TW201218218A - Transparent conductive film and method for manufacturing the same - Google Patents

Transparent conductive film and method for manufacturing the same Download PDF

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Publication number
TW201218218A
TW201218218A TW100115582A TW100115582A TW201218218A TW 201218218 A TW201218218 A TW 201218218A TW 100115582 A TW100115582 A TW 100115582A TW 100115582 A TW100115582 A TW 100115582A TW 201218218 A TW201218218 A TW 201218218A
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Taiwan
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transparent conductive
film
conductive film
quot
oxide
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TW100115582A
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Chinese (zh)
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TWI512765B (en
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Naka Tatami
Toshiyuki Oya
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Toyo Boseki
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • C23C14/086Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/3407Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Physical Vapour Deposition (AREA)
  • Position Input By Displaying (AREA)

Abstract

The invention provides a transparent conductive film having excellent resistance stability and pen input durability when it is used in a touch panel under high temperature and high humidity condition, as well as provides an effective method for manufacturing the same. The solution of the present invention is a transparent conductive film which is formed on at least one side of a transparent plastics film substrate by laminating a transparent conductive membrane. The said transparent conductive membrane not only comprises an indium oxide, and further comprises at least 0.1 to 5 mass% in average of a tin oxide, and at least 0.1 to 5 mass% in average of a substance selected from a specified substance group, as well as the specific resistance of the said transparent conductive is in the range of 4*10<SP>-4</SP> to 2.5*10<SP>-3</SP>Ω.cm.

Description

201218218 六、發明說明: 【發明所屬之技術領域】 本發明係關於在透明塑膠薄膜基材上積層以氣化銦為 主之透明導電膜而成的透明導電性薄膜及其製造方法,特 別是關於在用於汽車衛星導航系統用觸控面板時的高溫高 濕條件下的電阻值安定性優良,且手寫輸入耐久性優良之 透明導電性薄膜,及其有效率的製造方法。 [先前技術】 於透明塑膠薄膜基#上積層有透明且電阻小之薄膜的 透明導電性薄膜,利用其導電性之同途,係廣泛的使用於 例如像液晶顯示器及電致發光(EL)顯示器等的平板顯示 器、及觸控面板之透明電極等電氣/電子領域之用途。 近年來,由於附帶有觸控面板之汽車衛星導航系統的 普及,而求取即便在高溫高濕條件85 °C、85%R.H.下,電 阻值變動亦少之透明導電性薄膜。又,亦求取手寫輸入耐 久性優良之透明導電性薄膜。例如,於透明導電性薄膜之 高溫高濕條件85°C、85%R.H.下之電阻值變動,可以高溫 高濕安定性試驗後的電阻值除以高溫高濕安定性試驗前的 電阻值所得到的可靠度係數之值表示。可靠度係數理想上 係在0.8〜1.2之範圍。另一方面,手寫輸入耐久性試驗係以 5.0N之荷重實施30萬次直線滑動後,進行調查滑動部之外 觀及電氣特性之試驗。滑動部之外觀及電氣特性與手寫輸 入耐久性試驗前相比若無變化時,則認定試驗結果為良好 的。手寫輸入耐久性試驗結果良好之透明導電性薄膜已知 為將透明導電膜結晶化者。已研究有用以在透明導電联結 晶化下,讓可靠度係數接近1之方法(請參照專利文獻1、 4/56 201218218 ' ~ 2)。雖然專利文獻丨、2皆一致認為因透明導電膜為結 =手寫,耐久性比較優良’但此等專利文獻中關^透明 導電性溥膜在高溫高濕條件下之電阻值 , • 下所述。 論如 f利文獻1巾,記載了—種在將透明導電性薄膜 成膜前1由加熱塑膠薄膜基材來減低熱收縮率、 ,性薄膜。但是為了將塑膠薄膜基材在成膜前加熟不 付不準備加熱步驟,因增加了步驟數量 .札、 載於專利文獻]之透明導電性薄膜,在85^二,記 )〇〇小時後的電阻值成為未處理狀態之電阻 ·Η_' (前述之可靠度係數約為2),於高溫高濕條件倍左右 安定性也不充分。 ’、 之電阻值 專利讀2巾,記載了於透明導電 =電性_。但是在將透明導電性_籍由透明 广法予以成膜時’因自塑膠薄膜排 ::兮具空 :中所記载的將(氮氣)/ (氬氣+氮氣利文 固定的3GGG〜l3_ppm是非常困難的。沒奴控制在 專利域3巾,記載了與本發明之透明導 ^組成重複、乍看之下相當_之透 ^的使用 ^該專利文獻中的透明導電性_,A目的。記 =濕條件8VC、85%RH 變^非讓在高 :文獻3。中係在m3中添加有鎳、給值二=少,但在專 •:度、;〇: C、成膜氣體僅有Ar。在此條件“:中,基板 /皿円濕條件之8rc、85 %下,於高 .S在於:若讓透明__基材在^^變,大。其原 予以成膜時則水及有機氣體;大量產生,而:2=201218218 6. Technical Description of the Invention The present invention relates to a transparent conductive film in which a transparent conductive film mainly composed of indium trioxide is laminated on a transparent plastic film substrate, and a method for producing the same, and in particular, A transparent conductive film excellent in resistance value stability under high temperature and high humidity conditions for use in a touch panel for a car navigation system for automobiles, and excellent in handwriting input durability, and an efficient manufacturing method thereof. [Prior Art] A transparent conductive film having a transparent and low-resistance film laminated on a transparent plastic film base # is widely used in, for example, a liquid crystal display and an electroluminescence (EL) display by the same conductivity. Applications such as flat panel displays and transparent electrodes for touch panels, etc., in the electrical/electronic field. In recent years, due to the spread of the car satellite navigation system with a touch panel, a transparent conductive film having a small change in resistance even under high temperature and high humidity conditions of 85 ° C and 85% R.H. Further, a transparent conductive film excellent in hand resistance and excellent in durability was also obtained. For example, the resistance value of the transparent conductive film under high temperature and high humidity conditions of 85 ° C and 85% RH can be obtained by dividing the resistance value after the high temperature and high humidity stability test by the resistance value before the high temperature and high humidity stability test. The value of the reliability coefficient is expressed. The reliability coefficient is desirably in the range of 0.8 to 1.2. On the other hand, the handwriting input endurance test was conducted by investigating the sliding portion and the electrical characteristics after performing a linear sliding of 300,000 times with a load of 5.0 N. If the appearance and electrical characteristics of the sliding portion are unchanged from those before the handwriting input durability test, the test result is considered to be good. A transparent conductive film having a good handwriting input endurance test result is known as a crystallized transparent conductive film. A method for making the reliability coefficient close to 1 under transparent conductive junction crystallization has been studied (refer to Patent Document 1, 4/56 201218218 '~ 2). Although both the patent documents 丨 and 2 agree that the transparent conductive film is a junction = handwriting, the durability is relatively excellent. However, in these patent documents, the resistance value of the transparent conductive ruthenium film under high temperature and high humidity conditions is as follows. . For example, a film having a reduced heat shrinkage rate by heating a plastic film substrate before film formation of a transparent conductive film is described. However, in order to add the plastic film substrate before the film formation, the heating step is not required, because the number of steps is increased. Zha, the transparent conductive film contained in the patent document, at 85^2, after 〇〇 hours The resistance value is an unprocessed resistance Η _ ' (the reliability coefficient described above is about 2), and the stability is not sufficient in the case of high temperature and high humidity conditions. ', the resistance value of the patent read 2 towels, recorded in transparent conductive = electrical _. However, when the transparent conductivity is formed by the transparent method, the film is discharged from the plastic film:: the cookware is empty: (nitrogen) / (argon gas + nitrogen gas fixed 3GGG ~ l3_ppm is It is very difficult. No slaves are controlled in the patent field 3, and the use of the transparent conductive composition of the present invention is repeated, which is equivalent to the use of the transparent conductive property in the patent document. Note = wet condition 8VC, 85% RH change is not high: literature 3. The middle is added with nickel in m3, the value is two = less, but in the special: degree, 〇: C, film forming gas only There is Ar. In this condition ":, the substrate / dish dampness condition 8rc, 85%, in the high. S lies in: If the transparent __ substrate is changed, it is large. When it is filmed Water and organic gases; produced in large quantities, and: 2=

5/56 S 201218218 心令约烕長成不安定且不均質之透明導始 ΐ轉電膜因非晶質而缺之手寫輸入耐久性::若:: 尚溫向濕條件之w 丁日丨4 大。又m T ]電阻値會隨時間增 ^ ^電料以絲時若未使料反應 、乳氣’會造成所得之透明導電膜為氧缺⑷〇xv〇en ddlc】eney)部分多之透明導電膜,如此之透明導雷膜因非 1 質而缺4手寫輸人私性,又若置於高溫高祕件之^ ?晴卄下,由魏缺陷部分會反應,電阻值 二 尸曰·。增大。以專利文獻3之透明導電性薄膜確言忍在85&lt;:、了 8)°,Η.、ι_小時後的電阻值時,皆為初期的】5仵以上 (前述之可靠度係數為K5以上),在高溫高濕條件;— =安定性亦不充分。χ ’以專利文獻3之透明導電心 膜實施f寫輸人私性試驗時,筆魏部白化,進而」 特性顯著惡化。 一乳 〈先前技術文獻〉 〈專利文獻〉 〈專利文獻丨〉日本特開2007-133839號公報 〈專利文獻2〉日本特開2007-200823號公報 〈專利文獻3〉日本特開2003-239063號公報 【發明内容】 〈發明所欲解決之課題〉 本發明之目的係有鑑於上述過去之問題點,而提供在 用於觸控面板時的高溫高濕條件下之電阻值安定性、及手 寫輸入耐久性優良的透明導電性薄膜,及其有效率的製造 〈用以解決課題之手段〉 6/56 201218218 本發明係有鑑於上述狀況而土 a 透明導紐_及枝料料;之=上述課題之 ].—種透明導電性薄膜,复構成。 材之至少一面上積層透遵:係在透明塑膠薄膜基 薄膜,其特徵在於··該透明導成之透明導電性 外,還至少含有平均=除了含有氧化銦以 0.】〜5質量%之自物質 &quot;里/°之乳化錫、及平均 明導電膜之比電阻為4χ](Γ4〜2 _,出3之物質’且該透 物質群組A :氧化紹、氧化。 化鉬、氧化鎢、氧化$、^ ·、虱化鐵、氧化鎳、氧 ,、金、韵。现魏錯、氧化免、氧化鉻V氧化 材之匕==:?係在透明崎膜基, 薄膜,其待徵在於:除了含^而成之透明導電性 電膜卡至少含有平均〇】二化銦以外’該透明導 透明導電膜中至少含有5/56 S 201218218 The order of the heart is about the unstable and inhomogeneous transparent guide. The transfer film is lack of handwriting input durability due to amorphous:: If:: The temperature is still wet. 4 big. Moreover, m T ] resistor 値 will increase with time ^ ^ If the material is not reacted when the wire is used, the milk gas will cause the resulting transparent conductive film to be oxygen-deficient (4) 〇 xv〇en ddlc eney) part of the transparent conductive Membrane, such a transparent guided thunder film is lacking in the quality of the handwriting, and if it is placed under the high temperature and high secrets, it will be reflected by the Wei defect part, and the resistance value is two corpses. Increase. In the case of the transparent conductive film of Patent Document 3, it is confirmed that the resistance value after 85°, 8)°, Η., and ι_hour is the initial value of 5 仵 or more (the reliability coefficient is K5 or more. ), in high temperature and high humidity conditions; - = stability is not sufficient. χ ‘ When the transparent conductive core film of Patent Document 3 was used to perform the test of writing and translating humans, the white part of the pen was whitened, and the characteristics were significantly deteriorated. 。 。 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The object of the present invention is to provide resistance value stability and handwriting input endurance under high temperature and high humidity conditions for a touch panel in view of the above problems. A transparent conductive film excellent in properties and efficient production thereof (means for solving the problem) 6/56 201218218 The present invention is based on the above-mentioned situation, a transparent guide _ and a branch material; ]. A transparent conductive film, complex composition. The layer of the material is laminated on at least one side of the material: the transparent plastic film-based film is characterized in that it has a transparent conductive conductivity, and at least contains an average = except that it contains indium oxide at 0.] to 5% by mass. The specific resistance of the emulsified tin and the average bright conductive film of the material &quot;in/° is 4χ] (Γ4~2 _, the substance of 3) and the permeable group A: oxidation, oxidation, molybdenum, oxidation Tungsten, oxidized $, ^ ·, bismuth iron, nickel oxide, oxygen, gold, rhyme. Now Wei, oxidized, chrome oxide V oxidized material 匕 ==:? It is to be noted that: in addition to the transparent conductive film card containing at least the average 〇] indium difluoride, the transparent conductive transparent film contains at least

