WO1997001853A1 - Transparent conductive laminate and touch panel made by using the same - Google Patents

Abstract

Improving the accuracy of input is desired for touch panels, but is difficult to attain by using existing transparent electrode films. The formation of a transparent conductive film constituted of an oxide film having a particular composition comprising indium (In), zinc (Zn), titanium (Ti), and oxygen (O), or a transparent conductive film constituted of an oxide film having a particular composition comprising indium (In), zinc (Zn), titanium (Ti), gallium (Ga), and oxygen (O) on a transparent substrate has enabled the provision of touch panels having improved input accuracy.

Description

 9

Description Transparent Conductive Laminated Body and Touch Panel Technology Field Using It

 The present invention relates to a transparent conductive laminate in which a transparent conductive film is formed on an electrically insulating transparent substrate, a method for producing the same, and a sputter ring used for producing the transparent conductive laminate. And a sunset panel using the transparent conductive laminate. Background technology

 A transparent conductive laminate in which a transparent conductive film is formed on an electrically insulating transparent substrate is used as a drive electrode of a display element such as a liquid crystal display element or an electoran luminescence element, and a window electrode of a photoelectric conversion element such as a solar cell. Also, it is widely used as a material for forming electrodes and wirings requiring transparency, such as a transparent electrode film in a coordinate input device such as a touch panel.

As a method for manufacturing the transparent conductive laminate, a method of forming a transparent conductive film on a transparent substrate by a wet method, or a method of forming the transparent conductive film by a physical method such as a vacuum evaporation method, an ion plating method, and a sputtering method. There are known a method of forming a transparent conductive film on a transparent substrate by a chemical vapor deposition method (CVD method), and a method of forming the transparent conductive film on a transparent substrate by a vapor phase deposition method (PVD method). Among these methods, a method of forming a transparent conductive film by an ion plating method or a sputtering method is capable of forming a desired transparent conductive film on a transparent material having relatively low heat resistance such as a transparent resin substrate. Because it can be used, it is suitably used as a method for producing a transparent conductive laminate. By the way, the electrical characteristics required for the transparent conductive mm forming the transparent conductive laminate differ depending on the application. For example, when used as a transparent electrode film in a 511-type touch panel (including a touch screen, the same applies hereinafter), especially when used as a transparent electrode film in an analog touch panel, the electrical resistance is higher than that of a transparent conductive film for other uses. With the recent demand for higher input accuracy, Has been desired to have a surface resistance of 800 Ω Tl or more.

こ とができることから、 近年、 入力装置として多用されるようになってきた。 この 夕ヅチパネルには種々の原理のものがあるが、 入力位置の検出感度向上の要求に 伴い、 最近ではアナログ型が採用されつつある。 The touch panel is one of the input devices for inputting data to the computer (main storage device) such as a personal computer, word processor, electronic notebook, etc. Simply applying a load to the input surface with a finger or pen etc. Enter overnight

Because of this capability, they have recently become widely used as input devices. There are various types of push panels, but with the demand for improved input position detection sensitivity, analog types have recently been adopted.

 In an analog type touch panel, two transparent electrode substrates each having a transparent electrode and a transparent electrode film (resistive film) formed on a flat plate on the transparent electrode are arranged such that the transparent electrode films face each other. It is arranged while being kept at a predetermined interval by a spacer or the like, and one of the two transparent electrodes is located on the input surface side. Then, each of these transparent electrodes is made of the transparent electrode film so that the transparent electrodes are electrically connected to each other when a load is applied from the outside of the transparent electrode located on the input surface side. It is electrically connected to a predetermined drive circuit via electrode terminals and lead wires (extraction electrodes) provided at predetermined positions. Further, each of the transparent electrodes is also electrically connected to coordinate detection means using a comparison circuit, a microprocessor, an analog digital converter, and the like.

 In this analog type touch panel, when a load is applied from the outside of the transparent electrode Si located on the input surface side and the transparent electrodes are conducted, when the transparent electrodes are conducted, the predetermined end of one of the transparent electrode films is used. The circuit is arranged such that a current flows to a predetermined end of the other transparent electrode 1 through a portion where the conduction occurs. Then, the electric resistance value in this circuit changes according to the position coordinates of the location where the conduction occurs, that is, the location where the load is applied, and therefore, based on this change in the electrical resistance value, The position S ^ at which the load is applied is detected by the coordinate detecting means. For this reason, it is required that the transparent electrodes used for analog type touch panel have higher electric resistance and better uniformity of surface resistance than the transparent electrode film used for digital type touch panel. Is done.

As a transparent conductive film, a T〇 film formed by a physical vapor deposition method has conventionally been used for various purposes. The T〇 film can be changed by changing Is a transparent conductive capable of changing the resistivity of the resistivity in the case where is combines transparency and durability is less than 10- ³ Ω · cm. Therefore, in order to obtain an analog type touch panel with improved input accuracy by using this ITO film as transparent, it is necessary to make the film thickness of the T film very thin, about lOnm. However, such an extremely thin film does not escape from the island structure (see “Basic Technology of Thin Films” (The University of Tokyo Press), pp. 90-91), so that it can withstand practical use. Absent. For this reason, with regard to the material for the transparent electrode used in the analog type of touch panel, development of a transparent conductive laminate having a new high-resistance transparent conductive film in place of the ITO film is desired.

Than ITO film (that is the transparency and durability) is a film of a high electrical resistance, Ta ₂ 0 _2, S n comprising 1-20 molar% of at least one component of Ti_rei_2 or Zr_〇 ₂ 〇 ₂ high resistance conductive film (see JP-57- 109206 Patent Gazette) and formed of, Si_〇 transparent conductive metal oxide thin film _2, Ti_〇 _2, Al ₂ 〇 _3, Zr_〇 _2. A film in which at least one kind of metal oxide selected from the group consisting of MgO and Zn〇 is added in an amount of 0.5 to 2% in atomic ratio (see JP-A-6-349338) is known. ing.

However, the high-resistance conductive film disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 57-109206 has a very high surface resistance of 10 ⁶ Ω / b or more, so that it is practically used as an electrode for sunset panels. Not a target. In addition, since this high-resistance conductive film is formed by a wet method, it is necessary to heat ¾W to 400 ° C. or more in the drying process, which significantly restricts the material of the base material. Has the drawback that

On the other hand, the film specifically disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 6-349338 has a high surface resistance of 500 to 700 Ω / cm at an i of 17 nm, and has a high durability. Therefore, it is suitable as a transparent electrode film of an analog type touch panel. However, as described above, the surface resistance of the transparent electrode 1 of the analog type touch panel is approximately 800 Ω / b or more with the recent demand for higher input accuracy of the analog type touch panel. It has come to be desired. That is, JP-A-6-349338 described above In recent years, there has been a growing demand for higher input accuracy of analog type touch panels so that a film having a surface resistance of 500 to 700 Ω / mouth, which is specifically disclosed in US Pat.

 A first object of the present invention is to provide a transparent conductive laminate provided with a transparent conductive film having high electric resistance and a method for producing the same.

 Further, a second object of the present invention is to provide a sputtering target (hereinafter, simply referred to as “target”) useful for producing a transparent conductive laminate having a high electric resistance transparent conductive film. .

 A third object of the present invention is to provide a touch panel with improved input accuracy.

 The transparent conductive laminate of the present invention that achieves the above first object has the following two types (a) and (b). Is done.

 (a) An electrically insulating transparent S # and a transparent conductive film formed on the transparent layer, wherein the transparent conductive film is made of indium (In), Mlfi (Zn), titanium (Ti) and oxygen. (〇) is a constituent element, the atomic ratio of indium (In) to the total amount of indium (In) and ¾Ιδ (Zn) is 20/90 at%, and the atomic ratio of titanium (Ti) is 20/90 at%. Ti / (n + Zn + Ti) is composed of an oxidized film having 2.2 to 20 at%, and the transparent conductive film has a specific resistance and a point A, B, or A shown in FIG. A transparent conductive laminate (hereinafter, this transparent conductive laminate is referred to as a “transparent conductive laminate”) that is within the range of a rectangle having C and D as vertices.

(b) It has an electrically insulating transparent # and a transparent conductive film formed on the transparent, and the transparent conductive film is made of indium (In), (Zn), titanium (Ti), gallium (Ga). ) And oxygen (〇) as constituent elements, the atomic ratio n / (In + Zn) of indium (In) in the total amount of indium (In) and (Zn) is 20-90at%, and titanium (Ti) Oxidation where the total atomic ratio of gallium (Ga) (Ti + Ga) / (In + Zn + Ti + Ga) is 1-2 Oat% A transparent conductive laminate made of an object film (hereinafter, this transparent conductive laminate is referred to as “transparent conductive laminate II”).

 Further, the method for producing a transparent conductive laminate of the present invention that achieves the first object is as follows:

(θ) and 9 sets of frequency ί, Άcoarse if ゎ

(c) In addition to the electrically insulating transparent material, indium (en), Mie (Zn), titanium (Ti) and oxygen (〇) are the constituent elements, and the total amount of indium (In) and awake (Zn) Oxidation with an atomic ratio of indium (In) of In / (In + Zn) of 20 to 90 at% and an atomic ratio of titanium (Ti) of Ti / (In + Zn + Ti) of 2.2 to 20 at% A transparent conductive film consisting of an object film and having a Hi? And a specific resistance within a rectangle having vertices at points A, B, C, and D shown in Fig. 1 of the accompanying drawings is formed by physical vapor deposition. A method for producing a transparent conductive laminate (hereinafter, this method is referred to as “laminate production method I”).

 (d) Indium (In), ¾β (Zn), titanium (Ti), gallium (Ga), and oxygen (〇) are the constituent elements of indium (In) and zinc (Zn) The atomic ratio of indium (In) to the total amount of In / (In + Zn) is 20-90at%, and the atomic ratio of the total amount of titanium (Ti) and gallium (Ga) (Ti + Ga) / (In + Zn) + Ti + Ga) is a method of manufacturing a transparent conductive laminate comprising a transparent conductive film composed of an oxide J3 of l to 20 at% by physical vapor deposition. This is referred to as “Laminated body manufacturing method II.”)

 On the other hand, the targets of the present invention that achieve the second object are divided into the following two types.

(e) An oxide sintered body containing indium (In), S (Zn), titanium (Ti) and oxygen (〇) as constituent elements, and a general formula In ₂ 〇 ₃ (ZnO) _m (m = 2 ~ 7) containing a hexagonal layered compound represented by the formula:

The atomic ratio of indium (In) to the total amount of (Zn) InZ (In + Zn) is 20-90at%, and the atomic ratio of titanium (Ti) Ti / (In + Zn + Ti) is 2.2-20at. %, and that evening one Gedzuto that resistivity is below 10_ ² Qcm (hereinafter, this evening an Gedzuto as "evening one Gedzute".). (f) An oxide sintered body containing indium (In), zinc (Zn), titanium (Ti), gallium (Ga) and oxygen (〇) as constituent elements, and a general formula In ₂ 〇 ₃ (ZnO) _m (m = 2 to 7), and the atomic ratio In / (In + Zn) of indium (In) to the total amount of indium (In) and zinc (Zn) is 20 to A target with an atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of 90 at% and a total amount of titanium (Ti) and gallium (Ga) of l to 20 at% (hereinafter, this One gate is called "Target II."

 The evening panel according to the present invention that achieves the third object is classified into the following two types (h) and (h).

 (g) Two transparent sheets having a transparent electrode film formed in a predetermined pattern are provided, and the two transparent sheets are arranged at a predetermined interval with the transparent electrodes facing each other. In a touch panel in which the transparent electrode films are electrically connected to each other when a load is applied to the transparent electrode from the outside of one of the transparent ms¾¾, the transparent electrode formed on each of the two transparent electrode substrates is provided. At least one of the electrode films is composed of indium (In), zinc (Zn), titanium (Ti) and oxygen (〇), and the total amount of indium (In) and ¾ & (Zn) It consists of an oxide film with an atomic ratio of indium (In) occupying 20 / 90at% of In / (In + Zn) and an atomic ratio of titanium (Ti) of 2.2-20at% of TiZ (In + Zn + Ti). The range of the transparent electrode film, and the specific resistance of the square having the vertices at points A, B, C, and D shown in FIG.ヅ ヅ パ ネ ル ヅ ヅ ヅ ヅ ヅ ヅ ヅ ヅ o

(h) comprising two transparent electrode substrates having transparent electrodes S formed in a predetermined pattern, wherein the two transparent electrode substrates are arranged at predetermined intervals with the transparent electrode films facing each other; A transparent panel formed on each of the two transparent electrode substrates, wherein the transparent electrode films are electrically connected to each other when a load is applied to the transparent electrode substrate from the outside of one of the transparent electrode substrates. At least one of the films is made of indium (In), φβ (Zn), titanium (Ti), Gallium (Ga) and oxygen (O) are constituent elements, the atomic ratio of indium (In) to the total amount of indium (In) and zinc (Zn), InZ (In + Zn), is 20 to 90 at%, and the titanium ( A pixel panel (hereinafter, referred to as a panel) comprising an oxide film having an atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of l to 20 at% of the total amount of Ti) and the gallium (Ga) This evening's touch panel is called Touch Panel II.) BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is a graph showing the relationship between the transparent conductive film constituting the transparent conductive laminated body of the present invention or the transparent electrode film constituting the transparent panel of the present invention. FIG. 2 is a fi diagram showing an outline of the analog-type touch panel manufactured in (2) in Examples 44 to 46. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described in detail.

 First, the transparent conductive laminate of the present invention will be described. The view of the transparent conductive laminate I is, as described above, that the transparent conductive film constituting the transparent conductive laminate is an oxide having a specific composition. And the specific resistance of the transparent conductive film made of this oxide film is within the range of a rectangle having the vertices at points A, B, C, and D shown in FIG. 1 of the accompanying drawings.

(Including on the boundary line, hereinafter referred to as “in the region shown in FIG. 1”). First, the transparent conductive film made of the specific oxide film will be described. The line segment AB in FIG. 1 shows the relationship between the film thickness and the specific resistance of the oxide film having a surface resistance of 1 OkQ / port, and the line segment CD has the surface resistance of 800 Ω / port. This shows the relationship between ^] enjoyment and specific resistance for a certain film.

According to the study of the present inventors, the transparent conductive film having IU ¥ and specific resistance in the region shown in FIG. 1 contains one of indium (In) and tin (Sn), titanium (Ti), Silicon (Si), nickel (Ni), iridium (Ir), rhodium (Rh), cerium (Ce), zirconium (Zr), tantalum (Ta), supper (T1), hafnium (Hf), magnesium (Mg) ), Cobalt (Co) Oxygen (0) and at least one metal element selected from the group consisting of chromium, lead (Pb), chromium (Cr) and gallium (Ga), and the atomic ratio of the total amount of the metal elements (All metal elements selected from the metal element group) / [(11 or 3 n) + (All metal elements selected from the metal element group)] are also formed by an oxide film with 2.2 to 40 at%. be able to.

