JP6340789B2 - Transparent electrode and electronic device - Google Patents

Description

  The present invention relates to a transparent electrode and an electronic device, and more particularly, to a transparent electrode having both conductivity, light transmittance, and durability over time, and an electronic device including the transparent electrode.

In an electronic device such as a touch panel, a liquid crystal display device, an organic electroluminescence element, and a solar cell, as an electrode on the light extraction side (transparent electrode), indium tin oxide (SnO ₂ -In ₂ O ₃ : Indium Tin Oxide, hereinafter “ An oxide semiconductor material such as “ITO” is generally used. However, studies on a material aiming at lowering resistance by laminating ITO and silver are disclosed in, for example, JP-A-2002-15623. No. 2006 and Japanese Patent Application Laid-Open No. 2006-164961. However, since ITO uses indium, which is a rare metal, the material cost is high, and in order to lower the resistance, it is necessary to anneal at about 300 ° C. after film formation. We had problems such as limitations.

  In recent years, based on the above problems, studies have been made on the application of silver as a constituent material for transparent electrodes. Silver is superior in conductivity to the ITO, but has a problem of trade-off between resistance characteristics and transmittance.

  In such a situation, a technique for forming a thin film using an alloy of silver (Ag) and magnesium (Mg) having high electrical conductivity, or using a metal material that is inexpensive and readily available as a raw material instead of indium, is used. The technique to comprise is proposed (for example, refer patent document 1 and 2).

  In the invention described in Patent Document 1, by using an alloy of silver and magnesium as an electrode material, it is possible to obtain desired conductivity under thin film conditions as compared with an electrode formed by silver alone. It is said that both can be achieved.

  However, the resistance value of the electrode obtained by the method described in Patent Document 1 is at most about 100Ω / □, which is insufficient as the conductivity of the transparent electrode, and in addition to the problem that the drive voltage cannot be lowered, Since magnesium is easily oxidized, it has a problem that its performance tends to deteriorate due to long-term storage.

In addition, the invention described in Patent Document 2 discloses a transparent conductive film using a metal material such as zinc (Zn) or tin (Sn) that is inexpensive and easily available as a raw material instead of indium (In). Has been. However, with these alternative metals, the resistance value does not decrease sufficiently, and in addition, the ZnO-based transparent conductive film containing zinc has a characteristic that its performance tends to fluctuate by reacting with water. It has also been found that SnO ₂ -based transparent conductive films containing tin have a problem that processing by etching is difficult.

  On the other hand, an organic electroluminescence device using a thin film having a layer thickness of about 15 nm and a highly light-transmitting silver film as a cathode is disclosed (for example, see Patent Document 3). However, in the method proposed in Patent Document 3, since the formed silver film is still thick as an electrode, the light transmittance (transparency) as a transparent electrode is not sufficient, and migration (movement of atoms) It is easy to cause. Further, if the silver film is made thinner, it becomes difficult to maintain conductivity and the like, and therefore, development of a technique that achieves both light transmittance and conductivity is eagerly desired.

  On the other hand, the present inventors, in a transparent electrode having a silver thin film and an intermediate layer below it, form a silver thin film by containing a diazacarbazole derivative having an interaction with silver in the intermediate layer serving as a base. By improving the continuous film-forming property and forming a more uniform silver thin film, low resistance, high permeability and storage stability are achieved (for example, see Patent Document 4).

  However, in recent years, the demand for electronic devices has increased, and in particular, there has been a demand for lower resistance in response to the demand for a larger area. Further, in terms of visibility, higher light transmittance and more than several decades of electronic devices In order to make the life possible, high stability and durability against heat and oxygen in a storage environment are demanded.

JP 2006-344497 A JP 2007-031786 A US Patent Application Publication No. 2011/0260148 International Publication No. 2013/105569

  The present invention has been made in view of the above problems, and the problem to be solved is a transparent electrode that has both excellent electrical conductivity and light transmittance and is excellent in durability over time, and an electron including the transparent electrode. Is to provide a device.

  As a result of intensive studies in view of the above problems, the present inventor has a conductive layer and an intermediate layer provided adjacent to the conductive layer, and the conductive layer is made of copper, gold, and platinum. Any one selected metal element as a main component, the intermediate layer contains an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, and further a reducing oxide film removing agent A transparent electrode characterized in that it contains as a secondary component, and has both excellent light transmission and electrical conductivity, and has excellent durability over time, and an electronic device using the same can be realized. And found the present invention.

  That is, the said subject of this invention is solved by the following means.

［一般式（Ｉ）において、ＸはＮＲ _１ 、酸素原子又は硫黄原子を表す。Ｅ _１ 〜Ｅ _８ は、それぞれ独立にＣＲ _２ 又は窒素原子を表し、少なくとも１つは窒素原子を表す。Ｒ _１ 及びＲ _２ は、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アルキニル基、芳香族炭化水素基、芳香族複素環基、複素環基、アルコキシ基、シクロアルコキシ基、アリールオキシ基、アルキルチオ基、シクロアルキルチオ基、アリールチオ基、アルコキシカルボニル基、アリールオキシカルボニル基、スルファモイル基、アシル基、アシルオキシ基、アミド基、カルバモイル基、ウレイド基、スルフィニル基、アルキルスルホニル基、アリールスルホニル基又はヘテロアリールスルホニル基、アミノ基、ハロゲン原子、フッ化炭化水素基、シアノ基、ニトロ基、ヒドロキシ基、メルカプト基、シリル基、リン酸エステル基又はホスホノ基を表す。］ 1. A transparent electrode having an intermediate layer and a conductive layer provided on the intermediate layer,
The conductive layer contains, as a main component, any one metal element selected from copper, gold and platinum,
The intermediate layer comprises an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film removing agent, and the nitrogen atom of the organic compound is a nitrogen atom in a nitrogen-containing aromatic ring. The nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound is a compound having a structure represented by the following general formula (1):
And as a reducing oxide film removing agent, thiol compounds, thiopolyol compounds, thiocarboxylic acid compounds, aromatic thio compounds, derivatives of these compounds, alkali metal salts, ammonium salts or primary to tertiary amines of these compounds Contains salt as a minor component,
Furthermore, the said intermediate | middle layer contains the organic compound which has a nitrogen atom with an unshared electron pair which does not participate in the said aromaticity in the range of 85-99.7 mass% with respect to the total mass of the said intermediate | middle layer. A transparent electrode characterized by that.

[In General Formula (I), X represents NR ₁ , an oxygen atom or a sulfur atom. E _{1 to} E ₈ each independently represent CR ₂ or a nitrogen atom, and at least one represents a nitrogen atom. R ₁ and R ₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkynyl group, aromatic hydrocarbon group, aromatic heterocyclic group, heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group , Alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or hetero An arylsulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, a phosphate ester group, or a phosphono group. ]

  2. 2. The transparent electrode according to item 1, wherein the conductive layer contains copper as a main component.

  3. Item 1 or Item 2, wherein the intermediate layer contains the reducing oxide film removing agent in a range of 0.5 to 10.0% by mass with respect to the total mass of the intermediate layer. The transparent electrode according to Item 2.

  4). The intermediate layer contains the reducing oxide film removing agent in a range of 1.0 to 5.0% by mass with respect to the total mass of the intermediate layer. The transparent electrode according to any one of items 3 to 3.

5. A second intermediate layer opposite to the intermediate layer through the conductive layer;
The transparent electrode according to any one of items 1 to 4, wherein the conductive layer is sandwiched between the intermediate layer and the second intermediate layer.

  6). An electronic device comprising the transparent electrode according to any one of items 1 to 5.

  According to the present invention, it is possible to provide a transparent electrode that has both excellent conductivity and light transmittance and has excellent durability over time, and an electronic device including the transparent electrode.

  Although the expression mechanism and the action mechanism of the effect of the present invention capable of solving the above problems are not clarified by the configuration defined in the present invention, it is presumed as follows.