中選出之物質,此外, :里/°之自物質群A A 祕加量係相對於該透:工::二選出之物 減少,且該表層側連續地或逐步地 出之物質的添加量係2質量%以下:: 透明塑膠薄膜基材側之貝里/°以下,且该 物質群組a中選出之物:d:所含有的自該 加量多0.5〜5質旦〇/,曰 ' 斗σ置係比表層側之添 叫0·4〜2.5,% ·⑽。透.明導電膜之比電阻為 物質群組A:氧化銘、氧化鎵、氧化鐵、氧化錄'氧The selected material, in addition, the : / / / from the substance group AA secret addition amount relative to the penetration: work:: two selected items are reduced, and the surface side of the continuous or stepwise release of the substance 2% by mass or less:: Berry/° or less on the side of the transparent plastic film substrate, and the selected one of the substance group a: d: contains 0.5 to 5 mass denier/, from the addition amount, 曰' The addition of the bucket σ system to the surface side is 0·4~2.5,%·(10). The specific resistance of the transparent conductive film is material group A: oxidation, gallium oxide, iron oxide, oxidation

7/56 S 201218218 化鋼、氣化鎮、氣化給、氧化錯、^匕纪、氧化絡、氧化 猛、金、在白。 3. 如上述第丨或2項之透明導電性薄膜,其中泫 透明導電膜之厚度為l〇〜2〇()nm。 、 ux 4. :種透明導電性薄膜之製造方法,其係在透 明塑膠溥膜基材之至少—面上積層透明導電膜 之透明導電性薄膜的製造方法,其特徵在於:以❹ 法進行成膜,其中做為透明導電膜之原料之㈣㈣ ::除了含有氧化銦以外’還含有〇.卜5質量 :、及G〜5質量%之自物質群組A中選出之物質,= 2 2片以上的前述_把材,從自物質群組A中選 出之物質的添加量高之賤胸開始 :二 膜基材’且最後用於成膜之糊二^ 中選出的物質之添加量 = 二:’且,用於成膜之她材中所含有的自物 m t所選出的物質之添加量,係: 膜的_把材之添加量多0.5〜5質量%,且透明= 臊成朕時的基板溫度為_60〜50〇(:,且 導電 膜用之反痺性ϋ邮,5 \ 使用氧軋做為成 夂U生轧粗,乳軋分壓為】.0 3 物質群組Α:氣化鈕5 ϋ 10 Pa〇 氧化銷、氧化鎢、氛化於、、氧化鐵、氧化錦、 氧化錳、金、鉑。 孔化把、乳化鉻、 〈發明效果〉 依據本發明,提供在高溫高 之電阻值安定性、及手雜紐 c、85仙丑下 膜,及可有效率的進行其導電性薄 衣k方去。所得到的透明 8/56 ¥電性薄膜, 板等帛、λ 、在汽車衛星導航系統用觸控μ# :用途極為有〔面板及其它觸控面 【貧苑方式】 〈用 1乂 ♦ _、發明之形態〉 成之透明^$曝薄膜基材的至少—面上積岸透明,曾十 右Τ有平均〇1〜5暂气之外,透明導電膜 :和〜賢”/之二自::易’及遷明導電膜至少含 外,f + 貝夏/〇之下达自物質群紕A由^ , 主對瘦明導命π夕γ声古a , 中迭出的物質。此 自物質=巧基材側往 出的物質々之透明導電膜所含有的自二:= ,導電二塑膠 ’比表犀3有的自物貝砰組A中選出的物質 為4X10'^^.5〜5質量%,且透明導電膜之比電阻= 之氧化轉 Ω .、Cm。更佳為含有平均0.2〜4.5質量% 質君f組A 1 更佳為含有平均Ο.2〜4‘5質旦0/ 、 所含有的自,更佳為表層:透明 以下。又,出的物質之恭加量為1質=7/56 S 201218218 Steel, gasification town, gasification, oxidation, 匕, 氧化, oxidation, violent, gold, in white. 3. The transparent conductive film according to item 2 or 2 above, wherein the transparent conductive film has a thickness of 1 〇 2 〇 () nm. And ux 4. A method for producing a transparent conductive film, which is a method for producing a transparent conductive film in which a transparent conductive film is laminated on at least a surface of a transparent plastic ruthenium film substrate, which is characterized in that it is formed by a ruthenium method. The film, which is used as a raw material of the transparent conductive film, (4) (4) :: In addition to containing indium oxide, it also contains 〇. 5 mass: and G 5% by mass of the substance selected from the substance group A, = 2 2 pieces The above-mentioned _ material, the amount of the material selected from the substance group A is high, and the amount of the material selected from the second film substrate 'and finally used for film formation is equal to 2 : 'And, the amount of the substance selected by the material mt contained in the material for film formation is: 0.5 to 5 mass % of the film is added, and the transparency is = The substrate temperature is _60~50〇(:, and the conductive film is used for ruthenium, 5\ using oxygen rolling as the 夂U raw rolling, the milk rolling partial pressure is ..0 3 substance groupΑ : Gasification button 5 ϋ 10 Pa〇 oxidation pin, tungsten oxide, atmosphere, iron oxide, oxidized bromine, manganese oxide, gold, platinum. Emulsified chrome, <Effects of the Invention> According to the present invention, it is possible to provide a film having a high electrical resistance at a high temperature, a film having a high resistance value, and a film which can be efficiently and efficiently obtained. Transparent 8/56 ¥Electrical film, board, etc., λ, in the car satellite navigation system with touch μ#: extremely useful [panel and other touch surfaces [poor way] <1 ♦ ♦, invention The form> The transparent ^$ exposed film substrate at least - the surface of the bank is transparent, the ten right Τ has an average 〇 1~5 temporary gas, transparent conductive film: and ~ 贤" / bis from:: Yi' and Qianming's conductive film contain at least the outer part, f + Becha/〇 under the material group 纰A from ^, the main pair of thin and fat-like life π γ γ sound ancient a, the material in the middle. This self-material = skill The substance selected from the substrate side of the transparent conductive film contained in the second:=, conductive two plastics than the material selected from the table rhino 3, the material selected from the material is 4X10'^^.5~5 mass %, and the specific resistance of the transparent conductive film = oxidation to Ω., Cm. More preferably contains an average of 0.2 to 4.5% by mass. The mass of the group F is better than the average Ο .2~4 '5 quality denier 0/, the self contained, preferably the surface layer: transparent below. Also, the amount of the substance added is 1 quality =

〔的自物===,_膜所含 4·5質量0/〇。此外,透、貝之斗加里比表層側多 1〇、4〜2.G咖3Q·⑽範圍 膜之比電阻更佳係在4X 物質群組A:氧化紹、氧化 &quot; 化鉬、氧化鎢、 ·’乳化鐵、氧化鎳、氧 錳、金、翻 ’’口4鉛:氧化免、氧化路、氧化 為了製作在8rc、85%R.H•之高溫高濕條件下電阻值[The self-object ===, _ film contains 4·5 mass 0 / 〇. In addition, the penetration, the shell of the bucket is more than 1 〇, 4~2. G coffee 3Q · (10) range film specific resistance is better in the 4X substance group A: oxidation, oxidation &quot; molybdenum, tungsten oxide · 'Emulsified iron, nickel oxide, manganese manganese, gold, turn ''4 lead: oxidation, oxidation, oxidation in order to produce resistance values under high temperature and high humidity conditions of 8rc, 85% RH•

