薄膜的兩面上塗 布接著性改質層以外，藉由與實施例1同樣的方法，得到 接著性改質聚酯薄膜。再者，從對薄膜塗布起到乾燥爐入 口爲止，薄膜的通過時間在一面係0.8秒，在相反面係1.0 秒。 於上述接著性改質基材薄膜上，隔著接著性改質層B， 在一面積層硬被覆層C，在另一面積層光擴散層D’，而得 到光擴散薄膜。 首先，說明硬被覆層C的形成方法。 於上述接著性改質基材薄膜的接著性改質層B之一表 面上，將實施例1所使用之含有無機粒子的硬被覆劑，以 硬化後的膜厚成爲3μιη的方式，用美亞桿來塗布，在4〇 -123- 1360477 °C使乾燥6〇秒。再者，照射300mJ/cm2的紫外線， 硬化，在一面形成硬被覆層C。 其次，說明光擴散層D'的形成方法。 將下述所示的光擴散層用塗布液，塗布在與上 覆層C相反的接著性改質層B之表面上，在13 3分鐘。 使樹脂 述硬被 使乾燥A continuation-modified polyester film was obtained in the same manner as in Example 1 except that in Example 1, except that the adhesive layer was coated on both surfaces of the one-axis alignment polyester film. Further, from the application of the film to the inlet of the drying furnace, the passage time of the film was 0.8 seconds on one side and 1.0 second on the opposite side. On the above-mentioned adhesive modified base film, a light-diffusing film was obtained by hard-coating layer C on one area layer and light-diffusion layer D' on another area layer via adhesion-modified layer B. First, a method of forming the hard coating layer C will be described. On the surface of one of the adhesion-modifying layers B of the adhesive-modified base film, the hard coating agent containing the inorganic particles used in Example 1 was used to have a film thickness of 3 μm after curing. To coat, dry at 6〇-123-1360477 °C for 6 〇 seconds. Further, ultraviolet rays of 300 mJ/cm 2 were irradiated and cured, and a hard coating layer C was formed on one surface. Next, a method of forming the light diffusion layer D' will be described. The coating liquid for a light-diffusing layer shown below was applied onto the surface of the adhesion-modifying layer B opposite to the overcoat layer C for 13 minutes. Make the resin hard and dry

(光擴散層用塗布液的組成） (a) 粒子[26.3質量份] 球狀的丙烯酸系樹脂粒子（EpostarMAlOlO，日 株式會社製；平均粒徑ΙΟμιη) (b) 樹脂[19.5質量份] 丙烯酸系黏結劑樹脂溶液（三菱螺縈株式會社製 LR-1065;固體成分濃度：45質量％) (c) 溶劑[54.2質量份] •甲基乙基酮[24.2質量份] •丙二醇單甲基醚[15.0質量份] •丙二醇單甲基醚醋酸酯[15.0質量份] (實施例22) 除了於實施例1中，使塗布量成爲最終的固體 係0.02g/m2以外，藉由與實施例1同樣的方法，得 性改質聚酯薄膜》 其次，於上述接著性改質基材薄膜的接著性改 之表面上，與實施例1同樣地作，在一面積層含有 粒子的硬被覆層c，以得到硬被覆薄膜。 本觸媒(Composition of Coating Liquid for Light-Diffusing Layer) (a) Particles [26.3 parts by mass] Spherical acrylic resin particles (EpostarMAlOlO, manufactured by Nippon Co., Ltd.; average particle size ΙΟμηη) (b) Resin [19.5 parts by mass] Acrylic Adhesive resin solution (LR-1065, manufactured by Mitsubishi Screw Co., Ltd.; solid content concentration: 45 mass%) (c) Solvent [54.2 parts by mass] • Methyl ethyl ketone [24.2 parts by mass] • Propylene glycol monomethyl ether [ 15.0 parts by mass] propylene glycol monomethyl ether acetate [15.0 parts by mass] (Example 22) Except that in Example 1, the coating amount was changed to 0.02 g/m 2 as the final solid state, and the same as in Example 1. In the same manner as in the first embodiment, the hard coating layer c containing particles in one area layer is formed on the surface of the adhesive film of the adhesive-modified substrate. A hard coated film was obtained. Catalyst

Dianal 成分量 到接著 質層B 無機微 -124- 1360477 (實施例23) 除了於實施例1中，作爲塗布裝置，使用塗布液的接 盤容量、循環用槽的容量、及調配用槽的容量之比具有下 述條件的塗布裝置以外，藉由與實施例1同樣的方法，得 到薄膜的長度爲2000m、寬度爲1000mm、厚度爲125μιη 的接著性改質聚酯薄膜之捲筒。 (a) 塗布液的接盤之容量/循環用槽之容量=1/5 (b) 循環用槽的容量/調配用槽的容量=1/5 0Dianal component amount to the adhesive layer B. Inorganic micro-124-1360477 (Example 23) In addition to Example 1, the coating capacity of the coating liquid, the capacity of the circulation tank, and the capacity of the preparation tank were used as the coating device. A roll of an adhesive modified polyester film having a film length of 2000 m, a width of 1000 mm, and a thickness of 125 μm was obtained in the same manner as in Example 1 except for the coating apparatus having the following conditions. (a) Capacity of the coating liquid / Capacity of the circulating tank = 1 / 5 (b) Capacity of the circulating tank / Capacity of the mixing tank = 1 / 0 0