 Similarly, one of indium (In) and tin (Sri), titanium (T i), silicon (Si), nickel (Ni), iridium (Ir), and rhodium

(Rh), cerium (Ce), zirconium (Zr), tantalum (Ta), talmium (T1), hafnium (Hf), magnesium (Mg), conoreto (Co), lead (Pb), chromium (Cr ) And at least one metal element selected from the group consisting of gallium (Ga), zinc (Zn), and oxygen (〇) as constituent elements, and the atomic ratio of the total amount of the metal elements (metal element All metal elements selected from the group) /

[(In or Sn) + (all metal elements selected from the group of metal elements) + Zn] is 2.2 to 40 at%, and the atomic ratio of zinc (Zn) Zn / [(In or Sn) + (metal element The total thickness and specific resistance of the oxide film having an atomic ratio of 2.2 to 30 at% (excluding 2.2 at%) of + Zn] are also shown in FIG. A transparent conductive film in the region shown can be formed.

 However, in order to obtain a transparent conductive film having higher waking stability and electrical resistance stability over time, and having a film thickness and specific resistance in the region shown in FIG. It is desirable to form a transparent conductive film using an oxide film containing (Zn), titanium (Ti) and oxygen (0) as constituent elements.

 The above oxide film containing indium (In), ¾IS (Zn), titanium (Ti) and oxygen (〇) as constituent elements has an atomic ratio of the total amount of B (Zn) and titanium (Ti) ( Zn + Ti) / (In + Zn + Ti) is 2.2 to 50 at%, and the atomic ratio of indium (In) to the total amount of indium (In) and (Zn) ΙηΖ (In + Zn ) Is 20 to 90 at%, and the atomic ratio of titanium (Ti) Ti / (In + Zn + Ti) is 2.2 to 2 Oat%.

In the transparent conductive laminate of the present invention, indium oxide (MIS), MIS (Zn), titanium (Ti) among the oxide films having the film thickness and specific resistance in the region shown in FIG. And oxygen (O) as constituent elements, the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and ¾IS (Ζη) is 20-90at%, and that of titanium (Ti) A transparent conductive film is formed by an oxide film having an atomic ratio Ti / (In + Zn + Ti) of 2.2 to 20 at%.

 The above-mentioned indium in the transparent conductive film constituting the transparent conductive laminate I of the present invention

The atomic ratio In / (In + Zn) of (In) is 50 to 90 at% (however, excluding 50 at%) from the viewpoint that a transparent conductive film having a desired surface resistance value can be easily formed with high accuracy. Is more preferable. Also, the atomic ratio of the titanium (Ti) Ti /

(In + Zn + Ti) is more preferably 1 Oat% or less.

 The oxidized film having the above-mentioned properties is capable of forming a transparent conductive film having ff and specific resistance in the region shown in FIG.

 (1) amorphous,

 (2) A mixture of indium oxide, zinc oxide, and titanium oxide (crystalline except for compound ^ /)

 (3) a compound consisting of at least two of oxides of oxide, oxides and titanium oxides;

 (4) Mixing the compound of (3) with at least one of indium oxide, zinc oxide and titanium oxide,

Any of these may be used.

 In any of the above oxide films (1) to (4), since the 3151 ratio of visible light at a thickness of 2〇 Onm is approximately 85% or more, the transparent conductive film can be formed by setting the film thickness to 200 nm or less. It can be suitably used as an electrocoat. When the thickness of this oxide film exceeds 200 nm, light absorption in the visible region increases. On the other hand, when the thickness of the oxide film is less than 12 nm, it is difficult to form a practically usable transparent conductive film.

Therefore, in the transparent conductive laminate, as shown in FIG. 1, the HP of the transparent conductive film composed of the oxide film is set to 12 to 2 OO nm. The oxide film (transparent conductive film) preferably has a thickness of 12 to 100 nm when an analog-type solar panel with improved input accuracy is to be manufactured using the transparent conductive laminate I. It is particularly preferred that the thickness be 5 nm. Further, the surface resistance of the above-mentioned oxide film (the surface resistance of the transparent conductor can be adjusted as appropriate by changing the thickness of the oxide film. In the transparent conductive laminate I, if of the oxide film is multiplied by the surface resistance. The value of the specific resistance of the oxide film, which can be obtained by the above, is set to a value in the region shown in Fig. 1. When the specific resistance value is out of the region shown in Fig. 1, the analog type having improved input accuracy is obtained. It is difficult to obtain a transparent conductive laminate suitable for manufacturing touch panels of the type.Oxide film (the surface resistance of the transparent conductor is the same as that of the analog type with improved input accuracy using the transparent conductive laminate I). In the case of manufacturing a touch panel, it is preferable to set it to 1000 to 500 Ω / b.

 The 導電 膜 of the transparent conductive film made of the oxide film described above may be a single flat film or a predetermined た depending on the intended use of the transparent conductive laminate I or the like. . For example, when a transparent conductive film is used as a transparent electrode film of a digital type touch panel, the transparent conductive film is formed by using a predetermined mask at the time of film formation, or performing a predetermined patterning after film formation. By doing so, a desired parallel stripe pattern is formed. When the transparent conductive film is used as a transparent material for an analog type touch panel, the transparent conductive film can be formed by using a predetermined mask as necessary at the time of simulation, or as required after forming the film. By performing the evening, it is formed into one flat membrane.

 In the transparent conductive laminate I of the present invention, the transparent conductive film described above is formed on an electrically insulating transparent film.

The above transparent has electrical insulation properties and is visible light ^! The percentage should be approximately 70% or more. Specific examples thereof include polycarbonate resin, polyarylate tree S, polyester tree such as polyethylene terephthalate β, polyethersulfone resin, and amorphous polyolefin. Transparent polymer materials such as resin, polystyrene resin, acrylic resin, etc., films, sheets and plates made of glass such as soda-lime glass, lead glass, borosilicate glass, and Al-free glass Things. In order to obtain the transparent conductive laminate I as a component of the panel or its material, among the transparent substrates mentioned above, from the viewpoint of flexibility and cost, a poly-polycarbonate shelf, a polyarylate tree, etc. That consist of umbrella or polyethylene terephthalate preferable.

 Further, a gas barrier layer, a hard coat layer, an anti-fective layer, and the like may be provided on one or both surfaces of the transparent substrate as necessary. Specific examples of the gas barrier layer include those composed of an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, polyacrylonitrile, polychlorovinylidene, polyvinylidene fluoride, and the like. Specific examples of the hard coat layer include a titanium-based or silicic-based hard coat agent, and a material made of a polymer material such as polymethyl methacrylate and polyphosphazene. As a specific example of the antireflection layer, a fluorine-based acrylic polymer is used.

- such ffiS Oriritsu polymer primary, inorganic full Uz compound such as MgF ₂ or C aF _2, T I_〇 _{2, S i 0 2, Z} nO, B 12O3, AI inorganic oxides such as 2O3, and laminate thereof And those composed of a body.

 The transparent conductive laminate I of the present invention has a surface resistance as high as 800 Ω / port to 1 OkQ / T]. By using this as a transparent electrode film of a sunset panel or a material thereof, particularly a transparent electrode film of an analog type sunset panel or a material thereof, a sunset panel with improved input accuracy can be obtained. That is, the transparent conductive laminate I of the present invention is suitable as a constituent member or a material of a back panel, especially an analog back panel. It is also suitable as an electrophotographic copying substrate or the like.

 Among the transparent conductive films constituting the transparent conductive laminate I, the atomic ratio of indium (In) to the total amount of indium (In) and ¾IS (Ζη) is In / (In + Zn). Since the transparent conductive film of 50 to 90 at% (excluding 50 at%) is easy to form precisely with a target surface resistance value as described above, Among the transparent conductive laminates I of the present invention, those provided with a transparent conductive film of the above composition are suitable as constituent members or materials for easily obtaining a touch panel having desired input accuracy.

The transparent conductive laminate I of the present invention having the above-mentioned characteristics can be formed on a desired transparent surface by a method such as a sputter ring method, an ion plating method, a plasma CVD method, a spray pipe lysis method, and a sol-gel method. It can be obtained by forming a transparent conductive film composed of the above oxide film. It is preferable to manufacture it.

 Next, the transparent conductive laminate II of the present invention will be described.

 As described above, the transparent conductive laminate II of the present invention is characterized in that the transparent conductive film constituting the transparent conductive laminate II is formed of a specific composite oxide film. A transparent conductor made of a specific oxide film will be described.

 As described above, this transparent conductive film is formed of an oxide film containing indium (In), zinc (η), titanium (Ti), gallium (Ga), and oxygen (〇) as constituent elements. The oxide film is composed of only the above-mentioned constituent elements except for inevitable contaminants in the production process.

 In the above oxide film, the atomic ratio In / (en + Zn) of indium (In) to the total amount of indium (In) and ¾ | g (Ζη) is 20 to 90 at%, and titanium (Ti) ) And gallium (Ga), the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) is l-20at%.

 In the transparent conductive laminate II, the atomic ratio In / (In + Zn) of the indium (In) and the atomic ratio of the total amount of the titanium (Ti) and gallium (Ga) (Ti + Ga) / (In + Zn + The reason for limiting (Ti + Ga) to the above range is that if it is less than 1 at%, the electrical resistance of the oxide film becomes too low, and if it exceeds 20 at%, the electrical resistance of the oxide film becomes too high. It is.

 The atomic ratio In / (Ιη + Ζη) of the indium (In) is more preferably 50 to 9 Oat% from the viewpoint that a transparent conductive film having a desired surface resistance can be easily formed with high accuracy. Further, the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of the total amount of titanium (Ti) and gallium (Ga) is more preferably 5 to 18 at%.

 Since gallium (Ga) is a useful component for improving the transparency and stability of the oxide film, the atomic ratio of the gallium (Ga) is Ga / (In + Zn + Ti + Ga). ) Is preferably 8 to 15 at%.

 The above oxide film,

 (1) amorphous,

(2) Indium oxide, sublime oxide, titanium oxide, and gallium oxide Mixture (crystalline except for compounds.),

 (3) Compounds of at least two of indium oxide, oxide, titanium oxide and gallium oxide,

 (4) a mixture of the compound of the above (3) and at least one of indium oxide, oxide, titanium oxide, and gallium oxide;

Any of these may be used.

 In any of the oxide films (1) to (4), the transmittance of visible light at a thickness of 300 nm is approximately 85% or more. When the film thickness exceeds 30 nm, light absorption in the visible light region increases. If the win is less than 12 nm, it will be difficult to form a practically usable transparent conductive film. Therefore, in the transparent conductive laminate II, it is preferable that the thickness of the transparent conductive material (oxide film) constituting the transparent conductive laminate II be 12 to 300 nm. The thickness of the oxide film (transparent conductive film) is preferably 12 to 100 nm when an analog-type touch panel with improved input accuracy is to be manufactured using the transparent conductive laminate II. It is particularly preferable to set it to 15 to 50 nm.

 Further, the surface resistance of the above-described oxide film (transparent conductive film) can be appropriately adjusted by changing the values of and. This surface resistance is preferably set to 1000 to 5000 Ω / Ο when an analog type touch panel with improved input accuracy is manufactured using the transparent conductive laminate II.

 In the transparent conductive laminate 11, the transparent conductive film constituting the transparent conductive laminate 11 is formed of an oxide film having the above-described composition. The components other than the material film (transparent conductive film) are the same as those in the transparent conductive laminate of the present invention described above. Therefore, description of the oxide film (transparent conductive film) and constituent members other than the oxide film (transparent conductive film) will be omitted here.

The transparent conductive laminate 11 of the present invention described above is preferable as a transparent conductive material over the transparent conductive laminate described above in that the transparent conductive film has high transparency and high heat stability. The transparent conductive film constituting the transparent conductive laminate II can easily increase the surface resistance when its swelling is 12 to 300 nm from 800 Ω / port to 1 OkQ. Therefore, similar to the above-described transparent conductive laminate, it is suitable as a component member or a material of a back panel, particularly, an analog back panel. It is also suitable as an electrophotographic copying substrate.

 Among the transparent conductive films constituting the transparent conductive laminate II, the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and awake (Zn) is 50 to 9 Oat%. As described above, since a transparent conductive film having a target surface resistance value can be easily formed with high precision as described above, a transparent conductive film having the above composition is used in the transparent conductive laminate 11 of the present invention. Those provided are suitable as constituent members or materials thereof for easily obtaining a touch panel having desired input accuracy.

 The transparent conductive laminate II of the present invention having the above-mentioned tree is formed on a desired transparent material by a method such as a sputtering method, an ion plating method, a plasma CVD method, a spray pipe opening lysis method, and a sol-gel method. Although it can be obtained by forming a transparent conductive film composed of the oxide film of the above, it is preferable to manufacture the transparent conductive film by the laminate manufacturing method 11 of the present invention described later.

 Next, the method of manufacturing a laminate I of the present invention will be described.

 As described above, the laminate manufacturing method I of the present invention comprises indium (In), zinc (Zn), titanium (Ti) and oxygen (〇) as constituent elements on an electrically transparent ¾M, The atomic ratio of indium (In) to the total amount of indium (In) and ¾ & (Zn) is 20 / 90at%, and the atomic ratio of titanium (Ti) is Ti / (In + Zn + Ti). ) Is an oxide film having a concentration of 2.2 to 20 at%, and a transparent conductive film having a wake and a specific resistance in the region shown in FIG. 1 is formed by physical vapor deposition. Things.

 Here, as described above in the description of the transparent conductive laminate I of the present invention, the above-mentioned electrically insulating transparent material has electrical insulating properties and has a visible light transmittance of approximately 70%. %, And specific examples thereof are as described in the description of the transparent conductive laminate I of the present invention.

Further, the transparent conductive film formed on the transparent substrate is made of an oxide film having the above-described composition and electrical characteristics. Among the transparent conductive films, as already described in the description of the transparent conductive laminate of the present invention, indium (In) and zinc are used. More preferably, the oxide film has an atomic ratio InZ (In + Zn) of 50 to 90 at% to the total amount of (Zn), and the atomic ratio of titanium (Ti) is Ti / ( As for (In + Zn + Ti), those having 1 Oat% or less are more preferable.

 Specific examples of the physical vapor deposition method employed in the method for producing a laminate of the present invention for forming the transparent conductive film composed of the above oxide film include a sputtering method and an ion plating method. No. From the standpoint of obtaining a transparent conductive film having excellent uniformity and excellent adhesion to the transparency, it is more preferable to apply a single or multiple sputtering method (including a reactive sputtering method).

 When the sputtering method is applied as the physical vapor deposition method, various methods such as RF sputtering and DC sputtering can be applied as the sputtering method, but the productivity and the resulting oxide film can be used. In view of this, the DC sparging is generally preferred industrially. An example of the condition of the DC ring for the DC ring is as follows.

