JPWO2014103573A1 - Transparent electrode for touch panel, touch panel, display device, and method for manufacturing transparent electrode for touch panel - Google Patents

Abstract

The transparent electrode for a touch panel includes a nitrogen-containing layer and an electrode layer provided adjacent to the nitrogen-containing layer. The electrode layer is a layer formed adjacently between the start of film formation of the nitrogen-containing layer and 2 minutes after the film formation, and has a film thickness of 12 nm or less capable of measuring the sheet resistance. , Silver or an alloy containing silver as a main component.

Description

  The present invention relates to a transparent electrode for a touch panel, a touch panel, a display device, and a method for manufacturing the transparent electrode for a touch panel, and in particular, a transparent electrode for a touch panel suitable for thinning, a touch panel and a display device including the same, and further for this touch panel The present invention relates to a method for producing a transparent electrode.

  There are various types of touch panels arranged on the display surface side of the display panel, such as a resistive film type, a surface type capacitive type, a projected type capacitive type, an optical type, and an ultrasonic type. Capacitance type has the feature that multi-point input is possible, and practical use is progressing in smartphones.

  By the way, in the touch panel in which the electrodes are arranged over the entire surface of the panel surface as in the projected capacitive method, the display is arranged via the touch panel by configuring the electrodes using a transparent conductive material. The visibility of the image is secured. As such an electrode for a touch panel (that is, a transparent electrode), a metal oxide such as indium tin oxide (ITO) has been mainly used. However, although metal oxides such as ITO are excellent in light transmittance, the conductivity is not sufficient, voltage drop is likely to occur near the center of the panel, and an increase in the size of the touch panel is hindered. In addition, when the resistance value is to be kept low, a certain amount of film thickness is required. Therefore, when the electrode has a pattern as in the projected capacitance method, this pattern is easily visible, and as a result, the ground The visibility of the displayed image becomes lower.

  Therefore, in recent years, a configuration using metal nanowires having higher conductivity than ITO has been proposed as a transparent electrode for a touch panel (see, for example, Patent Document 1 below).

JP 2012-33466 A

  However, a transparent electrode using metal nanowires has a problem that when the amount of metal nanowires added is increased in order to reduce resistance, the visibility of a display image as a base is reduced due to light scattering in the metal nanowires. Was.

  Therefore, the present invention provides a transparent electrode for a touch panel that is a thin film but has sufficient light transmittance and sufficient conductivity, and further improves the visibility of a display image as a base by using this transparent electrode. An object of the present invention is to provide a touch panel and a display device, and to provide a method for producing the transparent electrode for a touch panel.

  In order to achieve such an object, the transparent electrode for a touch panel of the present invention comprises a nitrogen-containing layer configured using a compound containing a nitrogen atom, and an electrode layer provided adjacent to the nitrogen-containing layer. I have. In particular, the electrode layer has a film thickness of 12 nm or less capable of measuring the sheet resistance, and is configured using silver or an alloy containing silver as a main component. It is characterized in that it is a layer in which film formation is started within 2 minutes.

  Moreover, this invention is also a display apparatus provided with the touchscreen using the transparent electrode for touchscreens of such a structure, and the display panel arrange | positioned on this touchscreen and the touchscreen.

  Furthermore, the present invention is also a method of manufacturing a touch panel having such a configuration, a step of forming a nitrogen-containing layer using a compound containing nitrogen atoms, and a step of forming an electrode layer adjacent to the nitrogen-containing layer. Including. Particularly in the step of forming the electrode layer, the electrode layer starts to be formed between the start of the formation of the nitrogen-containing layer and 2 minutes after the end of the film formation, and silver or an alloy containing silver as a main component is added. The electrode layer is formed with a film thickness of 12 nm or less that allows the sheet resistance to be measured.

  The transparent electrode for a touch panel of the present invention configured as described above is provided with an electrode layer made of silver or a silver-based alloy adjacent to a nitrogen-containing layer formed using a compound containing nitrogen atoms. It is a configuration. As a result, when the electrode layer is formed adjacent to the nitrogen-containing layer, the silver atoms constituting the electrode layer interact with the compound containing the nitrogen atoms constituting the nitrogen-containing layer, so that silver aggregates. In addition, conductivity is ensured by being easily configured as a continuous film. The electrode layer has a thickness of 12 nm or less, so that the light absorption component or the reflection component is suppressed to a low level while ensuring the practicality as a film for an electrode. In particular, the electrode layer is a layer in which film formation is started between the start of film formation of the nitrogen-containing layer and 2 minutes after the film formation is completed, and as described in the following examples, It is possible to make the electrode layer adjacent to the layer a film having higher continuity, which also improves the conductivity and light transmittance of the electrode layer.

  As described above, according to the present invention, it is possible to provide a transparent electrode for a touch panel in which an electrode layer that substantially functions as an electrode has sufficient light transmittance and excellent conductivity. In addition, it is possible to provide a touch panel and a display device in which the visibility of a display image as a base is improved by using the transparent electrode for a touch panel.

It is a cross-sectional schematic diagram which shows the structure of the transparent electrode for touchscreens (2 layer structure) which concerns on 1st Embodiment of this invention. It is a figure which shows the structural formula of TBAC and Ir (ppy) ₃ for demonstrating the coupling | bonding mode of a nitrogen atom. It is a figure which shows the structural formula and molecular orbital of a pyridine ring. It is a figure which shows the structural formula and molecular orbital of a pyrrole ring. It is a figure which shows the structural formula and molecular orbital of an imidazole ring. It is a figure which shows the structural formula and molecular orbital of (delta) -carboline ring. It is sectional process drawing which shows the manufacturing method of the transparent electrode for touchscreens which concerns on 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the transparent electrode for touchscreens (3 layer structure) which concerns on 2nd Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the transparent electrode for touchscreens (4 layer structure) which concerns on 3rd Embodiment of this invention. It is a perspective view which shows the structure of the touchscreen which concerns on 4th Embodiment of this invention. It is a top view of two transparent electrodes which show the electrode structure of the touchscreen which concerns on 4th Embodiment of this invention. It is a schematic diagram which shows the planar arrangement | positioning of the electrode part of the touchscreen which concerns on 4th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 4th Embodiment of this invention, and is a figure equivalent to the AA cross section shown in FIG. It is a cross-sectional schematic diagram which shows the structure of the modification 1 of the touchscreen which concerns on 4th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the modification 2 of the touchscreen which concerns on 4th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 5th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 6th Embodiment of this invention. It is a schematic diagram which shows the planar arrangement | positioning of the electrode part of the touchscreen which concerns on 7th Embodiment of this invention. It is an enlarged view of the electrode part of the touchscreen which concerns on 7th Embodiment of this invention. It is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 7th Embodiment of this invention, and is a figure equivalent to the BB cross section shown in FIG. It is a perspective view which shows the structure of the display apparatus which concerns on 8th Embodiment of this invention. It is a block diagram of the manufacturing apparatus for producing the transparent electrode for touchscreens concerning 9th Embodiment of this invention. It is a schematic diagram which shows the structure of the modification 1 of the manufacturing apparatus which concerns on 9th Embodiment of this invention. It is a schematic diagram which shows the structure of the modification 2 of the manufacturing apparatus which concerns on 9th Embodiment of this invention. It is a schematic diagram which shows the structure of the modification 3 of the manufacturing apparatus which concerns on 9th Embodiment of this invention. 2 is a SEM image of a transparent electrode of Sample 5 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 6 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 7 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 8 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 9 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 10 produced in Example 1. 2 is an SEM image of a transparent electrode of Sample 11 produced in Example 1. 2 is a SEM image of a transparent electrode of Sample 12 produced in Example 1. 3 is a SEM image of a transparent electrode of Sample 13 produced in Example 1. It is a graph which shows the relationship between the effective unshared electron pair content [n / M] of a nitrogen containing layer which comprises a transparent electrode, and sheet resistance.

Hereinafter, embodiments of the present invention will be described in the following order based on the drawings.
1. 1. First embodiment: Transparent electrode for touch panel having a two-layer structure 2. Second embodiment: Transparent electrode for touch panel having a three-layer structure 3. Third embodiment: 4-layer structure transparent electrode for touch panel Fourth embodiment: Touch panel (configuration in which two transparent electrodes are provided on one transparent substrate)
4-1. Modification 1 of touch panel
4-2. Modification 2 of touch panel
4-3. Modification 3 of touch panel
5. Fifth embodiment: Touch panel (configuration in which a transparent electrode is provided on each of two transparent substrates)
6). Sixth embodiment: Touch panel (configuration in which transparent electrodes are provided on both sides of a single transparent substrate)
7). Seventh embodiment: Touch panel (configuration in which connection electrodes are provided together with two patterns of transparent electrodes on a transparent substrate)
8). Eighth embodiment: Display device (configuration using a touch panel)
9. Ninth embodiment: Manufacturing apparatus (apparatus for producing a transparent electrode for a touch panel)
9-1. Modification 1 of manufacturing apparatus
9-2. Modification 2 of manufacturing apparatus
9-3. Modification 3 of manufacturing apparatus

<< 1. First Embodiment: Transparent Electrode for Touch Panel with Two-Layer Structure >>
FIG. 1 is a schematic cross-sectional view showing a configuration of a transparent electrode for a touch panel (hereinafter referred to as a transparent electrode) according to a first embodiment of the present invention. The transparent electrode 1 shown in this figure has a two-layer structure in which a nitrogen-containing layer 3 and an electrode layer 5 are laminated. For example, the nitrogen-containing layer 3 and the electrode layer 5 are provided in this order on the transparent substrate 11. Among these, the nitrogen-containing layer 3 is characterized by being composed of a compound containing a nitrogen atom (N) that is stably bonded to silver which is the main material constituting the electrode layer 5. The electrode layer 5 constituting a substantial electrode portion in the transparent electrode 1 is a layer mainly composed of silver or silver (Ag), and is laminated in a state adjacent to the nitrogen-containing layer 3 here. Yes. The electrode layer 5 is characterized in that the film formation is started between the start of film formation of the nitrogen-containing layer 3 and 2 minutes after the film formation is completed.

  Below, a detailed structure is demonstrated in order of the transparent substrate 11 with which the transparent electrode 1 of such a laminated structure is provided, the nitrogen-containing layer 3 which comprises the transparent electrode 1, and the electrode layer 5. In FIG. In addition, the transparency of the transparent electrode 1 of the present invention means that the light transmittance at a wavelength of 550 nm is 50% or more.

<Transparent substrate 11>
The transparent substrate 11 on which the transparent electrode 1 of the present invention is formed may also serve as a front plate of a display panel, for example. Examples of such a transparent substrate 11 include glass, quartz, and a transparent resin film.

  Examples of the glass include silica glass, soda-lime silica glass, lead glass, borosilicate glass, and alkali-free glass. From the viewpoints of adhesion, durability, and smoothness with the nitrogen-containing layer 3 on the surface of these glass materials, if necessary, physical treatment such as polishing is performed, a film made of an inorganic material or an organic material, A hybrid film combining these films is formed. The particularly preferable transparent substrate 11 is a resin film that can give flexibility to the transparent electrode 1 and electronic devices such as a touch panel and a display device configured using the transparent electrode 1.

  Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

On the surface of the resin film, a film made of an inorganic material or an organic material or a hybrid film combining these films may be formed. Such coatings and hybrid coatings have a water vapor transmission rate (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) of 0.01 g / (measured by a method according to JIS-K-7129-1992. m ² · 24 hours) or less of a barrier film (also referred to as a barrier film or the like) is preferable. Furthermore, the oxygen permeability measured by a method according to JIS-K-7126-1987 is 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the water vapor permeability is 10 ⁻⁵ g / (m ² · 24 hours) or less high barrier film is preferable.

  The material for forming the barrier film as described above may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. be able to. Furthermore, in order to improve the brittleness of the barrier film, it is more preferable to have a laminated structure of these inorganic layers and layers (organic layers) made of an organic material. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.

  The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method described in JP-A-2004-68143 is particularly preferable.

<Nitrogen-containing layer 3>
The nitrogen-containing layer 3 is a layer configured using a compound containing nitrogen atoms (N), and is provided adjacent to the electrode layer 5 on the transparent substrate 11.

  The compound containing a nitrogen atom (N) constituting the nitrogen-containing layer 3 is particularly preferably the following compound. That is, the compound containing the nitrogen atom (N) constituting the nitrogen-containing layer 3 is a nitrogen atom that stably bonds to silver, which is the main material constituting the electrode layer 5, among nitrogen atoms contained in the compound. The non-shared electron pair is [effective unshared electron pair], and the content ratio of the [effective unshared electron pair] is within a predetermined range.

  Here, the “effective unshared electron pair” is an unshared electron pair that does not participate in aromaticity and is not coordinated to the metal among the unshared electron pairs of the nitrogen atom contained in the compound. The aromaticity here refers to an unsaturated cyclic structure in which atoms having π electrons are arranged in a ring, and is aromatic according to the so-called “Hückel's rule”. The condition is that the number is “4n + 2” (n = 0 or a natural number).

  [Effective unshared electron pair] as described above refers to an unshared electron pair possessed by a nitrogen atom regardless of whether or not the nitrogen atom itself provided with the unshared electron pair is a hetero atom constituting an aromatic ring. Is selected depending on whether or not is involved in aromaticity. For example, even if a nitrogen atom is a hetero atom constituting an aromatic ring, the lone pair of the nitrogen atom does not directly participate as an essential element in aromaticity, that is, a conjugated unsaturated ring An unshared electron pair that is not involved in the delocalized π-electron system on the structure (aromatic ring) as an essential element for the expression of aromaticity is [effective unshared electron] It is counted as one of the pair. On the other hand, even if a nitrogen atom is not a heteroatom constituting an aromatic ring, if the lone pair of the nitrogen atom is involved in aromaticity, the lone pair of the nitrogen atom Are not counted as [valid unshared electron pairs]. In each compound, the number n of [effective unshared electron pairs] described above matches the number of nitrogen atoms having [effective unshared electron pairs].

  Next, the [effective unshared electron pair] described above will be described in detail with a specific example.

  The nitrogen atom is a Group 15 element and has 5 electrons in the outermost shell. Of these, three unpaired electrons are used for covalent bonds with other atoms, and the remaining two become a pair of unshared electron pairs. For this reason, the number of bonds of nitrogen atoms is usually three.

For example, as a group having a nitrogen atom, an amino group (—NR ¹ R ² ), an amide group (—C (═O) NR ¹ R ² ), a nitro group (—NO ₂ ), a cyano group (—CN), diazo Group (—N ₂ ), azide group (—N ₃ ), urea bond (—NR ¹ C═ONR ² —), isothiocyanate group (—N═C═S), thioamide group (—C (═S) NR ¹ R ² ) and the like. R ¹ and R ² are each a hydrogen atom (H) or a substituent. The non-shared electron pair of the nitrogen atom constituting these groups does not participate in aromaticity and is not coordinated to the metal, and thus corresponds to [effective unshared electron pair]. Among these, the unshared electron pair possessed by the nitrogen atom of the nitro group (—NO ₂ ) is used for the resonance structure with the oxygen atom, but has a good effect as shown in the following examples. Therefore, it is considered that it exists on nitrogen as an [effective unshared electron pair] that is not involved in aromaticity and coordinated to a metal.