(c) 塗布輥及計量輥的真圓度與圓筒度：6/1 000mm (d) 從塗布機到乾燥爐之間沒有設置夾輥 其次，於上述接著性改質基材薄膜的接著性改質層B 之表面上，與實施例1同樣地作，在一面積層含有無機微 粒子的硬被覆層C，以得到硬被覆薄膜。 在實施例1〜23、比較例1〜14的方面，塗布液的組成 或特性係顯示於表1中，塗布·乾燥條件係顯示表2中， 熱定型條件係顯示於表3中，接著性改質基材薄膜的物性 及特性係顯示於表4中。又，於所得到的接著性改質聚酯 薄膜之捲筒的長度方向及寬度方向中，PEs表面分率的最 大値、最小値、霧度的最大値、最小値、對於硬被覆層的 密接性之最大値、最小値係顯示於表5中。再者，關於防 黏連性，全部測定點皆是〇。 -125- 1360477 [表i](c) Roundness and cylindricality of the coating roller and the metering roller: 6/1 000 mm (d) There is no nip between the coater and the drying furnace, and the adhesion of the film of the above-mentioned adhesive modified substrate On the surface of the modified layer B, in the same manner as in Example 1, a hard coating layer C containing inorganic fine particles in one area layer was obtained to obtain a hard coating film. In the examples 1 to 23 and the comparative examples 1 to 14, the composition and characteristics of the coating liquid are shown in Table 1, and the coating and drying conditions are shown in Table 2, and the heat setting conditions are shown in Table 3, and the adhesion is shown in Table 3. The physical properties and characteristics of the modified base film are shown in Table 4. Further, in the longitudinal direction and the width direction of the obtained roll of the adhesive modified polyester film, the maximum 値, the minimum 値 of the surface area of the PEs, the maximum 雾 of the haze, the minimum 値, and the adhesion to the hard coating layer The maximum and minimum tethers are shown in Table 5. Furthermore, regarding the anti-blocking property, all the measurement points are 〇. -125- 1360477 [Table i]

塗布麵成 塗布液 樹脂 粒子P1 粒子Ρ2 溶劑 界面活性劑 固體成 共聚合 平均 添加 平均 添加 -rl^/TD A 有無 配合 分 PEs/PU 粒徑 量 粒徑 量 替鲁卜卜 _ 前處 量 濃度 的質量比 μηι 質量％ μηι 質量％ 貝星rc 理 質量％ 質量％ 實施例1 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例2 50/50 0.04 0.45 0.20 0.02 60/40 陽離子 有 0.06 6.2 5.30 實施例3 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例4 60/40 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例5 40/60 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例ό 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例7 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.03 6.2 5.30 實施例8 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.10 6.2 5.30 實施例9 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例10 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例11 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 7.9 5.30 實施例12 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例13 50/50 0.04 0.45 0.20 0.02 60/40 非離子 無 0.06 6.2 5.30 實施例14 50/50 0.04 0.45 0.20 0.02 50/50 非離子 有 0.06 6.2 5.30 實施例15 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 4.6 5.30 實施例16 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例17 50/50 1.4 3.0 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例18 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 62 530 實施例19 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.03 6.2 5.30 實施例20 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例21 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例22 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 實施例23 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例1 20/80 一 — — — 100/0 非離子 — 無 — 10.00 比較例2 20/80 0.04 0.36 0.20 0.04 95/5 陰離子 無 0.06 4.8 10.93 比較例3 50/50 1.4 0.02 — — 60/40 非離子 Μ 0.06 4.6 4.87 比較例4 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例5 20/80 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例6 80/20 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例7 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例8 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例9 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 比較例10 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 9.0 5.30 比較例]1 50/50 0.04 0.45 0.20 0.02 60/40 — — 無 6.2 5.30 比較例12 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.60 6.2 5.30 比較例13 50/50 0.04 0.45 0.20 0.02 72/28 非離子 有 0.06 6.2 5.30 比較例14 50/50 0.04 0.45 0.20 0.02 60/40 非離子 有 0.06 6.2 5.30 -126- (S > 1360477 [表2]Coating surface into coating liquid resin particles P1 Particles Ρ2 Solvent surfactant solids in copolymerization average addition average addition-rl^/TD A with or without sub-component PEs/PU particle size particle size tirub _ front concentration Mass ratio μηι mass % μηι mass % Baystar rc mass % % by mass Example 1 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Example 2 50/50 0.04 0.45 0.20 0.02 60/40 Cation 0.06 6.2 5.30 Example 3 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 4 60/40 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 5 40/60 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example ό 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 7 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.03 6.2 5.30 Example 8 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion 0.10 6.2 5.30 Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 10 50/50 0.04 0.45 0.20 0.02 60/40 The ion has 0.06 6.2 5.30 Example 11 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 7.9 5.30 Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 13 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion no 0.06 6.2 5.30 Example 14 50/50 0.04 0.45 0.20 0.02 50/50 Non-ion has 0.06 6.2 5.30 Example 15 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 4.6 5.30 Example 16 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic with 0.06 6.2 5.30 Example 17 50/50 1.4 3.0 0.20 0.02 60/40 Nonionic with 0.06 6.2 5.30 Example 18 50/50 0.04 0.45 0.20 0.02 60/ 40 Nonionics 0.06 62 530 Example 19 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.03 6.2 5.30 Example 20 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Example 21 50/ 50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 22 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 23 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 1 20/80 One— — 100/0 Nonionic — None — 10.00 Comparative Example 2 20/80 0.04 0.36 0.20 0.04 95/5 Anion No 0.06 4.8 10.93 Comparative Example 3 50/50 1.4 0.02 — — 60/40 Nonionic Μ 0.06 4.6 4.87 Comparative Example 4 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 5 20/80 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 6 80/20 0.04 0.45 0.20 0.02 60/40 Non-ion There are 0.06 6.2 5.30 Comparative Example 7 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 8 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 10 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 9.0 5.30 Comparative Example] 1 50/50 0.04 0.45 0.20 0.02 60/40 — — No 6.2 5.30 Comparison Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.60 6.2 5.30 Comparative Example 13 50/50 0.04 0.45 0.20 0.02 72/28 Non-ion has 0.06 6.2 5.30 Comparative Example 14 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 -126- (S > 1360477 [Table 2]