That is, the sputtering atmosphere (atmosphere during film formation) is an inert gas atmosphere composed of He gas, Ne gas, Ar gas, Kr gas, Xe gas, Rn gas, or a mixed gas of inert gas and oxygen gas. an atmosphere, Supadzu evening when Kiri囲(Supadzu evening pressure) 1 X 10- ² Pa~5Pa about, evening one Gedzuto applied voltage (discharge voltage) is less than 10 00V. When importance is placed on the temporal stability of the electrical resistance value of the obtained transparent conductive film, the oxygen in the sputtering atmosphere is preferably low (for example, 5 × 1 CT ³ Pa or less). If the atmosphere during sputtering ^ E (spa pressure) is less than 1 X 1 〇— ² 〇 a, the plasma stability is poor, and if it exceeds 5 Pa, the resulting transparent conductive film has poor adhesion to the substrate. . If the gate application voltage (discharge voltage) is 1000 V or more, the transparent conductive film is damaged by plasma, and a transparent conductive film having desired electrical characteristics cannot be obtained, or the evening target is cracked. Is easy to occur. The preferred value of the gate application voltage (discharge voltage) is less than 800 V, and more preferably less than 500 V. In order to obtain a high-quality transparent conductive film, it is preferable to reduce the target applied voltage (discharge voltage) as much as possible. However, if the target voltage is extremely low, productivity problems arise. Therefore, evening gate applied voltage (discharge € H) The optimum value is appropriately selected in consideration of the required quality and productivity of the transparent conductive film in a comprehensive manner. Further, the substrate temperature (temperature of the transparent substrate) at the time of film formation is appropriately selected according to the heat resistance of the transparent substrate within a temperature range in which the transparent substrate is not deformed or deteriorated by heat.

 The target (sputtering target) may be a metal or an oxide as long as a target transparent conductive film can be formed. It is more preferable to use a gate. In the case of using an oxide getter, the yarn of the oxide getter can be appropriately selected depending on the sputter rate and the composition of the intended transparent conductive film. However, the relative density of the oxide target is preferably at least 80%, more preferably at least 90%, further preferably at least 95%. If the relative density of the oxide gate is less than 80%, the production becomes slow, and the evening gate itself and the film obtained therefrom tend to be blackened. In order to obtain a target having a high phase body density composed of oxidized sardines, sintering by HIP (hot isostatic pressure) or the like after molding by CIP (cold isostatic pressure), or sintering aid Preferably, it is used. Here, the relative density indicates the actual density of the sintered body with respect to the theoretical density calculated from the oxide density in terms of area fraction (the same applies hereinafter).

 Obtain a transparent conductive film with substantially uniform electrical resistance while preventing the occurrence of abnormal discharge or cracking in the getter during use and suppressing the influence of oxygen fibers in the sputtering atmosphere. From above, it is preferable to use the evening get T 1 of the present invention described later.

 By forming a transparent conductive film composed of a predetermined oxide film on the above-mentioned transparent material by the above-mentioned physical vapor deposition method, a desired transparent conductive laminate can be obtained. As described above in the description of the transparent conductive laminate of the present invention, Δ of the transparent conductive film at this time may be a single flat film or a target transparent conductive laminate. It may have a predetermined shape according to the use of the body and the like.

Then, in order to obtain a transparent conductive laminate including a transparent conductive film having higher transparency, after forming the transparent conductive film as described above, the key for further improving the transparency of the transparent conductive film. Needling may be performed. The above-mentioned annealing can be performed by heating the transparent conductive film to a temperature lower than the softening point of 60 ° C. to a transparent temperature T in an atmosphere having an oxygen partial pressure of 1 OhPa or more. The total pressure of the atmosphere during annealing can be appropriately selected within the range of 10 hPa to 10,000 hPa. The atmosphere at the time of annealing may contain an inert gas such as N ₂ , He, or Ar as a component other than oxygen. Therefore, the annealing can be performed in the atmosphere (oxygen partial pressure is about 203 hPa), and is most conveniently performed in the atmosphere.

 If the temperature at the time of annealing is 60 ° C or more, the effect of improving the transparency appears. However, in the range of less than the softening point of the above-mentioned transparency ¾W, the higher the temperature, the faster the effect of improving the transparency appears. Therefore, when the transparent substrate is made of an organic polymer material, annealing is preferably performed at about 80 to 200 ° C. for about 1 to 5 hours, although it depends on the material of the transparent substrate. When the transparent substrate is made of glass, it is preferable to anneal at about 150 to 300 ° C. for about 15 minutes to 1 hour.

 Next, the laminate manufacturing method II of the present invention will be described.

 As described above, the laminated body manufacturing method II of the present invention comprises, in addition to the electrically insulating transparent material, indium (In), (Zn), titanium (Ti), gallium (Ga) and oxygen (〇) as constituent elements. The atomic ratio of indium (In) to the total amount of indium (In) and MS (Zn) is 20 / 90at%, and titanium

A transparent conductive film consisting of an oxide film whose atomic ratio (Ti + Ga) / (en + Zn + Ti + Ga) of the total amount of (Ti) and gallium (Ga) is 1-2 Oat% It is characterized by being formed by a vapor deposition method.

 Here, the electrically insulating transparent substrate is, as already described in the description of the transparent conductive laminate II of the present invention, the same as the transparent substrate in the transparent conductive laminate I of the present invention, That is, any material having electrical insulation and a visible light ratio of about 70% or more may be used. Specific examples thereof are as described in the description of the transparent conductive laminate I of the present invention. is there.

Further, the transparent conductive film formed on the transparent substrate is made of an oxide film having the above composition. The composition of this transparent conductive film, including oxygen (〇), is within the above range. By appropriately adjusting the above, a transparent conductive film having more excellent transparency and stability than the transparent conductive film in the transparent conductive layer body I described above can be obtained. Among the transparent conductive films, as described above in the description of the transparent conductive laminate 量 of the present invention, the atomic ratio of indium (In) to the total amount of indium (In) and MIS (Zn) is In. It is more preferable to use an oxide film in which / (In + Zn) is 50 to 9 Oat%, and the atomic ratio of the total amount of titanium (Ti) and gallium (Ga) (T i + Ga) / (In + More preferably, the content of Zn + Ti + Ga) is 5 to 18 at%. The gallium (Ga) atomic ratio Ga / (en + Zn + Ti + Ga) is preferably 8 to 15 at%.

 As a specific example of the physical vapor deposition method employed in the laminate manufacturing method II of the present invention to form a transparent conductive film composed of the above oxide film, the description of the laminate manufacturing method I of the present invention is given below. For the same reason as in the laminate manufacturing method I, it is possible to apply the one-way or multi-way sparkling method (including the reactive sparkling method). More preferred.

 When the sputtering method is applied as the physical vapor deposition method, various methods such as RF sputtering and DC sputtering can be applied as the sputtering method, but the productivity and the resulting oxidation can be applied. In view of the film properties of the material film, DC sparging is generally preferred from an industrial viewpoint. As an example of the condition of the DC ring of the DC ring, the same conditions as those described in the description of the laminate manufacturing method of the present invention can be given.

 The target (sputtering target) may be a metal target or an oxide target as long as the target transparent conductive film can be formed. It is more preferable to use. When an oxide target is used, the thickness of the oxide target can be appropriately selected according to the sputter rate and the intended composition of the transparent conductive film. However, for the same reason as described in the description of the laminate production method I of the present invention, the relative density of the oxide gate is preferably 80% or more, more preferably 90% or more, It is more preferably at least 95%.

Prevents abnormal discharge during use and breaks in the evening get. Sealed, from the top of the electrical resistance to provide a substantially uniform transparent conductive film, it is preferable to use a target T ₂ of the present invention to be described later.

 By forming a transparent conductor m made of a predetermined oxide film on the above-mentioned transparent material by the above-mentioned physical vapor deposition method, a desired transparent conductive laminate can be obtained. As described in the description of the transparent conductive laminate II of the present invention, Δ of the transparent conductive film at this time is the same as that in the transparent conductive laminate of the present invention, that is, 1 It may be in the form of a single flat film or may have a predetermined shape according to the intended use of the transparent conductive laminate.

 Then, in order to obtain a transparent conductive laminate including a transparent conductive film having higher transparency, after forming the transparent conductive film as described above, annealing for further improving the transparency of the transparent conductive film is performed. Is preferably performed. This annealing can be performed in the same manner as described in the description of the method for manufacturing a laminate I of the present invention. Next, the gate of the present invention will be described.

As described above, the evening gate T1 of the present invention is composed of an oxide sintered body containing indium (In), (Zn), titanium (Ti) and oxygen (〇) as constituent elements, and has a general formula In ₂ The atomic ratio of indium (In) to the total amount of indium (In) and ΦΙδ (Ζη), including the hexagonal layering ^ represented by 〇 ₃ (ZnO) _m (m = 2-7) In / (In + Zn) is 20~90at%, and ί number that titanium (atomic ratio Ti / (in + Zn + Ti of Ti)) is 2. 2~20at%, volume resistivity of not more than 10_ ² Omega cm Things.

Here, the “hexagonal layered compound” referred to in the target T1 of the present invention means a substance exhibiting an X-ray diffraction pattern attributed to the hexagonal layered compound in X-ray diffraction measurement. The evening gate T1 of the present invention includes: an oxide sintered body composed of a compound in which titanium oxide is included in the hexagonal layered compound (hereinafter, referred to as “compound Α”); the oxide sintered body of titanium oxide consists of separate ¾¾g product is present in a state (hereinafter referred to as "set Narubutsu Α".), the reduction ^ besides Iotaita ₂ 〇 ₃ or of Α is Zetaita_〇 And an oxide sintered body composed of a composition having a composition obtained by further adding en ₂ 〇 ₃ or ZnO to the above-mentioned metal. Include.

The evening gate Tl preferably contains at least 4% by weight, preferably at least 8% by weight, more preferably at least 16% by weight of the above hexagonal layered layer. As described above, the evening gate T1 having the above-described system has a requirement that “# ¾ resistivity is 1 Cr ² Qcm or less”. The target has the remarkable effect of having this requirement that abnormal discharge and cracking of the getter at the time of film formation are prevented. Evening volume resistivity one Gedzuto T1 is preferably less 7X10- ³ Ω cm, and particularly preferably equal to or less than 5x10- ³ Qcm.

 Further, the relative density of the target T1 is preferably 80% or more, more preferably 90% or more, and even more preferably 95% or more. When the relative density of the evening gate T1 is less than 80%, the production becomes slower, and the evening gate itself and the film obtained therefrom tend to be blackened. In order to obtain a high-density gate made of an oxide sintered body, sintering by HIP (hot isostatic pressure) after molding with cip (cold isostatic pressure), or sintering aid Preferably, it is used.

 In the evening gate T1, the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and ffiiS (Zn) is 20-90at%, and titanium

Since the atomic ratio of Ti (Zn + Zn + Ti) is 2.2 to 2 Oat%, the indium (In), ¾fS (Zn), Indium with titanium (Ti) and oxygen (0) as constituent elements

The atomic ratio of indium (In) to the total amount of (In) and φ | β (Zn) is 20 / 90at%, and the atomic ratio of titanium (Ti) is Ti / (In + Zn + A transparent conductive film composed of an oxide film having Ti) of 2.2 to 20 at% and having a specific resistance in the region shown in FIG. 1 can be formed relatively easily.

When ¾W (plastic) is used as the transparent substrate, the fluctuation of the oxygen concentration in the sputtering atmosphere is affected by the desorbed gas from the substrate. Although unavoidable, when the target T1 is used, the effect of oxygen in the sputtering atmosphere is suppressed as described above, so that the transparent conductive film having the desired specific resistance is made free. Of course, it can be easily formed on a transparent polymer material with good reproducibility. it can.

 As already described in the manufacturing method I of the laminate of the present invention, the transparent conductive film formed on the transparent s # by the sputtering method using the evening gate T1 is indium ( Since it is preferable that the atomic ratio In / (In + Zn) of indium (In) in the total amount of (In) and (Zn) be 50 to 90 at% (excluding 50 at%), The atomic ratio In / (In + Zn) of indium (In) in the gate T1 is preferably set to 50 to 9 Oat%. In addition, the atomic ratio TiZ (In + Zn + Ti) of titanium (Ti) in the transparent conductive film formed on the transparent surface by the sputter ring method using the evening gate was determined in the method of manufacturing a laminate I of the present invention. As described above, since the content is preferably 1 Oat% or less, the atomic ratio Ti / (In + Zn + Ti) of titanium (Ti) in the target T1 is preferably 10 at% or less.

 Generally, when a transparent conductive film made of an oxide film is to be formed by a sputtering method using an evening get made of an oxide sintered body, the target is made of a transparent conductive film having a desired composition. Each of the elements constituting the film other than oxygen (0), and its oxides or compounds that become oxides by firing (chlorides, hydroxides, nitrates, acetates, metal alkoxides) ) Is used as a raw material, and these are mixed in a predetermined amount, and the mixture is calcined, if necessary, and then pulverized. Thereafter, the mixture or the mixture is calcined and then pulverized to obtain a mixture. The powder obtained can be obtained by molding and sintering the desired powder. At this time, it is preferable to use an oxide as the raw material from the viewpoint of obtaining the target at a low cost.

Then, ■ evening one target T1 of the present invention that the resistivity is not more than 10- ² Qcm can also be obtained by the above method. However, depending on the KoNaru the evening one Gedzuto T1, because in the above methods have the volume resistivity is not lower than 10- ² Qcm, in such a case, the sintering furnace after sintering above, Hodzutopuresu reduction Annealing is performed in a vacuum furnace or a reducing atmosphere in a furnace such as a furnace. Therefore to make this § two one ring, it is possible to obtain the evening one Gedzuto T1 aimed bulk resistivity is less than 10- ² Qcm.

As the reducing atmosphere for performing the above annealing, H ₂ gas, methane gas, An atmosphere composed of a reducing gas such as CO gas and an atmosphere composed of an inert gas such as Ar gas and N ₂ gas may be used. Annealing is preferably performed at 200 to 1000 ° C, and more preferably at 300 to 1000 ° C. C, more preferably 400-1000. C. Sufficient reduction is not performed below 200 ° C, and it is not economical to exceed 1000 ° C. The annealing time is preferably from 1 to 50 hours, more preferably from 2 to 30 hours, even more preferably from 3 to 20 hours. If the time is less than 1 hour, sufficient reduction is not performed, and if it exceeds 50 hours, it is not economical.

The annealing temperature in the case of performing the above annealing in a vacuum is preferably 200 to 1000 ° C, more preferably 200 to 700 ° C. (More preferably, the temperature is from 200 to 500 ° C. If the temperature is lower than 200 ° C., sufficient reduction is not performed. If the temperature exceeds 1000 ° C., ZnO or In ₂ 〇 _{3 in} the sintered body evaporates, and In the case where the cleaning is performed in a vacuum, the time is preferably 1 to 50 hours, more preferably 2 to 30 hours, and still more preferably 3 to 20 hours.

