1252328 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關防反射膜者。 【先前技術】 透過橋窗看展不物時’透過窗戶看景色時 戶表面映入外光，極不易看淸楚。因此，於櫥 構成之透明基材上進行貼附防反射膜者。 做爲此防反射膜者通常，於透明塑膠膜上 化合物、有機氟化合物所成單層之低折射率層 射層之防反射膜被使用之，同時亦於透明塑膠 低衍射率與高衍射層之2層以上層所成之防反 射膜被使用之。 此等防反射層係由金屬氧化物之無機化合 。防反射層係利用濕式塗層法、真空作業法所 於真空作業法之使用耗費成本太高，因此，以 進行形成者宜。惟，濕式塗層法之防反射性能 ’爲充份取得防反射性足之方法，被提出以組 法與氣相法後形成防反射層之方法（特開平1 ( 報）。惟，藉由濕式塗層法所形成之層與氣相 層相互間目前爲止無法有效取得完全密合者， 不足者。爲提昇密合性公知者有以特定組合物 射層之方法（特開2 0 0 3 — 〇 〇 5 〇 6 9號公報）， 得密合性不足者。 ，櫥窗、窗 窗、窗戶所 形成由無機 所成之防反 膜上形成由 射層的防反 物所構成者 形成者。由 濕式塗層法 不足，因此 合濕式塗層 >—72 8號公 法所形成之 取得耐久性 質構成防反 目前仍僅取 >4 > (2) Ϊ252328 【發明內容】 本發明目的係提供一種解決上述問題，藉由濕式塗層 法形成防反射層之中衍射率層後，藉由氣相法形成高衍射 率層之同時，此等層相互具良好密合性以及具備良好之物 理性及化學耐久性、與具備良好防反射性能之防反射膜者 〇 亦即，本發明之特徵係由透明基材、及其上所設置之 防反射層所成之防反射膜者，該防反射層係藉由滿足由設 置於透明基材上之第1層，設置於其上之第2層及設置於 其上之第3層所成、第1層及第2層爲至少1種選自鈦及 鉻所成群之金屬氧化物所成之下式者爲其特徵之防反射膜 者。 P 1 >P2 惟，P1=01/M1、P2 = 〇2/M2者，01爲構成第 1層之 氧元素之數，Ml爲構成第1層之金屬元素之數，〇2爲構 成第2層氧元素之數，M2爲構成第2層金屬元素之數者 〇 以下進行本發明之詳細說明。 <透明基材> 本發明中透明基材係保持防反射層之透明基材者。透 明基材以有機高分子之薄膜爲其工業生產性較佳者。 做爲有機高分子例如：聚酯（如：聚對苯二甲酸乙二 (3) 1252328 醇酯、聚乙烯萘）、聚（甲基）丙烯基（如：聚甲基丙烯 酸甲酯）、聚碳數酯、聚苯乙烯、聚乙烯醇、聚氯化乙烯 、聚氯化亞乙烯、聚乙烯、乙烯-醋酸乙烯共聚物、聚胺 基甲酸乙酯、三乙醯纖維素、玻璃紙等例。其中由透明性 、強度等面視之，又以聚對苯二甲酸乙二醇酯、聚碳酸酯 、聚甲基丙烯酸甲酯、三乙醯纖維素爲較佳者。 有機高分子薄膜可爲無延伸薄膜，亦可爲延伸薄膜者 。如：聚酯薄膜通常做爲雙軸延伸薄膜使用之、聚碳酸酯 薄目吴、三乙酸酯薄膜、玻璃紙薄膜通常做爲無延伸薄膜之 用者。透明基材中亦可形成密合性附與層。 透明基材理想厚度爲5〜1 0 0 0 // m者，惟，此厚度可 依其防反射膜之用途進行適當選取。 <硬塗佈層> 透明基材中爲附與所期待硬度於防反射膜，進行設定 硬塗佈層者宜。硬塗佈層以透明者佳，具適當硬度者。硬 塗佈層可使用如：電離放射線硬化樹脂、紫外線硬化樹脂 、熱硬化性樹脂者。特別以紫外線照射硬化型之丙烯樹脂 或有機矽樹脂、熱硬化型之聚矽氧烷樹脂爲更佳者。此等 樹脂可使用公知者。 形成硬塗佈層時，以表面呈平滑且均勻形成之塗佈方 袪爲宜。 硬塗佈層以含有平均粒徑〇 . 〇 1〜3 // m之透明無機微粒 子及/或有機微粒子者宜。該含有者又以混合分散之形態 -6 - (4) 1252328 者宜。藉此可取得稱爲抗眩耀之光擴散性者。而於此附與 光擴散性之硬塗佈層上形成防反射層後，影像之霧面減少 ’相較於僅進行光擴散性處理者更可取得明亮之影像。 <防反射層> 防反射層之第1層及第2層以至少1種選自鈦及鉻所 成群之金屬氧化物所成者較可取得理想衍射率及良好透明 性以及密合性者。 本發明中防反射層爲滿足下記關係式者。當滿足此條 件後，可取得防反射性能者。 P1>P2 惟，P1=01/M1、P2 = 02/M2者，01代表構成第 1層 氧元素之數，Ml爲構成第1層金屬元素之數，02爲構成 第2層氧元素之數，M2爲構成第2層金屬元素之數者。 爲滿足該元素比率，該防反射層之第1層爲源於鈦及 /或鉻之烷氧基化合物物質之層者宜。 源於鈦及/或鍩之烷氧化物物質之層係以溶劑稀釋鈦 及/或鉻之烷氧化物後，於塗佈、乾燥步驟中進行水解後 形成者宜。此時，塗佈後之塗佈層進行熱處理即可。此熱 處理於透明基材之熱變形溫度以下進行即可。如：透明基 材爲聚對第二甲基乙二醇酯薄膜時，可於約80〜150 °C之 溫度下進行熱處理3 0秒〜5分鐘者。藉由此熱處理後，可 形成氧化矽之凝膠膜。熱處理條件依其透明基材之種類、 厚度而異，因此，可適時選取之。 (5) 1252328 做爲鈦及/或鍩之烷氧基化合物具體例可使用下記式 所示之化合物者。此等可以單量體使用之，亦可以2〜6量 體使用之。 M ( OR ) 4 惟，Μ代表Ti或Zr、R代表碳數1〜；[〇之烷基。 防反射層之第1層及/或第2層中，亦可添加金屬氧 化物之微粒子，爲調整衍射率亦可添加有機矽化合物。 防反射層之第2層由可取得良好密合性及透明性觀點 視之，以滿足下記式者宜。 1.65^ P2 ^ 1.95 更理想者爲滿足下記式者。 1.75^ P2 ^ 1.90 當P2超出此範圍之上限則將變成低強度之防反射層 、不足下限則僅能取得與第1層密合性低者，產生光吸收 ，呈不良之透明性者。 第2層係以代表物理性氣相法之濺射法所形成者。藉 由塗佈法形成第2層後，不易調整P2於該範圍內者。濺 射法中，於薄膜形成時導入稀氣體後改變反應性氣體之組 成後，可輕易控制所形成之第2層P2者。 以濺射法形成第2層時，伴隨濺射所使用靶之原子爲 高能量而突出透明基材，取得對於透明基材之投錨效果， 無關透明基材之濕潤性，可取得強力密合於透明基材之第 2層。 更且，祀變大後，輕易進行大面積之濺射。 (6) 1252328 f-曰由私射法形成弟2層時，可利用使用氧化物做爲革巴 後，形成氧化鈦或氧化鉻之薄膜層（第2層）之方法、與 使用金屬做爲靶，於膜形成中導入稀氣體與氧化性氣體（ 如：氧、臭氧）後形成氧化鈦或氧化銷之薄膜層（第2層 )之方法（反應性濺射法）者。 藉由前者之方法時，不易調整第2層之P2。藉由後 者之方法（反應性濺射法）時，改變稀氣體與氧化性氣體 之組成後’可進行P 2之調整。更且，此方法中，可於膜 形成速度慢之氧化物形態與膜形成速度快之金屬形態當中 形成第2層之膜，因此，相較於前者方法，較具快速形成 膜之優點。故，藉由後者之方法（反應性濺射法）形成第 2層者佳。 更針對第2層之濺射方法進行詳細說明。 雜射係於電漿發光強度之測定方法與反應性氣體之流 量控制方法相互之組合裝置下進行者宜。做爲電漿發光強 度之測定方法者，設置可監視電漿發光領域之位置後，以 使用可測定電漿中金屬勃起發光強度（電漿發光強度）之 監控器者宜。做爲反應性氣體之流量控制方法者，將設定 値與監控器所測定之電漿發光強度進行比較演算後，自動 調節氣體流量調整並使測定値與設定値相等後，利用控制 各室之氧化性氣體流量裝置（以下稱「PEM」）者宜。 做爲組合電漿發光強度之測定方法與反應性氣體流量 控制方法之裝置者可使用市販之A I d e n e公司製之r P E Μ 0 5」者。 (7) 1252328 此時，使用氬氣體之金屬鈦或金屬鉻之靶進行放電時 (亦即，形成金屬鈦或金屬锆之薄膜時）之電漿發光強度 測定値做成90，將電漿發光強度之設定値設定爲小於此 値即可。當電漿發光強度之設定値變小則導入氧氣之閥的 開度變大，提昇氧化度（P 2 )，反之，該設定値變大則導 入氧氣之閥的開度變小，而降低氧化度（P2 )。亦即，：P2 採用反應性濺射後，藉由調整電漿發光強度後，可調整之 〇 爲使P2於本發明範圍內者，電漿發光強度以20〜30 者宜，更佳者爲22〜28。 反應性濺射法中，可使用如：直流磁控管方式、高周 波磁控管方式、雙列陰極磁控管方式、電子回旋加速器共 振方式者。此等任意方法本身均爲公知者。 第3層由可取得理想強度，衍射率及透明性之觀點視 之，以矽之氧化物膜爲理想者。第3層可任意以濕式法及 氣相法進行形成之，惟，低成本可形成者，又可取得高度 透明性者以濕式法之形成爲較佳者。以濕式法形成第2層 時，以使用矽之烷氧化物進行形成者宜。此時，可取得高 強度之防反射層者。 