塗布.乾燥條件 從塗布雛到乾燥步 驟入口爲止的通過時 間 (秒） μ CC) 乾燥時間 (秒） 風速 (m/s) 最終 塗布量 (g/m2) 實施例1 0.8 135 1.0 30 0.08 實施例2 0.8 135 1.0 30 0.08 實施例3 0.8 135 1.0 30 0.08 實施例4 0.8 135 1.0 30 0.08 實施例5 0.8 135 1.0 30 0.08 實施例ό 0.8 135 1.0 30 0.12 實施例7 0.8 135 1.0 30 0.08 實施例8 0.8 135 1,0 30 0.08 實施例9 0.7 135 0.8 30 0.08 實施例10 1.0 135 1.9 30 0.08 實施例11 0.8 135 1.0 30 0.08 實施例12 0.8/1.0 135 1.0 30 0.08 實施例13 0.8 135 1.0 30 0.08 實施例14 0.8 135 1.0 30 0.08 實施例15 0.8 135 1.0 30 0.08 實施例16 0.8 135 1.0 30 0.08 實施例17 0.8 135 1.0 30 0.08 實施例18 0.8 135 1.0 30 0.08 實施例19 0.8 135 1.0 30 0.08 實施例20 0.8 135 1.0 30 0.08 實施例21 0.8 135 1.0 30 0.08 實施例22 0.8 135 1.0 30 0.02 實施例23 0.8 135 1.0 30 0.08 比較例1 10 110 20 15 0.15 比較例2 10 80 20 20 0.10 比較例3 3.2 120 1.0 15 0.08 比較例4 3.2 135 1.0 30 0.08 比較例5 0.8 135 1.0 30 0.08 比較例ό 0.8 135 1.0 30 0.08 比較例7 0.8 135 1.0 30 0.08 比較例8 0.8 135 1.0 15 0.08 比較例9 0.8 135 1.0 30 0.20 比較例10 0.8 135 1.0 30 0.08 比較例11 0.8 135 1.0 30 0.08 比較例12 0.8 135 1.0 30 0.08 比較例13 0.8 135 1.0 30 0.08 比較例14 0.8 135 1.0 30 0.08 -127- (S ) 1360477 [表3]Coating. Drying conditions: passage time from the coating to the inlet of the drying step (seconds) μ CC) Drying time (seconds) Wind speed (m/s) Final coating amount (g/m2) Example 1 0.8 135 1.0 30 0.08 Example 2 0.8 135 1.0 30 0.08 Example 3 0.8 135 1.0 30 0.08 Example 4 0.8 135 1.0 30 0.08 Example 5 0.8 135 1.0 30 0.08 Example ό 0.8 135 1.0 30 0.12 Example 7 0.8 135 1.0 30 0.08 Example 8 0.8 135 1,0 30 0.08 Example 9 0.7 135 0.8 30 0.08 Example 10 1.0 135 1.9 30 0.08 Example 11 0.8 135 1.0 30 0.08 Example 12 0.8/1.0 135 1.0 30 0.08 Example 13 0.8 135 1.0 30 0.08 Example 14 0.8 135 1.0 30 0.08 Example 15 0.8 135 1.0 30 0.08 Example 16 0.8 135 1.0 30 0.08 Example 17 0.8 135 1.0 30 0.08 Example 18 0.8 135 1.0 30 0.08 Example 19 0.8 135 1.0 30 0.08 Example 20 0.8 135 1.0 30 0.08 Example 21 0.8 135 1.0 30 0.08 Example 22 0.8 135 1.0 30 0.02 Example 23 0.8 135 1.0 30 0.08 Comparative Example 1 10 110 20 15 0.15 Comparative Example 2 10 80 20 20 0.10 Comparative Example 3 3.2 120 1.0 15 0.08 Comparative Example 4 3.2 135 1.0 30 0.08 Comparative Example 5 0.8 135 1.0 30 0.08 Comparative Example ό 0.8 135 1.0 30 0.08 Comparative Example 7 0.8 135 1.0 30 0.08 Comparative Example 8 0.8 135 1.0 15 0.08 Comparative Example 9 0.8 135 1.0 30 0.20 Comparative Example 10 0.8 135 1.0 30 0.08 Comparative Example 11 0.8 135 1.0 30 0.08 Comparative Example 12 0.8 135 1.0 30 0.08 Comparative Example 13 0.8 135 1.0 30 0.08 Comparative Example 14 0.8 135 1.0 30 0.08 -127- (S ) 1360477 [Table 3]