The transparent electrode of the present invention has a conductive layer containing copper, gold, or platinum as a main component on the intermediate layer, and the intermediate layer has a copper atom, a gold atom, or a platinum atom. affinity with certain organic compounds having an unshared electron pair which does not participate in the aromaticity made (hereinafter, copper, gold, or also referred to as affinity compounds of platinum.) to the reducing oxide film remover, the organic The nitrogen atom of the compound is a nitrogen atom in a nitrogen-containing aromatic ring, the nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound is represented by the general formula (1) a compound having a structure represented, and as the reducing oxide film removing agent, thiol-based compounds, thio polyol compounds, thiocarboxylic acid compounds, aromatic thio compounds, alkaline derivatives or those compounds of these compounds An organic compound having a nitrogen atom having an unshared electron pair that does not participate in the aromaticity, wherein the intermediate layer contains a genus salt, an ammonium salt, or a primary to tertiary amine salt as an accessory component; It is contained within a range of 85 to 99.7% by mass with respect to the total mass of the intermediate layer,
By adopting such a configuration, when the conductive layer is formed on the intermediate layer, copper atoms, gold atoms, or platinum atoms constituting the conductive layer are contained in the intermediate layer, Copper, gold, or platinum on the surface of the intermediate layer by interacting with an organic compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity, which is an affinity compound with gold or platinum The diffusion distance of atoms is reduced, and aggregation of copper, gold, or platinum atoms at a specific location can be suppressed.

  That is, a copper atom, a gold atom, or a platinum atom is an intermediate layer surface containing an organic compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity having affinity with a copper, gold, or platinum atom. A two-dimensional nucleus is formed above, and a two-dimensional single crystal layer is formed around the two-dimensional nucleus, and the film is formed by a single-layer growth type (Frank-van der Merwe: FM type) film growth. .

  In general, copper atoms, gold atoms, or platinum atoms attached on the surface of the intermediate layer are bonded while diffusing the surface to form a three-dimensional nucleus and grow into a three-dimensional island shape. Although it is considered that an island-shaped film is easily grown by an island-shaped growth type (Volume-Weber: VW type) film, in the present invention, an unshared electron pair not involved in the aromaticity contained in the intermediate layer It is presumed that the organic compound having a nitrogen atom having the above structure prevents island-like growth in this manner and promotes monolayer growth.

  Therefore, although the layer thickness is thin, copper, gold, or platinum atoms are uniformly distributed, and a conductive layer having a uniform layer thickness can be obtained. As a result, it is possible to obtain a transparent electrode in which conductivity is ensured while maintaining light transmittance with a thinner layer thickness.

  In addition, the inclusion of a reducing oxide film remover as an accessory component effectively prevents the oxidation of copper, gold, or platinum, which is presumed to be the main cause of the deterioration of the performance of the transparent conductive layer due to oxygen over time. Or can be suppressed. This is because if the intermediate layer contains a reducing oxide film removing agent as an accessory component, even if an oxide film is formed on the conductive layer due to deterioration over time, oxidation occurs between the metal oxide and the organic compound. It is presumed that this is because a reduction reaction occurs and the function is recovered by reducing the oxide film. That is, by adopting the configuration defined in the present invention, it is possible to obtain a transparent electrode that can be thinned, has high light transmissivity, has excellent conductivity, and has excellent durability over time (oxygen resistance). I guess you can.

Schematic sectional view showing an example of the configuration of the transparent electrode of the present invention Process flow diagram showing an example of forming an electrode pattern on a transparent electrode by photolithography The perspective view which shows an example of a structure of the touchscreen which is an electronic device provided with the transparent electrode pair which has an electrode pattern The top view which shows an example of the electrode pattern of each transparent electrode which comprises a touch panel Plane schematic diagram showing an example of electrode parts constituting a touch panel Schematic sectional view showing an example of the configuration of the touch panel Schematic sectional view showing an example of the configuration of a touch panel that can be suitably used in the present invention Schematic sectional view showing an example of the configuration of a liquid crystal display device which is an electronic device equipped with the transparent electrode of the present invention

The transparent electrode of the present invention is a transparent electrode having an intermediate layer and a conductive layer provided on the intermediate layer, wherein the conductive layer is any one metal selected from copper, gold, and platinum. Containing an element as a main component, the intermediate layer comprising an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film remover , wherein the nitrogen atom of the organic compound is A nitrogen atom in the nitrogen-containing aromatic ring, the nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound has a structure represented by the general formula (1) a compound, and as the reducing oxide film removing agent, thiol-based compounds, thio polyol compounds, thiocarboxylic acid compounds, aromatic thio compounds, alkali metal derivatives or those compounds of these compounds , An ammonium salt or a primary to tertiary amine salt as an accessory component, and the intermediate layer further comprising an organic compound having a nitrogen atom having an unshared electron pair not involved in the aromaticity. A transparent electrode characterized in that it is contained within a range of 85 to 99.7% by mass with respect to the total mass, and has both excellent conductivity and light transmittance, and excellent durability with time (oxygen resistance). Can be realized. This feature is a technical feature common to the inventions according to claims 1 to 6.

  As an embodiment of the present invention, it is preferable that the conductive layer contains copper as a main component from the viewpoint that the above-described effects of the present invention can be more manifested.

  Moreover, it is excellent in the antioxidant effect that the said intermediate | middle layer contains the said reducing oxide film removal agent in the range of 0.5-10.0 mass% with respect to the total mass of the said intermediate | middle layer. It is preferable from a viewpoint which can express more, More preferably, the said intermediate | middle layer is containing the said reducing oxide film removal agent in 1.0-5.0 mass%.

  Moreover, as a structure of the transparent electrode of this invention, it has the 2nd intermediate | middle layer which opposes the said intermediate | middle layer through the said electroconductive layer, The said electroconductive layer is the said intermediate | middle layer and the said 2nd intermediate | middle. The structure sandwiched between the layers is preferable from the viewpoint of improving the scratch resistance of the conductive layer.

  In addition, an electronic device of the present invention includes the transparent electrode of the present invention. Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in this invention is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

[Basic configuration of transparent electrode]
The transparent electrode of the present invention is a transparent electrode having an intermediate layer and a conductive layer provided on the intermediate layer, wherein the conductive layer is any one metal selected from copper, gold, and platinum. An organic compound containing an element as a main component, the intermediate layer having a nitrogen atom having an unshared electron pair not involved in aromaticity (hereinafter also simply referred to as an organic compound having a nitrogen atom), and a reducing oxide film The nitrogen atom of the organic compound is a nitrogen atom in a nitrogen-containing aromatic ring, the nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound is is a compound having the structure represented by the general formula (1), and as the reducing oxide film removing agent, thiol-based compounds, thio polyol compounds, thiocarboxylic acid compounds, aromatic thio compound, Alkali metal salts of derivatives or those compounds of these compounds, the ammonium salt or the first to tertiary amine salts containing as an auxiliary component, further, the intermediate layer, an unshared electron pair that is not involved in the aromatic The organic compound having a nitrogen atom is contained within a range of 85 to 99.7% by mass with respect to the total mass of the intermediate layer . The transparent electrode having the above-described configuration is formed, for example, by laminating the intermediate layer and the conductive layer according to the present invention on a transparent substrate.

  FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the transparent electrode of the present invention.

  The transparent electrode 1 shown in FIG. 1A has a two-layer structure in which an intermediate layer 3 is provided on a substrate 11 and a conductive layer 5 is laminated on the intermediate layer 3.

  That is, the intermediate layer 3 and the conductive layer 5 are provided in this order on the substrate 11. The intermediate layer 3 according to the present invention is a layer containing an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, and further containing a reducing oxide film removing agent as a subcomponent, The conductive layer 5 according to the present invention laminated thereon is a layer containing any one metal element selected from copper, gold and platinum as a main component.

In the present invention, the intermediate layer 3 is characterized by containing an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention. It exists in the range of 85-99.7 mass% with respect to the total mass.

  Further, in the present invention, the intermediate layer 3 is characterized by containing the reducing oxide film removing agent according to the present invention as a subcomponent, but the subcomponent referred to in the present invention is based on the total mass of the intermediate layer, Meaning that the content of the reducing oxide film removing agent according to the present invention is 0.1% by mass or more and less than 50% by mass, preferably in the range of 0.5 to 10.0% by mass, More preferably, it exists in the range of 1.0-5.0 mass%.

  Further, in the present invention, the conductive layer 5 contains any one metal element selected from copper, gold and platinum as a main component. It means that the content of each metal element of copper, gold or platinum according to the present invention is 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass with respect to the total mass of the conductive layer. % Or more, particularly preferably only a metal element of copper, gold or platinum. In the conductive layer 5 according to the present invention, it is the most preferable aspect that each of copper, gold, or platinum does not form an alloy with other metal elements, but is composed of a single metal element. .

  Moreover, as shown in FIG. 1B, the layer structure of the transparent electrode 1 according to the present invention includes the intermediate layer 3A and the conductive layer 5 having the above-described structure on the substrate 11, and further includes a conductive layer. In another preferred embodiment, the second intermediate layer 3B is laminated on the conductive layer 5, and the conductive layer 5 is sandwiched between the intermediate layer 3A and the second intermediate layer 3B. Thus, by providing the second intermediate layer 3B on the conductive layer 5, the conductive layer 5 made of a metal element is not directly exposed to, for example, an oxygen atmosphere. Since the conductive layer 5 is protected by the second intermediate layer 3B, it is possible to prevent the occurrence of scratches and the like.