A nitrogen atom can also create a fourth bond by using an unshared electron pair. An example of this case will be described with reference to FIG. FIG. 2 shows the structural formula of tetrabutylammonium chloride (TBAC) and the structural formula of tris (2-phenylpyridine) iridium (III) [Ir (ppy) ₃ ].

  Among these, TBAC is a quaternary ammonium salt in which one of four butyl groups is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion. In this case, one of the electrons constituting the unshared electron pair of the nitrogen atom is donated to the ionic bond with the butyl group. For this reason, the nitrogen atom of TBAC is equivalent to the absence of an unshared electron pair in the first place. Therefore, the unshared electron pair of the nitrogen atom constituting TBAC does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

Ir (ppy) ₃ is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. The unshared electron pair of the nitrogen atom constituting this Ir (ppy) ₃ is coordinated to the iridium atom, and is utilized for coordination bonding. Therefore, the unshared electron pair of the nitrogen atom constituting Ir (ppy) ₃ does not correspond to the [effective unshared electron pair] that is not involved in aromaticity and coordinated to the metal.

  Moreover, a nitrogen atom is general as a hetero atom which can comprise an aromatic ring, and can contribute to the expression of aromaticity. Examples of the “nitrogen-containing aromatic ring” include pyridine ring, pyrazine ring, pyrimidine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring and the like.

  FIG. 3 is a diagram showing a structural formula and molecular orbitals of a pyridine ring which is one of the groups exemplified above. As shown in FIG. 3, in the conjugated (resonant) unsaturated ring structure in which the pyridine ring is arranged in a 6-membered ring, the number of delocalized π electrons is 6, so that 4n + 2 (n = 0 or natural number) Satisfy Hückel's law. Since the nitrogen atom in the 6-membered ring is substituted with —CH═, only one unpaired electron is mobilized to the 6π-electron system, and the unshared electron pair is essential for the expression of aromaticity. Not involved as a thing.

  Therefore, the unshared electron pair of the nitrogen atom constituting the pyridine ring corresponds to an [effective unshared electron pair] that does not participate in aromaticity and is not coordinated to the metal.

  FIG. 4 shows the structural formula and molecular orbitals of the pyrrole ring. As shown in FIG. 4, the pyrrole ring has a structure in which one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of π electrons is also six and satisfies the Hückel rule. Nitrogen-containing aromatic ring. Since the nitrogen atom of the pyrrole ring is also bonded to a hydrogen atom, an unshared electron pair is mobilized to the 6π electron system.

  Therefore, although the nitrogen atom of the pyrrole ring has an unshared electron pair, since this unshared electron pair is used as an essential element for the expression of aromaticity, it does not participate in aromaticity and is a metal. It does not fall under [Effective unshared electron pairs] that are not coordinated to.

FIG. 5 is a diagram showing the structural formula and molecular orbitals of the imidazole ring. As shown in FIG. 5, the imidazole ring has a structure in which two nitrogen atoms N ¹ and N ² are substituted at the ^1- and 3-positions in a 5-membered ring, and the nitrogen-containing π-electron number is also 6 It is an aromatic ring. Of these, one nitrogen atom N ¹ is a pyridine ring-type nitrogen atom that mobilizes only one unpaired electron to the 6π-electron system and does not utilize the unshared electron pair for the expression of aromaticity, This unshared electron pair of the nitrogen atom N ¹ corresponds to [effective unshared electron pair]. On the other hand, since the other nitrogen atom N ² is a pyrrole-ring-type nitrogen atom that mobilizes the unshared electron pair to the 6π electron system, the unshared electron pair of this nitrogen atom N ² is Does not fall under [Unshared electron pair].

Therefore, in the imidazole ring, only the unshared electron pair of one nitrogen atom N ¹ out of the two nitrogen atoms N ¹ and N ² constituting the ring corresponds to the “effective unshared electron pair”.

  The selection of the unshared electron pair at the nitrogen atom of the “nitrogen-containing aromatic ring” as described above is similarly applied to a condensed ring compound having a nitrogen-containing aromatic ring skeleton.

FIG. 6 is a diagram showing the structural formula and molecular orbital of the δ-carboline ring. As shown in FIG. 6, the δ-carboline ring is a condensed ring compound having a nitrogen-containing aromatic ring skeleton, and is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order. Of these, the nitrogen atom N ³ of the pyridine ring mobilizes only one unpaired electron to the π-electron system, and the nitrogen atom N ⁴ of the pyrrole ring mobilizes an unshared electron pair to the π-electron system. Together with the 11 π electrons from the carbon atoms that are formed, the total number of π electrons is an aromatic ring of 14.

Therefore, among the two nitrogen atoms N ³ and N ⁴ of the δ-carboline ring, the unshared electron pair of the nitrogen atom N ³ constituting the pyridine ring corresponds to [effective unshared electron pair], but constitutes a pyrrole ring. The unshared electron pair of the nitrogen atom N ⁴ that does not correspond to [Effective unshared electron pair].

  In this way, the unshared electron pair of the nitrogen atom constituting the condensed ring compound is involved in the bond in the condensed ring compound as well as the bond in the monocyclic compound such as pyridine ring and pyrrole ring constituting the condensed ring compound. To do.

  The [effective unshared electron pair] described above is important for exhibiting a strong interaction with silver which is the main component of the electrode layer 5. The nitrogen atom having such an [effective unshared electron pair] is preferably a nitrogen atom in the nitrogen-containing aromatic ring from the viewpoint of stability and durability. Therefore, the compound contained in the nitrogen-containing layer 3 preferably has an aromatic heterocycle having a nitrogen atom having [effective unshared electron pair] as a hetero atom.

Particularly in the present embodiment, the number n of [effective unshared electron pairs] with respect to the molecular weight M of such a compound is defined as, for example, the effective unshared electron pair content [n / M]. The nitrogen-containing layer 3 is characterized in that this [n / M] is composed of a compound selected so that 2.0 × 10 ⁻³ ≦ [n / M]. The nitrogen-containing layer 3 preferably has an effective unshared electron pair content [n / M] defined as described above in a range of 3.9 × 10 ⁻³ ≦ [n / M]. More preferably, the range is 5 × 10 ⁻³ ≦ [n / M].

  The nitrogen-containing layer 3 only needs to be configured using a compound having an effective unshared electron pair content [n / M] within the predetermined range described above, or may be configured only with such a compound. Further, such a compound and other compounds may be mixed and used. The other compound may or may not contain a nitrogen atom, and the effective unshared electron pair content [n / M] may not be within the predetermined range described above.

  When the nitrogen-containing layer 3 is configured using a plurality of compounds, for example, based on the mixing ratio of the compounds, the molecular weight M of the mixed compound obtained by mixing these compounds is obtained, and [effective non- The total number n of [shared electron pairs] is obtained as an average value of the effective unshared electron pair content [n / M], and this value is preferably within the predetermined range described above. That is, the effective unshared electron pair content [n / M] of the nitrogen-containing layer 3 itself is preferably within a predetermined range.

  In addition, if the nitrogen-containing layer 3 is composed of a plurality of compounds and the composition ratio (content ratio) of the compounds is different in the film thickness direction, the nitrogen on the side in contact with the electrode layer 5 The effective unshared electron pair content [n / M] in the surface layer of the containing layer 3 may be in a predetermined range.

[Compound I]
Hereinafter, specific examples of the compound constituting the nitrogen-containing layer 3 satisfying the above-described effective unshared electron pair content [n / M] of 2.0 × 10 ⁻³ ≦ [n / M] (No. 1 to No. 48). In each compound No. 1 to No. 48, a nitrogen atom having an [effective unshared electron pair] was marked with a circle. Table 1 below shows the molecular weight M of these compounds No. 1 to No. 48, the number n of [effective unshared electron pairs], and the effective unshared electron pair content [n / M]. In the copper phthalocyanine of the following compound 33, unshared electron pairs that are not coordinated to copper among the unshared electron pairs of the nitrogen atom are counted as [effective unshared electron pairs].

  In Table 1, the general formulas in the case where these exemplary compounds also belong to the general formulas (1) to (8a) representing other compounds described below are shown.

[Compound II]
Moreover, as a compound which comprises the nitrogen containing layer 3, in addition to the compound whose effective unshared electron pair content rate [n / M] is the predetermined range mentioned above, you may use another compound. As the other compound used for the nitrogen-containing layer 3, a compound containing a nitrogen atom is preferably used regardless of whether the effective unshared electron pair content [n / M] is in the predetermined range described above. Among them, a compound containing a nitrogen atom having [effective unshared electron pair] is particularly preferably used. Moreover, the compound which has a property required for every electronic device to which the transparent electrode 1 provided with this nitrogen-containing layer 3 is applied is used for the other compound used for the nitrogen-containing layer 3. For example, when this transparent electrode 1 is used as a transparent electrode for a touch panel, it is represented by the general formulas (1) to (8a) described below as a compound constituting the nitrogen-containing layer 3 from the viewpoint of film formability. A compound having the structure is preferably used.

  Among the compounds having the structures represented by the general formulas (1) to (8a), compounds that fall within the range of the effective unshared electron pair content [n / M] described above are included, and such compounds If so, it can be used alone as a compound constituting the nitrogen-containing layer 3 (see Table 1 above). On the other hand, if the compound having the structure represented by the following general formulas (1) to (8a) is a compound that does not fall within the range of the effective unshared electron pair content [n / M] described above, the effective unshared electron pair It can be used as a compound constituting the nitrogen-containing layer 3 by mixing with a compound having a content ratio [n / M] in the range described above.

  X11 in the general formula (1) represents -N (R11)-or -O-. E101 to E108 in the general formula (1) each represent -C (R12) = or -N =. At least one of E101 to E108 is -N =. R11 and R12 each represent a hydrogen atom (H) or a substituent.

  Examples of this substituent include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group). Etc.), cycloalkyl groups (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl groups (for example, vinyl group, allyl group, etc.), alkynyl groups (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon groups (aromatic Also called group carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group , Pyrenyl group, biphenylyl group), aromatic heterocyclic group (for example, Furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group Any carbon atom constituting the carboline ring is substituted with a nitrogen atom), phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group ( For example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group ( For example, Nonoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group) Etc.), arylthio groups (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryl Oxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group) Group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, Acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (For example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenyl group Carbonyloxy group, etc.), amide groups (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonyl) Amino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexyl) Aminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl Bonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group naphthylureido) Group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2 -Pyridylsulfinyl group etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2 -Ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group or heteroarylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, piperidyl group (also called piperidinyl group), 2,2,6,6 -Tetramethylpiperidinyl group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluoro) Phenyl group, etc.), cyano group Nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), phosphate ester group (for example, dihexyl phosphoryl group, etc.), phosphorous acid An ester group (for example, diphenylphosphinyl group etc.), a phosphono group etc. are mentioned.

  Some of these substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring. As these substituents, those which do not inhibit the interaction between the compound and silver (Ag) are preferably used, and those having a nitrogen atom having an effective unshared electron pair described above are particularly preferably applied. . In addition, the description regarding the above substituent applies similarly to the substituent shown in description of general formula (2)-(8a) demonstrated below.

  The compound having the structure represented by the general formula (1) as described above is preferable because a strong interaction can be expressed between the nitrogen atom in the compound and the silver constituting the electrode layer 5.

  The compound having the structure represented by the general formula (1a) is one form of the compound having the structure represented by the general formula (1), and X11 in the general formula (1) is -N (R11)-. A compound. Such a compound is preferable because the above interaction can be expressed more strongly.

  The compound having the structure represented by the general formula (1a-1) is one form of the compound having the structure represented by the general formula (1a), and a compound in which E104 in the general formula (1a) is -N = It is. Such a compound is preferable because the above interaction can be expressed more effectively.

  The compound having the structure represented by the general formula (1a-2) is another embodiment of the compound having the structure represented by the general formula (1a), and E103 and E106 in the general formula (1a) are represented by —N This is a compound marked with =. Such a compound is preferable because the number of nitrogen atoms is large and the above interaction can be expressed more strongly.

  The compound having the structure represented by the general formula (1b) is another embodiment of the compound having the structure represented by the general formula (1), and X11 in the general formula (1) is represented by -O-. -N = is a compound. Such a compound is preferable because the above interaction can be expressed more effectively.

  Furthermore, a compound having a structure represented by the following general formulas (2) to (8a) is preferable because the above interaction can be expressed more effectively.

  The general formula (2) is also an embodiment of the general formula (1). In the formula of the general formula (2), Y21 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof. E201 to E216 and E221 to E238 each represent -C (R21) = or -N =. R21 represents a hydrogen atom (H) or a substituent. However, at least one of E221 to E229 and at least one of E230 to E238 represents -N =. k21 and k22 represent an integer of 0 to 4, but k21 + k22 is an integer of 2 or more.

  In the general formula (2), examples of the arylene group represented by Y21 include o-phenylene group, p-phenylene group, naphthalenediyl group, anthracenediyl group, naphthacenediyl group, pyrenediyl group, naphthylnaphthalenediyl group, and biphenyldiyl. Groups (for example, [1,1′-biphenyl] -4,4′-diyl group, 3,3′-biphenyldiyl group, 3,6-biphenyldiyl group, etc.), terphenyldiyl group, quaterphenyldiyl group And kinkphenyldiyl group, sexiphenyldiyl group, septiphenyldiyl group, octiphenyldiyl group, nobiphenyldiyl group, deciphenyldiyl group and the like.

  In the general formula (2), examples of the heteroarylene group represented by Y21 include a carbazole ring, a carboline ring, a diazacarbazole ring (also referred to as a monoazacarboline ring, and one of carbon atoms constituting the carboline ring is nitrogen. The ring structure is replaced by an atom), a triazole ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a quinoxaline ring, a thiophene ring, an oxadiazole ring, a dibenzofuran ring, a dibenzothiophene ring, and an indole ring. And the like.

  As a preferred embodiment of the divalent linking group consisting of an arylene group, heteroarylene group or a combination thereof represented by Y21, among the heteroarylene groups, a condensed aromatic heterocyclic ring formed by condensing three or more rings is used. A group derived from a condensed aromatic heterocyclic ring formed by condensing three or more rings is preferably included, and a group derived from a dibenzofuran ring or a dibenzothiophene ring is preferable. Are preferred.

  In General formula (2), it is preferable that 6 or more of E201 to E208 and 6 or more of E209 to E216 are each represented by -C (R21) =.

  In the general formula (2), it is preferable that at least one of E225 to E229 and at least one of E234 to E238 represent -N =.

