JP6802842B2 - Manufacturing method of transparent electrode - Google Patents

Description

The present invention relates to a method for producing a transparent electrode, and more particularly, to a method for producing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device.

In recent years, organic electronic devices such as organic electroluminescent devices (hereinafter, also referred to as “organic EL devices”) and organic solar cells are required to be larger, lighter, more flexible, and the like. In particular, large organic electronic devices are required to have high luminous efficiency and power generation efficiency, and transparent electrodes having low electrical resistance are required.

As a means for reducing the electrical resistance of the transparent electrode, it is known to use a thin metal wire obtained by firing a metal nanoink on the transparent electrode.
By the way, from the viewpoint of weight reduction and flexibility of organic electronic devices, a film substrate such as polyethylene terephthalate (PET) is used as the substrate. By adopting flash firing in which only metal nanoink is heated and fired, the film is used. Damage to the substrate can be reduced (see, for example, Patent Documents 1 and 2).

In a transparent electrode using a thin metal wire, a transparent electrode that functions as a surface electrode can be formed by coating the thin metal wire with a transparent conductive layer. As a result, uniform surface emission is possible when used in an organic electronic device. Further, by filling the unevenness of the thin metal wire with a transparent conductive layer, it is possible to manufacture a transparent electrode having excellent rectifying characteristics and not causing leakage in the organic electronic device when used in an organic electronic device. In particular, from the viewpoint of the transparency of organic electronic devices and the productivity of transparent electrodes, the transparent conductive layer is required to be thin.

However, thinning the transparent conductive layer in the transparent electrode using a thin metal wire has a problem that the rectifying characteristics are deteriorated when the transparent electrode is used for an organic electronic device.

Japanese Unexamined Patent Publication No. 2014-038749 Japanese Patent No. 5408878

The present invention has been made in view of the above problems and situations, and the problem to be solved thereof is to provide a method for manufacturing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device. Is.

In order to solve the above problems, the present inventor flash-fires a metal nanoparticle-containing composition in an atmosphere in which the concentration of the oxygen-containing substance is within a specific range in the process of examining the cause of the above problems, and the metal wire is thin. It has been found that a method for producing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device can be provided by forming the above, and the present invention has been made.

That is, the above problem according to the present invention is solved by the following means.

1. 1. A method for manufacturing a transparent electrode having a metal fine wire formed in a pattern on a transparent resin substrate and a transparent conductive layer formed on the metal fine wire.
The process of printing the metal nanoparticle-containing composition in a pattern,
A step of drying the metal nanoparticle-containing composition printed in a pattern, and
A step of irradiating the dried metal nanoparticle-containing composition with flash light and firing it to form a fine metal wire.
A step of forming a transparent conductive layer having a thickness in the range of 30 to 300 nm on the thin metal wire, and
Have,
The step of forming the metal fine wire is characterized in that the metal nanoparticle-containing composition is fired in an atmosphere in which the concentration of the oxygen-containing substance is in the range of 50 to 2000 volume ppm to form the metal fine wire. A method for manufacturing a transparent electrode.

2. 2. The step of forming the metal fine wire is characterized in that the metal nanoparticle-containing composition is fired in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 2000 volume ppm to form the metal fine wire. The method for manufacturing a transparent electrode according to the first item.

3. 3. 2. The step according to item 1 or 2, wherein in the step of drying the metal nanoparticle-containing composition, the composition is dried in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 5000 volume ppm. A method for manufacturing a transparent electrode.

4. The method for producing a transparent electrode according to any one of items 1 to 3, wherein the thickness of the transparent conductive layer is in the range of 50 to 150 nm.

5. The method for producing a transparent electrode according to any one of items 1 to 4, wherein the transparent conductive layer contains a metal oxide.

6. The method for producing a transparent electrode according to any one of items 1 to 5, wherein a base layer is formed between the transparent resin substrate and the thin metal wire.

7. Item 6. The transparency according to Item 6, wherein the base layer contains a compound having a thiol group and a compound selected from poly (meth) acrylate and poly (meth) acrylamide having an aminoethyl group. Method of manufacturing electrodes.

8. Item 6. The item according to Item 7, wherein the compound having a thiol group is a condensate of a compound having a structure represented by the following general formula (I) and a monohydric or polyhydric alcohol or an amine. Method for manufacturing transparent electrodes.