 When the oxide gate T1 of the present invention is obtained using only the oxide as the raw material, the purity of the oxide, zinc oxide and titanium oxide of the raw material is preferably 99% or more, more preferably 99% or more, respectively. 9% or more, particularly preferably 99.99% or more. If it is less than 99%, a dense sintered body cannot be obtained even if it is sintered, and problems such as a high volume resistivity of the obtained evening gate occur.

 The average particle size of each raw material is preferably 0.01 to 1 Om, more preferably 0.05 to 5 m, and particularly preferably 0.1 to 5 m. If it is less than 0.01 m, it tends to wrinkle, and if it exceeds 10 zm, the mixture between the raw materials is poor, and a dense sintered body cannot be obtained even when it is sintered. If the average particle size of the raw material exceeds 10 m, it can be used by adjusting the average particle size to within the above range using a ball mill, roll mill, pal mill, jet mill, etc. .

 The production of the target T1 using the raw material composed of the above oxide can be performed, for example, as follows.

First, each raw material is put into a mixer such as a ball mill, a jet mill, a pearl mill and the like, and these are mixed to obtain a mixture. The mixing time is preferably 1 to 100 hours, more preferably 5 to 50 hours, particularly preferably 10 to 50 hours. 1 Less than an hour is not sufficient for mixing, and more than 100 hours is not economical. The mixing temperature is not particularly limited, and is preferably room temperature.

 The mixture obtained by the mixing may be calcined to promote the formation of a hexagonal layered compound. The calcination is preferably 800 to 1500 ° C, more preferably 900 to 1400 ° C, particularly preferably 1000 to 1300 ° C. If the temperature is lower than 800 ° C., no hexagonal layered conjugate is formed, and if the temperature is higher than 1500 ° C., evaporation of oxidation or oxidation occurs. The calcination time is preferably from 1 to: L00 hours, more preferably from 2 to 50 hours, particularly preferably from 3 to 30 hours. If the time is less than 1 hour, the formation of a hexagonal layered compound does not sufficiently occur, and if it exceeds 100 hours, it is not economical.

 The calcined product is preferably ground to keep the particle size in the range of 0.01 to 10111 (hereinafter, the powder obtained by crushing after calcination is referred to as "fine powder"). Crushing is performed in the same manner as mixing. Further, in order to generate the hexagonal layered compound, it is preferable to repeat calcination and pulverization.

 The mixture or the powder obtained by mixing the raw materials may be subjected to granulation treatment to improve the fluidity and the filling property during molding (hereinafter, the granulated product is referred to as “granulated material”). "). Granulation is performed by a conventional method such as a spray drying method. When the spray drying method is used, an aqueous solution or an alcohol solution of the powder is used, and polyvinyl alcohol or the like is used as a binder to be mixed with the solution. The granulation conditions vary depending on the solution concentration and the amount of binder added, but the average particle size of the granulated product is 1 to: LOOm, preferably 5 to 100 / m, and particularly preferably 10 to 1OOzm. Adjust so that If the average particle size of the granulated material exceeds 100 m, the fluidity during molding and the filling quality are poor, and the granulation effect is not obtained.

Next, the mixture obtained by mixing the raw materials, the anti-dust powder or the granulated product is molded by die molding, injection molding or injection molding. From the viewpoint of obtaining a sintered body having a high sintering density, it is preferable to mold by CIP (cold isostatic pressure) or the like. The shape of the molded body can be any of various types of materials suitable as a gate. Further, polyvinyl alcohol, methyl cellulose, polywax, oleic acid, or the like may be used as a molding aid. The molding pressure is preferably from 1 Okg / cm ² to 1 OOtZcm ² , more preferably from 100 kg / cm ² to 100 t / cm ² . Molding time is 10 minutes to 10:00 Between is preferred. If the molding pressure is less than 1 Okg / Zcm ² or if the molding time is less than 10 minutes, the density of the sintered body obtained after sintering cannot be increased. Next, the molded product obtained by the above-described molding is sintered. There is no particular limitation on the method of sintering the molded product, and normal pressure sintering may be used, or pressure sintering such as gas pressure sintering, HIP (hot isostatic pressing) sintering, or hot press sintering may be used.

The sintering temperature S is preferably 1200 to 1600 ° C, more preferably 1250 to 1550 ° C, and still more preferably 1300 to 1500. C. 1200. If it is less than C does not produce the hexagonal layered I spoon ^ ILN ₂ 〇 _{3 (ZnO) m (m =} 2~7), and 1600 ° C sublimes Exceeding indium oxide or zinc oxide, resulting in deviation of.

The sintering time depends on the sintering, but is preferably 1 to 50 hours, more preferably 2 to 30 hours, and particularly preferably 3 to 20 hours. If the time is less than 1 hour, the formation and sintering of the hexagonal layered compound will not be sufficiently performed, and if the time exceeds 50 hours, it is not economical. The atmosphere during sintering is an oxidizing atmosphere or a reducing atmosphere. Examples of the oxidizing atmosphere include an atmosphere composed of air or oxygen gas. Examples of the reducing atmosphere include an atmosphere composed of a reducing gas such as H ₂ gas, methane gas, and C〇 gas, and an inert gas such as Ar gas and N ₂ gas.

 The target T1 can be obtained by performing the steps up to sintering as described above, or by performing the above-described annealing as necessary after the sintering.

In the case of using the evening one Gedzuto T1 of the present invention, the | since «resistivity is below 10 one ² Qcm or more, abnormal discharge cracks in and evening one target induced occurs during the film used Is suppressed. Further, when the evening gate T1 of the present invention is used, the influence of the oxygen concentration in the sputtering atmosphere is suppressed.

 Next, the evening get T2 of the present invention will be described.

As described above, the target T2 of the present invention is made of an oxide sintered body containing indium (in), (Zη), titanium (Ti), gallium (Ga) and oxygen (0) as constituent elements. Indium (In) and 状! & (Zn) contain the hexagonal layered layer represented by the formula In ₂ 〇 ₃ (ZnO) _m (m = 2 to 7). ) Atomic ratio In / (In + Zn) is 20 ~ 90at%, titanium (Ti) I | «means that the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of the total amount of GaN and gallium (Ga) is l-20at%.

 Here, the “hexagonal layered” referred to in the target T2 of the present invention means the same substance as the “hexagonal layered compound” referred to in the aforementioned target T1 of the present invention. The evening gate T2 of the present invention is an oxide sintered body of ffi contained in the “oxide sintered body containing a hexagonal layered layer and titanium oxide” referred to in the above-mentioned evening gate T1 of the present invention. And an oxide sintered body of Itosei obtained by further adding a gallic acid sardine.

The evening gate T2 preferably contains 4% by weight or more, preferably 8% by weight or more, more preferably 16% by weight or more of the above hexagonal layer formation. Preferably bulk resistivity of evening one Gedzuto T2 having the composition described above is less than 10_ ² Qcm, more preferably less 7x 10- ³ Qcm, particularly preferably at most 5x10 one ³ Omega cm.

 Further, the relative density of the target T2 is preferably 80% or more, more preferably 90% or more, and still more preferably 95% for the same reason as in the above-mentioned evening get T1 of the present invention. That is all. In order to obtain a high-density evening gate made of an oxidized sinter product, it is necessary to mold it with CIP (cold hydrostatic pressure) and then sinter it with HIP (hot static 7 pressure) or the like. It is preferred to use auxiliaries.

 In the target T2, the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and ¾IS (Zn) is 20 to 90 at%, and titanium

Since the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of the total amount of (Ti) and gallium (Ga) is l-20at%, the corresponding one-time gate T2 is used By doing so, indium (In), (Zn), titanium (Ti), and oxygen (0) are the constituent elements, and indium (In) atoms occupy the total amount of indium (In) and zinc (Zn). Ratio In / (In + Zn) is 20 ~ 90at%, titanium

A transparent conductive film composed of an oxide film having an atomic ratio (Ti + Ga) / (en + Zn + Ti + Ga) of (Ti + Ga) / (en + Zn + Ti + Ga) of (Ti) and gallium (Ga) is relatively small. It can be easily formed.

As already described in the laminate production method II of the present invention, the transparent conductive film formed on the transparent film by the sputtering method using the evening gate T2. Of those consisting of, the one in which the atomic ratio In, (In + Zn) of indium (In) in the total amount of indium (In) and zinc (Zn) is 50-90 &% is preferable. The atomic ratio In / (In + Zn) of indium (In) in T2 is preferably set to 50 to 90 at%.

 In addition, the atomic ratio (Ti + Ga) / (In + Zn + Ti +) of the total amount of titanium (Ti) and gallium (Ga) in the transparent conductive film formed on the transparent substrate by sputtering using the target T2. Ga) is preferably 5 to 18 at% as described above in the method of manufacturing a laminate II of the present invention, so that the total of titanium (Ti) and gallium (Ga) in the evening gate T2 is used. The atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) is preferably 5 to 18 at%.

 The atomic ratio Ga / (In + Zn + Ti + Ga) of gallium (Ga) in the transparent conductive film formed on the transparent substrate by the sputter ring method using the evening gate T2 is determined by the laminate of the present invention. As already described in the manufacturing method II, it is preferable that the atomic ratio Ga / (In + Zn + Ti + Ga) of the gallium (Ga) in the target T2 be 8 to: L is preferably 5 at%.

The evening gate T2 of the present invention is the same as the above-mentioned raw material used for producing the evening gate T1 of the present invention, except that a gallium oxide or a compound which becomes a gallium oxide by firing is used. It can be manufactured in the same manner as the above-described evening gate T1 of the present invention. At this time, the body mounting the resistivity of the evening one Gedzuto T2 is urchin I described above, it is preferable that the following 1_〇- ² Qcm. The resistivity of the Tagedzuto T2 when the following 10- ² Qcm is abnormal discharge induced is possible and evening during use - that cracks get results is suppressed.

 Next, the touch panel I of the present invention will be described.

As described above, the touch panel I of the present invention includes two transparent electrode substrates each having a transparent electrode film formed in a predetermined pattern, and the two transparent electrode substrates connect the transparent electrode films to each other. A pair of transparent panels that are arranged to face each other at a predetermined interval, and that when the transparent substrate is subjected to a load from the outside of one of the transparent electrode substrates, the transparent substrates are conducted with each other; At least one of the transparent layers formed on the opposite side is indium (In), zinc (Zn) ₃ With titanium (Ti) and oxygen (〇) as constituent elements, the atomic ratio of indium (In) to the total amount of indium (In) and zinc (Zn), In / (In + Zn), is 20 to 90 at%, and titanium (Ti) consists of an oxide film having an atomic ratio of TiZ (In + Zn + Ti) of 2.2 to 20 at%, and the characteristic feature is that the transparent AM and specific resistance are in the region shown in FIG. It is assumed that.

 That is, in the touch panel I of the present invention, at least one of the two transparent electrode substrates constituting the same is the transparent conductive laminate I of the present invention described above (where the transparent conductive film of a predetermined shape is formed). The same shall apply hereinafter.).

 The thickness of the transparent conductive film (transparent electrode film) in the transparent conductive laminate I constituting the transparent electrode substrate should be 12 to 100 nm when the panel I of the present invention is an analog panel. And preferably 15 to 50 nm. In addition, the surface resistance of the transparent conductive film (transparent electrode!) In the transparent conductive laminate I forming the transparent electrode can be appropriately adjusted by changing the thickness and fllff. In the case where the evening panel I of the present invention is an analog evening panel, it is preferable that the width be 1000 to 5000 Ω / port.

 In order to easily obtain a touch panel having a desired input accuracy, the transparent conductive laminate I forming the transparent electrode layer is referred to as the transparent conductive laminate I of the present invention. As described in, the atomic ratio In / (In + Zn) of indium (In) in the transparent conductive film (transparent electrode model) that constitutes this is 50 to 90 at% (excluding 50 at%). ) Is preferred. At this time, the atomic ratio Ti / (en + Zn + Ti) of titanium (Ti) in the transparent conductive film (transparent m¾ film) is preferably 1 Oat% or less.

When one of the two transparent electrode substrates is formed of a transparent conductive laminate other than the above-described transparent conductive laminate of the present invention, the transparent conductive laminate other than the transparent conductive laminate I of the present invention may be used. It is preferable to use a transparent conductive film (transparent m¾ film) having excellent transparency and stable electric resistance over time, such as a 〇〇 film and a tin oxide film. In order to obtain an analog type touch panel having a high input accuracy, each of the two transparent electrode substrates is formed by the transparent conductive laminate I of the present invention described above. 97 1853.

 The toner panel I is configured in the same manner as the toner panel of ^ except that at least one of the two transparent sheets constituting the toner panel I is formed by the transparent conductive laminate I of the present invention described above. Is done. At this time, the two transparent substrates are arranged so that the transparent electrode films face each other while being kept at a predetermined interval by a spacer or the like, and one of the transparent electrodes si is opposed to the input surface side. To position. Then, each of these transparent electrodes is connected to each other so that the transparent electrodes are electrically connected to each other when a load is applied to the transparent electrode from the outside of the transparent electrode positioned on the input surface side. It is electrically connected to a predetermined drive circuit via terminals and lead wires (extraction mn) provided at predetermined positions on the film. In addition, each of the transparent electrodes is electrically connected to a comparison circuit, a microprocessor, and a coordinate detecting means using analog / digital conversion.

 It is preferable that the evening panel constructed as described above is a 3 inch type evening panel, and it is particularly preferred that the evening panel is an analog type evening panel. The principle of detecting the data input position in the touch panel I of the present invention is the same as that of ^, but at least one of the two transparent electrodes constituting the touch panel I is the transparent electrode of the present invention described above. The transparent conductive film was formed by the conductive laminate I, that is, the transparent conductive film was formed by an oxide film having a high surface resistance of 800 Ω / port to 1 Ok Q / port. For this reason, in the evening touch panel I of the present invention, it is difficult for data to be erroneously recognized at the time of coordinate detection, and it is possible to perform a stable data input stably. Next, the touch panel II of the present invention will be described.

As described above, the touch panel II of the present invention includes two transparent electrode substrates each having a transparent electrode film formed in a predetermined pattern, and the ^two transparent electrode substrates are connected to each other by the transparent film. Are arranged at predetermined intervals so as to face each other, and the transparent electrode films are conducted when a load is applied to the transparent electrode substrate from the outside of one of the transparent electrodes. At least one of the transparent electrode substrates formed on each of the transparent electrode substrates is composed of indium (I n), zinc (Z n), titanium (T i), gallium (G a), and oxygen (〇). Is the constituent element, and the atomic ratio of indium (In) to the total amount of indium (In) and (Zn) is In / 9

(In + Zn) is 20 to 90 at%, and the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of the total amount of the titanium (Ti) and the gallium (Ga) is l to 20 at%. It is assumed that an oxide film is used.