做爲矽之烷氧化物者可使用如：四乙基矽酸酯、四甲 基矽酸酯、四異丙氧基矽酸酯、四丁氧基矽酸酯者。此等 可以單量體使用之，亦可使用多量體者。 第3層中，亦可依其所期待膜之硬度，柔軟性及表面 性進行適當添加下記一般式所示之有機矽化合物。 -10- (8) 1252328 R】nR bSiX4_ (n+b) (R1、R2分別爲具有烷基、脂烯基、烯丙基或、鹵 素基、環氧基、胺基、氫硫基、甲基丙嫌基、氟基或氰基 之烷基、X爲碳數1〜8之烷氧基者’ a、b分別爲〇·】、或 2者，a + b爲2以下之數者。） 做爲由矽烷氧基化合物形成第3層之氧化矽膜之方法 者以藉由水解該砂院氧化合物後取得之溶膠於第2層上進 行塗佈、乾燥及硬化之方法者佳。 做爲調整溶膠之方法者以溶解該矽化合物於有機溶媒 後進行水解之方法者宜。做爲有機溶媒者可使用如：異丙 醇、甲醇、乙醇等醇；丁酮、甲基異丁酮等酮；醋酸乙酯 、醋酸丁酯等酯；甲苯、二甲苯等芳香族烴基；鹵化烴基 者。此等可單獨使用，亦可以混合物使用之。 矽烷氧化合物於溶媒中以烷氧基化合物爲1 〇〇%水解 及縮合時所發生之氧化矽換算下，以 〇. 1 %重量以上，更 佳者爲0 . 1〜1 0重量％之濃度進行溶解者宜。當濃度爲不足 0 . 1重量％時，則所形成之溶膠膜無法充份發揮所期待之 特性，超出1 0重量％則將不易形成透明均質膜而不理想 〇 取得溶液太少時可添加必要水量於水解中，於1 5〜3 5 °C，更佳者爲22〜28 °C之溫度下，0.5〜48小時，更佳者爲 2〜35小時進行攪拌、水解之。1252328 (1) Description of the Invention [Technical Field of the Invention] The present invention relates to an antireflection film. [Prior Art] When you look at the exhibition through the bridge window, when you look at the scenery through the window, the surface of the household is reflected in the external light, which is extremely difficult to see. Therefore, the antireflection film is attached to the transparent substrate formed of the cabinet. As an antireflection film for this purpose, an antireflection film of a low refractive index layer which is a single layer of a compound or an organic fluorine compound on a transparent plastic film is used, and a low diffraction rate and a high diffraction layer of a transparent plastic are also used. An antireflection film made of two or more layers is used. These antireflection layers are inorganically combined with metal oxides. The use of the anti-reflection layer by the wet coating method or the vacuum method is expensive because the use of the vacuum method is too high. Therefore, it is preferable to form it. However, the anti-reflection performance of the wet coating method is a method for obtaining an antireflection effect sufficiently, and a method of forming an antireflection layer by a group method and a vapor phase method is proposed (Special Kaiping 1 (Report). The layer formed by the wet coating method and the vapor phase layer have not been able to effectively achieve complete adhesion between them, and are insufficient. In order to improve the adhesion, a method of spraying a layer with a specific composition is known (Specially Opened 20) 0 3 — 〇〇5 〇6 No. 9 bulletin), those who have insufficient adhesion. The window, window, window, and window formed by the inorganic anti-reflection film formed by the anti-reflection of the shot layer. The wet coating method is insufficient, so that the durability of the wet coating layer formed by the public method of No. 72 No. 8 is still only taken > 4 > (2) Ϊ 252328 [Invention] The present invention It is an object of the present invention to provide a solution for solving the above problems. After forming a diffraction rate layer in an antireflection layer by a wet coating method, a high diffraction rate layer is formed by a vapor phase method, and the layers have good adhesion to each other and have Good physical and chemical durability, and An antireflection film having good antireflection properties, that is, the invention is characterized in that the antireflection film is formed of a transparent substrate and an antireflection layer provided thereon, and the antireflection layer is provided by satisfying The first layer on the transparent substrate, the second layer disposed thereon, and the third layer disposed thereon, and the first layer and the second layer are at least one selected from the group consisting of titanium and chromium. The anti-reflection film characterized by the metal oxide is P 1 > P2, P1 = 