熱定型條件 熱定型酿（。〇 各區的 通過時間 (秒） #1 區 #2 |ρα #3 區 #4 #5 ]ra #6 Ιπα #7 實施例1 200 225 230 230 210 170 120 4.5 實施例2 200 225 230 230 210 170 120 4.5 實施例3 190 205 220 220 210 170 120 4.5 實施例4 200 225 230 230 210 170 120 4.5 實施例5 200 225 230 230 210 170 120 4.5 實施例ό 200 225 230 230 210 170 120 4.5 實施例7 200 225 230 230 210 170 120 4.5 實施例8 200 225 230 230 210 170 120 4.5 實施例9 200 225 230 230 210 170 120 3.5 實施例10 200 225 230 230 210 170 120 6.6 實施例11 200 225 230 230 210 170 120 4.5 實施例12 200 225 230 230 210 170 120 4.5 實施例13 200 225 230 230 210 170 120 4.5 實施例14 200 225 230 230 210 170 120 4.5 實施例15 200 225 230 230 210 170 120 4.5 實施例16 200 225 230 230 210 170 120 4.5 實施例17 200 225 230 230 210 170 120 4.5 實施例18 200 210 215 220 225 230 170 4.5 實施例19 200 225 230 230 210 170 120 4.5 實施例20 200 225 230 230 210 170 120 4.5 實施例21 200 225 230 230 210 170 120 4.5 實施例22 200 225 230 230 210 170 120 4.5 實施例23 200 225 230 230 210 170 120 4.5 比較例1 200 205 210 213 215 220 170 4.5 比較例2 200 210 220 225 230 235 240 4.5 比較例3 200 205 210 213 215 220 170 4.5 比較例4 200 225 230 230 210 170 120 4.5 比較例5 200 225 230 230 210 170 120 4.5 比較例ό 200^ 225 230 230 210 170 120 4.5 比較例7 190 195 200 200 200 170 120 4.5 比較例8 200 225 230 230 210 170 120 4.5 比較例9 200 225 230 230 210 170 120 4.5 比較例10 200 225 230 230 210 170 120 4.5 比較例11 200 225 230 230 210 170 120 4.5 比較例12 200 225 230 230 210 170 120 4.5 比較例13 200 225 230 230 210 170 120 4.5 比較例14 200 225 230 230 210 170 120 4.5 -128- (S ) 1360477 [表4]Heat setting conditions Heat setting brewing (. Passing time of each zone (seconds) #1 Zone #2 |ρα #3区#4 #5 ]ra #6 Ιπα #7 Example 1 200 225 230 230 210 170 120 4.5 Implementation Example 2 200 225 230 230 210 170 120 4.5 Example 3 190 205 220 220 210 170 120 4.5 Example 4 200 225 230 230 210 170 120 4.5 Example 5 200 225 230 230 210 170 120 4.5 Example ό 200 225 230 230 210 170 120 4.5 Example 7 200 225 230 230 210 170 120 4.5 Example 8 200 225 230 230 210 170 120 4.5 Example 9 200 225 230 230 210 170 120 3.5 Example 10 200 225 230 230 210 170 120 6.6 Examples 11 200 225 230 230 210 170 120 4.5 Example 12 200 225 230 230 210 170 120 4.5 Example 13 200 225 230 230 210 170 120 4.5 Example 14 200 225 230 230 210 170 120 4.5 Example 15 200 225 230 230 210 170 120 4.5 Example 16 200 225 230 230 210 170 120 4.5 Example 17 200 225 230 230 210 170 120 4.5 Example 18 200 210 215 220 225 230 170 4.5 Example 19 200 225 230 230 210 170 120 4.5 Example 20 200 225 230 230 210 170 120 4.5 Example 21 200 225 230 230 210 170 120 4.5 Example 22 200 225 230 230 210 170 120 4.5 Example 23 200 225 230 230 210 170 120 4.5 Comparative Example 1 200 205 210 213 215 220 170 4.5 Comparative Example 2 200 210 220 225 230 235 240 4.5 Comparative example 3 200 205 210 213 215 220 170 4.5 Comparative example 4 200 225 230 230 210 170 120 4.5 Comparative example 5 200 225 230 230 210 170 120 4.5 Comparative example ^ 200^ 225 230 230 210 170 120 4.5 Comparative Example 7 190 195 200 200 200 170 120 4.5 Comparative Example 8 200 225 230 230 210 170 120 4.5 Comparative Example 9 200 225 230 230 210 170 120 4.5 Comparative Example 10 200 225 230 230 210 170 120 4.5 Comparative Example 11 200 225 230 230 210 170 120 4.5 Comparative Example 12 200 225 230 230 210 170 120 4.5 Comparative Example 13 200 225 230 230 210 170 120 4.5 Comparative Example 14 200 225 230 230 210 170 120 4.5 -128- (S ) 1360477 [Table 4 ]

接著性改質翻薄膜 接著性改質層 薄膜的評價 表面的 PEs相之 超過寬度 Ιμπι 的 PEs相 碎形 厚度 接難改 質層的硬 霧度 防黏連 與HC層(粒子：無） 的密接性(％) 面積率 次元 ㈣ 度指數 (%) 性 無溶劑 溶劑· (%) (nm) 型HC層 型HC層 實施例1 68 Μ 1.86 125 5.1 0.58 〇 95 100 實施例2 65 無 125 5.3 0.65 〇 100 100 實施例3 52 姐 /1 \\ 1.75 125 7.0 0.45 〇 100 100 實施例4 76 jfrrr /*、、 1.70 125 3.5 0.41 〇 95 97 實施例5 48 並 125 12.5 0.85 〇 100 95 實施例ό 52 無 125 7.3 0.65 〇 100 100 實施例7 75 dnL Λν? 125 6.5 0.61 〇 92 95 實施例8 64 ΛττΤ 撕 125 5.5 0.85 〇 100 100 實施例9 70 無 1.89 100 5.3 0.55 〇 100 100 實施例10 51 te 1.85 188 8.0 0.46 〇 100 100 實施例Π 61 Jhrr 撕 125 5.3 0.73 〇 100 100 實施例12 68 並 /1、、 125 5.3 0.78 〇 96 100 實施例13 66 無 125 5.5 0.54 〇 85 86 實施例14 70 無 125 5.2 0.56 〇 85 86 實施例15 87 無 125 4.0 0.47 〇 50 80 實施例16 69 無 125 5.0 0.57 〇 96 100 實施例17 69 有 125 5.3 3.40 〇 100 100 實施例18 50 有 125 7.9 0.47 〇 83 95 實施例19 68 有 125 7.9 0.47 〇 95 100 實施例20 68 無 125 5.1 0.58 〇 95 100 實施例21 68 無 125 5.1 0.58 〇 95 100 實施例22 79 無 125 4.3 0.78 〇 91 93 實施例23 68 無 125 5.1 0.58 〇 95 100 比較例1 8 熟 1.25 125 15.5 1.05 X 75 50 比較例2 — ΛγτΤ. 撕 125 15.3 0.75 X 84 60 比較例3 — 無 125 5.5 0.41 X 100 95 比較例4 30 Air 熙 1.58 125 15.1 0.73 X 93 79 比較例5 15 無 125 15.7 0.98 X 95 60 比較例6 93 有 1.40 125 2.8 0.47 〇 30 70 比較例7 — 無 125 4.1 0.62 X 78 65 比較例8 34 無 125 6.0 0.70 X 100 98 比較例9 32 Μ 125 6.5 0.54 X 100 92 比較例10 33 無 125 6.0 1.55 Δ 100 90 比較例11 91 無 125 3.5 0.38 〇 25 70 比較例12 34 4nt 挑 125 5.9 1.53 Δ 98 87 比較例13 32 無 125 6.8 2.20 X 95 88 比較例14 68 無 1.86 125 5.1 0.58 〇 95 100 -129- < S ) 1360477Next, the PEs phase of the evaluation surface of the modified film of the modified film is over the width of the PEs phase of the width Ιμπι, and the adhesion of the hard haze of the hardened layer to the adhesion of the hard layer to the HC layer (particle: none) (%) Area rate dimension (four) Degree index (%) Solvent-free solvent · (%) (nm) Type HC layer type HC layer Example 1 68 Μ 1.86 125 5.1 0.58 〇95 100 Example 2 65 No 125 5.3 0.65 〇100 100 Example 3 52 Sister/1 \\ 1.75 125 7.0 0.45 〇100 100 Example 4 76 jfrrr /*,, 1.70 125 3.5 0.41 〇95 97 Example 5 48 and 125 12.5 0.85 〇100 95 Example ό 52 None 125 7.3 0.65 〇100 100 Example 7 75 dnL Λν? 125 6.5 0.61 〇92 95 Example 8 64 ΛττΤ tear 125 5.5 0.85 〇100 100 Example 9 70 No 1.89 100 5.3 0.55 〇100 100 Example 10 51 te 1.85 188 8.0 0.46 〇100 100 Example Π 61 Jhrr tear 125 5.3 0.73 〇100 100 Example 12 68 and /1, 125 5.3 0.78 〇96 100 Example 13 66 No 125 5.5 0.54 〇85 86 Example 14 70 No 125 5.2 0.56 〇85 86 Example 15 87 No 125 4.0 0.47 〇50 80 Example 16 69 No 125 5.0 0.57 〇96 100 Example 17 69 There are 125 5.3 3.40 〇100 100 Example 18 50 There are 125 7.9 0.47 〇83 95 Example 19 68 There are 125 7.9 0.47 〇95 100 Example 20 68 No 125 5.1 0.58 〇95 100 Example 21 68 No 125 5.1 0.58 〇95 100 Example 22 79 No 125 4.3 0.78 〇91 93 Example 23 68 No 125 5.1 0.58 〇95 100 Comparison Example 1 8 Cooked 1.25 125 15.5 1.05 X 75 50 Comparative Example 2 - ΛγτΤ. Tear 125 15.3 0.75 X 84 60 Comparative Example 3 - No 125 5.5 0.41 X 100 95 Comparative Example 4 30 Air Hee 1.58 125 15.1 0.73 X 93 79 Comparative Example 5 15 No 125 15.7 0.98 X 95 60 Comparative Example 6 93 1.40 125 2.8 0.47 〇30 70 Comparative Example 7 - No 125 4.1 0.62 X 78 65 Comparative Example 8 34 No 125 6.0 0.70 X 100 98 Comparative Example 9 32 Μ 125 6.5 0.54 X 100 92 Comparative Example 10 33 None 125 6.0 1.55 Δ 100 90 Comparative Example 11 91 No 125 3.5 0.38 〇25 70 Comparative Example 12 34 4nt Pick 125 5.9 1.53 Δ 98 87 Comparative Example 13 32 No 125 6.8 2.20 X 95 88 Comparison Example 14 68 1.86 125 5.1 0.58 square 95 100 -129- < S) 1360477