 That is, the transparent panel II of the present invention has a structure in which at least one of the two transparent electrodes constituting the transparent panel has the above-described transparent conductive laminate II of the present invention (a transparent conductive film of a predetermined shape is formed). The same shall apply hereinafter.).

 The flljf of the transparent conductive film (transparent film) in the transparent conductive laminate 11 formed by forming the transparent fiber should be 12 to 100 nm when the evening panel II of the present invention is an analog evening panel. It is particularly preferable that the thickness be 15 to 50 nm. Further, the surface resistance of the transparent conductive film (transparent electrode film) in the transparent conductive laminate II forming the transparent electrode can be appropriately adjusted by changing the composition and the film thickness. When the analog touch panel II is used as the analog touch panel, it is preferable to set the resistance to 1000 to 5000Ω / port.

 In addition, in order to easily obtain a touch panel having a desired input accuracy, the transparent conductive laminate II forming the transparent electrode contact hole is described in the description of the transparent conductive laminate II of the present invention. As mentioned in the above, the atomic ratio In / (In + Zn) of indium (In) in the transparent conductive film (transparent electrode film) composing it is 50 to 90 at%, and titanium (Ti) and gallium ( It is preferable that the total atomic ratio of (Ga) (Ti + Ga) / (In + Zn + Ti + Ga) is 5 to 8 at%. At this time, the atomic ratio Ga / (In + Zn + Ti + Ga) of gallium (Ga) in the transparent conductive film (transparent electrode film) is preferably 8 to 15 at%.

When one of the two transparent electrode substrates is formed of a transparent conductive laminate other than the transparent conductive laminate II of the present invention described above, the `` Transparent conductive laminate other than the transparent conductive laminate II of the present invention '' is used. It is particularly preferable to use the above-described transparent conductive laminate of the present invention, but it is preferable to use a transparent conductive film having excellent transparency and stable electric resistance over time, such as an IT〇 film or a tin oxide film. A transparent conductive laminate on which a transparent electrode is formed may be used. To obtain an analog type touch panel with high input accuracy, each of the two transparent electrode substrates is formed by the transparent conductive laminate 11 of the present invention described above. Alternatively, it is preferable that one of them is formed by the above-described transparent conductive laminate II of the present invention, and the other is formed by the above-described transparent conductive laminate of the present invention. The touch panel II is the same as the touch panel I of the present invention described above, except that at least one of the two transparent sheets constituting the touch panel II is formed by the transparent conductive laminate II of the present invention described above. In addition, it is configured in the same way as the «Touch Panel». This evening panel is preferably a resistive evening panel, particularly preferably an analog evening panel.

 The principle of detecting the data input position in the touch panel II of the present invention is the same as that of the touch panel, but at least one of the two transparent mirrors constituting the touch panel II is the transparent touch panel of the present invention described above. A transparent electrode film formed by the conductive laminate II, that is, an oxide film that can easily increase the surface resistance to 800 Ω / port to 10 kΩ / k. is there. Therefore, the evening touch panel II of the present invention can easily obtain a panel which is less likely to be misidentified at the time of coordinate detection and which can perform stable data input stably.

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Spiritual example 1

 (1) Yuichi Gate Manufacturing ''

99.99% pure indium powder with indium powder (average particle size lm) 254g and 99.9% pure oxide powder (average particle size 1m) 39g and 99.99% pure titanium oxide powder (Average particle size: 1 m) Using 7 g as raw materials, these were put into a polyimide pot together with ethanol and alumina balls, and mixed for 2 hours by a planetary ball mill. The obtained mixed powder was placed in a mold, and pre-molded at a pressure of 100 kg / cm ^{2 by} a mold press molding machine. Next, after being compacted at a pressure of 4 t / cm ² by a cold isostatic press molding machine, it was sintered in an air atmosphere at 1300 ° C. for 4 hours in a sintering furnace. The obtained sintered body was subjected to vacuum in a vacuum furnace using a furnace. Heat treatment was further performed for 2 hours at C, and annealing was performed to obtain a target oxide sintered body (one of the gate I of the present invention).

The crystal structure of the sintered body was measured by X-ray diffraction (using an X-ray diffraction measurement device manufactured by Rigaku Corporation), and the hexagonal crystal of In ₂ 〇 ₃ (ZnO) 3 was obtained. Layered 9 01853 and the formation of In ₂ 〇 ₃ were observed.

 In addition, the compositional analysis was performed by ICP analysis (ICP emission spectroscopy: SPS-1500VR manufactured by Seiko Iden Kogyo Co., Ltd.), and the atomic composition ratio (excluding oxygen). From the results, the atomic ratio of indium (In) to the total amount of indium (ェ n) and Φ ウ ム δ (Zn) In / ((n + Zn) and the atomic ratio of titanium (Ti) Ti / (In + Zn + Ti) was determined for each. Furthermore, the density (relative density) of the oxide sintered body was determined. Table 1 shows these results.

 (2) Evening gate tree

 A test piece of 20 mm × 40 mm × 5 mm was cut out from the above oxide sintered body, and its resistivity was measured by a four-terminal method. Table 2 shows the results.

A disk-shaped oxide sintered body having a diameter of 4 inches and a thickness of 5 mm was prepared in the same manner as in (1) above, and a DC magnetron spade using this oxide sintered body target was prepared. The life test was carried out by performing the evening ring (DC magnetron sputtering) at a power of 5 W / cm ² for 100 hours continuously, and during this time, the occurrence of abnormal discharge and the presence or absence of evening get cracking were observed.

 At this time, a copper backing plate was used as the target, and indium metal was used as the bonding material. The occurrence of abnormal discharge was visually observed from the chamber viewport.

 Table 2 shows these results.

Sickle example 2 ~ 麵 example 5

 (1) Manufacturing of Yuichi Gate I

 A table was prepared in the same manner as (1) in Example 1 except that the amount of each raw material was changed.

An oxide sintered body having one of the compositions and relative densities shown in FIG. 1 (all of which were one of the gates I of the present invention) was obtained for each example.

 (2) Characteristics of evening gate

The resistivity of each oxide sintered gate was measured in the same manner as (2) in Example 1. Table 2 shows the results. Also, in the same manner as in (1) above, disk-shaped oxide sintered targets each having a diameter of 4 inches and a thickness of 5 mm were prepared for each Wei example. A life test was performed in the same manner as (2) in Example 1. The results are shown in Table 2.

Male example 6

 (1) Manufacturing of Yuichi Gate I

 Except that the amount of raw material used was changed and that annealing was not performed after sintering, the same procedure as in (1) in Example 1 was carried out. Got a gate.

 (2) Characteristics of evening gate

 The body resistivity of the above oxide sintered gate was measured in the same manner as (2) in Example 1. Table 2 shows the results.

 A disk-shaped oxide sintered body having a diameter of 4 inches and a thickness of 5 mm was prepared in the same manner as in (1) above.

A life test was performed in the same manner as (2) in 1. The results are shown in Table 2. table 1

(Hereinafter the margin) Table 2

表 2に示したように、 »例 1〜«例 6で製造した各酸化物焼結体夕一ゲヅ ト （いずれも本発明の夕一ゲヅト Iの 1つ） は、 抵抗率が 0. 3X10— ²〜 〇. 9xlO_²Qcmと低いことから、 実際に に使用しても異常放電の誘発 を起こし難く、 かつ、 夕一ゲヅト割れも生じにくいものである。

As shown in Table 2, each oxide sintered body manufactured in Examples 1 to 6 (one of the evening gates I of the present invention) has a resistivity of 0.1%. 3X10- since ² ~ 〇. 9XlO_ ² Qcm and low, actually difficult cause induction of even abnormal discharge used in and evening are those unlikely to occur even one Gedzuto cracking.

Male example 7

 (1) Manufacture of evening gate I

Purity 99. 99% 1] ₂ 〇 ₃ powder (average particle size 1111) 254g and 99.99% purity oxidized powder (average particle size 1 m) 4 Og and 99. 99% purity titanium oxide Example 1 except that 6 g of powder (average particle size 1 m) was used as the raw material.

In the same manner as in (1), the target oxide sintered body target (the one of the present invention :!) was obtained.

The crystal structure of this oxide sintered body target was measured by X-ray diffraction in the same manner as (1) in Example 1, and it was found that the hexagonal layered compound of In ₂ 〇 ₃ (ZnO) ₃ and the en ₂ 〇 ₃ Formation was observed. In addition, ^ was analyzed by ICP analysis in the same manner as (1) in Example 1, and the atomic ratio of indium (In) to the total amount of indium (In) and (Ζη) In / (In + Zn) was 79 at%. The relative density is 96%, cage resistivity was 0. 22x10- ² Ω cm.

(2) Measurement of specific resistance Using the above oxide sintered body, the oxygen concentration (oxygen partial pressure) in the sparging atmosphere at the time was variously changed within the range of 2.0 to 5.0 vol%, and the following conditions were satisfied. An IUP 80-100 nm transparent film was illuminated on a polyester film (Lumira 1 manufactured by Toray Industries, Inc.) using a DC magnetron sparing ring.

 Spa Ringer HSM-552 (manufactured by Shimadzu Corporation) Evening size 4 inches in diameter and 5 mm in thickness

 Discharge type DC magnetron

 No '0.3A

 · ¾ u U V

Background pressure 5x10- ⁴ Pa

Introducing gas (atmospheric gas) Ar + 0 ₂ Kongo gas

 Pressing pressure 1.4x10- ^

 Presspa: 5 minutes evening time

Spa pressure 1.4 x10 ^_1 Pa

 Non-rotating fiber • 6 r pm

 牵

 Table 3 shows the specific resistance of the transparent electrode film obtained under the above conditions.

表 3から明らかなように、 ¾ ^例 7で製造した酸化物焼結体夕一ゲヅト （本発 明の夕一ゲヅト Iの 1つ） を用いて得た透明電¾ の比抵抗は、 時のスパヅ 夕リング雰囲気 （雰囲気ガス） 中の酸素濃度が 2. 0〜5vol%の範囲のとき に 20. 5X10— ⁴〜21. 2x10— ⁴Ω cmの範囲内にあり、 酸素髓の変動 に伴う変動は小さい。

As is clear from Table 3, the specific resistance of the transparent electrode obtained by using the oxide gate of the oxide sintered body manufactured in Example 7 (one of the gates I of the present invention) is as follows. Of spa ヅ Evening ring atmosphere (atmospheric gas) when oxygen concentration is in the range of 2.0 to 5 vol% To 20. 5X10- ⁴ ~21. 2x10- in the range of ⁴ Omega cm, variation due to the variation of oxygen marrow is small.

Examples 8 to 13 (Manufacture of evening gate II)

With 99.99% purity In ₂ 〇 ₃ powder (average particle size lm) and 99.99% zinc oxide powder (average particle size and 99.99% titanium oxide powder (average particle size l〃m) Gallium oxide powder with a purity of 99.99% (average particle size: 1 m) was used as the raw material, and the amount of each raw material used was changed as appropriate.

In the same manner as in (1), oxide sintered body evening gates (all of which are one of the evening gates II of the present invention) having the following values shown in Table 4 were obtained for each example. _c

(Hereinafter the margin)

Table 4

 Sintered compound body

96% 0. 3X10-² 実施例 13 74, 0 ： 9.5 ： 4.0 ： 12.5 0 808 CD. at% 96% 0. 3x10—² Composition (In: Zn Ti: Ga) In / (In + Zn) (Ti + Ga) / (In + Zn + Ti + Ga) Relative density Volume resistivity Example 8 26 72.4: 1 0.6 26.4 at 1. 6at% 95% 0. 8x10- ² example Θ 51 32: 8.5 8,5 94% 0. 4X10- 2 example 10 64 29: 3.5 3.5 68. 8at 93% 0. 4X10-2 example 11 74 19, 8: 1.1: 5, 16.2 at% 96% 0.3x10-2 Example 12 74 9: 5: 12 t

96% 0. 3X10- ² Example 13 74, 0: 9.5: 4.0 :. 12.5 0 808 CD at% 96% 0. 3x10- 2

*: The unit is Ω cm ₍ C

1

 Bird

 〇 〇 O

c

Examples 14 to 16 (Manufacture of transparent conductive laminate I)

 180 m thick polyethylene terephthalate film (transparent)

Abbreviated as “PET film”. same as below. ) Or a glass plate (# 7059 manufactured by Koning Co .; size 16cm x 16cm, thickness 1. lmm; the same applies hereinafter)), and the atomic ratio (excluding oxygen) shown in Table 5 as a sparing ring In the following, the atomic composition ratios (referred to simply as “Ito Makoto”) of the sintered sinter product (each of which is one of the evening gates of the present invention) shown in Table 5 were used. Except for oxygen, hereinafter simply referred to as “composition”.) An oxide film (transparent conductive film) is formed on the PET film or the glass plate by the sputter method under the following conditions. A transparent conductive laminate I was obtained for each example. The composition of the oxide film was determined by induction plasma emission spectroscopy (ICP).

 31 \ —552 (manufactured by Shimadzu Corporation)

 Target size 4 inches in diameter, thickness 5mm

 Discharge type DC magnetron

 0.2A

 400V

Background pressure 5. 0x10 one ⁴ Pa

Introducing gas (atmospheric gas) 97vol% Ar + 3vol% 0 2 mixed gas

Puresupa' evening pressure 1. 4x10 one ⁴ Pa

 Prespa evening time 5 minutes

Sputtering evening pressure 1. 4X1_rei one ¹ Pa

 Spa evening time 4 minutes

 6 r pm For each of the obtained transparent conductive laminates I, the surface resistance, the standard deviation of the surface resistance, and the specific resistance of the oxide film (transparent conductive film) constituting the transparent conductive laminate I were determined. Was. The transmittance of light having a wavelength of 550 nm was determined for each transparent conductive laminate I. Table 6 shows the results.

The film thickness was measured separately using the slide glass dedicated for measurement under the above conditions. The ivy was measured by the stylus method using DE KTAK3030 of Sloane: fc. The surface resistance was measured by the four-terminal method using a mouthless FP manufactured by Mitsubishi Yuka Co., and the standard deviation of the surface resistance was determined five times under the above conditions for each example. From the surface resistance. The specific resistance is the flatness of the oxide film! It was calculated by multiplying the surface resistance measured at the center of ± by the enzyme of the haze oxide film on the slide glass (“Measurement of thin film materials · ¾5” (Technical Information Association) No. 114- See page 115). The light transmittance of the transparent conductive laminate I was measured using UV-3100 manufactured by Shimadzu Corporation.

 In addition, the transparent conductive laminate obtained in each example was placed in air. After standing for 300 hours under the condition of C, the surface resistance R of the oxide film (transparent conductive film) constituting the transparent electrode was measured in the same manner as described above, and the surface resistance R immediately after film formation was obtained. (Shown in the column of surface resistance in Table 5) R / R. I asked. Table 6 shows these results.