.9/56 •S 201218218 女足性及手寫輸入耐久性優良的透明導電膜,理想為做成 如下構成的透明導電膜。即於透明塑膠㈣基材側配置化 學安定性優良之透明導電膜,接著向著表㈣連續地或逐 步地積層物酬久性優良之翻導賴之構成。化學安定 性優良之透明導電膜發揮保持在8rc、85%rh :加古 J條件下的電阻值安定性之角色。物理耐久性優良:= 势電賊,及連續地或逐步地改變對膜厚方向之組成的透明 導電膜之構成,可發揮保持手寫輪入耐久性之作用。柄物 理1久性優良之透明導電勝配置於最表層之理由,係為了 施手寫輸入耐久性試驗時’防止透明導電膜最表層部 /刀磨耗而劣化。又’射m向來連續地或逐步地改辨 係為了發揮保持手寫輸入耐久性作用的理由,“ …針肢學安定性優良之透明導電膜予以説明。首先敛 述1丁〇 (氧化銦.錫)等的透明導電膜在85,c、Η之 ,溫高濕條件τ電阻值變動的現象。若將 · ·么 =電膜置…德Η.之高溫高濕條;= 二導=亍氧化,等的氧化物系透明導電膜二 二;ίΓ’若透明導電膜氧化則氧缺陷減少,導電 會大巾田惡化。又,即便是其它化學反應’導電性亦合亞 二透學安定性優良之透明導電膜較佳係断;: 乂透月¥電財之氧缺陷及麟等的化學上具活性 刀’或減少料部分暴露在高溫高声 :化;上具活性的部分之氧缺陷會造成導;性,=減咸 i化利4的部分|絲高&gt;s高*魏τ為有效的策 此處將透明導電膜限定於ίΤ0,來說明減少化學上具 10/56 201218218 - 活性之部分暴露在高㈣濕 上具活性的部分暴露在高溫㈣^方法^了,少化學 中的銦部位且化學上安定之^f兄下’添加不易插入I丁〇 _於:若將如前述之物質添加至=二二其中:因在 膜中的晶界及表面等之故。其結果^ 南溫高濕條件下可阻止lT〇 C、85/°R.H.之 C、85〇/〇R.H.之高、、作姓/、虱及水寻的反應,在%。 、本案判人專、、JT 的電阻值安定性非常良好。 導電膜使用之加在85 g .. O'里问濕條件下的電阻值安定性的紝| f 現错由將自物質群組A巾 女疋眺、。果,發 C、_.H.之高溫高濕條:二=4 85。 群组A為氧化紹、氧電阻值女疋性優良。:物質 化鶴、氧化給、氧纽氧化錄、氧她.、氧 及銷。特別日^ / 匕免、氧化鉻、氧化猛、金、 當有效果的?:化:化鎳:氧化鉬、氧化鈀、氧化鉻.為相 及表面等,故可== .C、85%R.H.之高:::条:下與氧氣及水的反應。在85。 可靠度係數為值安定性,若後述之 ,ΒΘ ^+、 .2則可%為較佳且令人滿意的。 夭/—疋 學安定性優良之透明導電膜因左ΓΤΟ中 :,群“中選出的物f,宜在:== 補強。物理耐久性優良之透 上有所 來講為結晶質之透明導電膜。此卜:=述所說’單純 電膜的定義。在h 處不結晶質之透明導 時,具有多角來狀·\电子顯微鏡下觀察透明導電膜層 ^ ^ f ^ MM W ^ ^ttot 150 t 4 # &quot; 〇 ^ 為.00 0‘50之h明導電膜稱為結 U/56 s 201218218 晶 京, 晶質部對結Μ部的比之方法,可由在 子賴鏡讀察時的結Μ部與非Μ部之面積 比计品出。做為使ΠΌ成為結晶㈣較佳條件之_,可卢 例如減少氧化细以外的物質之添加量。由; 性優良之透明導電膜除了含有氣化姻以外: 錫與自物質群組Α中選出的物f ',、力有乳化 日月、故不易成為結晶質的透 了_化學安定性與物理耐久性,而僅 =月專㈣之表層部分為結晶質之叮〇、讓透明塑膠薄 腺基材側之剌料_在1?〇充分添加自 選出的物質之非晶質膜,-實絶手寫而寸久性試驗,的$ 充分添加有自物質群组Α中選出的物質的非 化,,而恐有透明導電膜全部剝離之虞。因而,對化 |生與,理而1久性之兼顧進行專心研究。其結果發現了一種 透明導電膜’其係相對於透明導電膜之膜厚方向而言,扩 透明塑躍薄膜基材侧往表層連續地或逐步地減少自物質群 組Α中選出的物質之添加量,且表層側之透明導電膜所; 有的自物質群組A中選出的物質之添加量為2質量%以 下’而且透明塑膠薄膜基材側之透明導電膜所含有的自物 質群組A中選出的物質之添加量比表層側多〇5〜5質量% 之透明導電膜。自物質群組A中選出的物質之添加量多之 ,,塑膠薄膜基材側的透明導電膜,主要發揮了提升化學 女疋性之作肖。接著’藉由結晶化自物質群組A t選出的 物質之添加量少的表層側之透明導電膜,以及連續地或逐 步地減少自物質群組A中選出的物質之添加量來將透明導 電膜予以成膜·’由於内部應力伴隨著透明導電膜之積層界 面附近的BB彳。歪斜而適度地累積’ *增加透明導電膜整體 12/56 201218218 - 之硬度,故可大幅提升手寫輪入耐久性。可知藉 之透明導電膜能兼顧化學安定性與物该耐久性。' 一本發明中1透明導電_含有之氧化錫平均少^彳 - ,則恐有造成比電限大於2.5χ1〇-3Ω · Cm之虞,、: ^想。又,若添加有自物質群組A中選出的物質之^ ^膜中所含有的氧化錫平均多於5質量%,則透明導= 之表層側容易變成非晶質。結 寫輪 、喊 不太理相。更佳為透明墓+ 〇Λ ”’ '、性低落而 氧化锡Γ 電膜中含有+均〇.2〜4.5質量%之 本發明中’若透明導雷日替人 &gt; 々&amp; 1 α 出的物質平均少於所h之自物質群組切選 岣對ITO之被覆率“==:組A中選出的 J自物質群組A中選出的物質平二=電膜所含有 f愛填之比_的大:?1%,則透明 想仏 、〇 Ω ·cm,在實用上 二的。更佳為透明導電膜中合仕員用上為不理 \ %戟的物質群組Α中選〜4+5質量%如前 出:二表層例之透明導電膜所含有的自物質群 _舉電膜不“質量%,則表層側之透 卜不太it:為=有手寫輸入耐久性低落 中選出的物明導電膜所含有的 未择#, 卿貝之添加置為I質量%以下。 壤出的物、天明塑膠薄膜基材側之自物質群組Α中 切貝之添加夏比表厚 f *〇/〇^ ^ 的日日格歪斜減少,使内部肩力低下, 一之硬度亦降低。結果因手寫輸入而.9/56 •S 201218218 A transparent conductive film with excellent durability for women's foot and handwriting input is preferably a transparent conductive film having the following structure. That is, a transparent conductive film having excellent chemical stability is disposed on the side of the substrate of the transparent plastic (4), and then the composition of the laminated material is continuously or stepwisely extended to the table (4). The transparent conductive film excellent in chemical stability plays the role of maintaining the stability of the resistance value under the condition of 8rc, 85%rh: plus J. Excellent physical durability: = Potential electric thief, and the composition of the transparent conductive film which changes the composition of the film thickness direction continuously or stepwise, and can maintain the durability of the handwriting wheel. The reason why the transparent conductive material having excellent long-lasting property is disposed on the outermost layer is to prevent deterioration of the outermost layer portion/knife abrasion of the transparent conductive film in order to perform the handwriting input durability test. In addition, the reason why the "m" is continuously or gradually changed is to give a reason for maintaining the durability of the handwriting input, and the "transparent conductive film having excellent needle stability is explained. First, the butyl bismuth (indium oxide. tin) is described. ()) The transparent conductive film in the 85, c, Η, the temperature and high humidity conditions τ resistance value changes. If the · · = = electric film set ... Germany high temperature and high humidity strip; = two lead = 亍 oxidation Oxide-based transparent conductive film 22; 若 Γ If the transparent conductive film is oxidized, the oxygen deficiency is reduced, and the electric conduction will deteriorate. The transparent conductive film is preferably broken; the chemically active knife of the oxygen defect and the lining of the moon is reduced or the part of the material is exposed to high temperature and high sound; Leading; sex, = part of the salty i-profit 4 | silk height &gt; s high * Wei τ is an effective strategy here to limit the transparent conductive film to ίΤ0, to illustrate the reduction of chemical 10/56 201218218 - activity Part of the exposed part of the high (four) wet active part is exposed to high temperature (four) ^ method ^, less Indium in chemistry and chemically stable ^f brother 'addition is not easy to insert I 〇 _ _: If the above substances are added to = two two: due to the grain boundaries and surfaces in the film. The result ^ can prevent lT 〇 C, 85 / ° RH C, 85 〇 / 〇 RH high, the surname /, 虱 and water seeking reaction under the conditions of south temperature and high humidity, in the case. , JT's resistance value is very good. The conductive film is used in 85 g .. O' to ask the resistance value under the wet condition stability 纴 | f wrong by the material group A towel , fruit, C, _.H. high temperature and high humidity strip: two = 4 85. Group A is oxidized, oxygen resistance value is good female genital: materialized crane, oxidation, oxygen oxidation record, Oxygen, oxygen, and pin. Special day ^ / 匕, chrome oxide, oxidized violent, gold, when effective?: Chemical: nickel: molybdenum oxide, palladium oxide, chromium oxide. For phase and surface, etc. Can be == .C, 85% RH height::: strip: the reaction with oxygen and water. At 85. The reliability coefficient is value stability, if it is mentioned later, ΒΘ ^+, .2 can be compared Good and satisfying. 夭/ Cloth School good stability of the transparent conductive film in a left ΓΤΟ:, group "was selected from F, preferably in the: == reinforcement. A transparent conductive film which is excellent in physical durability and is crystallized. This Bu: = said the definition of 'simple electric film. When the transparent guide is not crystalline at h, it has a polygonal shape. The transparent conductive film layer is observed under an electron microscope ^ ^ f ^ MM W ^ ^ttot 150 t 4 # &quot; 〇^ is .00 0'50 h The bright conductive film is called U/56 s 201218218 Jing Jing, and the method of comparing the crystal part to the crust part can be calculated from the area ratio of the crotch portion to the non-claw portion when the sub-mirror is inspected. As a better condition for making ruthenium (4), it is possible to reduce the amount of addition of substances other than oxidized fine. From the transparent conductive film with excellent properties, in addition to containing vaporized marriage: tin and the material selected from the group of materials f', the force has emulsification, so it is not easy to become crystalline. _Chemical stability and physics Durability, and only the surface part of the monthly (4) is crystalline, and the transparent plastic thin gland base material side is made of _ _ 1 〇 fully added optional material of the amorphous film, - The handwriting and the long-term test, the $ is fully added with the substance selected from the substance group, and there is fear that the transparent conductive film is completely peeled off. Therefore, we will concentrate on the research of the combination of chemistry and health. As a result, it has been found that a transparent conductive film is formed by continuously or stepwisely reducing the substance selected from the substance group 往 to the surface layer with respect to the film thickness direction of the transparent conductive film. The amount of the transparent conductive film on the surface layer side; the amount of the substance selected from the substance group A is 2% by mass or less' and the self-substance group A contained in the transparent conductive film on the transparent plastic film substrate side The amount of the selected material is more than 5 to 5 mass% of the transparent conductive film added to the surface side. Since the amount of substances selected from the substance group A is large, the transparent conductive film on the side of the plastic film substrate mainly serves to enhance the chemical virginity. Then, 'the transparent conductive film on the surface side which is added by the crystallization of the substance selected from the substance group A t is small, and the amount of the substance selected from the substance group A is continuously or stepwisely reduced to transparently conduct the transparent conductive film. The film is formed into a film. 'The internal stress is accompanied by BB彳 in the vicinity of the laminated interface of the transparent conductive film. Accurately accumulating '* increases the hardness of the transparent conductive film as a whole 12/56 201218218 -, which greatly improves handwriting wheel entry durability. It is understood that the transparent conductive film can achieve both chemical stability and durability. 'In one invention, 1 transparent conductive _ contains less tin oxide than 彳 - , which may cause a specific electrical limit greater than 2.5 χ 1 〇 -3 Ω · Cm 虞, : ^ think. In addition, when the tin oxide contained in the film selected from the substance selected from the substance group A is more than 5% by mass on average, the surface layer side of the transparent conductive layer is likely to be amorphous. Write a round, shouting is not very reasonable. More preferably, it is a transparent tomb + 〇Λ ”' ', and the tin oxide Γ Γ Γ Γ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若The average material is less than the self-substance group of the h, and the coverage of ITO is “==: the material selected from group A in group A is equal to the material group A = the film contains f love filling The ratio of the ratio of _: 1%, the transparency is 仏, 〇 Ω · cm, in practical two. It is more preferable that the transparent conductive film is used in the group of materials that are ignored by the \ 戟 戟 戟 戟 戟 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 : : : : : : : : : : : : : : : : : : When the electric film is not "% by mass", the surface of the surface layer is not too large. It is not selected in the light-sensitive conductive film selected by the handwriting input durability, and the addition of the sapphire is set to 1% by mass or less. The material from the soil, the material group of the Tianming plastic film substrate side, the addition of the Cheby shell, the thickness of the Charpy table, the thickness of the f*〇/〇^ ^ is reduced, so that the internal shoulder force is low, and the hardness is also Reduced. The result is due to handwriting input

Ϊ3 /56 S 201218218 ~ 不太理想。若透明塑膠薄膜基材例 的物贤之添加量比表層惻多出超過群組A中選出 明導電膜之積層界面m近的晶格^以’因增加了在透 力,且應力集中於透明導電膜 陷^增加了内部應 手寫輪入耐久性試驗時,以透明導^因此,實施 使透明導電膜變得容易受損,^内之缺陷為起點而 而不太理想。又,更佳為透明^耐久性低下 膜所含有的自物質群組八中選出的物=側之透明導電 多1〜4.5質量%。 以之¥加t比表層惻 專心研究在85T、85%R H 古 值安定性及手寫怜入耐+ Γ^皿问濕條件下的電阻 方優良之透明導電性薄腺的㈣ 方法之結果,係在透2::Ϊ3 /56 S 201218218 ~ Not ideal. If the amount of the material of the transparent plastic film substrate is more than that of the surface layer, the crystal lattice which is closer to the layer interface m of the group A in which the conductive film is selected is used to increase the permeability and the stress is concentrated in the transparent layer. When the conductive film is trapped and the internal handwriting wheel penetration durability test is increased, the transparent conductive film is easily damaged, and the defect in the inside is not preferable. Further, it is more preferably transparent and has a low durability, and the material selected from the substance group 8 is more than 1 to 4.5% by mass. In addition, the surface layer of ¥ t 恻 恻 恻 恻 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 In penetration 2::