01/M1, P2 = 〇 2 / M2, 01 is the number of oxygen elements constituting the first layer. Ml is the number of metal elements constituting the first layer, 〇2 is the number of oxygen elements constituting the second layer, and M2 is the number of metal elements constituting the second layer. The present invention will be described in detail below. > In the present invention, the transparent substrate is a transparent substrate that holds the antireflection layer. The transparent substrate is preferably industrially productive with a film of an organic polymer. As an organic polymer such as polyester (eg, poly Ethylene terephthalate (3) 1252328 alcohol ester, polyethylene naphthalene), poly(methyl) propylene (eg polymethyl methacrylate), poly Examples of carbon number ester, polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride, polyethylene, ethylene-vinyl acetate copolymer, polyurethane, triethyl cellulose, cellophane, and the like. Among them, transparency, strength, etc., and polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and triethyl hydrazine cellulose are preferred. The organic polymer film can be There is no stretch film, and it can also be a stretch film. For example, polyester film is usually used as a biaxially stretched film, and polycarbonate thin film, triacetate film, and cellophane film are generally used as non-stretch film. An adhesive adhesion layer may also be formed in the transparent substrate. The transparent substrate preferably has a thickness of 5 to 1 0 0 // // m, but the thickness may be appropriately selected depending on the use of the antireflection film. <Hard coating layer> In the transparent substrate, it is preferable to set the hard coating layer with the desired hardness in the antireflection film. The hard coating layer is preferably transparent, and has a suitable hardness. As the hard coat layer, for example, an ionizing radiation hardening resin, an ultraviolet curable resin, or a thermosetting resin can be used. In particular, an ultraviolet ray-curable acryl resin, an organic oxime resin, or a thermosetting polyoxymethane resin is more preferable. These resins can be used by known ones. When the hard coat layer is formed, it is preferred to coat the surface in a smooth and uniform form. The hard coat layer is preferably one containing transparent inorganic fine particles and/or organic fine particles having an average particle diameter of 〜 1 to 3 // m. The inclusion is also in the form of mixed dispersion -6 - (4) 1252328. By this, it is possible to obtain a light diffusing property called anti-glare. On the other hand, when the antireflection layer is formed on the light-diffusing hard coat layer, the image of the matte side of the image is reduced, and a brighter image is obtained than that of the light diffusing process alone. <Anti-reflection layer> The first layer and the second layer of the anti-reflection layer are preferably made of at least one metal oxide selected from the group consisting of titanium and chromium, and have an excellent diffraction ratio, good transparency, and adhesion. Sex. In the present invention, the antireflection layer is a one that satisfies the following relationship. When this condition is met, the anti-reflection performance can be obtained. P1> P2, where P1 = 01/M1, P2 = 02/M2, 01 represents the number of oxygen elements forming the first layer, M1 is the number of metal elements constituting the first layer, and 02 is the number of oxygen elements constituting the second layer. M2 is the number of metal elements constituting the second layer. In order to satisfy the