 Furthermore, each of the transparent conductive laminates I obtained in each example is suitable or not as a component or a material of the analog-type touch panel, that is, the oxide film constituting the transparent conductive laminate I It was evaluated from the characteristics of the oxide film shown in Table 6 whether or not was suitable as a transparent electrode for an analog-to-digital type sunset panel. Table 6 shows the results.

Comparative Example 1

 In forming the oxide film, an example was used except that an oxide sintered body consisting of zinc (In), (Zn) and oxygen (0) was used as a sputtering target (see Table 5). An oxide film (transparent conductive film) having a composition outside the limited range of the present invention as shown in Table 5 was formed on the PET film in the same manner as in Examples 14 to 16 to form a transparent conductive laminate. I got

With respect to the oxide film (transparent conductive film) constituting the transparent conductive laminate, the same items as those obtained in Examples 14 to ^ Example 16 were determined in the same manner as in these examples. In addition, the light transmittance of the transparent conductive laminate was determined in the same manner as in Examples 14 to 16. Further, the suitability of the transparent conductive laminate as a component of the analog touch panel was determined in the same manner as in Examples 14 to 16. These results Table 5

 Table e

 * 1: Indicates the i¾i ratio of light at a wavelength of 550 nm with respect to the transparent electrode S.

 * 2: Indicates the results of evaluation of the suitability of analog type panel components or their materials.

... It is suitable as a configuration or material for obtaining an analog type touch panel with improved input accuracy. Δ: It can be used as a component or a material for obtaining an analog touch panel whose input accuracy has not been improved.

As is evident from Table 6, each of the oxide films obtained in Examples 14 to 16 had a high surface resistance of 1240 to 130 Ω / port and a high surface resistance. As can be seen from the value of the standard deviation, it can be obtained with good reproducibility. R / R shown in Table 6. As can be seen from the values, the oxide film has excellent Him properties, and in particular, the oxide films of Example 14 and Male Example 16 have high perpendicularity. From these facts, as shown in Table 6, the transparent conductive laminate obtained in each of the examples has a structure for obtaining an analog type touch panel, particularly an analog type touch panel with improved input accuracy. It can be seen that it has excellent tree growth suitable as a member or its material.

 On the other hand, since the oxide film obtained in Comparative Example 1 has a surface resistance of only 350 Ω / D, the transparent conductive laminate obtained in Comparative Example 1 has an analog type in which the input accuracy is not improved. Although it can be used as a component or a material for obtaining the same, it is unsuitable as a component or a material for obtaining an analog type touch panel with improved input accuracy.

Difficult example 17 ~ Dragon example 2 2 (Manufacture of transparent conductive laminate I)

 As shown in Table 7, 5S Example 14 to Example 16 were used except that the oxide sintered body was manufactured in the same manner as any one of ^ S Example 2 to Example 6 as the oxide gate. Similarly, a transparent oxide film (transparent conductive) shown in Table 7 was formed on the PET film or the glass plate, whereby »a transparent conductive laminate I was obtained for each example.

 For each of the oxide films (transparent conductive mm) constituting each transparent conductive laminate, the same items as those obtained in Examples 14 to 16 were obtained in the same manner as in these examples. The light efficiency in each transparent conductive laminate! ^ Example 14 ~! It was determined in the same manner as in Example 16. Furthermore, for each transparent conductive laminate, the suitability as a component of an analog type touch panel was evaluated as Example 14 ~ ^! Evaluation was performed in the same manner as in Example 16. Table 8 shows these results.

(Hereinafter the margin) Table 7 j te ft

table

 Light transmittance 1 Surface resistance R / Ro evaluation result of surface resistance 2 (%) (Ω / port) Standard deviation

 Example 17 180 85.2 5333 98 96 1.2 〇 Example 18 15 88.2 4200 49 6.3 1.2 〇 Example ί9 15 89.3 2000 33 3 1.2 〇 Example 20 15 89. 4 1200 15 1.8 1.3 〇 Example 21 15 89.4 1300 14 1.95 1.3 〇 Example 22 15 87.8 1300 17 2.03 1.3 〇

 X

 1, * 2: Same as 脚 6 leg.

〇 ϋ

As is evident from Table 8, each oxide film obtained in Examples 17 to ^^ Example 22 has a high surface resistance of 1200 to 5333 Ω As can be seen from the value of the standard deviation, it can be obtained with good reproducibility. Also, as can be seen from the R / Ro values shown in Table 8, it has excellent heat resistance. From these facts, as shown in Table 8, the transparent conductive laminate obtained in each of the examples is a component for obtaining an analog type touch panel, particularly an analog type touch panel with improved input accuracy. Alternatively, it is found that the material has excellent tree growth suitable for the material.

Examples 23 to 29 (Production of transparent conductive laminate)

 As shown in Table 9, the oxide sintered body was manufactured in the same manner as one of Examples 2 to ^^ Example 6 or the same as that used in Example 14 , Except that the oxygen concentration in the atmosphere during the film formation (sparing atmosphere) was changed by changing the type or composition of the introduced gas, and that some annealing was performed later. In the same manner as in 6, an oxide film (transparent conductive film) was formed on a PET film or a glass plate, whereby a transparent conductive laminate I was obtained for each example.

 For each of the oxide films (transparent conductive films) constituting each transparent conductive laminate, the same items as those obtained in Examples 14 to ^ ¾Example 16 were obtained in the same manner as these ^^ g examples. . In addition, the light transmittance of each transparent conductive laminate was determined in the same manner as in ^ S Example 14 to Wei Example 16. Furthermore, the suitability of each transparent conductive laminate as a component of the analog-type touch panel was evaluated in the same manner as in Examples 14 to 16 of ^ S. Table 10 shows these results. The composition of each oxide film (transparent conductive film) was the same as that of the oxide sintered body having the same composition! Example 17! It was the same as the oxide film (transparent conductive film) obtained in either of Example 22 and Example 14.

(Hereinafter the margin) Table Q

 * 2: Ar gas mixed with 1 vol% oxygen was introduced into the heating furnace and annealed at atmospheric pressure.

* 3: The oxygen Ar gas obtained by mixing 40 vol% was introduced into the heating furnace, and annealed at atmospheric pressure _c

O

 Film thickness Light transmittance Surface resistance Surface resistance Result 2 (nm) (%) (Ω / port) Standard deviation

 Example 23 180 86.2 5000 78 90.0 1.1 例 Example 24 15 89.0 5100 52 X 7.65 1.1 〇 Example 25 15 89.9 2800 30 4.2. Example 26 15 89.7 1500 18 2.25 1.1 〇 Example 27 15 90.0 1600 18 2.4 1.10

 0 1600 19 2.4

 Example 28 15 88. 1. 1 〇 Example 29 15 91.5 1350 23 2. 03 1.0 〇

* 1., * 2: Same as in Table 6.

9 As is clear from Table 10, each of the oxide films obtained in Example 23 to Example 5 has a high surface resistance of 150 to 500 However, since the substrate was subjected to the predetermined annealing treatment, the light emission rate was improved to 86.2 to 90.0%. Further, as can be seen from the value of the standard deviation of the surface resistance, it can be obtained with good reproducibility. In addition, R / R shown in Table 10. As can be seen from the value of, it has excellent properties. From these facts, as shown in Table 10, the transparent conductive laminate obtained in each of the examples is a component for obtaining an analog touch panel, particularly an analog touch panel with improved input accuracy. Alternatively, it can be seen that the material has excellent durability suitable for the material.

Pavement example 30 to Difficult example 36 (Manufacture of transparent conductive laminate II)

 As shown in Table 11, as in Example 14 to Example 16, except that the oxide sintered body was manufactured in the same manner as in any one of Examples 8 to 13 as an oxide gate. And an oxide film with the composition shown in Table 11 on a PET film or a glass plate

(Transparent conductive film) was formed, whereby a transparent conductive laminate II was obtained for each example. For each of the oxide film constituting the respective transparent electroconductive laminate (transparent conductive film), _c also the same items as determined by real施例1 4～¾5S Example 1 6 was determined in the same manner as those ^ examples The light transmittance of each transparent conductive laminate was determined in the same manner as in Examples 14 to 16. Furthermore, each transparent conductive laminate was evaluated for suitability as a constituent member of an analog type touch panel in the same manner as in Examples 14 to 16 of 5S. Table 12 shows these results.

(Hereinafter the margin)

Table 1 2

 Film thickness Light transmittance Surface resistance Surface resistance 麵 Result * 2 (nm) (%) (Ω / port) Standard deviation

Difficult 30 15 87.5 3600 25 5.4 1.1 〇 Difficult 31 160 86.9 5500 44 88 1.1 〇 Difficult 32 15 89.5 1020 44 1.53 1.2 錢 Difficult 33 33 89.9 1130 39 1.70 1.2 O Sample 34 15 90.2 2000 22 3.0 1.11 鶴 Crane 35 15 90.0 2200 24 〇 3.30 1.1 〇 Difficult 36 15 87 9 2100 26 3.15 1.2 2 1, * 2: Same as leg t in Table 6. e

As is evident from Table 12, each of the oxide films woven from Example 30 to Example 36 has a high surface resistance of 990 to 550 Ω / port, and has a surface resistance standard. As can be seen from the value of the quasi-deviation, it can be obtained with good reproducibility. Also, RZR shown in Table 12. As can be seen from the value of », it has excellent I» property. Based on these facts, the transparent conductive laminate obtained in each example is, as shown in Table 12, a configuration for obtaining an analog type touch panel, particularly an analog type touch panel with improved input accuracy. It can be seen that the material has excellent glue suitable as a member or its material. Example 3 7 to Wei 43 (Manufacture of transparent conductive laminate II)

 As shown in Table 13, the oxide sintered body was used as a gate ^! Examples 8 to 6 Using the same method as in any one of Examples 1 to 3, the oxygen concentration in the atmosphere at the time (sparing atmosphere) was changed by changing the type or composition of the introduced gas. An oxide film (transparent conductive film) was formed on a PET film or a glass plate in the same manner as in Example 30 to Example 36 except that annealing was performed under predetermined conditions after film formation. As a result, a transparent conductive laminate II was obtained for each 5S example.

 For each of the oxide films constituting each transparent conductive laminate, the same items as those obtained in Examples 14 to 16 were obtained in the same manner as these »examples. Further, the light S1 ratio in each transparent conductive laminate was determined in the same manner as in Example 14 to Example 16. Furthermore, the suitability of each transparent conductive laminate as a component of an analog-type touch panel was evaluated in the same manner as in Examples 14 to 16. Table 14 shows these results. The composition of each oxide film (transparent conductive film) was the same as that of any one of Examples 30 to 36 using oxide gates of the same composition.

(Hereinafter the margin) Three

* 1: made from a mixed gas of Ar gas and 〇 ₂ gas, the partial pressure of Ar gas indicates that the partial pressure of 0. 2P a, 0 ₂ gas is 2 X 10 'Pa * 2: oxygen 1 Ar gas mixed with vol% was introduced into the heating furnace, and was cleaned at atmospheric pressure.

* 3: Ar gas mixed with 40 vol% oxygen was introduced into the heating furnace and subjected to atmospheric pressure.

Four

 Film thickness Light transmittance Surface resistance Surface resistance evaluation result * 2 (nm) (%) (Ω / port) Standard deviation

 Difficult case 37 15 88.0 3600 24 ^ X 5.4 1.0 〇

 Difficult case 38 160 87.3 5800 40 93 1.0 〇

 Difficult case 39 15 90. 0 1120 40 〇 1. 7 1. 1 O

 Difficulties 40 15 90.2 1200 37 1.8 1.10 O

 麵 Example ”15 90.6 1100 36 1.7 O 1.2 o

 Decoration example 42 15 90. 4 1200 35 1.8 1.2 o

 Difficult example 43 15 88.8 1250 40 1.9.1.2.o

I, * 2: Same as leg; in Table 6.

As is clear from Table 14, Example 37 ~ ^! Each oxide film obtained in Example 43 has a high surface resistance of 1100 to 5800 Ωt] and has been subjected to a predetermined annealing treatment. It improved from 3 to 90.6%. Further, as can be seen from the value of the standard deviation of the surface resistance, it can be obtained with good reproducibility. In addition, R / R shown in Table 14. As can be seen from the value of, it has excellent mm properties. From these facts, as shown in Table 14, the transparent conductive laminate obtained in each of the examples is a component or a component for obtaining an analog type touch panel, particularly an analog type touch panel with improved input accuracy. It can be seen that the material has excellent characteristics suitable for the material.

Pavement example 44-Jongmyeong 46 (Manufacture of evening panel I)

 (1) Preparation of transparent electrode

 Using a biaxially stretched polyethylene terephthalate film: M (size: 300 mm x 10 m, thickness 125 zm; hereinafter referred to as “PET roll”) as the transparent material, the atom shown in Table 15 as a sprinkling ring evening gate It is shown in Table 15 by using an iron gate (excluding oxygen; hereinafter simply referred to as “thread fl ^”) of a sintered body (size: 5 inch X 15 inch X 5 mm thick). An oxide film having an atomic composition ratio (excluding oxygen; hereinafter, simply referred to as "Itosei") was as follows. The atomic composition ratio of the oxide film was determined by induction plasma emission spectroscopy (ICP).

First, mounting the PET roll Mirror traveling type DC magnetron Spa Uz evening ring device was the vacuum chamber to below 5x 10- ³ Pa. Next, argon gas (purity 99.99%) was introduced so that the pressure inside the vacuum chamber was 2 × 1 OPa, and the sputtering output was 1.6 W / cm ² (the applied voltage was 400 V / g). ), The infiltration temperature was set to 20 ° C, respectively, and a pressurization was performed. After the pressurizing, the mixed gas of argon gas and oxygen gas (ratio of argon gas to oxygen gas = 97: 3) is maintained at 2x1 C ^ An oxide film (transparent m @ film) was formed on one side of the PET roll at a running speed of 100 cm / min.

From the PET roll with the oxide film (transparent M) obtained as described above, a PET film with an oxide film with a size of 16 x 16 cm in plan view was cut out. Thus, a transparent film made of the transparent conductive laminate of the present invention was obtained.

 For each of the obtained transparent electrode substrates, the thickness, surface resistance, standard deviation of surface resistance, and specific resistance of the oxide film (transparent electrode film) constituting the transparent electrode substrate were determined. The transmittance of light having a wavelength of 550 nm was determined for each transparent electrode substrate. Table 16 shows the results.

 The thigh, surface resistance, standard deviation and specific resistance of the surface resistance of the oxide film (transparent electrode film), and the light transmittance of the transparent electrode substrate were as in Examples 14 to 16 respectively. It was determined similarly.