In addition, it is preferable to stack the second intermediate layer 3B because reflection on the surface of the conductive layer 5 made of a metal element can be reduced and light transmittance can be increased as a transparent electrode. .
Next, further detailed structural requirements will be described in the order of the substrate 11 used to hold the transparent electrode 1 having such a laminated structure, the intermediate layer 3 and the conductive layer 5 constituting the transparent electrode 1.

〔substrate〕
Examples of the substrate 11 used to hold the transparent electrode 1 of the present invention include glass and plastic, but are not limited thereto. The substrate 11 may be transparent or opaque, but when the transparent electrode 1 of the present invention is used in an electronic device that extracts light from the substrate 11 side, the substrate 11 should be transparent. Is preferred. Examples of the transparent substrate 11 that is preferably used include glass, quartz, and a 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 to the intermediate layer 1a, durability, and smoothness, the surface of these glass materials may be subjected to physical treatment such as polishing, if necessary, and from inorganic or organic substances. Or a hybrid film formed by combining these films may be used.

  Examples of the resin film include polyesters such as polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, Cellulose acetate propionate (abbreviation: 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, poly Methyl pentene, polyether ketone, polyimide, polyether sulfone (abbreviation: PES), polyphenyle Sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name; manufactured by JSR) or Apel (trade name; manufactured by Mitsui Chemicals, Inc.) And a resin film using a cycloolefin-based resin or the like.

On the surface of the resin film, a coating made of an inorganic substance or an organic substance (hereinafter, also referred to as “gas barrier film”) or a hybrid coating combining these films may be formed. Such coatings and hybrid coatings have a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS-K-7129-1992 of 0.01 g / (m The gas barrier film is preferably ² · 24 hours or less. Furthermore, the oxygen permeability measured by the method according to JIS-K-7126-1987 is 1 × 10 ⁻³ ml / (m ² · 24 hours · atm) or less, and the temperature is 40 ° C. and 90% RH. Thus, it is preferably a high gas barrier film having a water vapor permeability measured in accordance with JIS Z0208 of 1 × 10 ⁻⁵ g / (m ² · 24 hours) or less.

  The material for forming the gas barrier film as described above may be a material having a function of suppressing intrusion of factors causing deterioration of electronic devices such as moisture and oxygen, such as silicon dioxide and silicon nitride. Can be used. Furthermore, in order to improve the brittleness of the gas 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 producing the gas 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. A plasma polymerization method, a plasma CVD method (CVD: Chemical Vapor Deposition), a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

  On the other hand, when the substrate 11 is made of an opaque material, for example, a metal substrate such as aluminum or stainless steel, a film, an opaque resin substrate, a ceramic substrate, or the like can be used.

[Middle layer]
The intermediate layer 3 according to the present invention comprises an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film remover, and the nitrogen atom of the organic compound is a nitrogen-containing aromatic ring. A nitrogen atom therein, the nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound is a compound having a structure represented by the general formula (1), And as a reducing oxide film removing agent, thiol compounds, thiopolyol compounds, thiocarboxylic acid compounds, aromatic thio compounds, derivatives of these compounds, alkali metal salts, ammonium salts or primary to tertiary amines of these compounds An organic compound containing a salt as an accessory component, and the intermediate layer has a nitrogen atom having an unshared electron pair not involved in the aromaticity, A layer that is configured to contain in the range of 85 to 99.7% by weight relative to the total weight between layers. The method for forming such an intermediate layer 3 on the substrate 11 is not particularly limited, and specific examples of the film forming method include the ability to dissolve both an organic compound having a nitrogen atom and a reducing oxide film removing agent. Prepare an intermediate layer forming coating solution by dissolving in an organic solvent, etc., and use the coating solution to form a roller coating method, a gravure coating method, a knife coating method, a dip coating method, a spray coating method, an inkjet method, etc. And a method of forming a film using the above two components in a dry process such as a vapor deposition method (resistance heating method, EB method (electron beam method)), a sputtering method, a CVD method, or the like. It is done. In particular, a method of preparing a coating solution for forming an intermediate layer and forming a film using the coating solution is preferably applied.

  The intermediate layer 3 preferably has a layer thickness in the range of 1 to 100 nm, and more preferably in the range of 5 to 40 nm. Within this range, the effect can be obtained with any layer thickness. A layer thickness of 100 nm or less is preferable because the absorption component of the layer is reduced and the transmittance of the transparent electrode is improved. Moreover, it is preferable from a viewpoint that a uniform and continuous intermediate | middle layer can be formed as layer thickness is 5 nm or more.

(Organic compounds having nitrogen atoms with unshared electron pairs not involved in aromaticity)
In the transparent electrode 1 of the present invention, the intermediate layer 3 is composed of an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film remover, and the nitrogen atom of the organic compound Is a nitrogen atom in the nitrogen-containing aromatic ring, the nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring or a pyrimidine ring, and the organic compound is a compound having a structure represented by the general formula (1) is there.

As described above, the content of the organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity is within the range of 85 to 99.7 % by mass with respect to the total mass of the intermediate layer, and more preferably. Is in the range of 90.0 to 99.5% by mass, and particularly preferably in the range of 95.0 to 99.0% by mass.

  In the present invention, the “nitrogen atom having an unshared electron pair not involved in aromaticity” is a nitrogen atom having an unshared electron pair, and the unshared electron pair becomes an aromatic property of the unsaturated cyclic compound. A nitrogen atom that is not directly involved as an essential element. That is, a non-localized π electron system on a conjugated unsaturated ring structure (aromatic ring) has a nitrogen atom in which a lone pair is not involved as an essential element for aromatic expression in the chemical structural formula Say.

  Hereinafter, the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention will be described.

  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, so that the number of bonds of nitrogen atoms is usually three.

For example, 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), a diazo group (—N ₂ ), An azide group (—N ₃ ), a urea bond (—NR ¹ C═ONR ² —), an isothiocyanate group (—N═C═S), a thioamide group (—C (═S) NR ¹ R ² ), and the like. These correspond to the “nitrogen atom having an unshared electron pair not involved in aromaticity” of the present invention. R ¹ and R ² each represent a substituent.

Among these, for example, the resonance formula of a nitro group (—NO ₂ ) can be expressed as follows. Strictly speaking, the unshared electron pair of the nitrogen atom in the nitro group is used for the resonance structure with the oxygen atom, but in the present invention, it is defined that the nitrogen atom of the nitro group also has an unshared electron pair.

  On the other hand, a nitrogen atom can also create a fourth bond by utilizing an unshared electron pair. For example, as shown below, tetrabutylammonium chloride (abbreviation: TBAC) is a quaternary ammonium salt in which a fourth butyl group is ionically bonded to a nitrogen atom and has a chloride ion as a counter ion. .

Tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) ₃ ) is a neutral metal complex in which an iridium atom and a nitrogen atom are coordinated. Although these compounds have a nitrogen atom, the lone pair of electrons is used for ionic bond and coordinate bond, respectively. Is not applicable.

  That is, the present invention effectively uses a lone pair of nitrogen atoms that are not used for bonding.

In the structural formulas shown below, the left side shows the structure of tetrabutylammonium chloride (abbreviation: TBAC), and the right side shows the structure of tris (2-phenylpyridine) iridium (III) (abbreviation: Ir (ppy) ₃ ).

  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 a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, and a tetrazole ring.

  In the case of a pyridine ring, as shown below, in a conjugated (resonant) unsaturated ring structure arranged in a 6-membered ring, the number of delocalized π electrons is 6, so 4n + 2 (n = 0 or natural number) ) Satisfies the Hückel rule. 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 an unshared electron pair is essential for aromatic expression. Not involved as a thing.

  Therefore, the nitrogen atom of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention. The molecular orbital of the pyridine ring is shown below.

  In the case of a pyrrole ring, as shown below, one of the carbon atoms constituting the five-membered ring is substituted with a nitrogen atom, but the number of π electrons is six and satisfies the Hückel rule. A 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, it has been utilized as an essential element for the expression of aromaticity, and therefore the “unshared electron pair not involved in aromaticity” of the present invention. Does not correspond to "nitrogen atom having".

  The molecular orbital of the pyrrole ring is shown below.