element ratio, the first layer of the antireflection layer is preferably a layer derived from a titanium and/or chromium alkoxide material. The layer derived from the alkoxide material of titanium and/or bismuth is diluted with a solvent of titanium and/or chromium alkoxide, and then formed after hydrolysis in a coating and drying step. At this time, the applied coating layer may be subjected to heat treatment. This heat treatment may be carried out below the heat distortion temperature of the transparent substrate. For example, when the transparent substrate is a polyethylene terephthalate film, heat treatment can be carried out at a temperature of about 80 to 150 ° C for 30 seconds to 5 minutes. By this heat treatment, a gel film of cerium oxide can be formed. The heat treatment conditions vary depending on the type and thickness of the transparent substrate, and therefore, it can be selected as appropriate. (5) 1252328 As a specific example of the alkoxy compound of titanium and/or ruthenium, a compound represented by the following formula can be used. These can be used in a single unit, and can also be used in 2 to 6 parts. M ( OR ) 4 , Μ represents Ti or Zr, and R represents a carbon number of 1~; [〇 alkyl. In the first layer and/or the second layer of the antireflection layer, fine particles of metal oxide may be added, and an organic ruthenium compound may be added to adjust the diffraction rate. The second layer of the antireflection layer is preferably obtained from the viewpoint of obtaining good adhesion and transparency. 1.65^ P2 ^ 1.95 It is more desirable to satisfy the following formula. 1.75^ P2 ^ 1.90 When P2 is outside the upper limit of this range, it will become a low-intensity anti-reflection layer. If the lower limit is used, only the lower adhesion to the first layer will be obtained, and light absorption will occur, resulting in poor transparency. The second layer is formed by a sputtering method representing a physical vapor phase method. After the second layer is formed by the coating method, it is difficult to adjust P2 within the range. In the sputtering method, after the thin gas is introduced at the time of film formation and the composition of the reactive gas is changed, the formed second layer P2 can be easily controlled. When the second layer is formed by a sputtering method, the atom of the target used for sputtering is high energy and the transparent substrate is protruded, and the anchoring effect on the transparent substrate is obtained, and the wettability of the transparent substrate is not affected, and strong adhesion can be obtained. The second layer of the transparent substrate. Moreover, after the 祀 becomes large, a large area of sputtering is easily performed. (6) 1252328 f-曰 When the two layers are formed by the private shot method, the method of forming the thin film layer (the second layer) of titanium oxide or chromium oxide after using the oxide as the grain can be used as the method of using the metal. A method in which a thin film and a oxidizing gas (for example, oxygen or ozone) are introduced into a film to form a thin film layer (second layer) of titanium oxide or an oxidized pin in a film formation (reactive sputtering method). With the former method, it is difficult to adjust the P2 of the second layer. In the latter method (reactive sputtering method), the composition of the lean gas and the oxidizing gas is changed, and P 2 can be adjusted. Further, in this method, the film of the second layer can be formed in the metal form in which the film formation rate is slow and the film formation speed is