明導電膜而成之透明導電性薄 〔7 H 電膜之原料的’成為透明導 質量%氧化錫、及(Μ質量;卜,還含有〇·卜5 使用7 Η ,、,L… 自物負群組A中選出的物質, 物晳二㈣刚边濺鍍靶材’從自物質群組A中選出的 物負之添加景「暂1〇/、 τ tt, 07 薄膜A材J· 、 〇, 質起,依序成膜在透明塑膠 群二tV广於最後成膜的騎㈣所含有之自物質 群組A中選出的物質為2質量%以下, 含有之自物質群…選出的物=: 自物質群組最:成,濺_所含有的 的:貝 1,比用於最後之成膜 多^is ;;自物質群組a中選出的物質之添加量 沱,且使用—1透明導電膜成膜時之基板溫度為_6〇〜5〇 ]0七40_-3=做為成膜用反應性氣體,以氧氣分壓].Qx &lt;仃濺鍍法予以成膜之透明導電性薄膜之製 14/56 201218218 造方法。 ,為除了含有氧化她外還含⑸〜5質量%氧化錫、及 自物質群組A中選出的物質之透明導電膜的原 =之=餘材使用之片數,較佳為2〜4 #。使用前述賤 鍍糾之順序較佳從自物質群組Α中選出的物質之質量% 局的物質開始使用。更佳為基板溫度為·2〇〜(Γ〇讀成膜 的乳虱分壓之較佳範圍係2.0Χ〗〇-3〜30x]〇-3Pa。 =提升在85T、85%R,H.之高溫高濕條件下的電阻 以:疋、^2輸人私性,透明導電膜除了含有氧化銦 =導2少含有平均。·】〜5質_化爆、且 有平均…質量%之自物質群組A.中搜 出的物貝’此外’自物質群組A中選出的物質之添麻 相對於透料電膜之膜厚方向而言,由透 側往表層連續地或逐步地減少,又表層側之透明導電^才 含有的自物質群組Α中選出的物質之添加量為2 ,所 下’且透明塑膠薄膜基材側之透明導電膜所含有的里, 鮮組A中選出的物質之添加量係比表層側多^質 之透明導電性薄膜為優良之理由係如上所述 貝复% 為本發明透明導電膜之構成的方式,選擇複數^^成 材、及彼等濺鍍靶材之成膜順序等。 乂麵#巴 為了提升在85°C、85%R.H·之高溫高濕條件 值安定性及手寫輸入耐久性,較佳係將透明導 錢 膜時的基板溫度設在-60〜5(rc。此處基板溫度係以=成 板溫度之冷卻器的溫媒之溫度代替使用。透明:制基 材與玻璃及金屬等無機基材不同,含有許多有基 等。因此’若基材溫度高於5(rc,則將透=及水 15/56 胰予以戍 201218218 膜時,因會自透明塑膠薄膜基材放出大觉有機氣體及水, 此等氙體會與透明導電膜反應,而得到不安定之非均t透 明導電膜。從而,在85 ° C、85%R.H.之高溫高濕條件下的 電阻值安定性變差,且手寫輪入耐久性亦惡化。若基材溫 度小於5CTC,則因自透明塑膠薄膜基材不易放出有機氣體 及水,可得到安定之均質透明導電膜,於85°C、85%R.H. 之高溫高濕條件下的電阻值安定性及手寫輸入耐久性變 好。因要將基板溫度降到低於·6(Γ C這件事乃一般的冷卻器 無法對付,故在經濟上不適合。更佳為基板溫度在-20〜(Γ C。理由如下。若為水融點的〇°C以下,則氣體放出變得非 常少。又,因泛用冷卻器之最低溫度多為-20°C以上,在經 濟面上理想為-20 ° C以上。 為了提升在85°C、85%R.H.之高溫高濕條件下的電阻 值安定性及手寫輸入耐久性,較佳係使用氧氣做為成膜用 的反應性氣體。若不導入氧氣來成膜丨丁◦,則1丁〇膜容易 變成氧缺陷非常多的不安定膜。若將氧缺陷多的丨丁〇膜置 於85°C、85%R.H.之高溫高濕條件下,因氧缺陷部分進行 反應,電阻值隨著時間增加。又,氧缺陷多之I丁〇膜因不 易變成結晶質,若實施手寫輸入耐久性試驗,筆滑動部會 白化,從電氣特性來看亦為不宜。因此,為了減少ιτ〇膜 之氧缺陷,特佳係使用氧氣做為成膜用的反應性氣體。 構成本發明透明導電性薄膜之透明導電膜的厚度理想 為10〜200nm。若透明導電膜之厚度小於10nm則膜容易變 得不平均,因在高溫高濕條件下之電阻值安定性及手寫輸 入耐久性恐有變得不充分之虞而較不佳。又,若选明導電 膜之厚度比200nm厚,則總透光率容易變低而較為不理 16/56 201218218 想。又,本發明透明導電性薄膜之總透光率較佳為6 5〜9 5 %。 &lt;透明塑膠薄膜基材〉 用於本發明之透明塑膠薄膜基材係將有機高分子以熔 _ 融擠出或溶液擠出成薄膜狀,並按照需要在長度方向及/或 ' 寬度方向施加拉伸、冷卻'熱固定而成之薄膜,做為有機 高分子可舉出聚乙烯、聚丙烯、聚對酞酸乙二酯、聚2心 奈二曱酸乙一酯、聚對酞酸丙二酯、耐綸6、耐綸4、耐論 66、&gt;4綸]2、聚酿亞胺、聚隨胺醢亞胺、聚疏鱗、聚越喊 酮、聚碳酸酯、聚芳酯、纖維素丙酸酯、聚氣乙烯、聚偏 二氯乙烯、聚乙烯醇、聚醚醯亞胺、聚苯硫醚 '聚笨_、 聚本乙知ί、對位性聚苯乙稀、降获稀系聚合物等。 ' 此等有機高分子中較佳為聚對酞酸乙二酯、聚對酞酸 丙二酯、聚2,6-奈—曱酸乙二酯、對位性聚笨乙婦、降茨烯 系聚合物、聚竣酸酯、聚芳酯等。又,此等有機高分子亦 可與少量其它有機聚合物之單體共聚合、或與其它有機高 分子摻合。 ^ 用於本發明之透明塑膠薄膜基材的厚度係較佳在 ΚΚ300μιη之範圍’特佳在70〜260μηι之範圍。塑穋薄膜之 厚度在ΙΟμιη以下時機械強度不足,特別在用於觸控面板時 手寫輸入的變形有變大的傾向,耐久性容易變得不充分f 另一方面,若厚度超過300μηι,在用於觸控面板時,:使 薄膜變形之筆荷重容易變大而較不佳。 人 用於本發明之透明塑膠薄膜基材,在不損及本發明之 . 目的的範圍闪,亦可對前述薄膜施予電暈放電處理:輝 放電處理、火焰處理、紫外線照射處理、電子束照射吏理^ 臭氧處理等表面活性化處理。 17/56 201218218 將硬化型樹脂層形成於透明塑膠缚膜基材,且在其垮 凹凸化之硬化型樹脂層表面上進行透明導電膜的成腺^ 期待提升筆滑動耐久性。此效果主要有2點。第】點為藉 由增加透明導電性薄膜與硬化型樹脂層之附著力,因可= 止起&quot;因於筆滑動之透明導電膜的剝離,而提升筆滑動耐^ 性第2點為以筆滑動使透明導電薄膜與玻璃接觸時的ς 際接觸面積減少’因破璃面與透明導電膜之滑動性•好:1 而提升筆滑動耐久性。硬化㈣脂層的詳細内容記载 &lt;硬化型樹脂層&gt; 'a、。The conductive film made of transparent conductive film is thin [the raw material of 7 H electric film becomes transparent conductive mass% tin oxide, and (Μ quality; Bu, also contains 〇·卜5 using 7 Η , , , L... The substance selected in the negative group A, the material is clear. (4) The edge-sputtering target 'from the substance selected from the substance group A is added to the scene." Temporary 1〇/, τ tt, 07 Film A material J· 〇, quality, sequential film formation in the transparent plastic group 2 tV is wider than the final film formation, the material selected from the substance group A contained in the material group A is 2% by mass or less, and the material selected from the substance group... =: From the group of substances most: into, splashing _ contains: shell 1, more than the last film formation ^is;; the amount of substances selected from the substance group a 沱, and use -1 When the transparent conductive film is formed, the substrate temperature is _6 〇 〜5 〇] 0 七 40 _ 3 = as a reactive gas for film formation, and partial pressure of oxygen is used to form a transparent film. Conductive film made of 14/56 201218218. It is a transparent conductive material containing (5) to 5% by mass of tin oxide and selected from substance group A in addition to containing oxide. The original number of the film = the number of sheets used for the remaining material, preferably 2 to 4 #. The order of using the above-mentioned ruthenium plating is preferably from the mass of the substance selected from the group of materials . Preferably, the substrate temperature is ·2〇~(The preferred range of the nip point partial pressure of the film is 2.0Χ〗 〇-3~30x]〇-3Pa. =Uplift at 85T, 85%R, H. The resistance under high temperature and high humidity conditions is: 疋, ^2 input private, transparent conductive film in addition to indium oxide = lead 2 contains an average. ·] ~ 5 quality _ blasting, and the average ... mass% of the self-material The material extracted from the group A. in addition to the substance selected from the substance group A is continuously or gradually reduced from the transmissive side to the surface layer in terms of the film thickness direction of the transmissive electric film. Further, the transparent conductive material on the surface side contains the substance selected from the substance group 2, and the material selected in the transparent conductive film on the side of the transparent plastic film substrate is selected from the group A. The reason why the amount of addition is more than that of the transparent conductive film on the surface side is that the above is a structure of the transparent conductive film of the present invention. In the way of forming, the selection of multiple ^^ materials, and the film formation order of their sputtering targets, etc. 乂面#巴 in order to improve the high temperature and high humidity conditions at 85 ° C, 85% RH · stability and handwriting input endurance Preferably, the substrate temperature when the transparent money guiding film is used is set at -60 to 5 (rc. Here, the substrate temperature is replaced by the temperature of the warming medium of the cooler which is = plate temperature. Transparent: substrate and Different from inorganic substrates such as glass and metal, it contains many bases, etc. Therefore, if the substrate temperature is higher than 5 (rc, then the penetration = and water 15/56 of the pancreas will be applied to the 201218218 film, since it will be from the transparent plastic film base. The material emits a large amount of organic gas and water, and these bodies react with the transparent conductive film to obtain an unstable non-uniform transparent conductive film. Therefore, the stability of the resistance value under the high temperature and high humidity conditions of 85 ° C and 85% R.H. deteriorates, and the durability of handwriting wheel penetration also deteriorates. If the substrate temperature is less than 5 CTC, it is difficult to release organic gas and water from the transparent plastic film substrate, and a stable and uniform transparent conductive film can be obtained, and the resistance value stability under high temperature and high humidity conditions of 85 ° C and 85% RH can be obtained. And the handwriting input has improved durability. Because the substrate temperature is lowered below 6 (the C is a general cooler, it is not economically suitable. It is better to use a substrate temperature of -20~(Γ C. The reason is as follows. When the melting point is below 〇 °C, the gas emission is very small. Moreover, the minimum temperature of the general-purpose cooler is -20 ° C or more, and the economical surface is preferably -20 ° C or more. °C, 85% RH high-temperature and high-humidity resistance stability and handwriting input durability, preferably using oxygen as a reactive gas for film formation. If oxygen is not introduced to form a film, 1 butyl ruthenium film is easy to become an unstable membrane with a lot of oxygen defects. If the ruthenium ruthenium film with more oxygen deficiency is placed under high temperature and high humidity conditions of 85 ° C and 85% RH, the reaction is performed due to the oxygen deficiency. With the increase of time, the I-butyl film with many oxygen defects is not easy to become crystalline. If the handwriting input durability test is carried out, the sliding portion of the pen will be whitened, which is not suitable from the viewpoint of electrical characteristics. Therefore, in order to reduce the Oxygen deficiency of the membrane, especially the use of oxygen as a membrane for reactivity The thickness of the transparent conductive film constituting the transparent conductive film of the present invention is preferably 10 to 200 nm. If the thickness of the transparent conductive film is less than 10 nm, the film tends to become uneven, and the resistance value stability under high temperature and high humidity conditions and The handwriting input durability may be insufficient and it may be insufficient. Moreover, if the thickness of the conductive film is selected to be thicker than 200 nm, the total light transmittance is likely to be low and it is ignored. 16/56 201218218 The total light transmittance of the transparent conductive film of the present invention is preferably from 65 to 95%. <Transparent plastic film substrate> The transparent plastic film substrate used in the present invention is an organic polymer which is melted and melted. Or the solution is extruded into a film shape, and a film which is stretched and cooled in the longitudinal direction and/or the width direction as needed is thermally fixed, and examples of the organic polymer include polyethylene, polypropylene, and polypyrene. Ethylene glycol diester, poly(ethylene dipyridyl hexate), poly(p-propyl phthalate), nylon 6, nylon 4, Nai 66, &gt; 4 ruthenium 2, poly-imine, polyamine醢imine, poly-salt, poly- ketone, polycarbonate, polyarylate, cellulose propionate Polyethylene, polyvinylidene chloride, polyvinyl alcohol, polyether phthalimide, polyphenylene sulfide 'poly stupid _, 聚本乙知, aligning polystyrene, reducing rare polymers, etc. Among these organic polymers, polyethylene terephthalate, propylene terephthalate, polyethylene 2,6-naphthyl phthalate, and para-polyethylene An olefinic polymer, a polyphthalate, a polyarylate, etc. Further, these organic polymers may be copolymerized with a small amount of a monomer of another organic polymer or blended with other organic polymers. The thickness of the transparent plastic film substrate is preferably in the range of ΚΚ300 μm, particularly preferably in the range of 70 to 260 μm. The thickness of the plastic film is less than ΙΟμηη, and the mechanical strength is insufficient, especially when used for a touch panel. On the other hand, when the thickness exceeds 300 μm, when the thickness is more than 300 μm, when the touch panel is used, the pen load for deforming the film is likely to become large and is less preferable. The transparent plastic film substrate used in the present invention can be subjected to corona discharge treatment on the film without damaging the scope of the present invention: glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam Irradiation treatment ^ Surface treatment such as ozone treatment. 17/56 201218218 The hardened resin layer is formed on a transparent plastic film base material, and the transparent conductive film is formed on the surface of the hardened resin layer which is embossed and embossed. This effect has two main points. The second point is to increase the adhesion between the transparent conductive film and the hardened resin layer, and to improve the pen sliding resistance due to the peeling of the transparent conductive film by the pen sliding. The pen slide reduces the contact area of the transparent conductive film when it comes into contact with the glass. 'The sliding property of the broken glass surface and the transparent conductive film is good: 1 improves the sliding durability of the pen. The details of the cured (four) lipid layer are described as &lt;hardened resin layer&gt; 'a.