On the other hand, as shown below, the imidazole ring is a nitrogen-containing aromatic ring having a structure in which two nitrogen atoms are substituted at the 1- and 3-positions in a 5-membered ring, and also has 6 π electrons. . The nitrogen atom N ¹ is a pyridine ring-type nitrogen atom in which only one unpaired electron is mobilized to the 6π-electron system, and the unshared electron pair is not used for aromaticity expression. On the other hand, the nitrogen atom N ² is a pyrrole-ring nitrogen atom that mobilizes an unshared electron pair to the 6π electron system.

Therefore, the nitrogen atom N ¹ of the imidazole ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” in the present invention. The molecular orbital of the imidazole ring is shown below.

The same applies to a condensed ring compound having a nitrogen-containing aromatic ring skeleton. For example, as shown below, δ-carboline is an azacarbazole compound in which a benzene ring skeleton, a pyrrole ring skeleton, and a pyridine ring skeleton are condensed in this order. The nitrogen atom N ³ of the pyridine ring mobilizes only one unpaired electron, and the nitrogen atom N ⁴ of the pyrrole ring mobilizes an unshared electron pair to the π-electron system, respectively, to form a ring. Together with 11 π electrons from the atoms, the total number of π electrons is 14 aromatic rings.

Therefore, among the two nitrogen atoms of δ-carboline, the nitrogen atom N ³ of the pyridine ring corresponds to the “nitrogen atom having an unshared electron pair not involved in aromaticity” according to the present invention, but the nitrogen of the pyrrole ring The atom N ⁴ does not fall under this.

  Thus, even when the pyridine ring or pyrrole ring is incorporated in a condensed ring compound, its effect is not inhibited or suppressed, and there is no difference from when it is used as a single ring. Absent. The molecular orbital of δ-carboline is shown below.

  As described above, the “nitrogen atom having an unshared electron pair not involved in aromaticity” defined in the present invention is strong in copper, gold, or platinum that is the main component of the conductive layer. It is important for expressing the interaction. Such a nitrogen atom is preferably a nitrogen atom in a nitrogen-containing aromatic ring from the viewpoint of stability and durability.

  The organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention preferably has an aromatic heterocyclic ring, and the aromatic heterocyclic ring is preferably a pyridine ring.

  Moreover, it is preferable that the organic compound which has a nitrogen atom with a lone pair which does not participate in the aromatic property which concerns on this invention is an organic compound which has a bromine atom, an iodine atom, or a sulfur atom. By using these atoms, the organic compound contained in the intermediate layer can exhibit the intended effect of the present invention without depending on the main skeleton.

  Although there is no restriction | limiting in particular as a specific compound of the organic compound which has a nitrogen atom with a lone pair which does not participate in the aromatic property which concerns on this invention, It represents with the following general formula (I)-general formula (IV) A compound can be mentioned as an example.

  In the transparent electrode 1 of the present invention, examples of the organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity in the intermediate layer 3 include compounds represented by the following general formula (I).

In the above general formula (I), X represents NR ₁ , an oxygen atom or a sulfur atom. E _{1 to} E ₈ each independently represent CR ₂ or a nitrogen atom, and at least one represents a nitrogen atom. R ₁ and R ₂ each independently represents a hydrogen atom or a substituent.

In the general formula (I), examples of the substituent represented by R ₁ include an alkyl group, a cycloalkyl group, an alkynyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a heterocyclic group, an alkoxy group, and a cycloalkoxy group. , Aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, aryl Examples include a sulfonyl group or heteroarylsulfonyl group, amino group, halogen atom, fluorinated hydrocarbon group, cyano group, nitro group, hydroxy group, mercapto group, silyl group, phosphate ester group, and phosphono group.

In the general formula (I), examples of the substituent represented by R ₂ include the same substituents represented by R ₁ .

  The compound represented by the general formula (I) is preferably a compound represented by the following general formula (II).

In the general formula (II), E _{9 to} E ₁₅ each independently represent CR ₄ . R ₃ and R ₄ each independently represents a hydrogen atom or a substituent.

In the general formula (II), examples of the substituent represented by R ₃ and R ₄ include the same substituents as those represented by R ₁ in the general formula (I).

  Moreover, it is preferable that the compound represented by the said general formula (I) is a compound represented by the following general formula (III).

The general formula _(III), represents a CR ₅ to E 16 _{to E 22} independently. R ₅ represents a hydrogen atom or a substituent.

In the general formula (III), examples of the substituent represented by R ₅ include the same substituents as those represented by R ₁ in the general formula (I).

  Moreover, it is preferable that the compound represented by the said general formula (I) is a compound represented by the following general formula (IV).

In the general formula _{(IV), E} 23 ~E ₂₈ represents a CR ₇ independently. R ₆ and R ₇ each independently represents a hydrogen atom or a substituent.

In the general formula (IV), examples of the substituent represented by R ₆ and R ₇ include the same substituents as those represented by R ₁ in the general formula (I).

Below, have a nitrogen atom having an unshared electron pair which does not participate in the aromaticity of the present invention, specific examples of the nitrogen atom Oh Ru organic compound with a nitrogen atom of a nitrogen-containing aromatic in the ring, the general formula Examples of compounds represented by formulas (I) to (IV), examples of organic compounds having other structures, and examples of organic compounds to be referred to are shown in the present invention, but are limited to these exemplified organic compounds. Is not to be done.

  The organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity according to the present invention can be easily synthesized according to a conventionally known synthesis method.

(Reducing oxide film remover)
The intermediate layer according to the present invention is characterized by containing a reducing oxide film removing agent as an accessory component together with the organic compound having a nitrogen atom having an unshared electron pair not involved in the aromaticity described above.

  In general, one of the causes of deterioration of the performance of the transparent electrode with time is oxidation of a metal that is a main component of the conductive layer. In particular, when copper is the main component, the use and storage of the transparent electrode for a long time gradually promotes the oxidation reaction with oxygen in the atmosphere, so an oxide film made of a metal oxide is formed on the conductive layer. End up. Thereby, the performance of a transparent electrode falls.

  A reducing oxide film removing agent is an organic compound having an effect of removing an oxide film by a reduction reaction. As a result, even if an oxide film is formed on the conductive layer, a redox reaction occurs between the metal oxide and the reducing oxide film remover, and the function is restored by reducing the oxide film. A transparent electrode with improved resistance to oxygen and excellent durability over time can be produced.

  The subcomponent in the present invention means that the content of the reducing oxide film removing agent according to the present invention is 0.1% by mass or more and less than 50% by mass with respect to the total mass of the intermediate layer, Preferably it exists in the range of 0.5-10.0 mass%, More preferably, it exists in the range of 1.0-5.0 mass%.

The reducing oxide film removing agent used in the present invention, methanethiol, such thiol compounds of ethanethiol having main mercapto group, thio glycol, such as thio polyol compound of thioglycerol, thioacetic acid, thiopropionic acid, thiolactic Preferable examples include thiocarboxylic acid compounds such as glycolic acid and thiomalic acid, aromatic thio compounds such as thiobenzoic acid, thiosarcylic acid, and thiophenol, and derivatives and salts of these compounds. Examples of the salt include alkali metal salts, ammonium salts, and primary to tertiary amine salts. And these compounds may be used independently and may use 2 or more types together.

(Method for forming intermediate layer)
As a method for forming the intermediate layer according to the present invention, it may be formed by a wet process or a dry process.

  When the intermediate layer is formed by a wet process, an organic compound having a nitrogen atom having an unshared electron pair that does not participate in aromaticity and a reducing oxide film removing agent are combined with a desired ratio of organic compounds having a common dissolving ability. After dissolving in a solvent such as toluene, methyl ethyl ketone, ethyl acetate and alcohol to prepare a coating solution for forming an intermediate layer, a wet coating device such as a roller coater, gravure coater, knife coater, dip coater, spray coater, After applying on the substrate using an inkjet head or the like, the intermediate layer is formed by drying.

  On the other hand, examples of the dry process include a method of forming a film using the above two components in a dry process such as a vapor deposition method (resistance heating method, EB method (electron beam method), etc.), a sputtering method, and a CVD method. Among these, a method of using two components and performing co-evaporation so as to obtain a desired ratio by controlling the deposition rate of each component is preferably applied.

  Among these, after dissolving in an organic solvent to prepare a coating solution for forming an intermediate layer, the intermediate layer is formed by a wet process of wet coating. It is preferable from the point.