fast, and therefore, the film is more rapidly formed than the former method. Therefore, it is preferable to form the second layer by the latter method (reactive sputtering method). The sputtering method of the second layer will be described in detail. The miscellaneous system is preferably carried out under a combination of a method for measuring the luminous intensity of the plasma and a method for controlling the flow rate of the reactive gas. As a method for measuring the intensity of plasma luminescence, it is preferable to use a monitor capable of measuring the illuminance of metal erection (plasma luminescence intensity) in the plasma after monitoring the position in the field of plasma luminescence. As a method of controlling the flow rate of the reactive gas, after comparing the setting and the plasma luminous intensity measured by the monitor, automatically adjusting the gas flow rate adjustment and making the measured enthalpy equal to the set enthalpy, and controlling the oxidation of each chamber by using A gas flow device (hereinafter referred to as "PEM") is preferred. As a means for measuring the combined luminous intensity of the plasma and the method for controlling the reactive gas flow rate, a commercially available R P E Μ 0 5" manufactured by A I d e n e Co., Ltd. can be used. (7) 1252328 At this time, when the discharge is performed using a target of titanium metal or chromium metal of argon gas (that is, when a film of titanium metal or zirconium metal is formed), the luminescence intensity of the plasma is determined to be 90, and the plasma is illuminated. The setting of the intensity is set to be smaller than this. When the setting of the luminous intensity of the plasma becomes smaller, the opening degree of the valve into which the oxygen is introduced becomes larger, and the degree of oxidation (P 2 ) is increased. Conversely, when the setting becomes larger, the opening of the valve into which the oxygen is introduced becomes smaller, and the oxidation is lowered. Degree (P2). That is, after P2 is used for reactive sputtering, after adjusting the luminous intensity of the plasma, it can be adjusted so that P2 is within the scope of the present invention, and the luminous intensity of the plasma is preferably 20 to 30, and more preferably 22~28. In the reactive sputtering method, for example, a DC magnetron method, a high-frequency magnetron method, a double-row cathode magnetron method, or an electron cyclotron resonance method can be used. Any of these methods are well known per se. The third layer is preferable from the viewpoint of obtaining an ideal strength, a diffraction ratio, and transparency, and an oxide film of ruthenium. The third layer can be formed arbitrarily by a wet method or a vapor phase method, but it is preferable that the method can be formed at a low cost and a high transparency can be formed by a wet method. When the second layer is formed by a wet method, it is preferred to form it by using an alkoxide of ruthenium. In this case, a high-strength anti-reflection layer can be obtained. As the alkoxide of ruthenium, for example, tetraethyl phthalate, tetramethyl phthalate, tetraisopropoxy phthalate or tetrabutoxy phthalate can be used. These can be used in a single unit, and can also be used in a large number. In the third layer, an organic ruthenium compound represented by the general formula may be appropriately added depending on the hardness, flexibility and surface properties of the film desired. -10- (8) 1252328 R]nR bSiX4_ (n+b) (R1, R2 respectively have an alkyl group, a fatty alkenyl group, an allyl