[表5] 接著性改質層 的表面中PEs 相的面積率 (%) 霧度(％) 與HC層的密雛（％) 無溶劑型HC層 /接·改質層 溶劑稀釋型HC 層 /接著性改質層 最大値 最小値 最大値 最小値 最大値 最小値 最大値 最小値 實施例1 長度方向 73 63 0.59 0.56 100 94 100 96 寬度方向 72 64 0.59 0.56 100 96 100 97 實施例23 長度方向 77 60 0.6 0.56 100 93 100 95 寬度方向 75 61 0.6 0.56 100 91 100 94 -130-[Table 5] Area ratio (%) of the PEs phase in the surface of the subsequent modified layer Haze (%) and tightness of the HC layer (%) Solvent-free HC layer/attachment/modified layer solvent-diluted HC layer /Subsequent modified layer maximum 値 minimum 値 maximum 値 minimum 値 maximum 値 minimum 値 maximum 値 minimum 値 Example 1 Length direction 73 63 0.59 0.56 100 94 100 96 Width direction 72 64 0.59 0.56 100 96 100 97 Example 23 Length direction 77 60 0.6 0.56 100 93 100 95 Width direction 75 61 0.6 0.56 100 91 100 94 -130-

(S 1360477 m 6](S 1360477 m 6]