[Conductive layer]
The conductive layer 5 according to the present invention is a layer composed mainly of any one metal element selected from copper, gold and platinum, and is formed on the intermediate layer 3. Examples of the method for forming the conductive layer 5 according to the present invention include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, and the like. And a method using a dry process such as a CVD method. Among the film forming methods, the vapor deposition method is preferably applied. Further, the conductive layer 5 is formed on the intermediate layer 3 so that the conductive layer 5 is sufficiently conductive even without a high-temperature annealing treatment (for example, a heating process at 150 ° C. or higher) after the formation of the conductive layer. Although it can be expressed, if necessary, high-temperature annealing treatment or the like may be performed after film formation.

  In the present invention, the layer composed mainly of any one metal element selected from copper, gold and platinum is the copper according to the present invention with respect to the total mass of the conductive layer 5 as described above. , Meaning that the content of each metal element of gold or platinum is 90% by mass or more, preferably 95% by mass or more, more preferably 99% by mass or more, particularly preferably copper, gold or It is composed only of platinum metal elements, and an alloy of two or more metal elements is not formed. In the conductive layer 5 according to the present invention, it is the most preferable aspect that each of copper, gold, or platinum does not form an alloy with other metal elements, but is composed of a single metal element. .

  In the conductive layer 5 according to the present invention, a layer composed mainly of any one metal element selected from copper, gold, and platinum is divided into a plurality of layers as needed. It may be a configuration.

  Furthermore, the conductive layer 5 preferably has a layer thickness in the range of 4 to 20 nm. Preferably it exists in the range of 5-10 nm. A layer thickness of 20 nm or less is more preferable because the absorption component or reflection component of the layer is reduced and the transmittance of the transparent electrode is improved. A layer thickness of 4 nm or more is preferable because the layer has sufficient conductivity.

<Effect of transparent electrode>
As described above, the transparent electrode 1 of the present invention includes the intermediate layer 3 including a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film removing agent. It is the structure which provided the electroconductive layer 5 comprised by setting any 1 type of metal elements chosen from copper, gold | metal | money, and platinum as a main component on it. Thus, when the conductive layer 5 is formed on the intermediate layer 3, any one metal element selected from copper, gold, and platinum constituting the conductive layer 5 forms the intermediate layer 3. It interacts with a nitrogen atom having an unshared electron pair not involved in aromaticity, and the diffusion distance on the surface of the intermediate layer 3 of any one metal element selected from copper, gold and platinum is reduced, and copper, gold, Alternatively, the formation of platinum aggregation can be suppressed.

  As described above, in the formation of the conductive layer 5 composed mainly of any one metal element selected from copper, gold and platinum, an island-like growth type (Volume-Weber: VW type) is used. Thus, copper, gold, or platinum particles are easily isolated in an island shape, and when the layer thickness is thin, it is difficult to obtain conductivity and the sheet resistance value is increased. Therefore, in order to ensure conductivity, the layer thickness needs to be increased to some extent. However, if the layer thickness is increased, the light transmittance is lowered, which is not suitable as a transparent electrode.

  However, according to the transparent electrode 1 having the configuration defined in the present invention, on the intermediate layer 3 containing a compound having a nitrogen atom having an unshared electron pair not involved in aromaticity, a nitrogen atom and copper, gold and platinum Since the agglomeration of copper, gold, or platinum is suppressed by the interaction with any one kind of metal element selected from the above, the formation of the conductive layer 1b composed mainly of copper, gold, or platinum In this case, a single layer growth type (Frank-van der Merwe: FM type) film is grown.

  In the present invention, “transparent electrode 1” means that the light transmittance at a wavelength of 590 nm is 50% or more, but the above-described materials used for the intermediate layer 3 are copper, gold, Or it is a favorable film | membrane provided with the outstanding light transmittance compared with the electroconductive layer 5 which has platinum as a main component. On the other hand, the conductivity of the transparent electrode 1 is ensured mainly by the conductive layer 5. Therefore, as described above, the conductive layer 5 composed mainly of copper, gold, or platinum has a thinner layer and the conductivity is ensured. It is possible to achieve both improvement in light transmission and improvement in light transmittance.

  In addition, by including a reducing oxide film removing agent in the intermediate layer 3, the deterioration of the metal element constituting the conductive layer in an oxygen atmosphere is prevented, thereby providing a transparent electrode 1 having high durability over time. Was able to be realized.

《Use of transparent electrode》
The transparent electrode 1 of the present invention having the above-described configuration can be used for various electronic devices. Examples of electronic devices include, for example, touch panels, liquid crystal display elements, organic electroluminescence elements, LEDs (light emitting diodes), solar cells, etc. In these electronic devices, electrode members that require light transmission As described above, the transparent electrode 1 of the present invention can be used.

[Touch panel]
Hereinafter, as an example of an electronic device to which the transparent electrode of the present invention is applied, an example in which an electrode pattern by photolithography is formed on the transparent electrode of the present invention and then applied to a touch panel will be described.

(Patterning of transparent electrode)
The transparent electrode 1 of the present invention having an intermediate layer 3 and a conductive layer 5 mainly composed of copper, gold, or platinum adjacent to the intermediate layer 3 on the substrate 11 shown in FIG. The electrode pattern as shown in FIGS. 3 to 5 can be formed by, for example, a photolithography method using, for example, an etching solution containing an organic solvent.

<Etching solution: Organic solvent>
In the present invention, the etching solution preferably contains at least an organic solvent, and the organic solvent is not particularly limited, but is preferably an organic solvent having solubility to the intermediate layer, more preferably. , Ether alcohol, ketone and ester.

  Also, in the present invention, the solvent for each metal element is used in combination with the above-mentioned organic solvent in the present invention for the purpose of more completely dissolving and removing the conductive layer composed of copper, gold, or platinum. You can also.

<Manufacturing process>
Hereinafter, a method for forming an electrode pattern by photolithography will be described.

  The photolithographic method applied to the present invention includes resist coating such as curable resin, preheating, exposure, development (removal of uncured resin), rinsing, etching treatment with an organic solvent, and resist peeling. The transparent electrode is processed into a desired pattern as shown in FIGS.

  In the present invention, a conventionally known general photolithography method can be appropriately used. For example, as the resist, either positive or negative resist can be used. In addition, after applying the resist, preheating or prebaking can be performed as necessary. At the time of exposure, a pattern mask having a desired pattern may be disposed, and light having a wavelength suitable for the resist used, generally ultraviolet rays, electron beams, or the like may be irradiated thereon. After the exposure, development is performed with a developer suitable for the resist used. After the development, the resist pattern is formed by stopping the development with a rinse solution such as water and washing. Next, the formed resist pattern is pre-processed or post-baked as necessary, and then etched with an etching solution containing an organic solvent to dissolve the intermediate layer in a region not protected by the resist and to form a conductive layer. Remove. After etching, the remaining resist is removed to obtain a transparent electrode having an intended pattern. As described above, the photolithography method applied to the present invention is a method generally recognized by those skilled in the art, and the specific application mode is easily selected by those skilled in the art according to the intended purpose. be able to.

  Next, an electrode pattern forming method applicable to the present invention will be described with reference to the drawings.

  FIG. 2 is a process flow diagram showing an example of forming an electrode pattern on a transparent electrode by a photolithography method.

  As a first step, as shown in FIG. 2A, the intermediate layer 3 and the conductive layer 5 are laminated on the transparent substrate 11 to produce the unprocessed transparent electrode 1.

  2B, a resist film 6 made of a photosensitive resin composition or the like is uniformly applied on the conductive layer 5 in the resist film forming step shown in FIG. As the photosensitive resin composition, a negative photosensitive resin composition or a positive photosensitive resin composition can be used.

  As a coating method, it is applied on the conductive layer by a known method such as micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc., and a heating device such as a hot plate or oven. Can be pre-baked. Pre-baking can be performed, for example, using a hot plate or the like in the range of 50 ° C. or higher and 150 ° C. or lower for 30 seconds to 30 minutes.

Next, in the exposure step shown in FIG. 2C, using an exposure machine 8 such as a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner, etc., through a mask 7 produced with a predetermined electrode pattern, The resist film 6A to be removed in the next step is irradiated with light of about 10 to 4000 J / m ² (wavelength 365 nm exposure conversion). The exposure light source is not limited, and ultraviolet rays, electron beams, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.

  Next, in the developing step shown in FIG. 2 (d), the exposed transparent electrode is immersed in a developing solution to dissolve the resist film 6A in the region irradiated with light.

  As a developing method, it is preferable to immerse in a developer for 5 seconds to 10 minutes by a method such as showering, dipping or paddle. As the developer, a known alkali developer can be used. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates and borates, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, tetramethylammonium hydroxide. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as side and choline. After development, it is preferable to rinse with water, and then dry baking may be performed in the range of 50 ° C. to 150 ° C.