group, a halogen group, an epoxy group, an amine group, a hydrogenthio group, a The alkyl group of a propyl group, a fluorine group or a cyano group, and the alkoxy group having a carbon number of 1 to 8 'a and b are respectively 〇·, or 2, and a + b is 2 or less. The method of forming the third layer of the cerium oxide film from the decyloxy compound is preferably carried out by coating, drying and hardening the sol obtained by hydrolyzing the sand compound oxygen compound on the second layer. As a method of adjusting the sol, it is preferred to dissolve the ruthenium compound in an organic solvent and then hydrolyze it. As an organic solvent, an alcohol such as isopropanol, methanol or ethanol; a ketone such as methyl ethyl ketone or methyl isobutyl ketone; an ester such as ethyl acetate or butyl acetate; an aromatic hydrocarbon group such as toluene or xylene; and halogenation can be used. Hydrocarbon based. These may be used singly or as a mixture. The concentration of the decane-oxygen compound in the solvent is 〇. 1% by weight or more, more preferably 0.1 to 1% by weight, based on the cerium oxide generated when the alkoxy compound is hydrolyzed and condensed by 1% by weight. It is advisable to carry out the dissolution. When the concentration is less than 0.1% by weight, the formed sol film does not sufficiently exhibit the desired characteristics, and if it exceeds 10% by weight, it is difficult to form a transparent homogeneous film, and it is not preferable to add a solution when it is too small. The amount of water is stirred and hydrolyzed in the hydrolysis at a temperature of from 15 to 35 ° C, more preferably from 22 to 28 ° C, from 0.5 to 48 hours, more preferably from 2 to 35 hours.
水解時，以使用觸媒者宜。做爲觸媒者如：鹽酸、硝 酸、硫酸或醋酸等酸者宜。使觸媒之酸做成〇 . 〇 〇 〇〗〜]2N -11 - 1252328 Ο) ’更佳者Ο . Ο 〇 Ο 5〜5 N之水丨谷液進行添加者宜。此水溶液中 之水份做爲水解用之水使用者亦可，而總溶液之p Η調整 呈4〜10者宜。做爲觸媒者亦可使用氨等之鹽基者。 做爲取得溶膠之塗佈方法者，可使用一般塗層作業所 使用之方法者’如：旋轉塗層法、浸漬法、噴塗法、滾奉昆 塗層法、毛細現象塗層法、彈性版印刷法、網版印刷法、 珠狀塗層法、微影寫塗層法者。 於溶膠塗佈後’進行塗佈層之熱處理。此熱處理於透 明基材之熱變形溫度以下進行之。如··透明基材爲聚對苯 二甲基乙二醇酯時’以80〜150 °C之溫度，進行熱處理30 秒至5分鐘後形成氧化矽之凝膠膜即可。熱處理之條件依 其使用透明基材之種類、厚度而異，因此，可因應所使用 透明基材之種類進行決定之。 <防污層> 保護防反射層之表面後，爲更提高防污性亦可於防反 射層上形成防污層。做爲形成材料者可使用如：具有疏水 性之化合物者’具體例可使用如：氟碳、全氟矽烷、及此 等高分子化合物者。特別是爲提昇指紋擦拭污性時使用具 有抗油性之高分子化合物者宜。 防污層因應形成所使用材料，亦可使用真空蒸鍍法、 濺射法、離子磨擦法、電漿CVD法、電發聚合法等真空 製膜程序形成之’亦可使用微影寫法、網版法、浸漬法等 濕式程序之塗佈方法形成之。 (10) 1252328 設置防污層時’以不損及防反射層之機能下，形成防 污層膜厚爲1〜5 Onm者宜，大於此厚度時，將影響防反射 層之機能’反之’小於此厚度將不易出現防污性功能而不 理想。 本發明係提供一種藉由濕式塗層法形成防反射層之中 ft"射率層後’藉由氣相法形成高衍射率層之同時，此等層 相互具備良好密合性及良好物理性及化學性耐久性、且具 備良好防反射性能之防反射膜者。 【實施方式】 〔實施例〕 以下列舉實施例進行本發明更詳細之說明。 又’以下記方法進行評定薄膜特性。「份」爲重量份 者0 (1 )密合性 使防反射膜於6 0 °C下經過5 0 0小時後，藉由切割刀 由防反射層側以間隔2mm，切入縱橫各6條之切割網， 作成25個橫盤格。於此橫盤格上附上透明膠帶，以90 ° 剝離角度剝離透明膠帶，防反射膜上藉由目測計算所殘留 防反射層之橫盤格數，依以下基準進行評定之。 〇：殘留2 5個（無剝離） △ : 20〜24個 X : 1 9個以下 -13- (11) 1252328 (2) Μ、Ο之元素比率 利用 X線光電子分光裝置PHI — QUANT AN — 2000 ( PHI製），表面進行濺射之同時，測定Μ、〇之比率。 測射條件；Ar+、E = 0.5KeV、2mm□虹彩釉、濺射速 度1.5m/分鐘（Si〇2換算） (3 )裂化 將防反射膜卷於 8mm 0之棒、防反射層面呈外側卷 曲之，維持1 〇秒後，觀察防反射層、目測是否出現龜裂 〇 〇：無裂化 X :有裂化 〔塗料1〕 針對2 5份乙基矽酸酯進行添加3 7.6份乙醇，更加入 17.5份精製水、6份0.001 N HC1，於23°C下進行水解 2 4小時後做成塗層劑。 〔實施例1〕 使用易黏合處理之雙軸配向聚對苯二甲酸乙二醇酯膜 (帝人製：Ο P F W - 1 8 8 // m )做爲透明基材，於此單面使 U V硬化性硬塗層劑（J S R製：d e s ο 1 i t e Z 7 5 0 1 )以棒塗層 進行塗佈乾燥、uv硬化後設置硬塗佈層，再於硬塗佈層 -14- (12) 1252328 上以棒塗層塗佈四丁基鈦酸酯之4量體（商標：T B T B〜 4日本曹達製）之石油醚/n —丁醇（3 / ])溶液，]5 〇 °C下 乾燥]分鐘後，形成厚度約爲 Π 之防反射層之第] 層。When hydrolyzing, it is preferred to use a catalyst. As a catalyst, such as hydrochloric acid, nitric acid, sulfuric acid or acetic acid. Make the acid of the catalyst into 〇. 