 Further, after the transparent film obtained in each example was allowed to stand in air at 120 ° C. for 300 hours, an oxide film (transparent electrode β) constituting the transparent electrode was formed. The surface resistance R of the fiber was measured in the same manner as above. (Shown in the column of Surface resistance in Table 16). I asked. These results are also shown in Table 16.

 As shown in Table 16, each of the oxidized films formed in ^^ Example 44 to 、 SS Example 46 had a high surface resistance of 125 to 450 Ω / port. In addition, it can be obtained with good reproducibility as can be seen from the value of the standard deviation of the surface resistance. Further, as can be seen from the value of R / R o, the heat resistance is excellent, and in particular, the heat resistance of the tongue-shaped film obtained in Example 44 is high. From these facts, it can be seen that the transparent electrode obtained in each of the examples has excellent characteristics suitable for a transparent panel, particularly an analog type transparent panel.

 (2) Fabrication of evening panel

 From each of the PET rolls with the iridescent film (transparent m @ film) obtained in (1) above, a PET film with an iridescent film having a plane diameter of 16 x 16 cm was prepared. An analog type touch panel (each of which is one of the touch panel I of the present invention) whose outline is shown in FIG. 2 is shown in FIG. ^ Prepared for each example.

First, an electrode terminal 3a: 3 having a band shape with a width of 3 mm is formed on a pair of edges facing each other in an oxide film (transparent electrode) 2 constituting one of the transparent m fibers 1. b was provided by a silver paste (D-550, manufactured by Fujikura I-Daisei Co., Ltd.). Also, Similarly, the 3 mm wide strip-shaped electrode terminals 7 a and 7 are also formed on a pair of edges facing each other in the oxide film (transparent «W) 6 constituting the transparent 5. b was provided for each.

Next, the transparent electrode sickle 1 and the transparent fiber 5 are placed in an oxide film (transparent 2 and 6 are opposed to each other, and the direction connecting the electrode terminals 3a and 3b and the direction connecting the terminals 7a and 7b are viewed in plan. At this time, an oxide film (transparent electrode film) was formed using a spherical spacer (not shown) made of Si ₂ and having a particle size of 15 zm. The distance between 2 and 6 was 15 m.

Thereafter, the electrode terminals 3a and 3b provided on the oxide film (transparent electrode 31) 2 were connected to a 15 V DC power supply via the lead wires 10a and 10b. At this time, in the middle of the lead wire 10a is interposed a Suidzuchi 3 _1, in the middle of the lead wire 10b is interposed therebetween Suidzu switch S _2. The oxide film (transparent electrode film) electrode terminals 7 formed in the 6 a, and 7b and 15V DC power supply V ₂ of, and connected through a lead wire 11 a, l ib. At this time, in the middle of the lead wire 11 a is interposed a switch S _3, in the middle of the lead wire l ib was interposed therebetween switch S _4.

In this way, the electrostatic ¾¾ element 3 a, 3b and DC power supply, a and conductive «terminal 7 a, 7 b by electrically connecting a DC power source V _2, evening Dzuchipaneru 15 was obtained.

 (3) Performance evaluation of the touch panel

A ground is taken from the middle of the lead wire 1 Ob of the touch panel 15 made in (2) above, and a voltmeter 12 (see Fig. 2) is installed to measure the potential difference between the lead wire 10b and the lead wire 11a. after the switch Si, S ₂ and S ₃ are closed, and the Suidzu switch S ₄ to open. Under this condition, as shown by the arrow A in FIG. 2, along the line connecting the longitudinal center of the electrode terminal 3a and the longitudinal center of the electrode terminal 3b, the transparent electrode ¾ With the outer surface facing the electrode terminal 3b to the terminal 3a, a total of 100 points are provided at 1.5mm intervals for a total of 100 points, and pressure is applied by the input pen 13 (see Fig. 2) whose input end has a radius of curvature of lmm. Was determined by the following equation.

 100

Detection error = ∑ (I Vn-VnO | / | Vn ₊ 1-Vn |) / 100

n = l Vn: Measured voltage at the n-th pressing point

VnO: Theoretical voltage at the n-th pressing point In the above formula, I Vn—V _n0 I indicates the deviation of the measured voltage from the theoretical voltage. The smaller this value is, the less misleading the pressed position is, the more the touch panel is obtained. . In the above equation, I Vn ₊₁ — Vn I indicates a difference between measured voltages at two adjacent pressing points, and the larger this value is, the easier it is to detect the difference between the pressing positions as a potential difference with high accuracy.

 When the detection error was calculated by the above equation for the sunset panel obtained in each case, as shown in Table 16, the value was less than 0.1 in all the sunset panels. From this, it was confirmed that each sunset panel had high input accuracy.

Difficult example 4 7 (Manufacture of evening panel I)

 (1) Preparation of transparent ¾¾f

 Except that a glass plate (# 7059, made by Koning Co., Ltd., 'size 16 cm x l 6 cm, thickness 1. l mm) was used as the transparent material ^ I got Table 15 also shows the Ito Makoto in the sintered gate used in this case and the Makoto in the Oxide film.

 Regarding the oxide film (transparent electrode film) constituting the above transparent electrode substrate, Examples 44 to! ^ The same items as those obtained in (1) in Example 46 were obtained in the same manner as in these »examples. The light transmittance of the transparent electrode substrate was determined in the same manner as in (1) in Examples 44 to 46. Table 16 shows these results. As shown in Table 16, the above oxide film has a high surface resistance of 124 Ω / port and high reproducibility as can be seen from the standard deviation of the surface resistance. It can be. Also R / R. As can be seen from the values, the wisteria is also excellent. From these facts, it can be seen that the above-mentioned transparent substrate has excellent characteristics suitable as a transparent electrode substrate for a back panel, particularly an analog type back panel.

 (2) Fabrication and performance evaluation of evening touch panel

A total of two transparent AS guesses were made, and these were used as difficult examples 44 to 麵 examples 4 6 In the same manner as in (2) of (1), an analog type touch panel (one of the type of touch panel of the present invention) was manufactured, and its performance was the same as (3) in ^ Example 44 to ^^ Example 46. .

 As a result, as shown in Table 16, the value of the detection error of the above-mentioned touch panel was 0.03, and the input accuracy was high.

Comparative Example 2 to Comparative Example 3

 (1) Preparation of transparent sickle

 In producing the oxide film, the same procedure as in Example 44 to Example 46 was carried out except that the oxidized oxide sintered body of the yarn shown in Table 15 was used as a spatter ring.

In the same manner as in (1), an oxide film (transparent film) having a composition outside the limited range of the present invention as shown in Table 15 was formed on a PET film, and the transparent electrode was prepared for each comparative example. Was obtained.

 For each of the oxide films (transparent electrode films) constituting each transparent layer, the same items as those obtained in (1) in Examples 44 to 46 were obtained in the same manner as in these examples. The light transmittance of the electrode substrate was determined in the same manner as in (1) in Examples 44 to 46. The results are shown in Table 16.

 As shown in Table 16, the oxide film formed in Comparative Example 2 had an extremely high surface resistance of 5823ΟΩ / port. On the other hand, the oxide film formed in Comparative Example 3 has a surface resistance of only 400 Q / D, and does not satisfy the characteristics required for a transparent electrode film for obtaining a high accuracy input panel. ,

 (2) Fabrication and performance evaluation of the touch panel

Analog-type evening chips were prepared for each comparative example in the same manner as in (2) in Examples 44 to 46, and the performance was evaluated in the same manner as in (3) in Examples 44 to 46. As a result, as shown in Table 16, the touch panel of Comparative Example 2 was operated by 15 V DC power supplies V and V ₂ (see Fig. 2) because the surface resistance of the oxide film (transparent electrode film) was too high. It was not practical. Further, the value of the detection error of the touch panel of Comparative Example 3 was 1.6, and the input accuracy was extremely poor as compared with each touch panel obtained in (2) in Examples 44 to 46.

Table 16

 Film thickness Light transmittance Surface resistance R / Ro detection error of surface resistance (nm) (%) (Ω / port) Standard deviation

 Difficult case 15 89.9 1250 18 1.87 1.10.05 Example 45 23 87.9 4600 52 10.5 1.20.08 Difficult case 46 15 89.0 2500 36 3.75 1.20 .03 Difficult example 47 15 90.2 1240 14 1.86 1.10.03 Comparative example 2 15 86.3 58 230 1235 00 6.5 No operation Comparative example 3 15 89.8 400 13 0.6.3. 9 1.6

* 1: Indicates the transmittance of light with a wavelength of 55 Onm to the transparent electrode substrate.

 Re

Say

Example 48 to Observation Example 6 1

 First, two transparent conductive laminates I of the present invention were prepared for each of the difficult examples in the same manner as in any of Sickle example 15, 赚 example 17 to difficult example 22 and crane example 23 to 〜 example 29. Then, using these two transparent conductive laminates I as transparent substrates, respectively, in the same manner as in (2) in Examples 44 to 46, an analog type touch panel (both of the present invention) was used. One of the panels I) was manufactured for each example, and its performance (detection error) was evaluated in the same manner as (3) in Examples 44 to 46. Table 17 shows these results.

表 1 7に示したように、 例 48〜 例 6 1で得られた各夕ヅチパネルの 検出誤差の値は 0. 0 3〜0. 1であり、 いずれのタヅチパネルも入力精度の高 いものであった。 実施例 6 2〜鍾例 7 5 (夕ヅチパネル IIの製造）

As shown in Table 17, the detection error values of each touch panel obtained in Examples 48 to 61 are 0.03 to 0.1, and all touch panels have high input accuracy. Was. Example 6 2 ~ Zongyong 7 5 (Manufacture of ヅ パ ネ ル Panel II)

 First, two transparent conductive laminates II of the present invention were prepared for each of the examples in the same manner as in any of mso to Example 36 and Jongol 37 to Example 43. Then, by using these two transparent conductive laminates II as transparent, respectively, in the same manner as (2) in Example 44 to Example 46, an analog type switch panel (both of the switch panel of the present invention) was used. II) was prepared for each example, and its performance (detection error) was | ¾0 in the same manner as (3) in Examples 44 to 5¾46.

 The results are shown in Table 18. Table 18

表 1 8に示したように、 実施例 6 2〜 例 7 5で得られた各夕ヅチパネルの 検出誤差の値は 0. 0 3〜0 . 0 6であり、 いずれの夕ヅチパネルも入力精度の 高いものであった。 以上、 実施例を挙げて説明したように、 本発明の夕一ゲット Iまたは夕一ゲッ ト IIを用いたスパッタリング法等の物理的蒸着法等によって得ることができる本 発明の透明導電積層体 Iまたは透明導電積層体 IIは、 いずれも高電気抵抗の透明 導電膜を有しているので、 この透明導電積層体ェまたは透明導電積層体 IIを用い ることによって、 入力精度の高い本発明の夕ヅチパネル Iまたは夕ヅチパネル II を提供することが可能になる。

As shown in Table 18, the detection error values of each of the touch panels obtained in Examples 62 to 75 are 0.03 to 0.06. It was expensive. As described above with reference to the examples, as described above, the transparent conductive laminate I of the present invention which can be obtained by a physical vapor deposition method such as a sputtering method using the evening get I or the evening get II of the present invention. Alternatively, since each of the transparent conductive laminates II has a transparent conductive film having a high electric resistance, the use of the transparent conductive laminate D or the transparent conductive laminate II provides a high input accuracy of the present invention. Touch Panel I or Touch Panel II can be provided.

 As described above, according to the study by the inventors of the present invention, the thigh and the specific resistance

The transparent conductive film in the region shown in Fig. 1 is composed of one of indium (In) and tin (Sn), titanium (Ti), silicon (Si), nickel (Ni), iridium (Ir), Rhodium (Rh), cerium (Ce), zirconium (Zr), tantalum (Ta), thallium (T1), hafnium (Hf), magnesium (Mg), cobalt (Co), lead (Pb), chromium (Cr) And at least one metal element selected from the group consisting of gallium (Ga) and gallium (Ga), and oxygen (〇) as constituent elements, and the atomic ratio of the total amount of the metal elements (all metals selected from the group of metal elements) (Element) / [(111 or 311) + (all metal elements selected from the group of metal elements)] is 2.2 to 40 at%.

 Similarly, one of indium (In) and tin (Sn), titanium (T i), silicon (Si), nickel (Ni), iridium (Ir), and rhodium

(Rh), cerium (Ce), zirconium (Zr), tantalum (Ta), talmium (T1), hafnium (Hf), magnesium (Mg), conoreto (Co), lead (Pb), chromium (Cr ) And at least one metal element selected from the group consisting of gallium (Ga), zinc (Zn), and oxygen (〇) as constituent elements, and the atomic ratio of the total amount of the metal elements (metal element All metal elements selected from the group) /

[(In or Sn) + (all metal elements selected from the metal element group) + Zn] is 2, 2 to 40 at%, and the atomic ratio of zinc (Zn) Zn / [(In or Sn) + (metal element The total thickness of the oxide film whose specific thickness and specific resistance are as shown in Fig. 1 can also be achieved with an oxide film whose [+ Zn] is 2.2 to 30 at% (excluding 2.2 at%). A transparent conductive film inside can be formed.

For reference, these transparent conductive films are used when forming by the sputtering method. Table 19 and Table 20 show the atomic composition ratio of the evening get used and the atomic composition ratio of the transparent conductive film in the transparent conductive laminate obtained using the evening get. Also, the film thickness, light transmittance, surface resistance, standard deviation of surface resistance, specific resistance and R / R shown in Table 19 or Table 20 are shown. (Determined in the same way as “R / R.” In the above »example) is shown in Table 21 or Table 22. Table 21 or Table 22 shows the detection errors of the analog type touch panel obtained in the same manner as the above example using the transparent conductive laminate having the transparent conductive film shown in Table 19 or Table 20. I will write it together.

 Furthermore, one of indium (In) and tin (Sn) and aluminum (A1) and / or (Ge) are used as constituent elements, and the total amount of A1 and Ge (one of which is 0) The transparent conductive mil composed of an oxide film whose atomic ratio M / [(111 or 311) + M] is 2.2 to 40 at% is also shown in Fig. 1. Table 19 to Table 22 show the same data as described above for this oxide film because it can be within the region.

 In addition, each transparent conductive film was proved according to Sickle Example 14 to Fiber Example 16 described above.