  Next, as shown in FIG. 2E, an etching process using the etching solution 9 described above is performed.

  Specifically, for example, the transparent electrode 1 is immersed in an etching solution containing an organic solvent such as ether alcohol, ketone, ester, etc., and the intermediate layer 3 in a region not protected by the resist film 6 is dissolved and the intermediate layer A predetermined electrode pattern is formed by simultaneously removing the thin conductive layer held on the substrate.

  Finally, as shown in FIG. 2 (f), the resist film 6 on the conductive layer 5 is removed by dipping in a resist film remover, for example, N-300 manufactured by Nagase ChemteX Corporation.

<Configuration of touch panel>
Next, details of a representative embodiment will be described for the configuration of a touch panel to which the transparent electrode of the present invention can be applied.

[Embodiment 1: Configuration in which two transparent electrodes are provided on two transparent substrates]
FIG. 3 is a perspective view showing a schematic configuration of the touch panel 21a using the transparent electrode of the present invention described above and having the configuration shown in FIG. 7 described later. 4 is a plan view of two transparent electrodes 1-1 and 1-2 showing the electrode configuration of the touch panel 21. FIG.

  The touch panel 21 shown in these drawings is a projected capacitive touch panel. In the touch panel 21, the first transparent electrode 1-1 and the second transparent electrode 1-2 are arranged in this order on one main surface of the transparent substrates 11-1 and 11-2. Covered with.

  Each of the first transparent electrode 1-1 and the second transparent electrode 1-2 is the transparent electrode 1 on which the electrode pattern for the touch panel described with reference to FIGS. 1 and 2 is formed. Therefore, the first transparent electrode 1-1 has a configuration in which the first intermediate layer 3-1 and the first conductive layer 5-1 are laminated in this order. Similarly, the second transparent electrode 1-2 has a configuration in which a second intermediate layer 3-2 and a second conductive layer 5-2 are laminated in this order.

  Hereinafter, the detail of each main layer which comprises the touchscreen 21 is demonstrated in order from the transparent substrates 11-1 and 11-2 side. Here, description will be made with reference to FIGS. 3 and 4 and a schematic plan view of the electrode portion of FIG. 5 and a schematic cross-sectional view of FIG. 6 corresponding to the AA cross section. Moreover, the same code | symbol is attached | subjected to the component similar to having demonstrated in FIG.1 and FIG.2, and the overlapping description is abbreviate | omitted.

(Transparent substrate 11)
The transparent substrates 11-1 and 11-2 shown in FIGS. 3 and 5 are the substrate 11 (hereinafter also referred to as a transparent substrate) described in the previous transparent electrode 1.

(First intermediate layer 3-1 (first transparent electrode 1-1))
The first intermediate layer 3-1 is the intermediate layer 3 described in the previous transparent electrode 1, and is formed on the substrate 11. Here, as an example, the first intermediate layer 3-1 is patterned on the transparent substrate 11-1 in the same shape as the conductive layer 5-1.

(First conductive layer 5-1 (first transparent electrode 1-1))
The first conductive layer 5-1 is the conductive layer 5 described in the previous transparent electrode, and a plurality of x electrode patterns 5x1, 5x2, patterned on the first intermediate layer 3-1, (omitted). Etc. are configured. Each of the x electrode patterns 5x1, 5x2, (omitted) and the like are arranged in parallel while being spaced apart from each other, with each extending in the x direction. Each of these x electrode patterns 5x1, 5x2, (omitted), etc., for example, has a shape in which rhombus pattern portions arranged in the x direction are linearly connected in the x direction near the apex of the rhombus. .

  Further, x wirings 17x are connected to the respective end portions of the respective x electrode patterns 5x1, 5x2, (omitted) and the like. These x wirings 17x are wired in the peripheral area on the transparent substrate 11-1, and are drawn out to the edge of the transparent substrate 11-1. Each such x wiring 17x is configured as a first conductive layer 5-1 mainly composed of copper, gold, or platinum, similarly to the x electrode patterns 5x1, 5x2, (omitted) and the like. is there.

(Second intermediate layer 3-2 (second transparent electrode 1-2))
The second intermediate layer 3-2 is the intermediate layer 3 described in the previous transparent electrode 1, is formed on the transparent substrate 11-2, and is patterned in the same shape as the second electrode layer 5-2. Has been.

(Second electrode layer 5-2 (second transparent electrode 1-2))
The second electrode layer 5-2 is the conductive layer 5 described in the previous transparent electrode 1, and a plurality of y electrode patterns 5y1, 5y2 patterned on the second intermediate layer 3-2 (omitted). Etc. are configured. The y electrode patterns 5y1, 5y2, (omitted), etc. are arranged in parallel at intervals while being extended in the y direction perpendicular to the x electrode patterns 5x1, 5x2, (omitted), etc. Yes. Each of these y electrode patterns 5y1, 5y2, (omitted), etc., for example, has 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. 5, the rhombus pattern portions constituting the y electrode patterns 5 y 1, 5 y 2, (abbreviated), etc. are the rhombus pattern portions forming the x electrode patterns 5 x 1, 5 x 2, (abbreviated), etc. On the other hand, it is arranged at a position that does not overlap in plan view, and has a shape that occupies as large a range as possible without overlapping. Thereby, in the area | region of the center part of the transparent substrate 11-2, it comprises with x electrode pattern 5x1, 5x2, (omitted) etc. which were comprised by the 1st electrode layer 5-1, and 2nd electrode layer 5-2. The y electrode patterns 5y1, 5y2, (omitted) and the like thus made are difficult to be visually recognized.

  The y electrode patterns 5y1, 5y2, (omitted), etc. are stacked with the x electrode patterns 5x1, 5x2, (omitted), etc. only at the connecting portions of the rhombus electrode patterns. A second intermediate layer 3-2 is sandwiched between these stacked portions, thereby ensuring insulation between the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, (omitted), etc. It has become a state.

  In addition, each of the y electrode patterns 5y1, 5y2, (omitted) and the like is connected to a y wiring 17y at each end. These y wirings 17y are wired in the peripheral region on the transparent substrate 11-2, and are drawn out to the edge of the transparent substrate 11-2 so as to be aligned with the x wirings 17x. Each of the y wirings 17y is configured as a second conductive layer 5-2 mainly composed of copper, gold, or platinum, similarly to the y electrode patterns 5y1, 5y2, (omitted) and the like. is there.

  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 11-2.

(Front plate 13)
The front plate 13 illustrated in FIG. 3 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 used by selecting 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. 6). The material of the adhesive 15 is not particularly limited as long as it has optical transparency.

  The front plate 13 is provided with a light-shielding film that covers the peripheral edges of the transparent substrates 11-1 and 11-2. The x wiring 17x drawn from the x electrode patterns 5x1, 5x2, (omitted), and the like, and the y electrode pattern The y wiring 17y drawn from 5y1, 5y2, (omitted) or the like is prevented from being visually recognized from the front plate 13 side.

(Touch panel operation)
When the touch panel 21 as described above is operated, the x electrode patterns 5x1, 5x2, (omitted) and the y electrode patterns 5y1, 5y2, (omitted) are connected from the flexible printed circuit board connected to the x wiring 17x and the y wiring 17y. A voltage is applied to the above. 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 x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, ( It appears as a change in voltage. This change differs 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. Therefore, the position addressed by the x electrode pattern 5x1, 5x2, (omitted), etc. and the y electrode pattern 5y1, 5y2, (omitted), etc. where the voltage change is maximum is detected as the position touched by the finger or the touch pen. Is done.

(Effect of touch panel 21)
The touch panel 21 as described above uses, as the two-layer transparent electrodes 1-1 and 1-2, a transparent electrode having sufficient conductivity as well as the light transmittance described above. Thereby, the voltage drop at the time of enlarging the transparent electrode for touchscreens can be suppressed, maintaining the visibility of the display image of a foundation | substrate, and the touchscreen 21 can be enlarged.

  In particular, the touch panel 21 is a projection capacitive type having x electrode patterns 5x1, 5x2, (omitted), and the like, and electrode patterns 5y1, 5y2, (omitted), etc. arranged orthogonally thereto. Therefore, high conductivity is required for the x electrode patterns 5x1, 5x2, (omitted), etc., and the y electrode patterns 5y1, 5y2, (omitted), etc. However, these x electrode patterns 5x1, 5x2, (omitted), etc. and y electrode patterns 5y1, 5y2, (omitted), etc. are the conductive layers (electrode layers) 5 of the transparent electrode for touch panel described above. Thin film formation is possible while maintaining conductivity. Therefore, the x electrode patterns 5x1, 5x2, (omitted), etc. and the y electrode patterns 5y1, 5y2, (omitted), etc. are not easily recognized, and the visibility of the underlying display image via the touch panel 21 is degraded. Can also be prevented.