  Furthermore, in General formula (2), it is preferable that any one of E225-E229 and any one of E234-E238 represent -N =.

  Moreover, in General formula (2), it is mentioned as a preferable aspect that E221-E224 and E230-E233 are each represented by -C (R21) =.

  Further, in the compound having the structure represented by the general formula (2), it is preferable that E203 is represented by -C (R21) = and R21 represents a linking site, and E211 is also -C (R21). And R21 preferably represents a linking moiety.

  Further, E225 and E234 are preferably represented by -N =, and E221 to E224 and E230 to E233 are each preferably represented by -C (R21) =.

  The general formula (3) is also an embodiment of the general formula (1a-2). In the general formula (3), E301 to E312 each represent —C (R31) ═, and R31 represents a hydrogen atom (H) or a substituent. Y31 represents a divalent linking group composed of an arylene group, a heteroarylene group, or a combination thereof.

  Moreover, in General formula (3), as a preferable aspect of the bivalent coupling group which consists of an arylene group represented by Y31, heteroarylene group, or those combinations, the thing similar to Y21 of General formula (2) is mentioned. .

  The general formula (4) is also an embodiment of the general formula (1a-1). In the general formula (4), E401 to E414 each represent -C (R41) =, and R41 represents a hydrogen atom (H) or a substituent. Ar41 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring. Furthermore, k41 represents an integer of 3 or more.

  In the general formula (4), when Ar41 represents an aromatic hydrocarbon ring, the aromatic hydrocarbon ring includes benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene Ring, naphthacene ring, triphenylene ring, o-terphenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen And a ring, a picene ring, a pyrene ring, a pyranthrene ring, and an anthraanthrene ring. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

  In the general formula (4), when Ar41 represents an aromatic heterocycle, the aromatic heterocycle includes a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carbazole ring And azacarbazole ring. The azacarbazole ring refers to one in which at least one carbon atom of the benzene ring constituting the carbazole ring is replaced with a nitrogen atom. These rings may further have the substituents exemplified as R11 and R12 in the general formula (1).

  In the general formula (5), R51 represents a substituent. E501, E502, E511 to E515, E521 to E525 each represent -C (R52) = or -N =. E503 to E505 each represent -C (R52) =. R52 represents a hydrogen atom (H) or a substituent. At least one of E501 and E502 is -N =, at least one of E511-E515 is -N =, and at least one of E521-E525 is -N =.

  In the general formula (6), E601 to E612 each represent —C (R61) ═ or —N═, and R61 represents a hydrogen atom (H) or a substituent. Ar61 represents a substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocyclic ring.

  In the general formula (6), examples of the substituted or unsubstituted aromatic hydrocarbon ring or aromatic heterocycle represented by Ar61 include those similar to Ar41 in the general formula (4).

  In the general formula (7), R71 to R73 each represents a hydrogen atom (H) or a substituent, and Ar71 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  In the general formula (7), the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar71 may be the same as Ar41 in the general formula (4).

  The general formula (8) is also a form of the general formula (7). In the general formula (8), R81 to R86 each represent a hydrogen atom (H) or a substituent. E801 to E803 each represent —C (R87) ═ or —N═, and R87 represents a hydrogen atom (H) or a substituent. Ar81 represents an aromatic hydrocarbon ring group or an aromatic heterocyclic group.

  In the general formula (8), the aromatic hydrocarbon ring or aromatic heterocyclic ring represented by Ar81 may be the same as Ar41 in the general formula (4).

  The compound having the structure represented by the general formula (8a) is one form of the compound having the structure represented by the general formula (8), and Ar81 in the general formula (8) is a carbazole derivative. In the general formula (8), E804 to E811 each represent —C (R88) ═ or —N═, and R88 represents a hydrogen atom (H) or a substituent. At least one of E808 to E811 is -N =, and E804 to E807 and E808 to E811 may be bonded to each other to form a new ring.

[Compound III]
Further, as other compounds constituting the nitrogen-containing layer 3, in addition to the compounds having the structures represented by the general formulas (1) to (8a) as described above, compounds 1 to 166 shown below as specific examples are exemplified. Is done. These compounds are compounds containing nitrogen atoms that interact with silver constituting the electrode layer 5, and are preferable materials from the viewpoint of film formability. In addition, in these compounds 1-166, the compound applicable to the range of the above-mentioned effective unshared electron pair content [n / M] is also included, and if it is such a compound, the nitrogen-containing layer 3 is formed alone. It can be used as a constituent compound. Furthermore, among these compounds 1-166, there are compounds that fall under the general formulas (1)-(8a) described above.

[Examples of compound synthesis]
Specific examples of the synthesis of compound 5 are shown below as typical synthesis examples of the compound, but are not limited thereto.

Step 1: (Synthesis of Intermediate 1)
Under a nitrogen atmosphere, 2,8-dibromodibenzofuran (1.0 mol), carbazole (2.0 mol), copper powder (3.0 mol), potassium carbonate (1.5 mol), DMAc (dimethylacetamide) 300 ml Mixed in and stirred at 130 ° C. for 24 hours. The reaction solution thus obtained was cooled to room temperature, 1 L of toluene was added, washed with distilled water three times, the solvent was distilled off from the washed product under a reduced pressure atmosphere, and the residue was subjected to silica gel flash chromatography (n-heptane: Purification was performed using toluene = 4: 1 to 3: 1), and Intermediate 1 was obtained with a yield of 85%.

Step 2: (Synthesis of Intermediate 2)
Intermediate 1 (0.5 mol) was dissolved in 100 ml of DMF (dimethylformamide) at room temperature under air, NBS (N-bromosuccinimide) (2.0 mol) was added, and the mixture was stirred overnight at room temperature. The resulting precipitate was filtered and washed with methanol, yielding intermediate 2 in 92% yield.

Step 3: (Synthesis of Compound 5)
Under a nitrogen atmosphere, intermediate 2 (0.25 mol), 2-phenylpyridine (1.0 mol), ruthenium complex [(η ₆ -C ₆ H ₆ ) RuCl ₂ ] ₂ (0.05 mol), triphenyl Phosphine (0.2 mol) and potassium carbonate (12 mol) were mixed in 3 L of NMP (N-methyl-2-pyrrolidone) and stirred at 140 ° C. overnight.

After cooling the reaction solution to room temperature, 5 L of dichloromethane was added, and the reaction solution was filtered. Next, the solvent was distilled off from the filtrate under reduced pressure (800 Pa, 80 ° C.), and the residue was purified by silica gel flash chromatography (CH ₂ Cl ₂ : Et ₃ N = 20: 1 to 10: 1).

  After distilling off the solvent from the purified product under reduced pressure, the residue was dissolved again in dichloromethane and washed three times with water. The material obtained by washing was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the dried material in a reduced-pressure atmosphere to obtain Compound 5 in a yield of 68%.

<Electrode layer 5>
The electrode layer 5 is a layer formed using silver or an alloy containing silver as a main component, and is a layer provided adjacent to the nitrogen-containing layer 3 as shown in the schematic cross-sectional view of FIG. . In particular, the electrode layer 5 is characterized in that film formation is started between the start of film formation of the nitrogen-containing layer 3 and 2 minutes after the film formation is completed. Here, the period from the start of film formation of the nitrogen-containing layer 3 to 2 minutes after the film formation is not necessarily between 2 minutes after the film formation of the nitrogen-containing layer 3 is completely completed. In other words, the electrode layer 5 may be formed after the nitrogen-containing layer 3 has been formed and before the nitrogen-containing layer 3 has been formed. In this case, the vicinity of the interface between the nitrogen-containing layer 3 and the electrode layer 5 is configured as a mixed layer. And the electrode layer 5 in this case shall be comprised with the layer comprised only by the mixed layer and electrode material.

  The electrode layer 5 as described above is more preferably a layer in which film formation is started at the earliest possible timing from the start of film formation of the nitrogen-containing layer 3 to 1 minute after the film formation. As will be described later in the manufacturing method, the method for forming the nitrogen-containing layer 3 and the electrode layer 5 is not limited.

  Moreover, the electrode layer 5 has a film thickness of 12 nm or less that allows the sheet resistance to be measured. By setting the electrode layer 5 to a film thickness that allows the sheet resistance to be measured, the metal constituting the electrode layer 5 has two-dimensional continuity in the in-plane direction, and serves as an electrode film. Practicality is ensured. Moreover, the electrode layer 5 has a film thickness of 12 nm or less, so that the absorption component or reflection component in the electrode layer 5 is kept low, and the light transmittance of the transparent electrode 1 is ensured. Moreover, if the electrode layer 5 has a thickness of at least 4 nm, the conductivity of the transparent electrode 1 is ensured.

  The metal constituting the electrode layer 5 is, for example, silver (Ag) or an alloy containing silver as a main component. Silver (Ag) may contain palladium (Pd), copper (Cu), gold (Au), etc. added to ensure the stability of silver, and the purity of silver is 99% or more. And An alloy containing silver as a main component has a silver content of 50% or more. Examples of such alloys include silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn), silver gold (AgAu), silver aluminum (AgAl) Silver zinc (AgZn), silver tin (AgSn), silver platinum (AgPt), silver titanium (AgTi), silver bismuth (AgBi), and the like.

  Further, the electrode layer 5 as described above may have a configuration in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  The electrode layer 5 is preferably formed as an electrode pattern. As an electrode pattern of the electrode layer 5, for example, it is preferable that a plurality of electrode patterns are formed in a matrix. The matrix electrode pattern has a plurality of x electrode patterns or y electrode patterns, and each x electrode pattern or y electrode pattern is spaced from each other with each extending in the x direction or y direction. Arranged in parallel. Each of these x electrode patterns or y electrode patterns may have a shape in which rhombuses or other pattern portions arranged in the x direction are linearly connected in the x direction or the y direction. Further, each x electrode pattern and y electrode pattern are insulated by interposing an insulating film. Furthermore, the wiring pattern which consists of the electrode layer 5 may be connected to the edge part of each x electrode pattern and y electrode pattern, and this wiring pattern may be pulled out from the peripheral area on the transparent substrate 11 to an edge.

  Further, the transparent electrode 1 may have a configuration having either an x electrode pattern or a y electrode pattern, or may have a configuration having both an x electrode pattern and a y electrode pattern. Furthermore, the electrode pattern is not limited to the matrix shape, and may be other patterns.

<Protective layer>
The transparent electrode 1 having the electrode layer 5 as described above may be provided with a protective layer so as to cover the electrode layer 5. In this case, it is preferable that the protective layer has light transparency so as not to impair the light transparency of the transparent electrode 1.

  The protective layer includes a plate-like or film-like member that covers the electrode layer 5 of the transparent electrode 1, a protective layer that is configured using an inorganic material, an organic material, or a resin material that covers the electrode layer 5. This protective layer is provided so as to cover at least the electrode layer 5 in the transparent electrode 1.

  As a plate-like or film-like member constituting the protective layer, the same member as the above-described transparent substrate 11 can be used. Especially, since the transparent electrode 1 can be reduced in thickness, a thin resin film can be used preferably.

Furthermore, as with the transparent substrate 11, the resin film may be formed with a coating made of an inorganic material or an organic material, or a hybrid coating combining these coatings. The film has an oxygen permeability of 1 × 10 ⁻³ ml / (m ² · 24 h · atm) or less measured by a method according to JIS-K-7126-1987, and a method according to JIS-K-7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured in (1) is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  In addition, the protective layer composed of an inorganic material, an organic material, or a resin material is particularly composed of a material having a function of suppressing entry of a substance that causes deterioration of the electrode layer 5 such as moisture or oxygen. Is preferred. As such a material, for example, an inorganic material such as silicon oxide, silicon dioxide, or silicon nitride is used. Further, in order to improve the brittleness of the sealing film, a laminated structure may be formed by using a film made of an organic material together with a film made of these inorganic materials.

  The method for forming these films is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

<The manufacturing method of the transparent electrode 1>
Next, the manufacturing method of the transparent electrode 1 is demonstrated using FIG.

  First, as shown in FIG. 7A, the nitrogen-containing layer 3 is formed on the transparent substrate 11. The nitrogen-containing layer 3 can be formed by a method using a wet process such as a coating method, an inkjet method, a coating method, or a dip method, a method using a vapor deposition method (resistance heating, EB method, etc.), a dry process such as a CVD method, or the like. Can be mentioned. Among them, the vapor deposition method is preferably applied from the viewpoint that a homogeneous film is easily obtained and pinholes are hardly generated, but a sputtering method may be used.

  In the case where the nitrogen-containing layer 3 is formed by a vapor deposition method using a plurality of compounds, co-evaporation for simultaneously supplying a plurality of compounds from a plurality of vapor deposition sources is applied. If a polymer material is used as the compound, a coating method is preferably applied. In this case, a coating solution in which the compound is dissolved in a solvent is used. The solvent in which the compound is dissolved is not limited. Furthermore, if the nitrogen-containing layer 3 is formed using a plurality of compounds, a coating solution may be prepared using a solvent capable of dissolving the plurality of compounds.

  Next, as shown in FIG. 7B, between the start of film formation of the nitrogen-containing layer 3 and 2 minutes after the film formation is completed, a silver or an alloy containing silver as a main component is adjacent to the nitrogen-containing layer 3. The film formation of the electrode layer 5 constituted by using is started. The electrode layer 5 is formed using a wet process such as a coating method, an inkjet method, a coating method, or a dip method, or a dry process such as a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, or a CVD method. The method etc. are mentioned. Among these, the vapor deposition method is preferably applied from the viewpoint that it is easy to obtain a homogeneous film and that pinholes are not easily generated. However, a sputtering method may be used, and a composition suitable for the material used as the electrode layer 5 may be used. A membrane method is selected.

  In the case where the nitrogen-containing layer 3 is formed using a wet process, it is preferable to start forming the electrode layer 5 within 2 minutes after completion of the formation of the nitrogen-containing layer 3. Here, it is assumed that the period up to 2 minutes after the film formation of the nitrogen-containing layer 3 is up to 2 minutes after the completion of the curing and drying of the nitrogen-containing layer 3.

  As described above, a desired transparent electrode 1 is obtained on the transparent substrate 11.

<Effect of transparent electrode 1>
The transparent electrode 1 having the above-described configuration is configured such that an electrode layer 5 made of silver or an alloy containing silver as a main component is provided adjacent to a nitrogen-containing layer 3 formed using a compound containing nitrogen atoms. It is. Thus, when the electrode layer 5 is formed on the nitrogen-containing layer 3, the silver atoms constituting the electrode layer 5 interact with the compound containing nitrogen atoms constituting the nitrogen-containing layer 3, thereby producing silver atoms. The diffusion distance on the surface of the nitrogen-containing layer 3 is reduced, and aggregation of silver is suppressed. Therefore, in general, a silver thin film that is easily isolated in an island shape by film growth of a nuclear growth type (Volume-Weber: VW type) is a single-layer growth type (Frank-van der Merwe: FM type). As a result, a continuous film is formed. Accordingly, it is possible to obtain the electrode layer 5 having a uniform film thickness even though the film thickness is small.