又’用於本發明之前述硬化型樹脂若為藉由 f、紫外、純射、軒束照料能量而硬化之樹脂即^ =限制,可舉出聚魏樹脂、㈣酸樹脂 S 三聚氛胺樹脂、糊脂、物= 為主成;:賴來4,較佳係以㈣線硬化型樹崎 =此之紫外線我型樹脂,例如可舉出如多元 ㈣或f基丙崎酿之多官能性的丙稀酸酿樹脂 丙 異氰酸酯、多元醇及丙烯酸或曱美 〜 σ自二 成之多官能性胺甲酸酿丙烯酸心•二等合 t等多官能性樹脂中加人單官能性單體,例==於 鱗统_ 1基叫酸W、苯⑽_予_;1 乙场基 又’為了提昇透明導電性舊胺盘 ^ β 力,對硬化型樹脂層表面進行表面處==之附著 r:r例如為了增力…基、輝r =放電之放電處理法,為了增加胺基=光或 性基而以酸或驗處理之化學藥品處理法等。^极基等.極 18/56 201218218 紫外線硬化型樹月旨通常係添加光聚 做為光聚合起始劑,π μ 釔劑而使用。 “基之眾所;;JL遍,用術外線產生 了牛出各種本偶姻類、苯酮類、二苯 八 起始划之添加量通常較佳係每】00質 、、小。 脂為】〜5質量份。 貝里^外線硬化型樹 又,本發明之硬化型樹脂層中’除了主 合倂使用少量對基質之硬化型樹脂 =可树化型樹脂中產生相分離,將非相溶樹脂以粒子 刀散。藉由此非相溶樹脂之分散粒子,可於硬化型 树月曰衣面形成凹凸、提升廣範圍之表面粒度。—一 在硬化型樹脂為前述紫外線硬化型樹脂之情形,.做 g相溶樹脂係例示有聚_脂、聚婦烴樹脂、聚苯乙樹 知、聚醯胺樹脂等。 1 7 本發明中,於使用紫外線硬化型樹脂做為硬化型樹脂 曰之主要構成成分的硬化型樹脂,使用高 做為對硬化型樹脂不相溶之高分 月曰 μ, ,t±丄卜 门刀千树月日的情形,彼等之調 互比例較佳為母⑽質量份紫外線硬化型樹脂有01〜 樹脂,更佳為有0.2〜1Gf量份、特佳為有〇 5〜5 若前述聚酯樹脂之調配量為每1〇〇 =小於::質量份’則形成於硬化型樹脂=::: 筆'^有凸。^咸^之傾向’*法提升表面粗度’無法表現 」月動耐久性之進-步改良效果而較不佳。另—方面 則述聚醋樹脂之調配量為每⑽質量份紫外線硬化型樹脂 19/56 201218218 超過20質量份,則此硬化型樹脂層之強度變得容易降低, 耐藥品性容易惡化。 — 燕而,聚酯樹脂因與紫外線硬化型樹脂在折射率上有 差,,有提升硬化型樹脂層之霧值、惡化透明性之傾向, d仏。反過來說,積極利用起因於高分子量聚酯樹脂 /之刀指t的透雜惡化’可賴為具有高霧值之防眩機 鉋的防眩薄膜。 t 1述紫外線硬化型樹脂、光聚合起始劑及高分子量聚 =樹脂係分取共触溶劑溶解來㈣塗布液。使用 ㈣無特別限制’例如可單獨或混合使用如乙醇:等 料溶劑、如乙酸⑽、乙酸丁料料溶劑、如1 丁 ^ 酵早乙_系溶劑、如甲基異頂、環己嗣等酮系 '合':如甲笨、二甲笨、溶劑石油腦等芳香族烴系溶劑等。 等而;=分之濃度’可考慮對應塗布法之點度 八如1 澤。例如’塗布液中紫外線硬化型樹脂、光聚 20,分子f聚㈣脂之合計量所占比例通常為 已-要添加其他 材。塗布液被塗布於透明塑膠薄膜基 二布法、反向凹版塗布法等方法。 於此=布=布液在接著的乾燥步驟將溶劑蒸發去除。 微粒二==液中之高分子量聚賴脂變成 對朔职一型树月曰中析出。將塗膜乾燥後,藉由 硬線硬化型樹脂架橋/硬化形成 、乂驟,兩分子量聚酯樹脂之微粒 20/56 201218218 ' 子被固定於硬塗層中 ^ 起,提升廣I請之表㈣ =於硬化型麟層之表面形成突 =:軸層二度係較佳在。.】〜】5陶之範圍。 更么在〇〜10μ1Ώ之範圍 型樹脂層之厚度小於a 在硬化 另一方面,在超過]5_主之情形,不易形成充分的突起。 俨。 μη1之^形,由生產性的觀點來看較不 實施例 定於=3例Γΐ詳細說明本發明,但本發明非限 法施行。、 ,貫施例之各種測定評價係以下,述方 (1) 總透光率 依據JIS-K71(b ’使用日本電色工制 NDH-1001DP測定總透光率。 )衣 (2) 比電阻 α 4 定機係使 ‘ ^夂油化(股)製L0test AMCP_T400。比電阻係依據表 面电阻與(3)所得之膜厚的乘積獲得。 、又 (3) 透明導電膜之厚度(膜厚) 將積層有透明導電性薄膜層之薄膜試料片切成 10=m之大小’埋在電子顯微鏡用環氧樹脂中。將其固定 超薄切片機_’amie咖me)之試料固定架’製作平^於所埋 贼之試料片的短邊之斷面薄切片。接著,於此切片之薄膜 热顯著損傷的雜制粒式電子_微鏡(助[公司制、、 ,20! 〇) ’以加速電壓2〇〇kV、於明場㈨參叫觀; 干1萬倍進行照相攝影,由所得到的相片來求出膜厚。 21 /56 201218218 (4 )向溫向濕安定性試驗 為了確認在高溫高濕條件下之電阻值安定性,在85.. C、85%R.H.之條件下放1丨000小時。將溫度管理在+2·τ、 濕度管理在d;2%。用將在85»c、85%R.H ·之條件下放置】〇⑻ 小時悛之電阻值’除以在85。C、85%R.H·之條件下放置1 〇⑽ 小時前之電阻值之值(稱為可靠度係數),來確認電阻值安 定L。但尚溫尚濕安定性試驗後之電阻值測定係自8 $ ,‘〔、、 85%R.H.之尚溫高濕槽取出透明導電性薄膜,於2^。% 之狀態放S 30分後,f施電阻測定。可靠度係㈣ 〇·8〜丨.2之範囵。 〜 亍寫輸入耐久性試驗 將透明導電性薄膜做為一邊的面板使用,另一邊的面 板使用於玻璃基板上以電製CVD *、以厚度2〇聰·之姻_ 錫複合氧化物薄膜(氧化錫含量:1〇質量%)形成之透明 導電性賴(日本曹達公司製,S5(]G)tb 2片面板以透 :導電性賴面對面的方式,失著直徑3一之環氧樹脂粒 Λ卞乂配f以製作觸控面板。接著對聚縮酿製的筆(前 端,狀;〇.8mmR)施加遍之荷重,於觸控面板進行3〇 5人=回I5禹次)直線滑動試驗。此時的滑動距離設為 、滑動速度設為6〇咖/秒。此滑動耐久性試驗後,首 觀察滑動部是否有白化。接著,測定以㈣之筆 :::動部%的0N電阻(可動電極(薄膜電極)與 更觸時的電阻值)。⑽電阻理想為臟Ω以下。 更理想為】OkO以下。Further, the above-mentioned hardening type resin used in the present invention is a resin which is hardened by the energy of f, ultraviolet, pure shot or illuminating, that is, a polysulfide resin, (iv) acid resin S trimeric amine Resin, paste, and substance = main ingredient;: Lai Lai 4, preferably by (4) line-hardening type Shusaki = UV-type resin of this type, for example, multi-functional (four) or f-based Aromatic styrene resin propyl isocyanate, polyol and acrylic acid or yttrium ~ σ from the second of the multi-functional amine carboxylic acid acrylic acid core / di- entence t and other polyfunctional resins added monofunctional monomer, Example == in the squama _ 1 base called acid W, benzene (10) _ _; 1 B field base and 'in order to enhance the transparent conductive old amine disk ^ β force, the surface of the hardened resin layer surface == attachment r: r For example, in order to increase the force, the base, the glow = discharge, the discharge treatment method, the chemical treatment method such as acid or treatment for increasing the amine group = light or a group. ^ pole base, etc. pole 18/56 201218218 UV-curing tree is usually used to add photopolymerization as a photopolymerization initiator, π μ tanning agent. "Ji's public;; JL all, using the extra-operative line to produce a variety of benzoin, benzophenones, diphenyls starting from the beginning of the amount of addition is usually better than 00 quality, small. 】 5 parts by mass. Berry ^External hardening type tree, in the hardened resin layer of the present invention, in addition to the main hydrazine, a small amount of the matrix-hardened resin = eutectic resin is used to produce phase separation, which will be non-phase. The solvent-dissolving resin is dispersed by a particle knife. By dispersing particles of the non-coherent resin, irregularities can be formed on the surface of the hardened type of the tree, and a wide range of surface particle size can be improved. - The hardening type resin is the ultraviolet curing resin. In the case of the g-phase-soluble resin, poly-lipid, polyglycolic resin, polystyrene-based resin, polyamidamine resin, etc. are exemplified. In the present invention, an ultraviolet curable resin is used as a curable resin. The hardening type resin of the main component is high in use as the high-insoluble moon-shaped μ which is incompatible with the hardening type resin, and the t±丄 门 刀 千 千 千 千 千 千 千 千The mother (10) parts by mass of the ultraviolet curable resin has 01 to resin, more preferably 0 .2~1Gf parts, particularly preferably 〇5~5 If the amount of the above-mentioned polyester resin is 1 〇〇 = less than: : parts by mass 'is formed in the hardened resin =::: pen '^ has convex The tendency of the salty ^' method to improve the surface roughness 'cannot be expressed' is more difficult than the step-by-step improvement effect. On the other hand, when the amount of the polyester resin is more than 20 parts by mass per 10 parts by mass of the ultraviolet curable resin 19/56 201218218, the strength of the curable resin layer is liable to lower, and the chemical resistance is likely to deteriorate. — In addition, the polyester resin has a difference in refractive index from the ultraviolet curable resin, and has a tendency to increase the haze value of the curable resin layer and deteriorate the transparency, d仏. On the other hand, the anti-glare film which is caused by the high-molecular-weight polyester resin/knife tip t can be actively used as an anti-glare machine having a high haze value. T1 The ultraviolet curable resin, the photopolymerization initiator, and the high molecular weight poly=resin are obtained by dissolving the co-touch solvent to obtain a coating liquid. The use of (4) is not particularly limited 'for example, it may be used alone or in combination, such as ethanol: a solvent such as acetic acid (10), a butyl acetate solvent, such as a solvent, such as methyl isotopyl, cyclohexanthene, etc. The ketone system is a combination of an aromatic hydrocarbon solvent such as a stupid, a dimethicone, and a solvent petroleum brain. Equivalent; = concentration of concentration ' can be considered corresponding to the degree of coating method, such as 1 Ze. For example, the ratio of the ultraviolet curable resin in the coating liquid, the photopolymerization 20, and the total amount of the molecular f poly(tetra) fat is usually - other materials are added. The coating liquid is applied to a transparent plastic film base fabric method, a reverse gravure coating method, and the like. Here = cloth = cloth liquid is removed by evaporation in the subsequent drying step. The particle 2 == high molecular weight polylysate in the liquid becomes precipitated in the scorpion of the scorpion. After the coating film is dried, it is formed by hard-hardening resin bridging/hardening, and the two molecular weight polyester resin particles 20/56 201218218' are fixed in the hard coating layer. (4) = Forming a protrusion on the surface of the hardened type of lining =: The second degree of the axial layer is preferred. .] ~] 5 range of pottery. Further, in the range of 〇~10μ1Ώ, the thickness of the resin layer is less than a, and on the other hand, in the case of exceeding 5%, it is difficult to form sufficient protrusions. Hey. The shape of μη1 is less than that of the embodiment from the viewpoint of productivity. The present invention will be described in detail, but the present invention is not limited thereto. The various evaluations of the various examples are as follows. (1) The total light transmittance is based on JIS-K71 (b 'Using Nippon Denshoku NDH-1001DP to measure the total light transmittance.) Clothing (2) Specific resistance The α 4 fixed system makes the ' ^ 夂 oil (share) system L0test AMCP_T400. The specific resistance is obtained by multiplying the surface resistance by the film thickness obtained in (3). (3) Thickness (film thickness) of the transparent conductive film The film sample sheet in which the transparent conductive film layer was laminated was cut into a size of 10 = m and embedded in an epoxy resin for electron microscopy. The sample holder of the fixed ultra-thin slicer _'amie coffee me' was prepared and made into a thin section of the short side of the sample piece of the buried thief. Then, the film of the sliced film is thermally damaged by the granule-type electron micromirror (assisted [company, 、, 20! 〇)] with an accelerating voltage of 2〇〇kV, and in the bright field (nine) Photographic photography was performed 10,000 times, and the film thickness was obtained from the obtained photograph. 21 / 56 201218218 (4) Temperature and humidity stability test In order to confirm the stability of the resistance value under high temperature and high humidity conditions, put it under the conditions of 85.. C, 85% R.H. for 1 000 hours. The temperature is managed at +2·τ, and the humidity is managed at d; 2%. Divided by the resistance value of 〇(8) hours at 85»c, 85% R.H· divided by 85. Under the condition of C and 85% R.H., the value of the resistance value (called the reliability coefficient) of 1 〇 (10) hours is placed to confirm the resistance value stability L. However, the resistance value after the temperature and humidity stability test was determined from 8 US dollars, ‘[, 85% R.H., the temperature and high humidity groove was taken out of the transparent conductive film, at 2^. After the state of % is placed for S 30 minutes, the resistance is measured. Reliability is the standard of (4) 〇·8~丨.2. ~ The input durability test uses a transparent conductive film as one side panel, and the other side is used on a glass substrate to electrically CVD*, with a thickness of 2 〇 · _ _ _ _ _ _ _ _ _ _ _ Tin content: 1% by mass) Transparent conductive layer formed (S5(]G) tb 2 panel made by Japan Soda Co., Ltd., transparent: 3: epoxy resin enamel卞乂F with f to make the touch panel. Then apply the load to the polystyred pen (front end, shape; 〇.8mmR), and perform a linear sliding test on the touch panel for 3〇5 people=back to I5禹) . The sliding distance at this time is set to , and the sliding speed is set to 6 〇 coffee / sec. After this sliding durability test, the first observation of the sliding portion was whitened. Next, the 0N resistance (movable electrode (thin film electrode) and the more time-sensitive resistance value) of the (4) pen ::: moving portion % was measured. (10) The resistance is preferably not less than Ω. More ideally] below OkO.