  FIG. 7 is a schematic cross-sectional view for explaining a configuration of a touch panel that can be particularly preferably applied to the touch panel of the embodiment, and corresponds to a cross section taken along line AA shown in FIG. 5. The touch panel 21a shown in this figure 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. Other configurations are the same as those of the first embodiment described above. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel of previous Embodiment 1, and the overlapping description is abbreviate | omitted.

  That is, the touch panel 21a of the modification shown in FIG. 7 includes the first substrate 11-1 provided with the first transparent electrode 1-1 and the second substrate provided with the second transparent electrode 1-2. 11-2. These substrates 11-1 and 11-2 have the formation surfaces of the transparent electrodes 1-1 and 1-2 in the same direction, and are on the formation surface of the first transparent electrode 1-1 on the first substrate 11-1. In addition, the second substrate 11-2 is placed so as to be positioned.

  The first substrate 11-1 and the second substrate 11-2 are the same substrates 11 as described in the previous transparent electrode. The first transparent electrode 1-1 and the second transparent electrode 1-2 each have the same configuration as that of the first embodiment, and the intermediate layer is formed on the substrates 11-1 and 11-2, respectively. In this configuration, 3-1 and 3-2 and conductive layers 5-1 and 5-2 are stacked in this order.

  Furthermore, the configuration of each of the conductive layers 5-1 and 5-2 is the same as that of the first embodiment, and the x electrode patterns 5x1, 5x2, (omitted), etc. configured by the first conductive layer 5-1. , And the y electrode patterns 5y1, 5y2, (omitted) and the like configured by the second electrode layer 5-2 are difficult to be visually recognized and arranged. However, insulation between the first conductive layer 5-1 and the second conductive layer 5-2 was ensured by the second substrate 11-2 and the second intermediate layer 3-2. It is in a state.

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

[Embodiment 2: Configuration in which two transparent electrodes are provided on a transparent substrate]
FIG. 6 is a schematic cross-sectional view for explaining another example of the touch panel of the embodiment. The touch panel 21 shown in FIG. 6 includes a first transparent electrode 1-1 and a second transparent electrode on the transparent substrate 11. 1-2 is provided, and other configurations are the same as those in the first embodiment. For this reason, the same code | symbol is attached | subjected to the structure similar to the touch panel of previous embodiment, and the overlapping description is abbreviate | omitted.

[Application to liquid crystal display devices]
Next, an example in which the transparent electrode of the present invention is incorporated in a liquid crystal display device as an electronic device will be described.

  FIG. 8 is a schematic cross-sectional view showing an example of the configuration of a liquid crystal display device provided with the transparent electrode of the present invention. The liquid crystal display device is an example, and the present invention is not limited to this.

  The liquid crystal display device is generally referred to as a liquid crystal display or a liquid crystal panel, and liquid crystal display devices of various driving methods such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, and OCB are listed depending on the liquid crystal driving method. It is done. In general, a VA (MVA, PVA) type liquid crystal display device is preferably used as a liquid crystal display such as a TV or a liquid crystal panel.

  A liquid crystal display device 100 shown in FIG. 8 has a polarizing filter 101A that controls light entering and exiting from the backlight side, a glass substrate 102A that prevents electricity from leaking to other regions from the electrode portion, and a liquid crystal display. The transparent electrode 1A of the present invention, the alignment film 104A for aligning liquid crystal molecules in a certain direction, the liquid crystal 105, the spacer 106, the other alignment film 104B, the other transparent electrode 1B, and the RGB filters are applied to display the color. Color filter 103, the other glass substrate 102B, and the other polarizing filter 101B. The transparent electrodes 1A and 1B of the present invention have both excellent conductivity and light transmittance, and have a low sheet resistance value. Excellent durability (heat resistance and oxygen resistance).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

<< Preparation of transparent electrode >>
According to the method shown below, the transparent electrodes 1 to 64 were produced under the condition that the area of the conductive region was 5 cm × 5 cm. The transparent electrodes 1 to 3 are prepared as transparent electrodes having a structure having only a conductive layer, and the transparent electrodes 4 to 61 are a transparent electrode having a laminated structure of the intermediate layer 3 and the conductive layer 5. -64 produced the transparent electrode which consists of 3 layer laminated structure of 3 A of intermediate | middle layers, the electroconductive layer 5, and the 2nd intermediate | middle layer 3B.

[Preparation of transparent electrode 1]
According to the method shown below, the transparent electrode 1 of the comparative example which consists only of an electroconductive layer was produced.

A transparent non-alkali glass substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and this was mounted in a vacuum chamber of the vacuum deposition apparatus. On the other hand, copper (Cu) was loaded into a resistance heating boat made of tungsten and mounted in the vacuum chamber. Next, after reducing the pressure in the vacuum chamber to 4 × 10 ⁻⁴ Pa, the resistance heating boat was energized and heated, and the copper was 100 mass on the substrate within the range of the deposition rate of 0.1 to 0.2 nm / second. A transparent electrode 1 was produced by vapor-depositing a single film of a conductive layer composed of 8% and having a thickness of 8 nm.

[Preparation of transparent electrodes 2 and 3]
In the production of the transparent electrode 1, a conductive layer is composed of a single conductive layer in the same manner except that gold (Au) and platinum (Pt) are used instead of copper as a constituent metal element of the conductive layer. Transparent electrodes 2 and 3 were produced.

(Formation of intermediate layer by wet coating method)
In the following examples, the intermediate layer was formed by a wet coating method.
Moreover, the following compounds were used as a reducing oxide film removing agent.

Thioglycolic acid Ammonium thioglycolate Thiolingonic acid [Preparation of transparent electrode 4]
<Preparation of coating solution for intermediate layer formation>
Organic compound having nitrogen atom having unshared electron pair not involved in aromaticity: Exemplified compound (27) 1.0% by mass
Methyl ethyl ketone 99.0% by mass
Illustrative compound (27) was added to methyl ethyl ketone and dissolved while heating to prepare a 1.0 mass% coating solution for forming an intermediate layer.

<Formation of intermediate layer>
On the transparent non-alkali glass substrate, the prepared coating solution for forming an intermediate layer was wet-coated by a spin coating method to form a thin film. Subsequently, it heat-dried at 90 degreeC for 1 hour, and formed the intermediate | middle layer whose layer thickness is 35 nm.

(Formation of conductive layer)
Next, the substrate on which the intermediate layer was formed was transferred to the first vacuum chamber, and the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa. Then, the heating boat containing copper was energized and heated, and the deposition rate was 0.1. A transparent layer 4 was obtained by depositing a conductive layer made of copper alone having a layer thickness of 8 nm within a range of ˜0.2 nm / second.

[Preparation of transparent electrodes 5 and 6]
In the production of the transparent electrode 4, a conductive layer is composed of an intermediate layer and a conductive layer in the same manner except that the constituent metal element of the conductive layer is replaced with copper and gold (Au) and platinum (Pt) are used. Transparent electrodes 5 and 6 were produced.

[Preparation of transparent electrode 7]
<Preparation of coating solution for intermediate layer formation>
Thioglycolic acid (reducing oxide film remover) 1.0% by mass
Methyl ethyl ketone 99.0% by mass
Thioglycolic acid was added to methyl ethyl ketone and dissolved while heating to prepare a 1.0 mass% coating solution for forming an intermediate layer.

<Formation of intermediate layer>
On the transparent non-alkali glass substrate, the prepared coating solution for forming an intermediate layer was wet-coated by a spin coating method to form a thin film. Subsequently, it heat-dried at 90 degreeC for 1 hour, and formed the intermediate | middle layer whose layer thickness is 35 nm.

(Formation of conductive layer)
Next, the substrate on which the intermediate layer was formed was transferred to the first vacuum chamber, and the first vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa. Then, the heating boat containing copper was energized and heated, and the deposition rate was 0.1. A transparent electrode 7 was obtained by depositing a conductive layer made of copper alone having a layer thickness of 8 nm in a range of ˜0.2 nm / second.