  Moreover, the electrode layer 5 which comprises the transparent electrode 1 has a film thickness of 12 nm or less which can measure sheet resistance. As a result, the electrode layer 5 has a light absorption component or reflection component suppressed to a low level while ensuring practicality as a film for an electrode. Furthermore, the electrode layer 5 having such a thin film thickness has a uniform film thickness and continuity by being provided adjacent to the nitrogen-containing layer 3 as described above. Therefore, although the electrode layer 5 is an ultrathin film having a thickness of 12 nm or less as described above, the electrode layer 5 has conductivity capable of reliably measuring the sheet resistance.

  In particular, the electrode layer 5 is a layer obtained by starting film formation from the start of film formation of the nitrogen-containing layer 3 to 2 minutes after the film formation is completed, preferably within 1 minute. Thus, the electrode layer 5 can be a film having higher continuity, and the light transmittance and conductivity of the transparent electrode 1 provided with the electrode layer 5 are also improved. As will be described in detail in the following examples, the electrode layer 5 obtained by starting film formation between the start of film formation of the nitrogen-containing layer 3 and 2 minutes after the film formation is It is confirmed that the visibility of the base is good through the transparent electrode 1 having the electrode layer 5 and the sheet resistance is low even though it is a thin film.

  As described above, although the transparent electrode 1 is a thin film, it has improved light transmission and improved conductivity, and further suppresses light scattering due to the high continuity and homogeneity of the electrode layer 5. It will be As a result, the transparent electrode 1 has good visibility of the display image serving as a base, and can be suitably applied as a transparent electrode for a touch panel.

  Moreover, it was confirmed that such a transparent electrode 1 has a low sheet resistance although it is a thin film as compared with a transparent electrode using ITO, as will be described in detail in a later example. Thereby, since the voltage drop of the electrode layer 5 can be suppressed while suppressing the visibility of the patterned electrode layer 5 itself, it is also suitably used as a transparent electrode for an enlarged touch panel.

  Further, such a transparent electrode 1 is low in cost because it does not use indium (In), which is a rare metal, and has excellent long-term reliability because it does not use a chemically unstable material such as ZnO. Yes.

≪2. Second Embodiment: Three-layer Transparent Electrode for Touch Panel >>
FIG. 8 is a schematic cross-sectional view showing a configuration of a transparent electrode for a touch panel (hereinafter referred to as a transparent electrode) according to a second embodiment of the present invention. The transparent electrode 1a shown in this figure is different from the transparent electrode described with reference to FIG. 1 in that a high refractive index layer H is provided to form a three-layer structure, and other configurations are the same. For this reason, the same code | symbol is attached | subjected to the same component and the overlapping description is abbreviate | omitted.

  That is, the transparent electrode 1a having a three-layer structure has a three-layer structure in which a high refractive index layer H having a higher refractive index than that of the nitrogen-containing layer 3 is provided at a position where the nitrogen-containing layer 3 is sandwiched between the transparent electrode 1a. The high refractive index layer H, the nitrogen-containing layer 3 and the electrode layer 5 are provided in this order on the transparent substrate 11. Among these, the high refractive index layer H has the following configuration.

<High refractive index layer H>
The high refractive index layer H is a layer having a higher refractive index than the nitrogen-containing layer 3. The refractive index of the high refractive index layer H is preferably such that the refractive index (n) at a wavelength of 550 nm is 0.1 or more higher than the refractive index of the nitrogen-containing layer 3 (n = 1.7 to 1.8). More preferably, it is higher. Typically, a layer having a refractive index (n) of 2.0 or more at a wavelength of 550 nm is preferable. Such a high refractive index layer H is made of a material having the high refractive index and light transmittance described above, and includes, for example, titanium oxide (TiO ₂ : n = 2.3 to 2.4), oxidation Zirconium (ZrO: n = 2.4), cadmium oxide (CdO: n = 2.49), indium tin oxide (ITO: n = 2.1 to 2.2), indium zinc oxide (In ₂ O ₃ + ZnO: n = 2.0 to 2.4), zinc oxide (ZnO: n = 2.0 to 2.3), hafnium oxide (HfO ₂ : n = 1.9 to 2.1), tantalum pentoxide (Ta ₂₎ High refractive index materials such as O ₅ : n = 2.16), niobium oxide (Nb ₂ O ₅ : n = 2.2 to 2.4), cerium oxide (CeO ₂ : n = 2.2), and optical The material generally used for a film is mentioned.

  The high refractive index layer H is not used as the main material of the electrode even if it is made of a conductive material, but it may be made of a conductive material. For example, the electrode layer 5 is patterned so as to be conductive. Moreover, it is not necessary to have the film thickness required as an electrode.

  When the high refractive index layer H as described above is formed on the transparent substrate 11, examples of the film forming method include vapor deposition (resistance heating, EB method, etc.) or sputtering. In particular, a method using ion assist is suitable for EB deposition. As a method for forming such a high refractive index layer H, an appropriate method is selected depending on the material constituting the layer.

  Although illustration is omitted here, the transparent electrode 1a may be provided with a low refractive index layer in contact with the high refractive index layer H. In the configuration shown in FIG. 8, a surface opposite to the surface where the high refractive index layer H and the nitrogen-containing layer 3 are in contact, that is, a low refractive index layer is provided between the high refractive index layer H and the transparent substrate 11. Also good. By having the low refractive index layer in contact with the high refractive index layer H, the optical admittance can be adjusted, and the light transmittance of the transparent electrode is further improved.

Such a low refractive index layer is a layer having a lower refractive index than the high refractive index layer H. In particular, the refractive index at a wavelength of 550 nm is preferably lower than the high refractive index layer H by 0.1 or more, and more preferably lower than the high refractive index layer H by 0.3 or more. Such a low refractive index layer is composed of a material having a low refractive index and light transmittance. For example, low refractive index materials such as magnesium fluoride (MgF ₂ ), lithium fluoride (LiF), calcium fluoride (CaF ₂ ), aluminum fluoride (AlF ₃ ), and materials generally used for optical films. Can be mentioned.

<Effect of transparent electrode 1a>
In the transparent electrode 1a configured as described above, in addition to the effect of the transparent electrode of the first embodiment, a three-layer structure in which a high refractive index layer H is provided in contact with the nitrogen-containing layer 3, Reflection generated in the electrode layer 5 containing silver as a main component is suppressed, and light scattering in the transparent electrode for touch panel 1a is further suppressed. As a result, the transparent electrode 1a has a better visibility of the display image serving as a base, and can be more suitably applied as a transparent electrode for a touch panel.

≪3. Third Embodiment: Four-layer Transparent Electrode for Touch Panel >>
FIG. 9 is a schematic cross-sectional view illustrating a configuration of a transparent electrode for a touch panel (hereinafter referred to as a transparent electrode) according to a third embodiment of the present invention. The transparent electrode 1b shown in this figure is different from the transparent electrode described with reference to FIG. 1 in that two high refractive index layers H are provided to form a four-layer structure, and other configurations are the same. is there. For this reason, the same code | symbol is attached | subjected to the same component and the overlapping description is abbreviate | omitted.

  That is, the transparent electrode 1b having a four-layer structure has a four-layer structure in which the nitrogen-containing layer 3 and the electrode layer 5 are sandwiched between two high-refractive-index layers H. The refractive index layer H, the nitrogen-containing layer 3, the electrode layer 5, and the high refractive index layer H are provided in this order. Among these, the two high refractive index layers H may be the same as the high refractive index layer used in the transparent electrode having the three-layer structure shown in FIG.

  These two high refractive index layers H may be made of the same material, or may be made of different materials. Moreover, the film thickness may be the same or different. However, when the electrode layer 5 is patterned, the high refractive index layer H disposed adjacent to the electrode layer 5 out of the two high refractive index layers H is shown as the above high refractive index material. Of the materials, if it is made of a material having conductivity, it needs to be patterned in the same manner as the electrode layer 5, and if it is made of a material not having conductivity, patterning is required. It may or may not be done.

  The transparent electrode 1b may include a low refractive index layer that is not shown here. For example, in the transparent electrode 1b shown in FIG. 9, two low refractive index layers may be provided in a state where the two high refractive index layers H are further sandwiched from the outside. By having the low refractive index layer outside the high refractive index layer H, the light transmittance of the transparent electrode is further improved. These low refractive index layers are the same as the low refractive index layers described in the second embodiment.

<Effect of transparent electrode 1b>
Such a transparent electrode 1b has a configuration in which the nitrogen-containing layer 3 and the electrode layer 5 are sandwiched between two high-refractive-index layers H. The high-refractive-index layer H, the nitrogen-containing layer 3, the electrode layer 5, and the high-refractive-index layer H The rate layer H is laminated in this order. Thereby, the transparent electrode 1b can further improve the light transmittance by suppressing the reflection generated in the electrode layer 5 as compared with the transparent electrode having the three-layer structure shown in FIG. It is possible to improve the visibility of the display image.

<< 4. Fourth Embodiment: Touch Panel >>
(Configuration with two layers of transparent electrodes on one transparent substrate)
FIG. 10 is a perspective view showing a schematic configuration of a touch panel according to the fourth embodiment of the present invention. FIG. 11 is a plan view of two transparent electrodes 1-1 and 1-2 showing the electrode configuration of the touch panel.

  The touch panel 21 shown in these drawings is a projected capacitive touch panel. In the touch panel 21, a first transparent electrode 1-1 and a second transparent electrode 1-2 are arranged in this order on one main surface of one transparent substrate 11, and the upper part is covered with a front plate 13. ing. Each of the first transparent electrode 1-1 and the second transparent electrode 1-2 is a transparent electrode for a touch panel having a two-layer structure described with reference to FIG. Therefore, the first transparent electrode 1-1 has a configuration in which the first nitrogen-containing layer 3-1 and the first electrode layer 5-1 are laminated in this order. Similarly, the second transparent electrode 1-2 has a configuration in which a second nitrogen-containing layer 3-2 and a second electrode layer 5-2 are laminated in this order.

  Hereinafter, details of the main layers constituting the touch panel 21 will be described in order from the transparent substrate 11 side. Here, description will be made with reference to FIG. 10 and FIG. 11 together with the schematic plan view of the electrode portion of the touch panel according to the present embodiment of FIG. 12 and the schematic cross-sectional view of FIG. . Moreover, the same code | symbol is attached | subjected to the component similar to having demonstrated in previous embodiment, and the overlapping description is abbreviate | omitted.

<Transparent substrate 11>
The transparent substrate 11 is the transparent substrate 11 described in the previous transparent electrode for touch panel.

<First Nitrogen-Containing Layer 3-1 (First Transparent Electrode 1-1)>
The first nitrogen-containing layer 3-1 is the nitrogen-containing layer described in the previous transparent electrode for a touch panel, and is formed on one main surface of the transparent substrate 11. Here, as an example, the first nitrogen-containing layer 3-1 is provided so as to cover the entire surface of one main surface of the transparent substrate 11. May be patterned in the same shape.

<First electrode layer 5-1 (first transparent electrode 1-1)>
The first electrode layer 5-1 is the electrode layer described in the previous transparent electrode for touch panel, and is configured as a plurality of x electrode patterns 5x1, 5x2,... Patterned on the first nitrogen-containing layer 3-1. Has been. Each of the x electrode patterns 5x1, 5x2,... Is arranged in parallel with an interval between each other in a state of extending in the x direction. Each of these x electrode patterns 5x1, 5x2,... Has, for example, a shape in which rhombus pattern portions arranged in the x direction are linearly connected in the x direction in the vicinity of the apex of the rhombus.

  Moreover, x wiring 17x is connected to each x electrode pattern 5x1, 5x2,. These x wirings 17 x are wired in the peripheral region on the transparent substrate 11 and are drawn out to the edge of the transparent substrate 11. Each of the x wirings 17x may be configured as the first electrode layer 5-1 mainly composed of silver, as in the case of the x electrode patterns 5x1, 5x2,. It may be composed of an electrode layer.

<Second nitrogen-containing layer 3-2 (second transparent electrode 1-2)>
The second nitrogen-containing layer 3-2 is the nitrogen-containing layer described in the previous transparent electrode for touch panel, and is formed on one main surface of the transparent substrate 11 so as to cover the first electrode layer 5-1. ing. The second nitrogen-containing layer 3-2 is provided so as to cover at least the first electrode layer 5-1, and expose at least the terminal portion of the x wiring 17x. Here, as an example, the second nitrogen-containing layer 3-2 is provided in such a manner that the terminal portion of the x wiring 17x is exposed and the other portion covers the entire main surface of the transparent substrate 11. However, it may be patterned in the same shape as a second electrode layer 5-2 described below.

<Second electrode layer 5-2 (second transparent electrode 1-2)>
The second electrode layer 5-2 is the electrode layer described in the previous transparent electrode for touch panel, and is configured as a plurality of y electrode patterns 5y1, 5y2,... Patterned on the second nitrogen-containing layer 3-2. Has been. Each of the y electrode patterns 5y1, 5y2,... Is arranged in parallel with a distance from each other in a state of extending in the y direction orthogonal to the x electrode patterns 5x1, 5x2,. Each of these y electrode patterns 5y1, 5y2,... Has, for example, a shape in which rhombus pattern portions arranged in the y direction are linearly connected in the y direction in the vicinity of the apex of the rhombus.

  Here, as shown in FIG. 12, the rhombus pattern portions constituting the y electrode patterns 5y1, 5y2,... Are viewed in plan view with respect to the rhombus pattern portions forming the x electrode patterns 5x1, 5x2,. It is arranged at a position that does not overlap, and has a shape that occupies as large a range as possible without overlapping. Accordingly, in the central region of the transparent substrate 11, the x electrode patterns 5x1, 5x2,... Constituted by the first electrode layer 5-1, and the y electrode constituted by the second electrode layer 5-2. Patterns 5y1, 5y2,... Are difficult to visually recognize.

  Each of the y electrode patterns 5y1, 5y2,... Is stacked with each of the x electrode patterns 5x1, 5x2,. The second nitrogen-containing layer 3-2 is sandwiched between these laminated portions, and thereby the insulation between the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,. ing.

  Further, a y wiring 17y is connected to each end portion of each y electrode pattern 5y1, 5y2,. These y wirings 17y are wired in the peripheral region on the transparent substrate 11, and are drawn out to the edge of the transparent substrate 11 so as to be aligned with the x wirings 17x. Each of such y wirings 17y may be configured as a second electrode layer 5-2 containing silver as a main component, similarly to the y electrode patterns 5y1, 5y2,. It may be composed of an electrode layer.

  A flexible printed circuit board or the like is connected to the x wiring 17x and the y wiring 17y drawn to the edge of the transparent substrate 11.