硬被覆薄膜 光學機能層的構成 接著改質層B 特性 —面 另一面 切削面的PU 相之面積率 (%) 與含有««子 的HC層之密接性 (%) 纖硬度 實施例1 HC層 一 45 95 〇 實施例2 HC層 一 46 96 〇 實施例3 HC層 一 52 96 〇 實施例4 HC層 一 33 94 〇 實施例5 HC層 一 59 92 〇 實施例6 HC層 — 52 99 〇 實施例7 HC層 — 41 91 〇 實施例8 HC層 一 47 98 〇 實施例9 HC層 _ 43 94 〇 實施例10 HC層 — 52 96 〇 實施例11 HC層 一 48 94 〇 實施例12 HC層 HC層 45 95 〇 實施例13 HC層 一 46 82 〇 實施例14 HC層 — 44 82 〇 實施例15 HC層 — 34 80 〇 實施例16 HC層 — 44 95 〇 實施例17 HC層 — 44 94 〇 實施例18 HC層 一 53 92 〇 實施例19 HC層 一 45 96 〇 實施例20 HC層 透鏡層 45 96 〇 實施例21 HC層 光擴散層 45 95 〇 實施例22 HC層 一 未測定 85 〇 實施例23 HC層 — 45 95 〇 比較例1 HC層 一 82 40 〇 比較例2 HC層 一 — 43 〇 比較例3 HC層 — — 88 〇 比較例4 HC層 — 63 70 〇 比較例5 HC層 一 75 48 〇 比較例6 HC層 一 12 62 〇 比較例7 HC層 — — 50 〇 比較例8 HC層 — 62 90 〇 比較例9 HC層 — 62 89 〇 比較例10 HC層 一 62 84 〇 比較例11 HC層 — 29 45 〇 比較例12 HC層 — 61 83 〇 比較例13 HC層 一 62 83 〇 比較例14 HC層 _ 45 98 X -13 1- (:s ) 1360477 產業上的利用可能件 本發明的硬被覆薄膜，由於維持高的硬度，同時與含 有無機微粒子的硬被覆層之密接性優良，故適合作爲稜鏡 透鏡片、光擴散薄膜、抗反射（AR)薄膜、透明導電性薄膜 、紅外線吸收薄膜、電磁波吸收薄膜等的顯示器用光學機 能性薄膜之基材。The structure of the hard-coated thin film optical functional layer is followed by the modified layer B characteristic—the area ratio (%) of the PU phase on the other face of the face and the adhesion (%) of the HC layer containing the «« sub-hardness. Example 1 HC layer A 45 95 〇 Example 2 HC layer - 46 96 〇 Example 3 HC layer - 52 96 〇 Example 4 HC layer - 33 94 〇 Example 5 HC layer - 59 92 〇 Example 6 HC layer - 52 99 〇 Implementation Example 7 HC layer - 41 91 〇 Example 8 HC layer - 47 98 〇 Example 9 HC layer _ 43 94 〇 Example 10 HC layer - 52 96 〇 Example 11 HC layer - 48 94 〇 Example 12 HC layer HC Layer 45 95 〇 Example 13 HC layer - 46 82 〇 Example 14 HC layer - 44 82 〇 Example 15 HC layer - 34 80 〇 Example 16 HC layer - 44 95 〇 Example 17 HC layer - 44 94 〇 Implementation Example 18 HC layer-53 92 〇 Example 19 HC layer-45 96 〇 Example 20 HC layer lens layer 45 96 〇 Example 21 HC layer light diffusion layer 45 95 〇 Example 22 HC layer one not determined 85 〇 Example 23 HC layer - 45 95 〇Comparative example 1 HC layer-82 40 〇Comparative example 2 HC layer one— 43 〇Comparative Example 3 HC layer - 88 〇 Comparative Example 4 HC layer - 63 70 〇 Comparative Example 5 HC layer - 75 48 〇 Comparative Example 6 HC layer - 12 62 〇 Comparative Example 7 HC layer - 50 〇 Comparative Example 8 HC layer - 62 90 〇Comparative Example 9 HC layer - 62 89 〇Comparative example 10 HC layer-62 84 〇Comparative example 11 HC layer - 29 45 〇Comparative example 12 HC layer - 61 83 〇Comparative example 13 HC layer-62 83 〇Comparative Example 14 HC layer _ 45 98 X -13 1- (:s ) 1360477 INDUSTRIAL APPLICABILITY The hard coating film of the present invention maintains high hardness and adheres to a hard coating layer containing inorganic fine particles. Since it is excellent, it is suitable as a base material for an optical functional film for display such as a 稜鏡 lens sheet, a light diffusing film, an antireflection (AR) film, a transparent conductive film, an infrared absorbing film, or an electromagnetic wave absorbing film.

又，本發明的硬被覆薄膜，除了用於顯示器用光學機 能性薄膜，亦可使用於要求遮蔽性的用途》於該情況下， 作爲基材的熱塑性樹脂薄膜，較佳爲使用含白色顔料或空 洞的白色薄膜。 【圖式簡單說明】 第1圖係本發明的硬被覆薄膜中所用的接著性改質基 材薄膜之接著性改質層的表面，以掃描型探針顯微鏡的相 位測定模式所觀察到的相位像之說明圖。 第2圖係於第1圖的相位像中，明色相與暗色相的界 面之輪廓經影像處理軟體所強調的相位像之說明圖。 第3圖係於強調第2圖的明色相與暗色相的界面之輪 廓的相位像中，暗色相經影像處理軟體所塗滿的相位像之 說明圖。 第4圖係於強調第2圖的明色相與暗色相的界面之輪 廓的相位像中，顯示明色相與暗色相的邊界線之說明圖。 第5圖顯示接著性改質層的表面所附有的傷痕之表面 形狀，使用三次元非接觸表面形狀計測裝置，以波形模式 所計測時，傷痕的高低差之說明圖。 -132- 1360477 第6圖顯示於實施例1-23與比較例1、4-6、8-14中， 接著性改質層的表面之PEs相的面積率與接著性改質層的 樹脂成分中PEs質量比係不對應的說明書。 第7圖顯示塗布液的接盤、循環用槽、調配用槽的配 置、及塗布液的循環路徑之說明圖。 第8圖係於切削本發明的硬被覆薄膜時，以掃描型探 針顯微鏡的相位測定模式所觀察的接著性改質層之切削面 ，經色均一化處理而強調對比的相位像之說明圖。Moreover, the hard coating film of the present invention can be used for applications requiring shielding properties in addition to optical functional films for displays. In this case, it is preferred to use a white pigment or a thermoplastic resin film as a substrate. A hollow white film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a phase of an adhesion modifying layer of a bond-modified substrate film used in a hard coating film of the present invention, which is observed in a phase measurement mode of a scanning probe microscope. Like the illustration. Fig. 2 is an explanatory view of the phase image emphasized by the image processing software in the phase image of Fig. 1, the outline of the interface between the bright phase and the dark phase. Fig. 3 is an explanatory view showing a phase image in which the dark color is applied to the image processing software in the phase image of the outline of the interface between the bright phase and the dark phase in Fig. 2. Fig. 4 is an explanatory view showing a boundary line between a bright phase and a dark phase in the phase image of the outline of the interface between the bright phase and the dark phase in Fig. 2; Fig. 5 is a view showing the surface shape of the flaw attached to the surface of the adhesive modified layer, and the height difference of the flaw when measured in a wave pattern using a three-dimensional non-contact surface shape measuring device. -132- 1360477 Fig. 6 shows the area ratio of the PEs phase on the surface of the subsequent modified layer and the resin component of the adhesion modifying layer in Examples 1-23 and Comparative Examples 1, 4-6, and 8-14. The quality ratio of the PEs in the medium does not correspond to the specification. Fig. 7 is an explanatory view showing the arrangement of the coating liquid, the circulation tank, the arrangement of the preparation tank, and the circulation path of the coating liquid. Fig. 8 is an explanatory view showing the phase image of the contrast-modified layer which is observed by the color uniformization process in the cutting surface of the adhesive layer observed in the phase measurement mode of the scanning probe microscope when the hard coating film of the present invention is cut. .