[Preparation of transparent electrode 8]
<Preparation of coating solution for intermediate layer formation>
Organic compound having nitrogen atom with unshared electron pair not involved in aromaticity: Exemplified compound (27) 0.95% by mass
Thioglycolic acid (reducing oxide film remover) 0.05% by mass
Methyl ethyl ketone 99.00% by mass
Each compound was added to methyl ethyl ketone and dissolved while heating to prepare a 1.0 mass% coating solution for forming an intermediate layer.

<Formation of intermediate layer>
On the transparent non-alkali glass substrate, the prepared coating solution for forming an intermediate layer was wet-coated by a spin coating method to form a thin film. Subsequently, it heat-dried at 90 degreeC for 1 hour, and formed the intermediate | middle layer whose layer thickness is 35 nm.

(Formation of conductive layer)
Next, the substrate prepared in advance and transferred to the second vacuum chamber and formed with the intermediate layer was transferred to the second vacuum chamber in a vacuum state, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then replaced with copper. Then, a heating boat containing silver was energized and heated, and a conductive layer made of silver alone having a layer thickness of 8 nm was deposited at a deposition rate in the range of 0.1 to 0.2 nm / second. A transparent electrode 8 was obtained by laminating a conductive layer made of silver.

[Preparation of transparent electrodes 9 to 61]
In the production of the transparent electrode 8, the type and content ratio of the organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and the oxide film removing material by reduction reaction, the material and layer thickness of the conductive layer , And the types of substrates were changed as shown in Tables 1 to 3, respectively, and transparent electrodes 9 to 61 were produced in the same manner as the transparent electrode 8.

[Preparation of transparent electrodes 62-64]
In the production of the transparent electrode 12 (conductive layer: copper), the transparent electrode 13 (conductive layer: gold), and the transparent electrode 14 (conductive layer: platinum), after forming each conductive layer, the conductive layer In the same manner, except that the second intermediate layer 3B is formed with the same contents as the intermediate layer 3A, and the conductive layer 5 is sandwiched between the intermediate layer 3A and the second intermediate layer 3B. 62-64 were produced.

  In Tables 1 to 3, the following abbreviations were used.

Compound (N): an organic compound compound having a nitrogen atom having an unshared electron pair which does not participate in the aromaticity (R): reducing oxide film removing agent R1: thioglycolic acid R2: Ammonium thioglycolate R3: Chiori apple acid Comparative 1: Comparative Compound 1
Comparative 2: Comparative compound 2
Comparative 3: Comparative compound 3
PET: Polyethylene terephthalate film Structural formulas of Comparative Compounds 1 to 3 are shown below.

<< Evaluation of transparent electrode >>
About the produced said transparent electrodes 1-64, according to the following method, the measurement and evaluation of the light transmittance, sheet resistance value, and time-dependent durability (electrode lifetime in oxygen environment) were performed.

(Measurement of light transmittance)
About each produced said transparent electrode, the light transmittance (%) in wavelength 590nm was measured using the substrate used for preparation of each transparent electrode using the spectrophotometer (Hitachi U-3300).

[Measurement of sheet resistance]
About each produced said transparent electrode, the sheet resistance value (ohm / square) was measured by the 4-terminal 4 probe method constant current application system using the resistivity meter (MCP-T610 by Mitsubishi Chemical Corporation).

[Evaluation of durability over time: Measuring the lifetime of transparent electrodes in an oxygen environment]
Measure the time required for the sheet resistance value to be twice the initial value by continuously applying a current of 10 A to each transparent electrode produced under an oxygen atmosphere (temperature: 23 ° C., oxygen concentration: 100% by volume). did.

  Next, a relative value with a time taken for the sheet resistance value of the transparent electrode 8 (conductive layer: silver) to be twice the initial value as 100 was determined and used as a measure of durability over time. The larger the value, the better the durability over time and the longer the transparent electrode lifetime.

  The results obtained as described above are shown in Tables 1 to 3.

  As is clear from the results shown in Tables 1 to 3, the conductive layer is composed of copper, gold or platinum, and the intermediate layer has an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity. The transparent electrode of the present invention, which contains a reducing oxide film remover as an accessory component, is superior in light transmittance, sheet resistance characteristics, heat and oxygen durability to the comparative example, and has a transparent electrode lifetime. I understand that it is long.

  In contrast to the transparent electrode 8 having a conductive layer composed of silver that has been widely used in the past, the transparent electrode of the present invention has improved light transmission as an electrode, reduced sheet resistance, and particularly oxidation resistance. It can be seen that an excellent effect is exhibited.

  Moreover, the transparent electrode which used copper as a constituent metal of an electroconductive layer has expressed the effect which was more excellent about each item with respect to the transparent electrode which used gold | metal | money, or the transparent electrode which used platinum.

  Further, in the transparent electrodes 57 to 61, the ratio of the compound (N) to the compound (O) in the intermediate layer is more preferably in the range of 99.5: 0.5 to 90:10. In addition, particularly excellent effects are exhibited within the range of 99: 1 to 95: 5.

  Further, in the transparent electrodes 62 to 64, the conductive layer 5 is sandwiched between the intermediate layer 3A and the second intermediate layer 3B, whereby surface reflection is suppressed and the transmittance is improved. I understand. In addition, it was confirmed that the durability with time of the transparent electrode was further improved, and in addition, the scratch resistance of the conductive layer was improved.

1, 1-1, 1-2, 1A, 1B Transparent electrode 3, 3A, 3B, 3-1, 3-2 Intermediate layer 5, 5-1, 5-2 Conductive layer 5x1, 5x2, 5x3, etc. x electrode Pattern (first conductive layer)
5y1, 5y2, 5y3, etc. y electrode pattern (second conductive layer)
6 Resist film 7 Mask 8 Exposure machine 9 Etch solution 11 Transparent substrate 13 Front plate 15 Adhesive 17, 17x, 17y Wiring 21, 21a Touch panel 100 Liquid crystal display device 101A, 101B Polarizing filter 102A, 102B Glass substrate 103 Color filter 104A, 104B Alignment film 105 Liquid crystal 106 Spacer

Claims (6)

A transparent electrode having an intermediate layer and a conductive layer provided on the intermediate layer,
The conductive layer contains, as a main component, any one metal element selected from copper, gold and platinum,
The intermediate layer comprises an organic compound having a nitrogen atom having an unshared electron pair not involved in aromaticity and a reducing oxide film removing agent, and the nitrogen atom of the organic compound is a nitrogen atom in a nitrogen-containing aromatic ring. The nitrogen-containing aromatic ring is a pyridine ring, a pyrazine ring, a pyrimidine ring or a triazine ring, and the organic compound is a compound having a structure represented by the following general formula (1):
And as a reducing oxide film removing agent, thiol compounds, thiopolyol compounds, thiocarboxylic acid compounds, aromatic thio compounds, derivatives of these compounds, alkali metal salts, ammonium salts or primary to tertiary amines of these compounds Contains salt as a minor component,
Furthermore, the said intermediate | middle layer contains the organic compound which has a nitrogen atom with an unshared electron pair which does not participate in the said aromaticity in the range of 85-99.7 mass% with respect to the total mass of the said intermediate | middle layer. A transparent electrode characterized by that.

[In General Formula (I), X represents NR ₁ , an oxygen atom or a sulfur atom. E _{1 to} E ₈ each independently represent CR ₂ or a nitrogen atom, and at least one represents a nitrogen atom. R ₁ and R ₂ are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkynyl group, aromatic hydrocarbon group, aromatic heterocyclic group, heterocyclic group, alkoxy group, cycloalkoxy group, aryloxy group , Alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group or hetero An arylsulfonyl group, an amino group, a halogen atom, a fluorinated hydrocarbon group, a cyano group, a nitro group, a hydroxy group, a mercapto group, a silyl group, a phosphate ester group, or a phosphono group. ]   The transparent electrode according to claim 1, wherein the conductive layer contains copper as a main component.   The said intermediate | middle layer contains the said reducing oxide film removal agent in the range of 0.5-10.0 mass% with respect to the total mass of the said intermediate | middle layer, The Claim 1 or Claim characterized by the above-mentioned. Item 3. The transparent electrode according to Item 2.   The said intermediate | middle layer contains the said reducing oxide film removal agent in 1.0-5.0 mass% with respect to the total mass of the said intermediate | middle layer, The Claim 1 characterized by the above-mentioned. Item 4. The transparent electrode according to any one of Items 3 to 3. A second intermediate layer opposite to the intermediate layer through the conductive layer;
The transparent electrode according to any one of claims 1 to 4, wherein the conductive layer is sandwiched between the intermediate layer and the second intermediate layer.   An electronic device comprising the transparent electrode according to any one of claims 1 to 5.

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