<Front plate 13>
The front plate 13 illustrated in FIGS. 10 and 13 is a plate material on which a portion corresponding to the input position on the touch panel 21 is pressed. Such a front plate 13 is a plate material having optical transparency, and the same material as the transparent substrate 11 is used. Further, the front plate 13 may be made by selecting and using a material having optical characteristics as required. Such a front plate 13 is attached to the second transparent electrode 1-2 side by, for example, an adhesive 15 (see FIG. 13). The material of the adhesive 15 is not particularly limited as long as it has optical transparency and insulating properties.

  Further, the front plate 13 is provided with a light-shielding film that covers the peripheral region of the transparent substrate 11 (see FIG. 10), the x wiring 17x drawn from the x electrode patterns 5x1, 5x2,..., And the y electrode patterns 5y1, 5y2. ,... Is prevented from being viewed from the front plate 13 side.

<Touch panel operation>
When operating the touch panel 21 as described above, voltages are applied to the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,... From a flexible printed circuit board connected to the x wiring 17x and the y wiring 17y. Apply it. In this state, when a finger or a touch pen touches the surface of the front plate 13, the capacitance of each part existing in the touch panel 21 changes, and the voltages of the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,. It appears as a change. This change varies depending on the distance from the position touched by the finger or touch pen, and is greatest at the position touched by the finger or touch pen. For this reason, the position addressed by the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,.

<Effect of touch panel>
The touch panel 21 as described above uses, as the two-layered transparent electrodes 1-1 and 1-2, a transparent electrode for a touch panel that has sufficient light conductivity as well as light transmission described above and that suppresses light scattering. ing. As a result, it is possible to improve the visibility of the display image as a base. In addition, since the conductivity is sufficient, a voltage drop when the transparent electrode for the touch panel is enlarged can be suppressed, and the touch panel 21 can be enlarged.

  In particular, the touch panel 21 is a projection capacitive type having x electrode patterns 5x1, 5x2,... And y electrode patterns 5y1, 5y2,. Therefore, the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,. However, since these x electrode patterns 5x1, 5x2,... And y electrode patterns 5y1, 5y2,... Are the electrode layers 5 of the transparent electrode for touch panel described above, they can be made thin while maintaining conductivity. is there. Therefore, the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,... Themselves are difficult to be visually recognized, and even the touch panel 21 having a patterned transparent electrode is a display image serving as a base through the patterned electrodes. It is possible to improve the visibility.

<< 4-1. Touch panel modification 1 >>
FIG. 14 is a schematic cross-sectional view illustrating Modification 1 of the touch panel of the present invention described above, and corresponds to a cross section taken along the line AA of FIG. As shown in FIG. 14, the touch panel 21a of Modification 1 is shown in FIG. 13 only using a three-layer transparent electrode (see FIG. 8) as the two transparent electrodes 1a-1 and 1a-2. Different from touch panel. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel shown in FIG. 13, and the overlapping description is abbreviate | omitted.

  That is, in the touch panel 21a of the first modification shown in FIG. 14, the first transparent electrode 1a-1 and the second transparent electrode 1a-2 are arranged in this order on one main surface of the transparent substrate 11, and the upper part is The front plate 13 is covered with an adhesive 15. Each of the first transparent electrode 1a-1 and the second transparent electrode 1a-2 is a transparent electrode for a touch panel having a three-layer structure described with reference to FIG. Therefore, the first transparent electrode 1a-1 includes, in order from the transparent substrate 11 side, the first high refractive index layer H-1, the first nitrogen-containing layer 3-1, and the first electrode layer 5-1. Are stacked. Similarly, the second transparent electrode 1a-2 includes, in order from the first transparent electrode 1a-1, the second high refractive index layer H-2, the second nitrogen-containing layer 3-2, The electrode layer 5-2 is laminated.

  Here, the first high refractive index layer H-1 and the second high refractive index layer H-2 have the following configurations.

<First High Refractive Index Layer H-1 (First Transparent Electrode 1a-1)>
The first high refractive index layer H-1 is the high refractive index layer described in the previous transparent electrode for touch panel, and is formed on one main surface of the transparent substrate 11. Here, as an example, the first high refractive index layer H-1 is provided so as to cover the entire surface of one main surface of the transparent substrate 11, but the first nitrogen-containing layer 3 described above. -1 may be patterned in the same shape as the first electrode layer 5-1. The first high refractive index layer H-1 is configured using a material appropriately selected from the materials shown as the above high refractive index materials.

<Second High Refractive Index Layer H-2 (Second Transparent Electrode 1a-2)>
The second high refractive index layer H-2 is the high refractive index layer described in the previous transparent electrode for touch panel, and is formed on one main surface of the transparent substrate 11 so as to cover the first electrode layer 5-1. It is filmed. Such a second high refractive index layer H-2 is made of a material having a good insulating property among the materials shown as the high refractive index material. Such a second high refractive index layer H-2 is provided so as to cover at least the terminal portion of the x wiring 17x while covering the first electrode layer 5-1. Here, as an example, the second high refractive index layer H-2 is provided in such a manner that the terminal portion of the x wiring 17x is exposed and the other portion covers the entire main surface of the transparent substrate 11. However, it may be patterned in the same shape as the second electrode layer 5-2 together with the second nitrogen-containing layer 3-2.

  The second high-refractive index layer H-2 may be made of the same material as the first high-refractive index layer H-1 as long as it has an insulating property, or may be made of a different material. It may be configured. Further, the film thickness may be the same as or different from the first high refractive index layer H-1.

<Effect of Touch Panel 21a of Modification 1>
The touch panel 21a of the first modification uses the three-layered transparent electrode (see FIG. 8) described above as the first transparent electrode 1a-1 and the second transparent electrode 1a-2. Thus, the reflection generated in the first electrode layer 5-1 and the second electrode layer 5-2 mainly composed of silver as compared with the touch panel configured using the transparent electrode having the two-layer structure shown in FIG. 13. Is suppressed, and the visibility of the display image as a further base can be improved.

≪4-2. Touch panel modification 2 >>
FIG. 15 is a schematic cross-sectional view showing Modification 2 of the touch panel of the present invention described above, and corresponds to a cross section taken along the line AA of FIG. As shown in FIG. 15, the touch panel 21b of Modification 2 is shown in FIG. 13 only using a four-layer transparent electrode (see FIG. 9) as the two transparent electrodes 1b-1 and 1b-2. Different from touch panel. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel shown in FIG. 13, and the overlapping description is abbreviate | omitted.

  That is, in the touch panel 21b of Modification 2 shown in FIG. 15, the first transparent electrode 1b-1 and the second transparent electrode 1b-2 are arranged in this order on one main surface of the transparent substrate 11, and this upper part is The front plate 13 is covered with an adhesive 15. Each of the first transparent electrode 1b-1 and the second transparent electrode 1b-2 is a transparent electrode for a touch panel having a four-layer structure described with reference to FIG. Here, it is assumed that the first transparent electrode 1b-1 and the second transparent electrode 1b-2 share one high refractive index layer. Therefore, the first transparent electrode 1b-1 includes, in order from the transparent substrate 11 side, the first high refractive index layer H-1, the first nitrogen-containing layer 3-1, and the first electrode layer 5-1. The second high refractive index material H-2 is laminated. Similarly, the second transparent electrode 1b-2 includes, in order from the transparent substrate 11 side, a second high refractive index layer H-2, a second nitrogen-containing layer 3-2, and a second electrode layer 5-2. The third high refractive index layer H-3 is laminated.

  Here, the transparent substrate 11 to the second electrode layer 5-2 include the first high refractive index layer H-1 and the second high refractive index layer H-2, and have been described with reference to FIG. The same touch panel modification 1 is applied. The third high refractive index layer H-3 has the following configuration.

<Third high refractive index layer H-3>
The third high-refractive index layer H-3 is the high-refractive index layer described in the previous transparent electrode for touch panel, and is formed on one main surface of the transparent substrate 11 so as to cover the second electrode layer 5-2. It is filmed. Such a third high refractive index layer H-3 is made of, for example, a material having a good insulating property among the materials shown as the high refractive index material. In this case, as shown in the drawing, the third high refractive index layer H-3 is provided so as to cover at least the second electrode layer 5-2 and expose at least the terminal portion of the y wiring 17y. To do. On the other hand, the third high refractive index layer H-3 is a conductive material such as indium tin oxide (ITO) or indium zinc oxide (In ₂ O ₃ + ZnO) among the materials shown as the high refractive index material. In the case of using a material having a property, the third high refractive index layer H-3 is patterned so as to be conductive in the same manner as the second electrode layer 5-2.

  The third high refractive index layer H-3 is made of the same material as the first high refractive index layer H-1 and the second high refractive index layer H-2 as long as the above configuration is maintained. May be made of different materials, may have the same film thickness, or may have different film thicknesses. Furthermore, when the third high refractive index layer H-3 is made of an adhesive material, it may also serve as the adhesive 15.

<Effect of Touch Panel 21b of Modification 2>
The touch panel 21b of Modification 2 uses the transparent electrode having the four-layer structure described above (see FIG. 9) as the first transparent electrode 1b-1 and the second transparent electrode 1b-2. As a result, the first electrode layer 5-1 and the second electrode layer 5-containing silver as a main component further than the touch panel of the modification example 1 using the transparent electrode having the three-layer structure shown in FIG. The reflection generated in 2 is suppressed, and it becomes possible to further improve the visibility of the display image serving as a base.

<< 4-3. Touch panel modification 3 >>
Although illustration is omitted here, as a modification 3 of the touch panel, a configuration in which the second high refractive index layer H-2 used in the touch panel 21b of the modification 2 shown in FIG. 15 is omitted is illustrated. . In this case, the configuration from the first nitrogen-containing layer 3-1 to the second electrode layer 5-2 is sandwiched between two high refractive index layers.

  Even in the configuration of the third modification example, the reflection generated in the first electrode layer 5-1 and the second electrode layer 5-2 mainly composed of silver as compared with the configuration of the first modification example is further increased. It becomes suppressed, and it becomes possible to further improve the visibility of the display image serving as a base.

≪5. Fifth embodiment: Touch panel >>
(Configuration with transparent electrodes on each of two transparent substrates)
FIG. 16: is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 5th Embodiment of this invention. Also in the touch panel of the present embodiment, the schematic configuration of the touch panel, the electrode configuration of the transparent electrode for the touch panel, and the planar arrangement of the electrode portion of the touch panel are the same as the configurations shown in FIGS. This corresponds to 12 AA cross sections.

  The touch panel 22 shown in FIG. 16 has a configuration in which a first transparent electrode 1-1 and a second transparent electrode 1-2 are provided on one main surface of two transparent substrates 11-1 and 11-2. The rest of the configuration is the same as the configuration of the touch panel shown in FIG. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel shown in FIG. 13, and the overlapping description is abbreviate | omitted.

  That is, the touch panel 22 shown in FIG. 16 includes a first transparent substrate 11-1 provided with a first transparent electrode 1-1 and a second transparent substrate 11- provided with a second transparent electrode 1-2. And 2. These transparent substrates 11-1 and 11-2 have the formation surfaces of the transparent electrodes 1-1 and 1-2 in the same direction, and the formation of the first transparent electrode 1-1 on the first transparent substrate 11-1. On the surface, the second transparent substrate 11-2 is placed so as to be positioned. The upper part of the second transparent electrode 1-2 provided on the second transparent substrate 11-2 is covered with the front plate 13 with the adhesive 15 interposed therebetween.

  The 1st transparent substrate 11-1 and the 2nd transparent substrate 11-2 are the transparent substrates 11 similar to the structure demonstrated by the transparent electrode for touchscreens above. Each of the first transparent electrode 1-1 and the second transparent electrode 1-2 is a transparent electrode for a touch panel having a two-layer structure described with reference to FIG. On the -2, nitrogen-containing layers 3-1, 3-2 and electrode layers 5-1, 5-2 are laminated in this order.

  Further, the laminated first transparent substrate 11-1 and second transparent substrate 11-2 are bonded together by an adhesive not shown here, and also by this adhesive. The first electrode layer 5-1 and the second electrode layer 5-2 are insulated.

  Even the touch panel 22 as described above can be operated in the same manner as the touch panel shown in FIG.

<Effect of touch panel>
Even with the touch panel 22 having such a configuration, the use of the transparent electrode for a touch panel, which is the thin film described above, has sufficient light conductivity and sufficient conductivity, and light scattering is suppressed. Similarly to the touch panel described with reference to FIG. 13, it is possible to improve the visibility of a display image serving as a base and increase the size of the panel.

  The touch panel 22 having the above-described configuration can be combined with each of the touch panel modifications 1 to 3 described above, and each effect can be obtained by combining the touch panels 22 with each other.

  For example, when the touch panel of this embodiment is combined with the touch panel modification 1 shown in FIG. 14, the two-layered transparent electrodes 1-1 and 1-2 in the touch panel 22 shown in FIG. Replace with the transparent electrode of the three-layer structure shown. In this case, a high refractive index layer is provided between the first transparent substrate 11-1 and the first nitrogen-containing layer 3-1, and further, the second transparent substrate 11-2 and the second nitrogen-containing layer 3- 2 is provided with a high refractive index layer.

  Further, when the touch panel of the present embodiment is combined with the touch panel modification 2 shown in FIG. 15, the two-layered transparent electrodes 1-1 and 1-2 in the touch panel 22 shown in FIG. It is replaced with a transparent electrode having a four-layer structure. In this case, of the two high refractive index layers constituting each transparent electrode, each high refractive index layer provided adjacent to the electrode layers 5-1 and 5-2 is shown as the above high refractive index material. Of the materials, it is configured using a material having good insulation, or if it is configured of a conductive material, it is patterned in the same manner as the adjacent electrode layers 5-1, 5-2. And

  Furthermore, the touch panel of this embodiment applies the above-described modification 3 of the touch panel, and has two high positions only at a position where the configuration from the first nitrogen-containing layer 3-1 to the second electrode layer 5-2 is sandwiched. It can also be set as the structure which provided the refractive index layer.

≪6. Sixth Embodiment: Touch Panel >>
(Configuration with transparent electrodes on both sides of a single transparent substrate)
FIG. 17: is a cross-sectional schematic diagram which shows the structure of the touchscreen which concerns on 6th Embodiment of this invention. Also in the touch panel of the present embodiment, the schematic configuration of the touch panel, the electrode configuration of the transparent electrode for the touch panel, and the planar arrangement of the electrode portion of the touch panel are the same as the configurations shown in FIGS. This corresponds to 12 AA cross sections.

  A touch panel 23 shown in FIG. 17 is provided with a first transparent electrode 1-1 on one main surface side of one transparent substrate 11, and a second transparent electrode 1-2 on the other main surface side of the transparent substrate 11. Each component is the same as the configuration of the touch panel shown in FIG. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel shown in FIG. 13, and the overlapping description is abbreviate | omitted.