〇 〇 〇 〗 〖~2N -11 - 1252328 Ο) ‘Better Ο. Ο 〇 Ο 5~5 N Water glutinous rice liquid should be added. The water in the aqueous solution may be used as the water for hydrolysis, and the p Η of the total solution is preferably adjusted to 4 to 10. As a catalyst, you can also use a base such as ammonia. As a method for obtaining a coating method for a sol, a method for a general coating operation can be used, such as a spin coating method, a dipping method, a spray coating method, a rolling coating method, a capillary phenomenon coating method, and an elastic version. Printing method, screen printing method, bead coating method, lithography writing coating method. The heat treatment of the coating layer was carried out after the sol coating. This heat treatment is carried out below the heat distortion temperature of the transparent substrate. For example, when the transparent substrate is poly(p-xylylene glycol), the gel film of cerium oxide may be formed by heat treatment at a temperature of 80 to 150 ° C for 30 seconds to 5 minutes. The conditions of the heat treatment vary depending on the type and thickness of the transparent substrate to be used, and therefore, it can be determined depending on the type of the transparent substrate to be used. <Antifouling layer> After protecting the surface of the antireflection layer, an antifouling layer can be formed on the antireflection layer in order to further improve the antifouling property. As the material for formation, for example, a compound having hydrophobicity can be used. Specific examples thereof include fluorocarbon, perfluorodecane, and the like. In particular, it is preferable to use a polymer compound having oil resistance in order to improve fingerprint wiping. The antifouling layer may be formed by a vacuum film forming process such as a vacuum deposition method, a sputtering method, an ion rub method, a plasma CVD method, or an electron polymerization method, depending on the material to be used. The coating method of a wet process such as a plate method or a dipping method is formed. (10) 1252328 When setting the anti-fouling layer, the film thickness of the anti-fouling layer should be 1~5 Onm under the function of not damaging the anti-reflection layer. If it is larger than this thickness, it will affect the function of the anti-reflection layer. If the thickness is smaller than this, the antifouling function will not easily occur, which is not desirable. The present invention provides a method for forming a high-diffraction layer by a vapor phase method by forming a high-diffraction layer by a vapor phase method by forming a ft"aluminescence layer in an anti-reflection layer by a wet coating method, and these layers have good adhesion to each other and good physical properties. Anti-reflective film with good anti-reflective properties and chemical durability. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples. Further, the film properties were evaluated by the following methods. "Parts" are parts by weight. 0 (1) Adhesiveness After the anti-reflection film is allowed to pass at 60 ° C for 500 hours, the cutting blade is cut into the longitudinal and lateral directions by 2 mm at intervals of 2 mm from the side of the anti-reflection layer. Cut the net and make 25 horizontal plates. Scotch tape was attached to the horizontal panel, and the scotch tape was peeled off at a peeling angle of 90 °, and the number of the horizontal discs of the residual antireflection layer was calculated by visual observation on the antireflection film, and evaluated according to the following criteria. 