Μ出所含有之氧化錫、及自·物質群組A ’選出的物質之平均添加率的測定 22/56 201218218 切取試料(約15cm2)置入石英製三角瓶,加入2〇ml 之6mol/】鹽酸,為了不讓酸揮發以薄膜密封。在室溫下偶 爾搖動,放置9天,將ITO層溶解。取出剩下的薄膜,將 溶解啕]丁0層之鹽酸做為測定液。溶解液令的、Sn、物 質群組A係使用〗CP發光分析裝置(製造商名:Rigaku,裝 置型號:CIROS-120 EOP),以校正曲線法來求出:各元^ 之測定波長係選擇無干涉、靈敏度高之波長。又,標準溶 液係稀釋市售之ln、Sn、物質群組A的標準溶液來使用。 (7)於透明導電膜之膜厚方向變動之物質群組八的添 加量之測定 灰測疋中使用ULVAC-PHI公司製ESCA5801MC。 料係在充分進行預先排氣後放入測定室。以光電子外溢 度為45度、分析直徑^ 進行評價。飯刻時的離子: 類使用Αι*離子。表面、及__組成比鱗擇光雷子』 及奧傑峰(Anger peak)等各種峰間之重疊影響小、且對 能得到充分的靈敏度之峰來予以算出。例如&amp;刊ς 3d5/2、Ni2細等。又,背景值係於雪萊咖邮法^去 自物質_Α中選出的物f之添加量係以下述物質群组 =弧内的物質計算。表層側之透明導電膜所含有的自4 :君=選,質之添加量係使用經_ , 疋-貝料。又,透明__基材側之透明導電財= 相當於⑴轉電咖㈣ 之厚度為止時的測定資料。 + &lt;之尽度值少]m· 物質群組A:氧化鋁(Al2〇〇、 化鐵⑽)、氧化錄(叫氧化糊。〇3)、;=^ 23 / 56 201218218 +H(Hf〇2)、氧化鍅(ZKV) m (CrA)、氧統(叫)、金uuw0⑻鐵 (8)透明導翁膜之非晶質部對結晶質部之比例 電'剛層之純_切成一 之大小,將導電性_面朝夕卜,貼在適當 面。將苴修替祛,一 &lt;田々何細現上 ρ μ ” / 身又π溥切片機之技術製作大致平行 於溥膜表面之超薄切片。 又1仃 以穿透式電子顯微鏡(jE0L公”,1ΕΜ·2_ 此切片,選擇沒有明顯損傷之導電性薄膜表面部分,以二 速電壓纖二、直接倍率40000倍進行照相攝影。 接著计异出於穿透式電子顯微鏡下觀察時的結晶質部 與非晶質部之面積比。 、 &gt;實,例、比較例中使同之透明塑膠薄膜基材為兩面具 角易接者層(easy-adhesion layer)之雙軸配向透明ΡΕΤ薄膜 (東洋紡績公司製,Α434〇,厚度188μηι)。做為硬化型樹 脂層,其係在100質量份含有光聚合起始劑之丙烯酸系樹 脂(大曰精化工業公司製,SE1KABEAM (註冊商標) EXF-01J)中調配3質量份的共聚合聚酯樹脂(東洋紡績公 司製’ BYRON (註冊商標)2〇〇、重量平均分子量丨8,〇〇〇), 添加做為溶劑之曱苯/MEK (8/2 :質量比)混合溶媒至固體 成刀敬度為50質置%,並進行攪拌、均勻溶解來調製硬化 樹脂層的塗布液。以塗膜之厚度成為5μπι之方式,使用絲 棒(meyerbar)塗布調製之塗布液。於80Τ進行1分鐘乾燥 便’使用紫外線照射裝置(Eyegraphics公司製, UB042-5AM-W型)照射紫外線(光量·· 300mJ/cm2),將塗 膜硬化。 24/56 201218218 (實施例1〜119) -7。又,各 實施例之透,導電膜製作條件係記载於表 實施例中共通的妓作條件係如下所述。 • 將透明塑_膜放人真空槽,抽真空至2.Qxl(r4p 著以成為表Μ之乳氣分壓值的方式將氧氣導入 導 入氬氣做為惰性氣體,使總壓成為〇.5Pa。 /、 以]W/Cm2=電力密度將電力施加至含氧化錫之氧化 铜燒結革巴材、不含氧化錫之氧化鋼燒結乾材、或 = 與選自物質群組A的物質之氧化鋼燒結革巴材 平= 控藏鍍法,於塗布有透明塑躍薄膜基材的硬化 = 面將透明導電膜予以成膜。此時,以得到理‘二二 的方式’如”〜7所示,選擇各種濺 =成膜。至於剩是變化薄膜通爾上時的速度工 將成膜有透明導電膜之薄膜在12代孰處理]. 後’實施各評價項目之測定。測定結果示於表Μ。 (比較例1〜124) .錄例之透料電作條件係記載於表8〜]4。 二124中係有使用含氧化錫與氧化狀氧化姻燒 =才,不同’除此之外採用與上述實施例説明之固定 條件。將成膜有透明導電膜之薄膜於mrc献 . 小日禮,實施各評價之測定。測定結果示於表22〜撕 25/56 201218218 26 56 1 Η ί ί ί w —,1 H ί Η fr 5 5. fP 3: u&gt; 52 鴆 r^ 5 碘 ?r· X c ? M ί 1 A i( i I 職 5. O _ X —1 H it S ?! 11 1 V i »( if 5 r ί' t. P ή t, 严 P r r* r. r&gt; r- r: Γ Γ* Ϊ. r r t. s- ί n r t r n r r r* r· ¢- r r ε* R r K C f r· - λ t &gt;* t ?· it 尸 ,t* r (r &gt; i gi ^ ^ ^ ^ t;· Λ r r1! »* * *1 m ,芦: r r U. «» »v &lt; « * ^ ~ »陬 r r1! n r C ^ «: ^ -w篆 *· * w. » »· » r pZ f n c: r r. ^ w. ►-» £ *,·减 &gt; » _ Γ· 0· C. tt 1.1 l- V £ * Λ Λ 1* »靡 ·*·,;· p p ς t K l&gt;v t^. ^ *酋、姝 ^ » :ii r V. r P u. Ϊ· :;-·w _ 5 » ;· *· .· f *、 C ?; r· £农r ^ »c 、· i · •㈠ r ?r P C. Λ ^ ^ P- F ^ « « 4 » * * or* Ϊ: «. Ϊ »&gt;&gt; *- ¢, * * « m m i· d r r t f r z. 1 t ^ ΙΛ M Jj, »*. « « » · · / ϊ* ;r p r ^ r r Z. 5:ϋ E _ W爹 « « « &lt;Λ * m i1· ^ .· p r ? r ς t ti E ·» j£ « « *1 t ··贿 ί· ;· ·· r r $ η p ί δ〆 u- u »· * m • * ·. V · / r f ^ ? r ς Ϊ JP. t L/. V&gt; ^ *·,·《 • _·陳 /··、· £ Ϊ.· r i-υ. ς * * * cj、 w ^ - ϊ » « * ·、-;* n r ·Τ t ^ F F ,t κ * «V ~螓 i&quot; t* ;t ί!? ί ^ is. f f £ ^ Λ r n fJ: ^ ·&gt; u. 鼠1^ ·ς »· »· m t. t -ί -· « • » ϊ-r -ί· 秦》. η r Z ¢. t ^ --i: 賊甿Mt ~ »靡 :.:·, c: K E 躕 * m P 7»Z r σ £ K IT B ^ ί. IT &lt; Λ ». * · ·· ;·, P ^ Si ε: -ί -1 * ** r C 1: ^ W ί. 啤衰: *- P t v· r Z, 5· R K ·- »-» » Λ ^ a; » » - σ ^ &amp; ε u ^ 减_、· » ». ·. ·· — —-— — 1L 9C K »- ~ rf- c炉 f,K 卢 flf A* 1 «c K w X· ·»· r p. 声· c h b r p ^ r r π 炙暴P -.-* A : *j m • · / r r ”· r r^ ς, r $. ^ *&gt;·►·/ * * » » if/ r1 ς. ^ Λ ,· Λ 〇i n *; t · ^ • K *i K “ £· ‘ t β· Π k ,f\ ·&gt; - w ·» p rw V» C u&gt; - ,-/1 u- 'J\ f. tn c -ί 2. ij s- i! ϊ ^ ^ r £ s: ε 5 t _卜 c- ·« «&amp; »- τ c e c (j c U· i· ;w •力 c ί·Λ c&lt; e c· - s· 'β\ c (/. •c. -φ *; ϊ- 5 &amp; m卜 ··/&lt; •-Λ - w e e e c CM *A ~ w c- c e c Ml £ • T 乙§ k c· k c c c C k e c c e c· i p fci ^ C w a &gt; c e 〇 ο ? c — c w e “ e X O «. e &gt; e a. e ». o u. e *. •“ X •“ y. c· u- b 知 c 知 e *. u. b φ »; i *产 (/1 v&gt; Ut w» t/&gt; g C/l Ut (/1 1Λ vt = b » » •5» £ S· τ λ e I R ί* (/&gt; c; LA z. β床* =5¾ ·=·*/♦ C/l • • tn “ί =S2* t/&gt; * (X • ^ ^ e = S =5 β 二 R g K* s Κ» s s _s^ 1 * * &gt;二Determination of the average addition rate of the tin oxide contained in the material and the substance selected from the substance group A' 22/56 201218218 The sample (about 15 cm 2 ) was cut into a quartz flask and 2 ml of 6 mol/hydrochloric acid was added. In order to prevent the acid from volatilizing, the film is sealed. The mixture was occasionally shaken at room temperature for 9 days to dissolve the ITO layer. The remaining film was taken out, and hydrochloric acid in which ruthenium was dissolved was used as a measuring liquid. The dissolved solution, Sn, and substance group A are obtained by using the CP luminescence analyzer (manufacturer name: Rigaku, device model: CIROS-120 EOP), and are determined by the calibration curve method: the measurement wavelength of each element is selected. No interference, high sensitivity wavelength. Further, the standard solution was diluted with a commercially available standard solution of ln, Sn, and substance group A. (7) Measurement of the amount of addition of the substance group VIII in the film thickness direction of the transparent conductive film ESCA5801MC manufactured by ULVAC-PHI Co., Ltd. was used for the ash measurement. The material is placed in the measurement chamber after sufficient pre-venting. The evaluation was carried out with a photoelectron overflow of 45 degrees and an analysis diameter ^. Ions at the time of cooking: Classes use Αι* ions. The surface and the __composition ratio are different from the peaks such as the scales and the Anger peak, and the peaks with sufficient sensitivity are calculated. For example, & Publications 3d5/2, Ni2, etc. Further, the background value is based on the content of the material f selected from the material Α, which is calculated by the following substance group = substance in the arc. The surface of the transparent conductive film contained in the surface of the transparent conductive film is selected from the group of _, 疋-bean. Further, the transparent conductive material on the side of the transparent __ is equivalent to the measurement data at the time of (1) the thickness of the electric coffee maker (4). + &lt;The minimum value is less]m· Substance group A: Alumina (Al2〇〇, iron (10)), Oxidation record (called oxidized paste. 