  That is, the touch panel 23 shown in FIG. 17 includes a first transparent electrode 1-1 and a second transparent electrode 1-2 provided on both surfaces of the transparent substrate 11. Further, the upper part of the second transparent electrode 1-2 is covered with the front plate 13 with the adhesive 15 interposed therebetween.

  The transparent substrate 11 is the same transparent substrate 11 as described in the previous transparent electrode for a touch panel. Each of the first transparent electrode 1-1 and the second transparent electrode 1-2 is a transparent electrode for a touch panel having a two-layer structure described with reference to FIG. Among these, the 1st transparent electrode 1-1 is the structure by which the nitrogen containing layer 3-1 and the electrode layer 5-1 were laminated | stacked in this order from the one main surface side of the transparent substrate 11. FIG. On the other hand, the second transparent electrode 1-2 has a configuration in which a nitrogen-containing layer 3-2 and an electrode layer 5-2 are laminated in this order from the other main surface side of the transparent substrate 11.

  In the touch panel 23 having such a configuration, one main surface side of the first transparent electrode 1-1 may be covered with a protective layer (not shown).

  Even the touch panel 23 as described above can be operated in the same manner as the touch panel shown in FIG.

<Effect of touch panel>
Even with the touch panel 23 having such a configuration, the use of the transparent electrode for a touch panel, which is the thin film described above, has sufficient conductivity as well as light transmittance, and also suppresses light scattering. Similarly to the touch panel described with reference to FIG. 13, it is possible to improve the visibility of a display image serving as a base and increase the size of the panel.

  The touch panel 23 having the above-described configuration can be combined with each of the first to third modifications of the touch panel described above, and each effect can be obtained by combining.

  For example, when the touch panel of this embodiment is combined with the touch panel modification 1 shown in FIG. 14, the two-layered transparent electrodes 1-1 and 1-2 in the touch panel 23 shown in FIG. Replace with the transparent electrode of the three-layer structure shown. In this case, a high refractive index layer is provided between the transparent substrate 11 and the first nitrogen-containing layer 3-1, and a high refractive index layer is further provided between the transparent substrate 11 and the second nitrogen-containing layer 3-2. The configuration is provided.

  When the touch panel of the present embodiment is combined with the touch panel modification 2 shown in FIG. 15, the two-layered transparent electrodes 1-1 and 1-2 in the touch panel 23 shown in FIG. 17 are shown in FIG. It is replaced with a transparent electrode having a four-layer structure. In this case, of the two high refractive index layers constituting each transparent electrode, each high refractive index layer provided adjacent to the electrode layers 5-1 and 5-2 is shown as the above high refractive index material. Of the materials, it is configured using a material having good insulation, or if it is configured of a conductive material, it is patterned in the same manner as the adjacent electrode layers 5-1, 5-2. And

  Furthermore, the touch panel according to the present embodiment applies the above-described modification 3 of the touch panel, and has two high refractions at a position where the configuration from the first electrode layer 5-1 to the second electrode layer 5-2 is sandwiched. It can also be set as the structure which provided the rate layer.

≪7. Seventh Embodiment: Touch Panel >>
(Configuration in which connection electrodes are provided together with two patterns of transparent electrodes on a transparent substrate)
FIG. 18 is a schematic diagram showing a planar arrangement of electrode portions of the touch panel according to the seventh embodiment of the present invention. FIG. 19 is an enlarged view of the electrode portion of the touch panel. FIG. 20 is a schematic cross-sectional view illustrating a configuration of the touch panel according to the seventh embodiment, and corresponds to a cross section taken along line BB in FIGS. 18 and 19. In the following description, the same components as those of the touch panel shown in FIG. 13 are denoted by the same reference numerals, and redundant description is omitted.

  The touch panel 24 shown in these drawings includes a transparent electrode 1 having a two-layer structure having an electrode layer 5 having x electrode patterns 5x1, 5x2,... And y electrode patterns 5y1, 5y2,. Further, an interlayer insulating film 73 and a connection electrode 75 are further provided on the upper portion. The upper portion where the transparent electrode 1, the interlayer insulating film 73, and the connection electrode 75 are provided is covered with the front plate 13 via the adhesive 15.

  That is, the touch panel 24 includes the transparent substrate 11, the transparent electrode 1 provided on one main surface of the transparent substrate 11, and the interlayer insulating film 73 and the connection electrode 75 provided on the upper portion. The transparent electrode 1 is a transparent electrode for a touch panel having a two-layer structure described with reference to FIG. 1, and has a configuration in which a nitrogen-containing layer 3 and an electrode layer 5 are laminated in this order on a transparent substrate 11. Among these, the electrode layer 5 is characterized by having x electrode patterns 5x1, 5x2,... And y electrode patterns 5y1, 5y2,.

<Transparent substrate 11 and nitrogen-containing layer 3>
The transparent substrate 11 and the nitrogen-containing layer 3 are the same as those described in the previous transparent electrode for touch panel. The nitrogen-containing layer 3 is provided as an example so as to cover the entire surface of one main surface of the transparent substrate 11, but is patterned in the same shape as the electrode layer 5 as in the previous embodiment. May be.

<Electrode layer 5>
The electrode layer 5 is the same as that described for the transparent electrode for a touch panel, and a plurality of x electrode patterns 5x1, 5x2,... Patterned on the nitrogen-containing layer 3 and a plurality of y electrode patterns 5y1, 5y2,...

  Each of the x electrode patterns 5x1, 5x2,... Is arranged in parallel with an interval between each other in a state of extending in the x direction. Each of these x electrode patterns 5x1, 5x2,... Has, for example, a shape in which rhombus pattern portions arranged in the x direction are linearly connected in the x direction in the vicinity of the apex of the rhombus. These x electrode patterns 5x1, 5x2,... Are all provided adjacent to the nitrogen-containing layer 3.

  Each of the y electrode patterns 5y1, 5y2,... Is arranged in parallel with a distance from each other in a state of extending in the y direction orthogonal to the x electrode patterns 5x1, 5x2,. Here, each y electrode pattern 5y1, 5y2,... Provided adjacent to the nitrogen-containing layer 3 is composed of a plurality of patterns A arranged in the y direction. All of these patterns A are provided adjacent to the nitrogen-containing layer 3.

  The pattern A is, for example, a rhombus, and is arranged with an interval enough to maintain an insulating state without overlapping with the x electrode patterns 5x1, 5x2,. Thus, the x electrode patterns 5x1, 5x2,... And the pattern A constituting the y electrode patterns 5y1, 5y2,. Further, the pattern A has a shape that occupies as large a range as possible within a range having an interval sufficient to maintain an insulating state with the x electrode patterns 5x1, 5x2,. Thereby, in the area | region of the center part of the transparent substrate 11, the pattern A which comprises x electrode pattern 5x1, 5x2, ... and y electrode pattern 5y1, 5y2, ... becomes a structure difficult to visually recognize.

  .. And x electrode patterns 5x1, 5x2,... And y electrode patterns 5y1, 5y2,... Are connected to x wirings 77x or y wirings 77y at their respective ends as in the previous embodiment.

<Interlayer insulating film 73>
The interlayer insulating film 73 is formed in a pattern so as to cover at least the upper portion of each of the x electrode patterns 5x1, 5x2,. As long as the pattern A of the y electrode patterns 5y1, 5y2,... Is exposed, the interlayer insulating film 73 may be provided so as to cover the diamond-shaped portions of the x electrode patterns 5x1, 5x2,.

<Connection electrode 75>
The connection electrode 75 is formed in a pattern on the upper part of the interlayer insulating film 73. The connection electrode 75 is provided in a state in which a plurality of patterns A arranged in the y direction are connected in the vicinity of the apex of the rhombus. And the connection electrodes 75 linking these in the y direction form y electrode patterns 5y1, 5y2,.

  The connection electrode 75 is disposed at each position where the connection electrode 75 intersects a portion connecting the rhombus patterns of the x electrode patterns 5x1, 5x2,. In these intersecting portions, the interlayer insulating film 73 covers the portion connecting the rhombic patterns of the x electrode patterns 5x1, 5x2,..., And the connection electrode 75 is disposed on the x electrode patterns 5x1, 5x2,. It is laminated through. Therefore, the insulation between the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,.

  The connection electrode 75 may be a general electrode material such as silver, or an electrode material having optical transparency such as ITO. From the viewpoint of the visibility of the underlying display image via the touch panel 24, Preferably, an electrode material having optical transparency is used.

  Although the example in which the connection electrode 75 is provided in the upper layer of the transparent electrode 1 has been described here, the connection electrode 75 may be provided in the lower layer of the transparent electrode 1. In this case, as in the previous example, the connection electrode 75 is disposed at each position where the connection electrode 75 intersects the portion connecting the rhombic patterns of the x electrode patterns 5x1, 5x2,. And the connection electrode 75 and the pattern A which comprises each y electrode pattern 5y1, 5y2, ... are connected through the connection hole provided in the nitrogen containing layer 3. FIG. Further, at least the nitrogen-containing layer 3 is sandwiched between the connection electrode 75 and the portion connecting the rhombic patterns of the x electrode patterns 5x1, 5x2,. Therefore, also in the example in which the connection electrode 75 is provided in the lower layer of the transparent electrode 1, insulation between the x electrode patterns 5x1, 5x2,... And the y electrode patterns 5y1, 5y2,. It is in the state.

<Effect of touch panel>
Even with the touch panel 24 having such a configuration, the transparent electrode for a touch panel, which is a thin film as described above, has sufficient light conductivity and sufficient conductivity, and suppresses light scattering. Similarly to the touch panel described with reference to FIG. 13, it is possible to improve the visibility of a display image serving as a base and increase the size of the panel.

  The touch panel 24 having the above-described configuration can be combined with each of the first to third modifications of the touch panel described above, and the respective effects can be obtained by combining the touch panels.

  For example, when the touch panel of this embodiment is combined with Modification 1 of the touch panel shown in FIG. 14, the transparent electrode 1 having the two-layer structure in the touch panel 24 shown in FIG. 20 is replaced with the transparent having the three-layer structure shown in FIG. Replace with electrode. In this case, a high refractive index layer is provided between the transparent substrate 11 and the nitrogen-containing layer 3.

  Further, when the touch panel of the present embodiment is combined with the touch panel modification 2 shown in FIG. 15, the two-layer transparent electrode 1 in the touch panel 24 shown in FIG. 20 is replaced with the four-layer transparent electrode shown in FIG. Replace with In this case, of the two high refractive index layers constituting the transparent electrode, the high refractive index layer provided adjacent to the electrode layer 5 has good insulating properties among the materials shown as the above high refractive index materials. It is preferable to use a simple material. In this case, the high refractive index layer may cover the interlayer insulating film 73 and the connection electrode 75 together with the electrode layer 5, and may also serve as the adhesive 15. Furthermore, if this high refractive index layer is made of a conductive material, it is assumed that it is patterned in the same manner as the adjacent electrode layer 5.

≪8. Eighth Embodiment: Display Device >>
(Configuration using touch panel)
FIG. 21 is a perspective view showing a configuration of a display device according to the eighth embodiment of the present invention. The display device 31 shown in this figure is a display device with an information input function in which a touch panel is provided on the display surface of the display panel 33, and uses one of the touch panels of the present invention described above as the touch panel. is there. Here, for example, the touch panel shown in FIG. 13, that is, the touch panel 21 is used.

  The display panel 33 is not particularly limited. For example, the display panel 33 may be a flat display panel such as a liquid crystal display panel or a display panel using an organic electroluminescent element, or a CRT (Cathode Ray Tube) display. good. The display panel 33 is not limited to a display panel that displays moving images, and may be a display panel for still images.

  The touch panel 21 is arranged on the image display surface of the display panel 33 so as to cover the display surface. Further, the touch panel 21 and the display panel 33 may be further accommodated in a frame-shaped case member 35 as necessary, and a front plate made of a transparent plate material may be further provided on the case member 35.

  Thereby, the user can input the position information of the contact portion to the touch panel 21 by bringing a finger or a touch pen into contact with a part of the display image displayed on the display panel 33 via the touch panel 21. .

<Effect of display device>
By using the touch panel 21 described above, the display device 31 having such a configuration is excellent in display characteristics and can be reduced in thickness and size.

≪9. Ninth Embodiment: Manufacturing Apparatus >>
(Apparatus for producing transparent electrodes for touch panels)
FIG. 22 is a schematic diagram showing the configuration of the manufacturing apparatus according to the ninth embodiment of the present invention. The manufacturing apparatus 40 shown in this figure is a configuration example of a manufacturing apparatus suitably used for manufacturing the transparent electrode for a touch panel (transparent electrode) described above. Here, as an example, the configuration of the manufacturing apparatus 40 will be described as being used for manufacturing the transparent electrode having the two-layer structure described with reference to FIG.

  A manufacturing apparatus 40 shown in FIG. 22 is a film forming apparatus used when producing a transparent electrode on one main surface of the transparent substrate 11, and includes a film forming chamber 41, a holding member 43 for the transparent substrate 11, and a first supply source 45a. And a second supply source 45b. Of these, the arrangement of the first supply source 45a and the second supply source 45b is particularly characteristic. Hereinafter, details of these components and details of materials used in the manufacturing apparatus will be described.

<Deposition chamber 41>
The film forming chamber 41 can be in a reduced pressure state, and is configured as a so-called vacuum chamber (vacuum chamber).

<Holding member 43>
The holding member 43 is for holding the transparent substrate 11 on which the transparent electrode is manufactured in a constant state in the film forming chamber 41. The holding member 43 is also configured as a transfer means for moving the held transparent substrate 11 in one direction. The direction in which the transparent substrate 11 is moved (moving direction x) is any one of the extending directions of one main surface a where the transparent electrode is formed in the transparent substrate 11.

  For example, as shown in the figure, when the transparent substrate 11 is a long one that flexibly bends and is wound and unwound between two rolls, the transparent member 11 is wound as the holding member 43. Two rolls are used that take up or unwind. When the transparent substrate 11 is rigid and does not bend, the holding member 43 can be transferred in the movement direction x while supporting the transparent substrate 11 in a predetermined state in the film forming chamber 41. Suppose that

  The transfer of the transparent substrate 11 in the moving direction x by the holding member 43 is performed at a speed v. The speed v is a speed at which the electrode layer 5 is formed with a film thickness of 12 nm or less on the one main surface a side of the transparent substrate 11 by supplying an electrode material 47b from a second supply source 45b described later. . Such a speed v is set by, for example, the supply amount of the electrode material 47b from the second supply source 45b and the size of the supply region Sb of the electrode material 47b with respect to the one main surface a. The speed v is also a relative moving speed between the transparent substrate 11 and a first supply source 45a and a second supply source 45b described later.

  In the case where the transparent electrode 1 patterned on the transparent substrate 11 is produced using the manufacturing apparatus 40, a mask is disposed opposite to the main surface a of the transparent substrate 11 transferred by the holding member 43. The mask is also transferred in the same direction as the transparent substrate 11.