〇: Residue 2 5 (no peeling) △ : 20~24 X : 1 9 or less - 13 - (11) 1252328 (2) Element ratio of Μ and 利用 using X-ray photoelectron spectroscopy PHI — QUANT AN — 2000 (PHI system), the ratio of ruthenium and osmium was measured while sputtering was performed on the surface. Measurement conditions; Ar+, E = 0.5KeV, 2mm □ iridescent glaze, sputtering speed 1.5m / min (Si〇2 conversion) (3) Cracking anti-reflection film rolled on 8mm 0 rod, anti-reflection layer is curled on the outside After 1 sec., observe the anti-reflection layer and visually check for cracks. 无 No cracking X: Cracking [Coating 1] Add 3 7.6 parts of ethanol to 25 parts of ethyl phthalate, and add 17.5. A portion of purified water, 6 parts of 0.001 N HCl, was hydrolyzed at 23 ° C for 24 hours to form a coating agent. [Example 1] A biaxially oriented polyethylene terephthalate film (manufactured by Teijin: PFPFW - 1 8 8 // m) which is easy to be bonded was used as a transparent substrate, and UV hardening was performed on one side thereof. Hard coating agent (made by JSR: des ο 1 ite Z 7 5 0 1 ) coated and dried with a bar coating, uv hardened and then provided with a hard coating layer, and then hard coated layer - 14 - (12) 1252328 A solution of tetraether titanate (trademark: TBTB~4, manufactured by Nippon Soda) of petroleum ether/n-butanol (3 / ]) was applied as a bar coating, and dried at 5 ° C. After a minute, a second layer of an antireflection layer having a thickness of about Π is formed.
取得薄膜裝設於P EM組裝之濺射裝置，減壓至3 X 1 0 — 3 P a。隨後投入A r氣體後，氣壓做爲〇. 5 P a，靶中利 用Τι加入1 kW之電力進行濺射，測定此時之Ti電漿發 光強度做爲90。之後，設定電漿發光強度，導入〇2氣體 後，使Ti之電漿發光強度保持於25之同時打開開關，開 始對於薄膜進行成膜，使防反射層之第2層形成2 5 nm者 。更以棒塗層塗佈塗料1後1 5 0 °C下進行乾燥1分鐘，形 成厚度1 0 〇 n m防反射層之第3層，取得防反射膜。 〔實施例2〕The film was placed in a P EM assembled sputtering apparatus and depressurized to 3 X 1 0 - 3 P a . After the introduction of the Ar gas, the gas pressure was taken as 〇. 5 P a, and the target was irradiated with 1 kW of electric power for sputtering, and the light intensity of the Ti plasma at this time was measured as 90. Thereafter, the plasma luminous intensity was set, and after the 〇2 gas was introduced, the plasma of the Ti was kept at 25 while the switch was turned on, and the film was formed to form a film so that the second layer of the antireflection layer was formed at 25 nm. Further, the coating material 1 was applied with a bar coating layer and dried at 150 ° C for 1 minute to form a third layer having a thickness of 10 〇 n m of the antireflection layer, and an antireflection film was obtained. [Example 2]
形成防反射層之第2層時，使Ti之電漿發光強度做 成2 7之外，與實施例1同法進行之。 〔實施例3〕 形成防反射層之第2層時，使Ti之電漿發光強度做 成3 0之外，與實施例1同法進行之。 〔實施例4〕 形成防反射層之第2層時，以Zr做爲靶之使用之外 :與實施例1同法進行之。 -15- (14) 1252328 (14)When the second layer of the antireflection layer was formed, the plasma luminescence intensity of Ti was made to be 27, and the same procedure as in Example 1 was carried out. [Example 3] When the second layer of the antireflection layer was formed, the plasma luminescence intensity of Ti was made 30, and the same procedure as in Example 1 was carried out. [Example 4] When the second layer of the antireflection layer was formed, the use of Zr as a target was carried out in the same manner as in Example 1. -15- (14) 1252328 (14)
表] 實 施 例1 實 施 例2 實 施 例3 實 施 例4 實 施 例5 比 較 例1 比 較 例2 電漿發 光強度 25 27 3 0 25 20 3 5 — P2 (M2/02) 1.86 1.80 1.69 1.85 1 .94 1.52 1.49 P 1 (Ml/Ol) 2.06 1.9 1 1.85 2.00 2.10 1.62 1.66 密合性 〇 〇 〇〜△ 〇 〇 X X 裂化 〇 〇 〇 〇 X 〇 〇Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Plasma luminescence intensity 25 27 3 0 25 20 3 5 — P2 (M2/02) 1.86 1.80 1.69 1.85 1.94 1.52 1.49 P 1 (Ml/Ol) 2.06 1.9 1 1.85 2.00 2.10 1.62 1.66 Adhesion 〇〇〇~△ 〇〇XX Cracking 〇〇〇〇X 〇〇
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