〇3),;=^ 23 / 56 201218218 +H(Hf 〇2), yttrium oxide (ZKV) m (CrA), oxygen system (called), gold uuw0 (8) iron (8) transparent guide film of the amorphous portion of the proportion of the crystalline portion of the electric 'gang layer pure _ cut into One size, the conductivity _ face to face, attached to the appropriate side. The technique of 苴 苴 祛 祛 一 一 一 々 々 々 々 々 々 々 ” ” ” ” ” / / / / / / 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥 溥”, 1ΕΜ·2_ This slice, select the surface portion of the conductive film without obvious damage, and take a photo with a two-speed voltage fiber and a direct magnification of 40,000 times. Then, the crystal quality is observed under a transmission electron microscope. The area ratio of the portion to the amorphous portion. In the actual example and the comparative example, the transparent plastic film substrate is a two-axis alignment transparent enamel film of an easy-adhesion layer ( It is made of Toyobo Co., Ltd., Α434Α, thickness 188μηι). It is a hardened resin layer, which is 100 parts by mass of an acrylic resin containing a photopolymerization initiator (made by Otsuka Seika Co., Ltd., SE1KABEAM (registered trademark) EXF -01J) 3 parts by mass of a copolymerized polyester resin (BYRON (registered trademark) 2〇〇, weight average molecular weight 丨8, 〇〇〇) manufactured by Toyobo Co., Ltd., and benzene/MEK (as a solvent) 8/2: mass ratio) mixed The coating liquid of the hardened resin layer was prepared by mixing the solvent to the solid, and the mixture was stirred and uniformly dissolved to prepare a coating liquid of the cured resin layer. The coating liquid was coated with a wire rod (meyer bar) so that the thickness of the coating film was 5 μm. After drying for one minute at 80 便, the ultraviolet ray irradiation device (manufactured by Eyegraphics Co., Ltd., UB042-5AM-W type) was used to irradiate ultraviolet rays (light quantity: 300 mJ/cm 2 ) to cure the coating film. 24/56 201218218 (Example 1~ 119) -7. Further, the conditions for the production of the conductive film in each of the examples are as follows. The conditions of the common conditions described in the table examples are as follows: • The transparent plastic film is placed in a vacuum chamber and evacuated to 2 .Qxl (r4p introduces oxygen into the argon gas as an inert gas in such a manner as to become the partial pressure value of the emulsion, so that the total pressure becomes 〇.5Pa. /, W/Cm2 = power density applies electric power to Tin oxide-containing copper oxide sintered leather material, tin oxide-free oxide steel sintered dry material, or = oxidized steel sintered leather with material selected from substance group A, flat material = controlled plating method, coated with Hardening of transparent plastic film substrate = surface will be transparent conductive film At this time, in the manner of obtaining the 'two-two' method, as shown in "~7, various sputterings are selected to form a film. As for the speed at which the film is changed, the film is formed with a transparent conductive film. The film was subjected to measurement in each of the 12th generations. After the measurement, the measurement results were shown in Table 1. (Comparative Examples 1 to 124) The conditions of the dielectric materials of the recording examples are shown in Table 8 to 4. In the case of 124, the use of tin oxide-containing oxides and oxidized oxides is different, except that 'the fixed conditions described in the above examples are employed. The film in which the transparent conductive film was formed was placed on the mrc. The measurement of each evaluation was carried out. The measurement results are shown in Table 22~Tear 25/56 201218218 26 56 1 Η ί ί ί w —,1 H ί Η fr 5 5. fP 3: u&gt; 52 鸩r^ 5 Iodine?r· X c ? M ί 1 A i( i I job 5. O _ X —1 H it S ?! 11 1 V i »( if 5 r ί' t. P ή t, 严 P rr* r. r&gt; r- r: Γ Γ* Rr. rr t. s- ί nrtrnrrr* r· ¢- rr ε* R r KC fr· - λ t &gt;* t ?· it corpse, t* r (r &gt; i gi ^ ^ ^ ^ t; Λ r r1! »* * *1 m , Lu: rr U. «» »v &lt; « * ^ ~ »陬r r1! nr C ^ «: ^ -w篆*· * w. » »· » r pZ fnc: r r. ^ w. ►-» £ *,·minus &gt; » _ Γ· 0· C. tt 1.1 l- V £ * Λ Λ 1* »靡·*·,;· pp ς t K l&gt;vt^. ^ *Emirates, 姝^ » :ii r V. r P u. Ϊ· :;-·w _ 5 » ;· *· .· f *, C ?; r· £农r ^ » c , · i · • (a) r ?r P C. Λ ^ ^ P- F ^ « « 4 » * * or* Ϊ: «. Ϊ »&gt;&gt; *- ¢, * * « mmi· drrtfr z. 1 t ^ ΙΛ M Jj, »*. « « » · · / ϊ* ;rpr ^ rr Z. 5:ϋ E _ W爹« « « &lt; Λ * m i1· ^ .· pr ? r ς t ti E ·» j£ « « *1 t ··Bribe ί· ;··· rr $ η p ί δ〆u- u »· * m • * ·. V · / rf ^ ? r ς Ϊ JP. t L/. V&gt; ^ *·,·· • _·Chan/ ···· £ Ϊ.· r i-υ. ς * * * cj, w ^ - ϊ » « * ·, -;* nr ·Τ t ^ FF , t κ * «V ~螓i&quot;t*; t ί!? ί ^ is. ff £ ^ Λ rn fJ: ^ ·&gt; u. Rat 1^ ·ς »· »· m t. t -ί -· « • » ϊ-r -ί· Qin. η r Z ¢. t ^ --i: thief 氓 Mt ~ »靡:.:·, c: KE 蹰* m P 7»Z r σ £ K IT B ^ ί. 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201218218 龙W « y έ: £· ί 矿ic哇s S. 彔 OC 2 r-· NS c C C ; v£ C C C C c ·/: 匕s 丄♦: C c c V. c r» &gt;/·. c C C C c c c c c c r ^ ^ s* ε. Τ £-^ t 5 Q sr s?r » ®N. .-^ ^ i 二— 贫《 ♦ 11 S5 c \£ e oc C c·' e N C i/I r&lt; c tf] c c c e c ^ IT -¾ 社 w疙 F £ V Q ^ ^ ^ κ - «? 5c &lt; &lt;苗友 « \e e&gt; 'C e 〆 e n v. M C 7; fsl e trl c e c e c 和择sc ^&lt;s F ΪΓ &quot; «孩 c \C c &gt;c 1/. W; tf, tr. v. c N ?: fSJ CT ?: c o c e c 扣*: g £Γ fe3 fir «Γ W 贫¥ r·* es c w: - ri c c c e »c e c M c ri c Γ4 V, r4 is s&lt;&lt; G i 1 •Cl - I- &lt;r Z. ·,、c « • Λ e % il 电· z ·.、c a • Λ e % tl .s I il *?之 ..' O • m, e s &lt;E - € S * s 写泛. *ΰ. ^ i:i * ? ξ I f e *1 * 2 s v. 15 1? c .? -I ^ 2 O έ=: —g a&lt; * s =: ii i J fr i » ? gr “, Ii !&amp; § •匀 j5 贫· § .G gr c * c- * ^ 右 44 lr c&gt; c c e «•c· c ”· c ri O; c 1/: «Λ κΐ a w · i?5 ^x K&gt; r· c X «&gt;&gt;ϊ ♦&lt;&gt; Iz X oc c X &quot;V X T〇 X V X % ·*. c X 盖 c :· C ; M «Γ 祝2 相5 « c r·* «e Γ» \d oc o P~ r- g&quot; c r~ c e r^* r~ 妄· v| c r^&quot; c r~* oe c g c 3 OC «5 n &lt;*i Z Si 〇3 *Λ £. J2 NS 客 Si 03 卜 Si 〇3 tc , 5 Si a3 e X Si o3 S! 〇3 ^3 2 3* »T s: ^3 -m 201218218 i表1 5 丨所5己载,贫施例I〜丨丨9 ;,己栽之透明導電性 淠膜其可靠度係數有丨()〜丨2,於85.,c、K5%R卜丨之高溫高 f條件下之電阻安定性優良。又,總透光率、比電阻亦具 =用水準㈣於使用,且手雜W、性亦優良。至於表 -8中比丫乂洌j〜】24之結果’其比電阻、於μ η 濕條件下的電阻安定性、手寫輸人耐久性、總透 先干寺任—性能皆不足,較不佳。 產業上的可利用性 如上所述’依據本發 离.、扣古、p. a从 7挺供在C、85〇/uR.H之 下定性及機,心 觸控面板之用途相當有航*統賴控面板及其它 [圖式簡單說明】 益〇 [主要元件符號說明】 益〇 »»»、 54 / 56201218218 龙W « y έ: £· ί mine ic w s S. 彔 OC 2 r-· NS c CC ; v £ CCCC c ·/: 匕s 丄♦: C cc V. cr» &gt;/·. c CCC ccccccr ^ ^ s* ε. Τ £-^ t 5 Q sr s?r » ®N. .-^ ^ i II - Poverty ♦ 11 S5 c \£ e oc C c·' e NC i/I r&lt ; c tf] cccec ^ IT -3⁄4 社 w疙F £ VQ ^ ^ ^ κ - «? 5c &lt;&lt;Miaoyou « \e e&gt; 'C e 〆en v. MC 7; fsl e trl cecec Sc ^&lt;s F ΪΓ &quot; «Child c \C c &gt;c 1/. W; tf, tr. v. c N ?: fSJ CT ?: cocec buckle*: g £Γ fe3 fir «Γ W ¥ r·* es cw: - ri ccce »cec M c ri c Γ4 V, r4 is s&lt;&lt; G i 1 •Cl - I- &lt;r Z. ·,,c « • Λ e % il z ·.,ca • Λ e % tl .s I il *?.. ' O • m, es &lt;E - € S * s Write pan. *ΰ. ^ i:i * ? ξ I fe *1 * 2 s v. 15 1? c .? -I ^ 2 O έ=: —g a&lt; * s =: ii i J fr i » ? gr “, Ii !&amp; § • uniform j5 poor · § .G Gr c * c- * ^ right 44 lr c&gt; cce «•c· c ”· c ri O; c 1/: «Λ κΐ aw · i?5 ^x K&gt; r· c X «&gt ;&gt;ϊ ♦&lt;&gt; Iz X oc c X &quot;VXT〇XVX % ·*. c X cover c :· C ; M «Γ 2 phase 5 « cr·* «e Γ» \d oc o P~ r- g&quot; cr~ cer^* r~ 妄· v| cr^&quot; cr~* oe cgc 3 OC «5 n &lt;*i Z Si 〇3 *Λ £. J2 NS Guest Si 03 Bu Si 〇3 tc , 5 Si a3 e X Si o3 S! 〇3 ^3 2 3* »T s: ^3 -m 201218218 i Table 1 5 丨 5 5 own, poor example I ~ 丨丨 9 ; The reliability of the transparent conductive enamel film is 丨()~丨2, which is excellent in resistance stability under the conditions of high temperature and high f of 85., c, K5%R. In addition, the total light transmittance and specific resistance are also in accordance with the use of water (4), and the hand is also excellent in W. As for the results in Table -8, the results of 丫乂洌j~24 are less than the resistance, the stability of the resistance under wet conditions of μ η, the durability of handwriting, and the performance of the total permeable temple. good. The industrial applicability is as described above. 'Based on this issue, deduction, p. a from 7 is available for C and 85〇/uR.H for qualitative and machine, the use of the heart touch panel is quite voyage * Depends on the control panel and other [simple description of the schema] 〇 [main component symbol description] 益〇»»», 54 / 56