<First supply source 45a>
The first supply source 45 a is arranged on the one main surface a side of the transparent substrate 11 transferred by the holding member 43, and supplies the compound 47 a in a gaseous state toward the one main surface a of the transparent substrate 11. The first supply source 45a is fixed in the film forming chamber 41 and is provided across the width direction of the transparent substrate 11 perpendicular to the moving direction x. The compound 47a supplied from the first supply source 45a is a compound constituting the nitrogen-containing layer described in the first embodiment.

Such a first supply source 45a may be, for example, a so-called heating boat for vapor deposition film formation, and the compound 47a housed in the boat is gasified by heating to form one main surface a of the transparent substrate 11. It is the structure which spouts toward. Such a first supply source 45 a is configured to form a nitrogen-containing layer on one main surface “a” of the transparent substrate 11 transferred by the holding member 43.
Here, a region where the compound 47a gasified by the first supply source 45a is supplied to the transparent substrate 11, that is, a region where the compound 47a adheres on one main surface a of the transparent substrate 11 is defined as a supply region Sa. The time when the predetermined position of the moving transparent substrate 11 reaches the supply region Sa is defined as the start of film formation of the nitrogen-containing layer 3, and the time when it is removed from the supply region Sa is defined as the end of film formation of the nitrogen-containing layer 3.

  In addition, when there are a plurality of compounds constituting the nitrogen-containing layer, a plurality of first supply sources 45a for supplying the respective compounds are prepared, and these first supply sources 45a are arranged in a direction perpendicular to the moving direction x. The plurality of types of compounds 47a that are gasified from each first supply source 45a and ejected from each first supply source 45a are supplied to the same supply region Sa on the one main surface a of the transparent substrate 11. 1 supply source 45a is arranged.

<Second supply source 45b>
The second supply source 45b is disposed on the one main surface a side of the transparent substrate 11 transferred by the holding member 43, and the electrode material 47b mainly composed of silver is gaseous toward the one main surface a of the transparent substrate 11. Is supplied by The second supply source 45b is fixed in the film forming chamber 41 and is provided across the width direction of the transparent substrate 11 perpendicular to the moving direction x. The electrode material 47b supplied from the second supply source 45b is a material constituting the electrode layer described in the first embodiment, and is mainly silver (Ag).

  Such a second supply source 45b may be, for example, a so-called heating boat for vapor deposition film formation. The electrode material 47b accommodated in the boat is gasified by heating, and the one main surface a of the transparent substrate 11 is a. It is the structure which spouts toward. Such a second supply source 45 b is configured to form an electrode layer containing silver as a main component on one main surface a of the transparent substrate 11 transferred by the holding member 43. Here, a region where the electrode material 47b gasified by the second supply source 45b is supplied to the transparent substrate 11, that is, a region where the electrode material 47b adheres on one main surface a of the transparent substrate 11 is defined as a supply region Sb. The time when the predetermined position of the moving transparent substrate 11 reaches the supply region Sb is set as the start of film formation of the nitrogen-containing layer 3.

  The second supply source 45b described above is disposed downstream of the first supply source 45a in the moving direction x of the transparent substrate 11. It is characteristic that the second supply source 45b is arranged at a predetermined distance d between the second supply source 45b and the first supply source 45a. This interval d is between a predetermined position of the moving transparent substrate 11 after the start of film formation of the nitrogen-containing layer by the first supply source 45a and until 2 minutes after the film formation is completed, preferably within 1 minute. The second supply source 45b is set to a size at which film formation of the electrode layer is started. Here, it is assumed that the interval d is set so that the film formation of the electrode layer is started up to 2 minutes (preferably up to 1 minute) after the film formation of the nitrogen-containing layer.

  Such an interval d is expressed as follows. That is, the speed v of the movement of the transparent substrate 11 in the movement direction x, the supply region Sa of the compound 47a from the first supply source 45a to one main surface a of the transparent substrate 11, and the one of the transparent substrate 11 from the second supply source 45b. A supply region Sb of the electrode material 47b to the main surface a and a distance d1 in the moving direction x are set. In this case, the distance d in the moving direction x between the first supply source 45a and the second supply source 45b is set within a range of d1 ≦ v × 2 minutes (preferably d1 ≦ v × 1 minutes).

  In addition, when the electrode material which comprises an electrode layer is a plurality containing materials other than silver (Ag), the several 2nd supply source 45b which supplies each electrode material is prepared, These 2nd supply sources 45b are arranged in a direction perpendicular to the moving direction x, and a plurality of types of electrode materials 47b which are gasified and ejected from each second supply source 45b are the same supply region on one main surface a of the transparent substrate 11. Each 2nd supply source 45b is arrange | positioned so that it may be supplied to Sb.

  By using the manufacturing apparatus 40 as described above, a nitrogen-containing layer is formed on the one main surface a side of the transparent substrate 11, and the nitrogen-containing layer is adjacent to the nitrogen-containing layer, after the start of film formation of the nitrogen-containing layer Within 2 minutes after the film formation is completed, an electrode layer mainly composed of silver can be formed with a film thickness of 12 nm or less.

≪9-1. Modification 1 of manufacturing apparatus >>
FIG. 23 is a schematic diagram for explaining a first modification of the manufacturing apparatus of the present invention described above. As shown in FIG. 23, the manufacturing apparatus 40a has a configuration in which a partition wall 49 is provided in the film forming chamber 41, and the other configuration is the same as the configuration of the manufacturing apparatus shown in FIG.

  The partition wall 49 includes a supply region Sa of the compound 47a from the first supply source 45a and a supply region Sb of the electrode material 47b from the second supply source 45b between the first supply source 45a and the second supply source 45b. Is provided at a position for separating. The partition wall 49 is provided in a state that does not hinder the transfer of the transparent substrate 11 by the holding member 43.

  In the manufacturing apparatus 40a of Modification 1 as described above, by providing the partition wall 49, the compound 47a from the first supply source 45a and the electrode material 47b from the second supply source 45b are applied to each part of the inner wall of the film forming chamber 41. Adhesion to each other is prevented, and cross-contamination in the film formation chamber 41 can be prevented. As a result, by forming a nitrogen-containing layer and an electrode layer with good film quality, it becomes possible to produce a transparent electrode with ensured performance.

≪9-2. Modification 2 of manufacturing apparatus >>
FIG. 24 is a schematic diagram for explaining a second modification of the manufacturing apparatus of the present invention described above. As shown in FIG. 24, in the manufacturing apparatus 40b, the first supply source 45a and the second supply source 45b are arranged so that the supply region Sa of the compound 47a and the supply region Sb of the electrode material 47b partially overlap each other. It is a configuration. Other configurations are the same as those of the manufacturing apparatus shown in FIG.

  In this case, as in the manufacturing apparatus shown in FIG. 22, the distance d between the first supply source 45a and the second supply source 45b is such that the nitrogen content by the first supply source 45a is relative to a predetermined position of the moving transparent substrate 11. It is set so that the film formation of the electrode layer 5 by the second supply source 45b is started after the film formation of the layer 3 is started until the film formation is completed. Note that, when the electrode layer 5 is started to be formed in the modified example 2, the electrode material 47b is a main part of the transparent substrate 11 in a region where the supply region Sa and the supply region Sb overlap at a predetermined position of the moving transparent substrate 11. Suppose that it adheres on the surface a.

  However, the distance d1 between the supply area Sa and the supply area Sb in the moving direction x of the transparent substrate 11 is in a range where | d1 | ≦ v × 2 minutes (preferably d1 ≦ v × 1 minutes), and d1 <0. To be. However, the absolute value of the interval d1 is | d1 | <Sb in the movement direction x without exceeding the supply region Sb of the electrode material 47b. In this case (d1 <0), | d1 | <Sa is also true in the movement direction x. Thereby, after the film formation of the nitrogen-containing layer by the supply of the compound 47a is started, the film formation of the electrode layer by the supply of the electrode material 47b is started.

  Here, the supply region Sa of the compound 47a and the supply region Sb of the electrode material 47b partially overlap each other, thereby forming a nitrogen-containing layer formed by the supply of the compound 47a and the supply of the electrode material 47b. A mixed region of the compound 47a and the electrode material 47b is formed between the electrode layers to be formed. The electrode layer is a layer composed of a mixed region and a region of only the electrode material 47b, and is a layer capable of measuring sheet resistance. For this reason, the size of the distance d1 with respect to the supply region Sb of the electrode material 47b is such that the film resistance of the electrode layer formed only by the electrode material 47b is less than 12 nm so that the sheet resistance can be measured. It shall be set so that it may become (for example, 2 nm) or more.

  In the manufacturing apparatus 40b of Modification 2 as described above, the compound 47a and the electrode material 47b are mixed between the nitrogen-containing layer composed of the compound 47a and the electrode layer composed of the electrode material 47b as described above. It becomes possible to form the co-deposited layer. This makes it possible to produce a transparent electrode with good adhesion between the nitrogen-containing layer and the electrode layer, in addition to the same effects as those of the ninth embodiment.

≪9-3. Modification 3 of manufacturing apparatus >>
FIG. 25 is a schematic diagram for explaining a third modification of the manufacturing apparatus of the present invention described above. As shown in FIG. 25, in the manufacturing apparatus 40c, the holding member 51 of the transparent substrate 11 is configured as a cylindrical rotating drum, and the first supply source 45a and the second supply source 45b are arranged along the outer periphery. It is in. Other configurations are the same as those of the manufacturing apparatus shown in FIG.

  That is, the holding member 51 is a cylindrical rotary drum, and holds the transparent substrate 11 in a state of being wound around a part of the side periphery. Since the transparent substrate 11 wound around the holding member 51 moves along the cylindrical side periphery as the holding member 51 rotates, the circumferential direction becomes the moving direction x. Such a holding member 51 is disposed, for example, between two rolls for unwinding and winding the long transparent substrate 11 that is flexibly bent. The winding of the transparent substrate 11 by the roll serves as a driving source, and the transparent substrate 11 unwound from one roll moves along the side periphery of the holding member 51 and is wound around the other roll. ing.

  The transfer of the transparent substrate 11 in the moving direction x is performed at the speed v as in the other embodiments. The speed v is also a relative moving speed between the transparent substrate 11 and the first supply source 45a and the second supply source 45b.

  The first supply source 45 a and the second supply source 45 b are disposed along the circumference concentric with the holding member 51 in the outer peripheral portion along the side circumference of the holding member 51. The first supply source 45 a and the second supply source 45 b are arranged along the moving direction x of the transparent substrate 11 held by the holding member 51.

  The arrangement state of the first supply source 45a and the second supply source 45b with respect to the moving direction x of the transparent substrate 11 is the same as in the other embodiments. That is, the distance d between the first supply source 45a and the second supply source 45b is set to a predetermined position on the moving transparent substrate 11 after the start of film formation of the nitrogen-containing layer by supplying the compound 47a from the first supply source 45a. Is set to start film formation of the electrode layer by supplying the electrode material 47b from the second supply source 45b within a period of 2 minutes after the film formation is completed, preferably 1 minute. The distance d1 between the supply region Sa of the compound 47a and the supply region Sb of the electrode material 47b is d1 ≦ v × 2 minutes (preferably d1 ≦ v × 1 minutes).

  Although illustration is omitted here, it is assumed that the holding member 51, the first supply source 45a, and the second supply source 45b are arranged in a film forming chamber configured as a vacuum chamber.

  Even in the manufacturing apparatus 40c of Modification 3 like this, adjacent to the nitrogen-containing layer composed of the compound 47a, between the start of film formation of this nitrogen-containing layer and 2 minutes after the end of film formation, An electrode layer composed of an electrode material 47b mainly composed of silver can be formed with a film thickness of 12 nm or less.

  In addition, the manufacturing apparatus 40c of this modification 3 can be set as the structure combined with the modification 1 or the modification 2 shown in FIG. Thereby, it is possible to obtain the effects obtained in the respective modifications together.

  In the manufacturing apparatus according to the ninth embodiment and the first to third modifications described above, the transparent substrate 11 and each supply source are relatively moved by transferring the transparent substrate 11 in the predetermined movement direction x by the holding member. The configuration to be moved to has been described. However, the relative movement between the transparent substrate 11 and each supply source may be a configuration in which each supply source is moved with respect to the fixed transparent substrate 11. Even in such a configuration, the arrangement state of each supply source with respect to the transparent substrate 11 that moves relative to each supply source is the same as in each of the above-described embodiments and modifications. A transparent electrode can be formed similarly to the manufacturing apparatus of 9th Embodiment and the modifications 1-3.

  Moreover, although the manufacturing apparatus of each structure demonstrated above is an example of the manufacturing apparatus used in order to manufacture the transparent electrode (2 layer structure) of 1st Embodiment demonstrated using FIG. 1, in other embodiment, it is. It can also be applied to the production of the transparent electrode described. For example, if the manufacturing apparatus of each configuration is applied to manufacture of the transparent electrode (three-layer structure) of the second embodiment described with reference to FIG. 8, the transparent substrate 11 is moved with respect to the first supply source 45a. What is necessary is just to add the supply source of the material for forming a high refractive index layer on the opposite side to the direction (movement direction x) to make. If the manufacturing apparatus of each configuration is applied to the manufacture of the transparent electrode (four-layer structure) of the third embodiment described with reference to FIG. 9, the first supply source 45a and the second supply source 45b are provided. What is necessary is just to add the supply source of the material for forming a high refractive index layer in two positions to pinch | interpose.

  Even in the case of manufacturing the transparent electrode shown in FIGS. 1, 8, and 10, the manufacturing apparatus according to the ninth embodiment and the first to third modifications is applied to the arrangement relationship between the supply sources. can do.

≪Preparation of transparent electrode for touch panel≫
Here, the transparent electrodes for touch panels (hereinafter referred to as transparent electrodes) of Samples 1 to 20 were produced on a transparent substrate so that the area of the conductive region was 5 cm × 5 cm. As the transparent substrate, a polyethylene terephthalate (PET) substrate was prepared. Table 2 below shows the configuration of each layer in each transparent electrode of Samples 1-20. Below, the preparation procedure of each transparent electrode of samples 1-20 is demonstrated.

<Preparation of transparent electrode of sample 1>
An ITO film (film thickness 100 nm) was formed on one main surface of the transparent substrate by sputtering. Thereby, a transparent electrode having a single layer structure using an ITO film as an electrode layer was produced.

<Preparation of transparent electrodes of samples 2 to 4>
In each of Samples 2 to 4, an electrode layer using silver nanowires was formed on one main surface of the transparent substrate by a coating method. Thus, a transparent electrode having a single-layer structure using only silver nanowires and having only an electrode layer was produced. At this time, the silver nanowire dispersion liquid is applied so that the film thickness after applying the silver nanowire dispersion liquid on the transparent substrate and then drying is 50 nm for sample 2, 100 nm for sample 3, and 150 nm for sample 4. The coating film thickness of was adjusted.