(Hereinafter the margin)

Table 19

 Original composition ratio excluding oxygen (at%) Composition ^ Brown sintered body Yuichi Get Oxide film (transparent conductor)

"Example 1 In: Ti 95.5: 4.5 95.0: 5.0 ^ Example 2 In: Ga 95.5: 4.5 95.0: 5.0 Example 3 In: Si 97.5: 2.5 97.0: 3.0 Reference Example 4 In: Ni 97.0: 2.0 97.0: 3.0 Reference Example 5 In: Ir 97.5: 2.5 97.0: 3.0 Reference Example 6 In: Rh 97.5: 2.0 97.0: 3.0 Reference Example 7 In: Ce 97.5: 2.o 97.0: 3.0 Reference Example 8 In: Zr 97.5: 2.5 97.0: 3.0 Reference Example 9 In: Tl 97.5: 2.5 97.0: 3.0 c

Reference Example 10 In: Hf 97.5: 2.5 97.0: 3.0 Reference Example 11 In: Mg 97.5: 2.5 97.0: 3.0 Reference Example 12 In: Al 97.5: 2.5 97.0: 3.0

 Example 13 In Ta 97.5: 2.5 97.0: 3.0 Example 14 In Co 97.5: 2.5 97.0: 3.0 Reference Example 15 In Pb 97.5: 2.5 97.0: 3.0 Reference Example 16 In Ge 97.5: 2.5 97.0: 3.0 Reference Example 17 In Cr 97.5: 2 , 5 97.0: 3.0 Reference example 18 Sn Ti 95.5: 4.5 95.0: 5.0

 Example 19 Sn Ga 95.5: 4.5 95.0: 5.0 Reference Example 20 Sn Si 97.5: 2.5 97, 0: 3.0 Reference Example 21 Sn Ni 97.5: 2.5 97.0: 3.0 Reference Example 22 Sn Ir 97.5: 2.5 97.0: 3.0

 Sn Rh 97.5: 2.5 97.0: 3.0

Sn Ce 97.5: 2.5 97.0: 3.0 Reference Example 25 Sn Zr 97.5: 2.5 97.0: 3.0 Reference Example 26 Sn Tl 97.5: 2.5 97.0: 3.0 Reference Example 27 Sn Hf 97.5: 2.5 97.0: 3.0 Reference Example 28 Sn Mg 97.5: 2.5 97.0 : 3.0

 Sn Al 97.5: 2.5 97.0: 3.0 Reference example 30 Sn Ta 97.5: 2.5 97.0: 3.0

 ^ Example 31 Sn Co 97.5: 2.5 97.0 ： 3.0

 Sn • Pb 97.5: 2.5 97.0: 3.0 Reference Example 33 Sn: Ge »7.0: 2.5 97.0: 3.0

Sn Cr 97. δ: 2.5 97.0: 3.0 #Example 35 In Ti 63.0: 37.0 62.0: 38.0 Reference Example 36 In: Si 63.0: 37.0 62.0: 38.0 Reference Example 37 In: i 63.0: 37.0 62.0: 38.0 Reference Example 38 In: Ir 63.0: 37.0 62.0: 38.0 Example 39 In: Rh 63.0: 37.0 62.0: 38.0 Example 40 In: Ce 63.0: 37.0 62.0: 38: 0 table

 Atomic composition ratio (at%) excluding oxygen Composition of sintering sintered body Yuichi Gate Oxide

In: Zr: 62.0: 38.0 in: 11 DO. U: 07. ϋ ο. Ϋ: ο. Ϋ

： Αι DO. U ： 0 ί. ϋ θ . U : ο. UIn: Hi 63.0: 37.0 62.0: 38.0 Dream: ^ Example 44 In: g 63.0: 37.0 62.0: 38.0

: Αι DO. U: 0 ί. Ϋ θ. U: ο. U

^ Fi Example 4 in. La fi DOQ. N U.. 0 f. Λ U

 U Do. U. f. U 06. υ. 00. U 丄 Π. R D DO. U. 0 i. UD U. oo. U 丄. 1ι6 DO. U: 0 ί. U .1): οο. Υ 丄 Π: bo. U: of. U 62.0 ： 38.0 in: ba bo.0: 37.0 62.0 ： 38.0

Sn: Ti 63.0: 37.0 62.0: 38.0

Sn: Si 63.0: 37.0 62.0: 38.0 Reference Example 54 Sn: Ni 63.0: 37.0 62.0: 38.0 Reference Example 55 Sn: Ir 63.0: 37.0 62.0: 38.0

 Sn: Rh 63.0: 37.0 62.0: 38.0

Sn: Ce 63.0: 37.0 62.0: 38.0

Sn: Zr 63.0: 37.0 62.0: 38.0 ^ Example δ9 Sn: TI 63.0: 37.0 62.0: 38.0 β

Reference example () ϋ Sn: Hi 63.0: 37.0 62.0: 38.0

Sn: Mg 63.0: 37.0 62.0: 38.0 Reference Example 62 Sn: Al 63 .: 37.0 62.0: 38.0 Reference Example 63 Sn: Ta 63.0: 37.0 62.0: 38.0 Reference Example 64 Sn: Co 63.0: 37.0 62.0: 38.0 Reference Example 65 Sn : Pb 63.0: 37.0 62.0: 38.0 Reference Example 66 Sn: Ge 63.0: 37. 62.0: 38.0 Reference Example 67 Sn: Cr 63.0: 37.0 62.0: 38.0 Reference Example 68 Sn: Ga 63.0: 37. 62.0: 38.0 Reference Example 69 In : Ti 73.0: 27.0 72.0: 28.0 ginseng example / U In: Si 73.0: 27.0 72.0: 28.0 Reference example 71 In: Al 73.0: 27.0 72.0: 28.0 Reference example 72 In: Zr 73.0: 27.0 72.0: 28.0 Reference example 73 In: Zn 73.: 27.0 72.0: 28.0 Reference Example 74 In: Ga 73.0: 27.0 72.0: 28.0 Example 75 In: Ga: Zn 87.: 3.5: 9.5 85.0: 4.0: 11.0 Example 76 In: Ga: Zn 63.0: 7.5: 29 δ 62.0: 8.0: 30.0 Table 2

* 1: Transparent «S5 Indicates the ratio of 50 nm light to the SS plate. Table 2 2

 * 1: Indicates the transmittance of light with a wavelength of 550 nm to the transparent electrode * plate.

Claims

The scope of the claims 1. It has an electrically insulating transparent s and a transparent conductive film formed on the transparent, and the transparent conductive film is made of indium (In), 鹏 (Zn), titanium (Ti) and oxygen (〇 ) As the constituent elements, the atomic ratio of indium (In) to the total amount of indium (In) and (Ζη) is 20 to 90 at%, and the atomic ratio of titanium (Ti) is Ti / (In). + Zn + Ti) in the range of 2.2 to 20 at%, and the thickness and specific resistance of the transparent conductive film are peaks at points A, B, C, and D shown in FIG. That is within the range of the rectangle 2. The transparent conductive film according to claim 1, wherein the indium (In) atomic ratio In / (In + Zn) in the transparent conductive film is 50 to 90 at% (excluding 50 at%). 3. The transparent conductive laminate according to claim 1, wherein an atomic ratio of titanium (Ti) in the transparent conductive film Ti / (In + Zn + Ti) is 1 at% or less.  4. An electrically insulating transparent film and a transparent conductive film formed on the transparent film, wherein the transparent conductive film is made of indium (In), (Zn), titanium (Ti), gallium (Ga) and With oxygen (〇) as a constituent element, the atomic ratio of indium (In) to the total amount of indium (In) and zinc (Zn): 20 / 90at% of En / (In + Zn), and titanium (Ti) A transparent conductive laminate comprising an oxide film having a total atomic ratio of gallium (Ga) (Ti + Ga) / (In + Zn + Ti + Ga) of 1 to 20 & 1%.  5. The transparent conductive laminate according to claim 4, wherein the indium (In) atomic ratio In / (In + Zn) in the transparent conductive film is 50 to 9 Oat%.  6. The transparent conductive laminate according to claim 4, wherein the thickness and the specific resistance of the transparent conductive film are within a rectangle having the vertices at points A, B, C, and D shown in FIG. 1 of the accompanying drawings. . 7. Indium (In), Zinc (Zn), Titanium (Ti) and Oxygen (〇) are the constituent elements on the electrically insulating transparent substrate, and occupy the total amount of indium (In) and ffilfi (Zn) The atomic ratio n / (In + Zn) of indium (In) is 20 ~ 9 Oat%, titanium oxide (Ti): an oxide film with an atomic ratio Ti / (In + Zn + Ti) of 2.2 to 20 at%, and the specific resistance shown in FIG. A method for producing a transparent conductive laminate, comprising forming a transparent conductive film within a square having A, B, C, and D as vertices by a physical vapor deposition method. 8. Transparent conductive material in which the atomic ratio In / (en + Zn) of indium (In) to the total amount of indium (In) and zinc (Zn) is 50 to 90 at% (excluding 50 at%). The method according to claim 7, wherein a film is formed.  9. The method according to claim 7, wherein a transparent conductive film having an atomic ratio Ti / (In + Zn + Ti) of titanium (Ti) of 10 at% or less is formed. 10. The method according to claim 7, wherein the physical vapor deposition method is a sputtering method. 11. After the transparent conductive film is formed by physical vapor deposition, the transparent conductive film is heated in an atmosphere with an oxygen partial pressure of 1 OhPa or more at a temperature of 60 ° C to less than the softening point temperature of the transparent substrate. The method according to claim 7, wherein the cleaning is performed.  12. Indium (In), Zinc (Zn), Titanium (Ti), Gallium (Ga) and Oxygen (〇) are the constituent elements on the electrically insulating transparent substrate, and indium (In) and zinc (Zn) Atomic ratio of indium (In) to the total amount of In / (In + Zn) is 20 to 90 at%, and the atomic ratio of the total amount of titanium (Ti) and gallium (Ga) (Ti + Ga) / ((n + A method for producing a transparent conductive laminate, comprising: forming a transparent conductive film containing 1 to 20 at% of Zn + Ti + Ga) by physical vapor deposition.  13. A transparent conductive film consisting of an oxide film in which the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and ¾ίβ (Zn) is 50 to 9 Oat%. 13. The method of claim 12, wherein forming.  14. A transparent conductive film having a film thickness and a specific resistance within a quadrangular shape having vertices at points A, B, C, and D shown in FIG. 1 of the accompanying drawings. 13. The method according to 13.  15. The method according to claim 12, wherein the physical vapor deposition method is a sputtering method. 16. After forming a transparent conductive film by physical vapor deposition, 60 in an atmosphere with a partial pressure of 10 hPa or more. 13. The method according to claim 12, wherein the annealing is performed under a temperature condition of C to less than the softening point 透明 of the transparent material. 17. An oxide sinter composed of indium (In), ffi g (Zn), titanium (Ti) and oxygen (〇) as constituent elements, having the general formula In ₂ 〇 ₃ (Zn〇) _m (m = 2 to 7), and the atomic ratio of indium (In) to the total amount of indium (In) and difficult (Zn), In / (In + Zn), is 20 to 9 Oat%. , the atomic ratio Ti / (in + Zn + Ti ) is 2. 2 to 20 at% titanium (Ti), and that evening one Gedzuto that body ¾ resistivity is less than 10- ² Qcm. 18. The evening getter according to claim 17, wherein the atomic ratio In / (In + Zn) of indium (In) in the total amount of indium (In) and ffi fi (Zn) is 50 to 9 Oat%.  19. The target according to claim 17, wherein the atomic ratio Ti / (In + Zn + Ti) of titanium (Ti) is 1 Oat% or less. 20. Indium (an In), M $ 8 (Zn), made of titanium (Ti), gallium (Ga) and oxygen (〇) and the constituent element oxide sintered body, the general formula an In ₂ 0 ₃ (Zn〇) The atomic ratio of indium (In) to the total amount of indium (In) and zinc (Zn), including the hexagonal layered compound represented by _m (m = 2 to 7) In / (In + Zn ) Is 20-90at%, and the atomic ratio (Ti + Ga) / (In + Zn + Ti + Ga) of the total amount of titanium (Ti) and gallium (Ga) is l-20at%. get.  21. The evening getter according to claim 20, wherein the atomic ratio In, (In + Zn) of indium (In) in the total amount of indium (In) and ffifS (Zn) is 50 to 9 Oat%. 22. Two transparent substrates having a transparent layer formed in a predetermined pattern are provided, and the two transparent electrode substrates are arranged at a predetermined interval with the transparent electrode films facing each other, and In a touch panel in which the transparent electrodes conduct when a load is applied to the transparent electrode substrate from the outside of one of the electrode substrates, a transparent electrode film formed on each of the two transparent electrode substrates is provided. At least one of them is indium (ジ η), zinc (Ζη), titanium (Ti) and With oxygen (〇) as a constituent element, the atomic ratio In / (In + Zn) of indium (In), which accounts for the total amount of indium (In) and MIS (Zn), is 20 to 90 at%, and titanium (Ti) ) Is an oxide film having an atomic ratio TiZ (n + Zn + Ti) of 2.2 to 20 at%, and the film thickness and specific resistance of the transparent film are shown in FIG. A touch panel that is within the range of a rectangle whose vertices are A, B, C, and D.  23. Atomic ratio of indium (In) in a transparent conductive film containing indium (In), ¾I8 (Zn), titanium (Ti), and oxygen (〇) as constituent elements 23. The separator panel according to claim 22, wherein (In + Zn) is 50 to 90 at% (excluding 50 at%).  24. The atomic ratio of titanium (Ti) in the transparent conductive film containing indium (In), ¾ (Ζη), titanium (Ti), and oxygen (0) as Ti / (In + Zn + Ti) is 10 &%. 23. The touch panel according to claim 22, wherein: 25. The touch panel according to claim 22, wherein the touch panel is an i-type touch panel. 26. The evening panel according to claim 22, which is an analog evening panel. 27. Two transparent electrode substrates having transparent electrodes 1 formed in a predetermined pattern are provided, and the two transparent electrode substrates are arranged at a predetermined interval with the transparent electrode films facing each other, A transparent panel formed on each of the two transparent electrode substrates, wherein the transparent electrode substrate conducts when a load is applied to the transparent electrode substrate from the outside of one of the transparent electrode substrates. At least one of the electrode films is composed of indium (In), Φίδ (Zn), titanium (Ti), gallium (Ga) and oxygen (〇), and indium (In) and zinc. The atomic ratio of indium (In) to the total amount of (Zn) is 20 to 90 at%, and the atomic ratio of the total amount of titanium (Ti) and the gallium (Ga) (Ti + Ga A touch panel comprising an oxide film in which / (In + Zn + Ti + Ga) is 1 to 20 at%. 28. Atomic ratio of indium (In) in transparent m Zn film composed of indium (In), zinc (Ζη), titanium (Ti)., Gallium (Ga) and oxygen (〇). In / (In + Zn) Is 50 to 9 Oat%, as set forth in Claim 27. The above-mentioned evening panel.  29. The recommendation and specific resistance of the transparent film with indium (In), (Zn), titanium (Ti), gallium (Ga) and oxygen (〇) as constituent elements are shown in Fig. 1 of the attached drawings. 28. The touch panel according to claim 27, wherein the touch panel is within a rectangle having A, B, C, and D as vertices. 30. A touch panel according to claim 27, which is a resistive touch panel c 31. A touch panel according to claim 27, which is an analog touch panel.