Claims (1)

201218218 申請專利範圍: 七 1. 種透明導電性薄瞑, 至少一面上積層透明道;、在透明塑膠薄膜基材之 膜,1特忾—毛馭而成之透明導電性薄 外,^少^有平均電膜除了含有氧化銦以 ::電膜之比電阻為愤、2.5=4::.,且該透 其中該物質群組人為:氧 Y ^ , 2· 氧化鎳、氧化鉬、氧化鎢、氧化:匕f:氧化鐵、 免、氧化鉻、氧化缝、金、銷。、°、乳化錯、氧化 一種透明導電性薄腹, 至少一面上藉# .#、 /、仏在透明塑膠薄膜基材之 Ή積層透明導電膜而成之 = 二、捋徵在於··除了含有氧化銦以外, 兒膜中至少含有平均01〜5質 。^ ν 透明導電膜中至少含有、,之虱化錫,及在該 …出之物質,二=:物=自物質群组 物質的添加量係相對於該透明導出之 地減少,且;側往表層側連續地或逐步 且,亥表層側之透明 物質群組A中選出之物質的、“有的自該 〜山心吻貝的添加 所旦 :,且該透明塑膠薄膜基材側之透明導電二里 層側之添加量多0.5〜5質量%,:=㈡係比表 阻為4χ]〇·4〜2.5x】n⑽;I月蛉•之比電 其中該物質群組A為.:氧 # 氧化鎳、氧化鉬、氧化_」氧化鎵、氧化鐵、 乳化鶴乳化給、氧化錯、氧化 55 / 56 201218218 &quot; 纪、氧化鉻 '氣化锰、金、麵u 3. 如申請專利_第】或2項之透明導電性薄膜,其 中該透明導電娱之厚度為1 ()、2〇〇nm。 ’、 4. -種透明導電性薄膜之製造方法,其係在透明朔萨 薄膜基材之至少一面上積層透明導電膜而成之明 導電性薄膜的製造方法,其特徵在於:以濺鍍法進 行成膜’其中做為透明導電膜之原料之㈣妹^ 除了含有氣化銦以外’還含有0.1〜5質rn: 錫、及〇〜5質量%之自„鮮^中選出之^質, 使用2片以上的前述,從自物質群組 選出之物質的添加量高之濺錢 於透明塑膠薄膜基材上,且最後二::: 材中所含有之自物質群組A中 …巴 為2質量%以下,且最初❹、^的物質之添加量 含有的自物.質群組A中所選出的物:政鍍靶:中所 比最後用於成膜之⑽把材多〇〜之二加里,係 導電膜成膜時的基板溫度為·6〇〜5〇;質&quot;%,且透明 做氧氣 】·0χ ] 0 〜40X I 〇”pa ; —氣刀 I 為 其中該物質群組A為:氧 技 氧化鎳、氧化鉬、氧化鎢、氣仆2化鎵、氧化鐵、 鈀、氧化鉻、氧化錳、金、鉑。一氧化錯、氧化 56 / 56 201218218 四、 指定代表圖: (一) 本案指定代表圖為:無 (二) 本代表圖之元件符號簡單說明: • 益〇 五、 本案若有化學式時,請揭示最能顯示發明特徵的化學式: 。201218218 Patent application scope: VII. 1. Transparent conductive thin enamel, transparent film on at least one side; in transparent plastic film substrate film, 1 special 忾 忾 驭 驭 透明 透明 透明 ^ ^ ^ ^ ^ ^ The average electric film contains indium oxide in addition to: the specific resistance of the electric film is anger, 2.5=4::., and the group of the substance is: oxygen Y ^ , 2 · nickel oxide, molybdenum oxide, tungsten oxide Oxidation: 匕f: iron oxide, free, chromium oxide, oxidized seam, gold, pin. , °, emulsification, oxidation, a transparent conductive thin abdomen, at least one side of the #.#, /, 仏 Ή 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明 透明In addition to indium oxide, the membrane contains at least an average of 01 to 5 mass. ^ ν The transparent conductive film contains at least, and the tin-tellurized material, and the substance in the material, the amount of the substance added to the material group is reduced relative to the transparent source, and The side of the surface layer is continuously or stepwise, and the substance selected from the group A of the transparent substance on the surface of the sea surface is "added from the addition of the mountain heart to the shell: and the transparent conductive film substrate side is transparently conductive. The amount of addition on the side of the second layer is 0.5 to 5 mass%, and the ratio of (2) is 4 χ] 〇 4 to 2.5 x 】 n (10); I 蛉 之 之 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中# Nickel oxide, molybdenum oxide, oxidation _" gallium oxide, iron oxide, emulsified crane emulsified, oxidized, oxidized 55 / 56 201218218 &quot; chrome, chrome oxide 'manganese, gold, surface u 3. If you apply for a patent _ The transparent conductive film of the first or second item, wherein the transparent conductive entertainment has a thickness of 1 (), 2 〇〇 nm. ', 4. A method for producing a transparent conductive film, which is a method for producing a conductive film obtained by laminating a transparent conductive film on at least one surface of a transparent glazed film substrate, characterized by sputtering The film-forming material (which is used as a raw material of the transparent conductive film) (in addition to containing indium sulfide) also contains 0.1 to 5 mass rn: tin, and 〇 5% by mass of the selected material from the fresh Using two or more of the above, the amount of the substance selected from the substance group is high on the transparent plastic film substrate, and the last two::: material contained in the substance group A... 2% by mass or less, and the amount of the substance added in the initial ❹, ^ contains the substance selected from the substance group A: the political plating target: the medium is used for film formation (10) Erjiali, the substrate temperature at the time of film formation of the conductive film is ·6〇~5〇; quality &quot;%, and transparent oxygen]·0χ] 0 ~40X I 〇"pa ; - air knife I is the substance group Group A is: oxygen technology nickel oxide, molybdenum oxide, tungsten oxide, gas gallium, gallium oxide, iron oxide, palladium, Chromium oxide, manganese oxide, gold, platinum. 1. Oxidation error, oxidation 56 / 56 201218218 IV. Designation of representative drawings: (1) The representative figure of the case is: No (2) The symbol of the symbol of the representative figure is simple: • Benefits 5. If there is a chemical formula in this case, please reveal The chemical formula that best shows the characteristics of the invention:
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