第9圖係於第8圖的經色均一化處理之相位像中，以2 條紅線顯示應觀察相分離構造的範圍之說明圖。 第10圖係於第8圖的相位像中，以影像處理軟體所二 値化的相位像之說明圖。 第1 1圖係在第1 0圖之經二値化的相位像，將第9圖 的2條紅線黏貼於同樣位置的相位像之說明圖。 第12圖係在第11圖的相位像中，以影像處理軟體來 塗紅2條紅線所不包圍的部分後，相位像的說明圖。 【主要元件符號說明】 1 暗色相（以共聚合聚酯當作主成分的聚酯相） 2 明色相（以聚胺甲酸酯當作主成分的聚胺甲酸酯相） 3 起因於粒子的突起 4 明色相與暗色相的界面之輪廓經強調的線 5 接著性改質層的表面之凹凸的輪廓曲線 6 傷痕的谷部 7 傷痕的頂部 -133- 1360477Fig. 9 is an explanatory view showing the range of the phase separation structure to be observed by two red lines in the phase image of the color uniformization process of Fig. 8. Fig. 10 is an explanatory diagram of a phase image which is dimmed by the image processing software in the phase image of Fig. 8. Fig. 1 is an explanatory diagram of a phase image in which the two red lines of Fig. 9 are adhered to the same position in the second phase of the second embodiment. Fig. 12 is an explanatory diagram of a phase image in a phase image of Fig. 11 in which a portion of a red line is not covered by an image processing software. [Explanation of main components] 1 Dark phase (polyester phase with copolymerized polyester as the main component) 2 Bright phase (polyurethane phase with polyurethane as the main component) 3 Caused by particles The protrusion 4 is the boundary of the interface between the bright phase and the dark phase. The line 5 is emphasized. The contour of the surface of the modified layer is contoured. 6 The valley of the flaw 7 The top of the flaw -133- 1360477

8 實 施 例 1-23 9 比 較 例 1、4-6 8- 14 10 塗 布 機 11 塗 布 液 接盤 12 模 頭 13 循 環 用 槽 14 調 配 槽 15 基 材 薄 膜 16 夾 輥 17 硬 被 覆 層C 18 接 著 性 改質層 B 19 熱 塑 性 樹脂薄1 摸 A 20 顯 示 硬 被覆層 C 與 接著性改質層B的 界 面 之 線 2 1 從 界 面 2 0起 » 到 與接著性改質層的 內 部 成 垂直方 向 離 20nm的深度 ，所平行移動的線 -134-8 Example 1-23 9 Comparative Example 1, 4-6 8- 14 10 Coater 11 Coating liquid tray 12 Die 13 Recirculation groove 14 Preparation groove 15 Substrate film 16 Clamping roller 17 Hard coating layer C 18 Subsequent Modification layer B 19 Thermoplastic resin thin 1 Touch A 20 The line 2 1 showing the interface between the hard coating layer C and the adhesion modifying layer B is from the interface 20 to the direction perpendicular to the inside of the adhesive layer 20 nm. Depth, parallel moving line -134-

Claims (1)