<Preparation of transparent electrodes of samples 5 to 19>
In each of Samples 5 to 19, on one main surface of the transparent substrate, as shown in Table 2 below, a layered structure of a nitrogen-containing layer composed of each compound and an electrode layer using silver on the top is provided. A transparent electrode was produced.

  In the production of the transparent electrodes of Samples 5 to 7, the following compound 10 containing nitrogen, which was shown as the compound III above, was used as the compound constituting the nitrogen-containing layer. This compound 10 is a compound included in the general formula (2).

  In the production of the transparent electrodes of Samples 8 to 10, the following compound 94 containing nitrogen, which was shown as the compound III above, was used as the compound constituting the nitrogen-containing layer. This compound 94 is a compound included in the general formula (1a).

  In the production of the transparent electrodes of Samples 11 to 13, the following compound 99 containing nitrogen, which was shown as the compound III above, was used as the compound constituting the nitrogen-containing layer.

  In the production of the transparent electrodes of Samples 14 to 16, the following compound No. 48 containing nitrogen, which was shown as the above compound I, was used as the compound constituting the nitrogen-containing layer. This compound No. 48 is a compound contained in the general formulas (1a-1), (7), and (8a).

  In the production of the transparent electrodes of Samples 17 to 19, the following compound No. 46 containing nitrogen, which was shown as the above compound I, was used as the compound constituting the nitrogen-containing layer. This compound No. 46 is a compound contained in the general formula (1a-1).

  The procedure for producing the transparent electrodes of Samples 5 to 19 is as follows. First, the transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, in preparation of each transparent electrode, each said compound was put into the resistance heating boat made from a tantalum, respectively. These substrate holders and a heating boat were mounted in the first vacuum chamber of the vacuum deposition apparatus. Furthermore, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

In this state, first, the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then heated by energizing a heating boat containing each compound, and deposited on a transparent substrate at a film formation rate of 0.3 nm / second. A nitrogen-containing layer composed of each compound having a film thickness of 25 nm was provided.

Thereafter, an electrode layer was formed on the nitrogen-containing layer. At this time, an interval from the time when the film formation of the previous nitrogen-containing layer is completed to the time when the electrode layer is formed is defined as a film formation interval.
Then, the transparent substrate on which the nitrogen-containing layer is formed is transferred from the first vacuum chamber to the second so that the film formation interval becomes each film formation interval (1 minute, 2 minutes, or 10 minutes) shown in Table 2 below. It moved to the vacuum chamber and formed the electrode layer into a film. This second vacuum tank was prepared in a state where the pressure in the tank was reduced to 4 × 10 ⁻⁴ Pa in advance and the heating boat containing silver was further heated before the transparent substrate was transferred. In the second vacuum chamber, an electrode layer made of silver with each film thickness (8 nm or 12 nm) was formed at a film formation rate of 0.02 nm / second as shown in Table 2 below.

  Thus, transparent electrodes of Samples 5 to 19 each having a laminated structure of the nitrogen-containing layer and the upper electrode layer were obtained.

<Preparation of Transparent Electrode of Sample 20>
In the production of the transparent electrode of Sample 20, a transparent electrode having a four-layer structure having two high refractive index layers was produced on one main surface of the transparent substrate as shown in Table 2 below.

A high refractive index layer made of niobium oxide (Nb ₂ O ₅ ) is formed with a film thickness of 0.1 nm on one main surface of the transparent substrate, and a nitrogen-containing layer using the compound 94 is formed with a film thickness of 25 nm by vapor deposition. Formed. Subsequently, an electrode layer made of silver (Ag) was formed to a thickness of 12 nm by a vapor deposition method, and a high refractive index layer made of niobium oxide (Nb ₂ O ₅ ) was formed to a thickness of 30 nm. Thus, a transparent electrode having a four-layer structure including a high refractive index layer, a nitrogen-containing layer, an electrode layer, and a high refractive index layer was produced.

At this time, the transparent substrate is fixed to a substrate holder of a commercially available electron beam evaporation apparatus, niobium oxide (Nb ₂ O ₅ ) is placed in a copper heating boat, and these substrate holder and the heating boat are connected to a vacuum of the electron beam evaporation apparatus. It attached to the vacuum chamber of the vapor deposition apparatus. Moreover, the compound 94 was put into the resistance heating boat made from tantalum, and was attached in the 1st vacuum chamber of a vacuum evaporation system. Furthermore, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after reducing the vacuum chamber of the electron beam evaporation apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing niobium oxide (Nb ₂ O ₅ ) is irradiated with an electron beam and heated, and the deposition rate is 0.1 nm / A high refractive index layer made of niobium oxide (Nb ₂ O ₅ ) having a thickness of 30 nm was provided on the transparent substrate in seconds.

Next, the transparent substrate formed up to the high refractive index layer is transferred to the first vacuum chamber of the vacuum deposition apparatus while being vacuumed, and the first vacuum chamber is depressurized to 4 × 10 ⁻⁴ Pa, and then placed on a heating boat containing the compound. Heated with electricity. Thus, a nitrogen-containing layer composed of the compound 94 having a film thickness of 25 nm at a deposition rate of 0.3 nm / second was provided on the high refractive index layer.

Next, the transparent substrate 11 formed up to the nitrogen-containing layer was transferred to the second vacuum chamber while maintaining a vacuum, and an electrode layer made of silver was formed at a deposition interval of 1 minute. At this time, this second vacuum tank is prepared in a state where the pressure in the tank is reduced to 4 × 10 ⁻⁴ Pa in advance and the heating boat containing silver is further heated before transferring the transparent substrate. It was. Then, an electrode layer made of silver having a film thickness of 12 nm was formed at a film formation rate of 0.02 nm / second.

After that, again, the transparent substrate formed up to the electrode layer was transferred to the vacuum chamber of the electron beam evaporation apparatus while being vacuumed, the inside of the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then niobium oxide (Nb ₂ O ₅ ) was contained. The heated boat was heated by irradiation with an electron beam, and a high refractive index layer made of niobium oxide (Nb ₂ O ₅ ) having a thickness of 30 nm was provided on the transparent substrate at a deposition rate of 0.1 nm / second. Thereby, the transparent electrode of the sample 20 which laminated | stacked the high refractive index layer, the nitrogen containing layer, the electrode layer using silver, and the high refractive index layer in this order was produced.

<Evaluation of each sample of Example 1>
About each transparent electrode of the samples 1-20 produced above, sheet resistance (surface resistance) and the visibility of a character were evaluated. The sheet resistance was measured using a resistivity meter (MCP-T610 manufactured by Mitsubishi Chemical Corporation) by a four-terminal four-probe method constant current application method. Visibility of characters was evaluated by evaluating the visibility of the characters through five levels by superimposing a transparent substrate on which a transparent electrode was formed on the image representing the characters. The five-level evaluation was performed from two angles of 0 ° and 45 °, with the normal direction to the electrode surface of the transparent electrode being 0 °, and this was averaged. These evaluation results are shown in Table 2 below.

<Evaluation result of Example 1>
In Table 2, Samples 5 to 7, Samples 8 to 10, Samples 11 to 13, Samples 14 to 16, and Samples 17 to 19 having different materials constituting the nitrogen-containing layer were respectively compared. As a result, if the materials constituting the nitrogen-containing layer are the same, the transparent electrode having a shorter film formation interval between the nitrogen-containing layer and the electrode layer has a lower sheet resistance and higher character visibility. In particular, the transparent electrodes of Samples 5, 6, 8, 9, 11, 12, 14, 15, 17, and 18 having a film formation interval of 2 minutes or less, that is, up to 2 minutes after the film formation of the nitrogen-containing layer is completed. In the transparent electrode having the electrode layer that started film formation, the sheet resistance was 10 Ω / sq. The visibility of the characters is secured to 4.0 or more, and it was confirmed that the characters were suitably used as a transparent electrode for a touch panel.

  26 to 28 show SEM images (magnification: 100,000 times) of the transparent electrodes of Samples 5 to 7, respectively. When these were compared, it was clear that the film formation state of silver constituting the electrode layer was different depending on the film formation interval as described below. That is, in the transparent electrode of Sample 5 (film formation interval 1 minute) shown in FIG. 26, the continuity of silver constituting the electrode layer was high, and almost no portion not covered with silver was seen. Moreover, although the transparent electrode of Sample 6 (film formation interval 2 minutes) shown in FIG. 27 is inferior to Sample 5 (film formation interval 1 minute), the continuity of the electrode layer was ensured. On the other hand, in the transparent electrode of Sample 7 (deposition interval 10) shown in FIG. 28, the continuity of the electrode layer was low, and the portion not covered with the electrode layer (black display portion in the figure) was conspicuously confirmed.

  29 to 31 show SEM images (magnification: 100,000 times) of the transparent electrodes of Samples 8 to 10. When these were compared, the film formation state of silver constituting the electrode layer was different depending on the film formation interval in the same tendency as in FIGS.

  Similarly, FIGS. 32 to 34 show SEM images (magnification: 100,000 times) of the transparent electrodes of Samples 11 to 13, respectively. Even when these were compared, the film formation state of the silver constituting the electrode layer was different depending on the film formation interval in the same tendency as in FIGS.

  Thus, in the transparent electrode of the present invention having an electrode layer in which the film formation interval between the nitrogen-containing layer and the electrode layer is started within 2 minutes, that is, up to 2 minutes after the film formation of the nitrogen-containing layer is completed. Confirmed that the electrode layer adjacent to the nitrogen-containing layer was formed by film growth closer to the single-layer growth type (Frank-van der Merwe: FM type) than the nuclear growth type (Volume-Weber: VW type) It was done.

  Moreover, if the material which comprises the nitrogen containing layer provided adjacent to the electrode layer is the same, the silver (white display part in a figure) which comprises an electrode layer is so short that the film-forming interval of a nitrogen containing layer is short. It was confirmed that it was more connected and its continuity was high.

  Further, as shown in Table 2 above, the transparent electrode of the sample 20, that is, the transparent electrode using the high refractive index layer, has good character visibility, and light transmission through the transparent electrode provided with the high refractive index layer. The effect of improving the property and reducing the light scattering property was confirmed.

  In contrast, the transparent electrode having a single layer structure using ITO of Sample 1 was only 100 nm thick, but only a higher sheet resistance than that of Samples 5 to 20 was obtained. Moreover, in the transparent electrode of the single layer structure using the silver nanowires of samples 2 to 4, the value of the sheet resistance with respect to the film thickness is higher than that of the transparent electrodes of samples 5 to 20, and in sample 4 having the lowest sheet resistance, Character visibility was very low at 1.5 due to light scattering.

In FIG. 35, compounds No. 1 to No in which the effective unshared electron pair content [n / M] is 2.0 × 10 ⁻³ ≦ [n / M] ≦ 1.9 × 10 ⁻² .20 for a transparent electrode in which an electrode layer having a film thickness of 6 nm is provided on the upper part of the nitrogen-containing layer, the effective unshared electron pair content [n / M] of the compound constituting the nitrogen-containing layer, and each transparent electrode The graph which plotted the value of the sheet resistance measured about was shown.

From the graph of FIG. 35, when the effective unshared electron pair content [n / M] is in the range of 2.0 × 10 ⁻³ ≦ [n / M] ≦ 1.9 × 10 ⁻² , the effective unshared electron pair content is included. As the value of the rate [n / M] is larger, the sheet resistance of the transparent electrode tends to be lower. If the effective unshared electron pair content [n / M] = 3.9 × 10 ⁻³ is a boundary and the range is 3.9 × 10 ⁻³ ≦ [n / M], the sheet resistance is dramatically increased. It was confirmed that the effect of lowering was obtained.

  The above results were the same even when the nitrogen-containing layer was formed by coating.

  From the above, a thin film is obtained in order to obtain light transmissivity by selecting and using a compound constituting the nitrogen-containing layer provided adjacent to the electrode layer using the effective unshared electron pair content [n / M] as an index. However, it was confirmed that an electrode layer having low resistance (that is, a transparent electrode) was obtained.

≪Production of touch panel≫
Each of the transparent electrodes (samples 5, 6, 8, 9, 11, 12, 14, 15, 17, 18, and 20) manufactured in Example 1 is overlapped with each other to provide a simple touch panel. Produced.

<Evaluation and Evaluation Result of Each Sample of Example 2>
About each produced touch panel, the visibility of the character was evaluated by the method similar to Example 1. FIG. As a result, it was confirmed that good character visibility was obtained to the same extent as the transparent electrodes of Samples 5, 6, 8, 9, 11, 12, 14, 15, 17, 18, and 20.

1, 1a, 1b ... Transparent electrode for touch panel (transparent electrode)
1-1, 1a-1, 1b-1 ... 1st transparent electrode 1-2, 1a-2, 1b-2 ... 2nd transparent electrode 3 ... Nitrogen-containing layer 3-1 ... 1st nitrogen-containing layer 3 -2 ... second nitrogen-containing layer 5 ... electrode layer 5-1 ... first electrode layer 5-2 ... second electrode layer 5x1, 5x2, 5x3, ... x electrode pattern (first electrode layer)
5y1, 5y2, 5y3,... Y electrode pattern (second electrode layer)
21, 22, 23, 24 ... touch panel 31 ... display device 33 ... display panel H ... high refractive index layer H-1 ... first high refractive index layer H-2 ... second high refractive index layer H-3 ... first 3 high refractive index layer

Claims (7)

A nitrogen-containing layer composed of a compound containing nitrogen atoms;
An electrode layer provided adjacent to the nitrogen-containing layer,
The electrode layer has a film thickness of 12 nm or less capable of measuring sheet resistance, and is composed of silver or an alloy containing silver as a main component, and after the film formation of the nitrogen-containing layer is started and after the film formation is completed A transparent electrode for a touch panel, which is a layer in which film formation has started within 2 minutes. The transparent electrode for a touch panel according to claim 1, wherein the electrode layer is a layer in which film formation is started from the start of film formation of the nitrogen-containing layer to 1 minute after the film formation is completed. The transparent electrode for touchscreens of Claim 1 or 2 provided with the high refractive index layer whose refractive index is higher than the said nitrogen containing layer in the position which pinches | interposes the said nitrogen containing layer between the said electrode layers. The transparent electrode for a touch panel according to claim 1, wherein the electrode layer and the nitrogen-containing layer are sandwiched by a high refractive index layer having a higher refractive index than the nitrogen-containing layer. A touch panel comprising the transparent electrode for a touch panel according to claim 1. A touch panel according to claim 5;
And a display panel disposed on the touch panel. Forming a nitrogen-containing layer using a compound containing a nitrogen atom;
Forming an electrode layer adjacent to the nitrogen-containing layer,
In the step of forming the electrode layer, the electrode layer starts to be formed between the start of film formation of the nitrogen-containing layer and 2 minutes after the end of film formation, and silver or an alloy containing silver as a main component The manufacturing method of the transparent electrode for touchscreens which forms an electrode layer with the film thickness of 12 nm or less which can measure sheet resistance using.