1360477 修正本 第096118643號「硬被覆薄膜及光學機能性薄膜」專利案 (100年6月8日修正） 十、申請專利範圍：1360477 Amendment to Patent No. 096118643 "Hard Covered Film and Optical Functional Film" (Amended on June 8, 100) X. Patent Application: 1.—種硬被覆薄膜’其特徵爲該硬被覆薄膜包含：在熱塑性 樹脂薄膜Α的一面或兩面上，形成有含共聚合聚酯及聚胺 甲酸酯的接著性改質層B之接著性改質基材薄膜，與在該 薄膜的任一面之接著性改質層B的表面上之含無機微粒子 的硬被覆層C’所積層而成的A/B/C或B/A/B/C之層構成， 其中 該熱塑性樹脂薄膜A之厚度係在30〜300μιη的範圍內， 且熱塑性樹脂薄膜Α係以選自由聚對酞酸乙二酯、聚對酞 酸丙二酯、聚2,6-萘二甲酸乙二酯、對排聚苯乙烯、原冰 片烯系聚合物、聚碳酸酯及聚芳酯構成之群組的至少一種 作爲構成成分； 該接著性改質層B具有聚酯（PEs)相與聚胺甲酸酯（PU) 相的微相分離構造或奈米相分離構造，該聚酯（PEs)與聚胺 甲酸酯（PU)的質量比（PEs/PU)係30/70〜70/30，而且使用掃 描型探針顯微鏡以相位測定模式來觀察硬被覆薄膜的切削 面時，在從接著性改質層B與硬被覆層C的界面起到深度 2Onm爲止的範圍內，下述式（1)所定義的接著性改質層B 之聚胺甲酸酯相（在相位像顯示明色相）的面積率係30%以 上且60%以下， PU相的面積率（％).= (PU相的面積/測定面積）x 1 〇〇…（1) 該硬被覆層C係具有丙烯酸酯系官能基的樹脂且其厚度 1360477 修正本 係在0.1〜30μιη的範圍內。 2· —種硬被覆薄膜，其特徵爲該硬被覆薄膜包含：在熱塑性 樹脂薄膜Α的一面或兩面上，形成有含共聚合聚酯及聚胺 甲酸酯的接著性改質層B之接著性改質基材薄膜，與在該 薄膜的任一面之接著性改質層B的表面上之含無機微粒子 的硬被覆層C，所積層而成的A/B/C或B/A/B/C之層構成 ，其中1. A hard coating film characterized in that the hard coating film comprises: an adhesive layer B containing a copolymerized polyester and a polyurethane on one or both sides of a thermoplastic resin film A/B/C or B/A/B formed by laminating a thin film of the inorganic fine particles on the surface of the adhesive layer B on either side of the film a layer composition of /C, wherein the thickness of the thermoplastic resin film A is in the range of 30 to 300 μm, and the thermoplastic resin film is selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate, and poly 2 At least one of a group consisting of ethylene 6-naphthalenedicarboxylate, a para-isolated polystyrene, a norbornene-based polymer, a polycarbonate, and a polyarylate as a constituent component; the adhesive-modified layer B has a poly The microphase separation structure or the nano phase separation structure of the ester (PEs) phase and the polyurethane (PU) phase, the mass ratio of the polyester (PEs) to the polyurethane (PU) (PEs/PU) 30/70 to 70/30, and when the scanning surface of the hard coating film is observed in a phase measurement mode using a scanning probe microscope, In the range from the interface between the adhesion-modified layer B and the hard coating layer C to a depth of 2 Onm, the polyurethane phase of the adhesion-modifying layer B defined by the following formula (1) (in the phase image display) The area ratio of the bright phase is 30% or more and 60% or less, and the area ratio (%) of the PU phase. = (area of the PU phase / measured area) x 1 〇〇 (1) The hard coating layer C has acrylic acid. The resin of the ester functional group and the thickness thereof is 1360477. The correction is in the range of 0.1 to 30 μm. 2. A hard coating film characterized in that the hard coating film comprises: an adhesive layer B containing a copolymerized polyester and a polyurethane on one or both sides of a thermoplastic resin film. The modified base film and the hard coating layer C containing inorganic fine particles on the surface of the adhesion modifying layer B on either side of the film are laminated A/B/C or B/A/B /C layer composition, of which 該熱塑性樹脂薄膜A之厚度係在30〜300μιη的範圍內， 且熱塑性樹脂薄膜Α係以選自由聚對酞酸乙二酯、聚對酞 酸丙二酯、聚2,6-萘二甲酸乙二酯、對排聚苯乙烯、原冰 片烯系聚合物、聚碳酸酯及聚芳酯構成之群組的至少一種 作爲構成成分； 該接著性改質層B具有聚酯（PEs)相與聚胺甲酸酯（PU) 相的微相分離構造或奈米相分離構造，該聚酯（PEs)與聚胺 甲酸酯（PU)的質量比（PEs/PU)係30/70〜70/30，接著性改質 層B的塗布量爲0.00 5〜0.20 g/m2，而且使用掃描型探針顯 微鏡以相位測定模式來觀察接著性改質層B的表面時，下 述（2)式所定義的接著性改質層B之表面的聚酯相（在相位 像顯示暗色相）的面積率在5卜11^54111的範圍內係35%以上 且低於9 0 % ’ PEs相的面積率（％) = (PEs相的面積/測定面積）x 100…（2) 該硬被覆層C係具有丙烯酸酯系官能基的樹脂且其厚度 係在0.1〜的範圍內。 1360477 修正本 3.如申請專利範圍第1或2項之硬被覆薄膜，其中硬被覆層 C中的無機微粒子之含量係20〜80質量。/。。 如申請專利範圍第1或2項之硬被覆薄膜，其中於熱塑性 樹脂薄膜中不含有或含有5 0PPm以下的粒子，於接著性改 質層中含有0.1〜20質量％的粒子。 5.如申請專利範圍第4項之硬被覆薄膜，其中粒子係矽石粒 子。 φ, 6.—種光學機能性薄膜，其爲在如申請專利範圍第1或2項 之硬被覆薄膜的與硬被覆層C之相反面上，積層有從硬被 覆層、光擴散層、稜鏡狀透鏡層、電磁波吸收層、近紅外 線遮斷層、透明導電層所選出的至少1層之光學機能層。 7.—種光學機能性薄膜，其爲在如申請專利範圍第1或2項 之硬被覆薄膜的硬被覆層C上，積層有抗反射層或防污層 的光學機能性薄膜。 ΦThe thickness of the thermoplastic resin film A is in the range of 30 to 300 μm, and the thermoplastic resin film is selected from the group consisting of polyethylene terephthalate, propylene terephthalate, and poly 2,6-naphthalene dicarboxylate. At least one of a group consisting of a diester, a para-polystyrene, a norbornene-based polymer, a polycarbonate, and a polyarylate as a constituent component; the adhesive-modified layer B has a polyester (PEs) phase and a poly The microphase separation structure or the nano phase separation structure of the urethane (PU) phase, the mass ratio of the polyester (PEs) to the polyurethane (PU) (PEs/PU) is 30/70 to 70/ 30. The coating amount of the adhesive layer B is 0.005 to 0.20 g/m2, and when the surface of the adhesive layer B is observed in a phase measurement mode using a scanning probe microscope, the following formula (2) The area ratio of the polyester phase (in the phase image showing the dark phase) of the surface of the modified layer B is defined to be more than 35% and less than 90% of the area ratio of the PEs phase in the range of 5 11 11^54111. (%) = (area of the PEs phase/measured area) x 100 (2) The hard coating layer C is a resin having an acrylate functional group and its thickness is Within the scope 0.1~. 1360477 Amendment 3. The hard coated film according to claim 1 or 2, wherein the content of the inorganic fine particles in the hard coating layer C is 20 to 80 mass. /. . The hard coating film according to claim 1 or 2, wherein the thermoplastic resin film does not contain or contain particles of 50 ppm or less, and the binder layer contains 0.1 to 20% by mass of particles. 5. The hard coated film of claim 4, wherein the particles are vermiculite particles. Φ, 6. An optical functional film which is formed on the opposite side of the hard coating film C as in the first or second aspect of the patent application from the hard coating layer, the light diffusion layer, and the rib At least one optical functional layer selected from the mirror lens layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer. An optical functional film which is an optical functional film in which an antireflection layer or an antifouling layer is laminated on a hard coating layer C of a hard coating film according to claim 1 or 2. Φ
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