(In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them is an alkyl group having 1 to 10 carbon atoms. Is an integer from 0 to 2, and n is 0 or 1.)

According to the above means of the present invention, it is possible to provide a method for producing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device.

Although the mechanism of expression and the mechanism of action of the effects of the present invention have not been clarified, it is inferred as follows.

The method for producing a transparent electrode of the present invention is characterized in that the metal nanoparticle-containing composition is calcined in an atmosphere in which the concentration of the oxygen-containing substance is in the range of 50 to 2000 parts by volume ppm. By setting the concentration of the oxygen-containing substance within the above range, rapid oxidation and sulfurization of the fine metal wire can be prevented. As a result, it is considered that it is possible to suppress the increase in resistance of the thin metal wire when forming the transparent conductive layer, and to provide a transparent electrode having excellent conductivity. Further, it is possible to suppress the growth of minute crystals of metal oxides and metal sulfides on the fine metal wire, improve the surface smoothness of the fine metal wire, and provide a transparent electrode having excellent rectification characteristics when applied to an organic electronic device. it is conceivable that.

Sectional drawing which shows the schematic structure as an example of the transparent electrode which concerns on this invention. Sectional drawing which shows the schematic structure as another example of the transparent electrode which concerns on this invention. Schematic diagram of a manufacturing apparatus applicable to the method for manufacturing a transparent electrode of the present invention. Sectional drawing which shows schematic structure as an example of an organic EL element

In the method for producing a transparent electrode of the present invention, in a step of forming a fine metal wire, the metal nanoparticle-containing composition is fired in an atmosphere where the concentration of an oxygen-containing substance is in the range of 50 to 2000 parts per million to form the fine metal wire. It is characterized by doing. This feature is a technical feature common to the inventions according to each claim.

In an embodiment of the present invention, in the step of forming a thin metal wire, the metal nanoparticle-containing composition is fired in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 2000 parts per million to form the fine metal wire. It is preferable to do so.

Further, from the viewpoint of improving the rectifying characteristics, in the step of drying the metal nanoparticle-containing composition, it is preferable to dry in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 5000 volume ppm.

Further, from the viewpoint of thinning and improving the rectifying characteristics, the thickness of the transparent conductive layer is preferably in the range of 50 to 150 nm.

Further, from the viewpoint of improving conductivity and rectifying characteristics, it is preferable that the transparent conductive layer contains a metal oxide.

Further, from the viewpoint of improving the adhesion between the transparent resin substrate and the fine metal wire and the transparent conductive layer, it is preferable to form a base layer between the transparent resin substrate and the thin metal wire, and a thiol group is added to the base layer. It is more preferable that the compound having the compound and a compound selected from poly (meth) acrylate and poly (meth) acrylamide having an aminoethyl group are contained.

Further, from the viewpoint of improving the adhesion between the transparent resin substrate and the fine metal wire and improving the performance of the organic electronic device, the compound having a thiol group has a structure represented by the above general formula (I) and a monovalent compound. Alternatively, it is preferably a polyhydric alcohol or a condensate with an amine.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

<< Composition of transparent electrode >>
In the transparent electrode according to the present invention, at least a metal thin wire formed in a pattern and a transparent conductive layer formed on the metal fine wire are sequentially laminated on a transparent resin substrate (hereinafter, also simply referred to as a substrate). It is composed of. The transparent conductive layer may be formed so as to cover the entire thin metal wire.
FIG. 1 shows a schematic cross-sectional view as an example of the transparent electrode according to the present invention.
As shown in FIG. 1, the transparent electrode 10 according to the present invention has a metal thin wire 2 formed in a pattern on a transparent resin substrate 1 and a transparent conductive layer 3 formed on the metal fine wire 2. ..

The transparent electrode 10 according to the present invention may be provided with another layer, if necessary.
For example, as shown in FIG. 2, the base layer 4 may be provided between the transparent resin substrate 1 and the thin metal wire 2.
Further, the gas barrier layer 5 may be provided between the transparent resin substrate 1 and the base layer 4, or the particle-containing layer 6 may be provided on the surface of the transparent resin substrate 1 opposite to the base layer 4. It may be provided. The particle-containing layer 6 is preferably arranged as the outermost layer.

<< Manufacturing method of transparent electrode >>
Hereinafter, the method for producing a transparent electrode of the present invention will be described in detail by taking a transparent electrode having a base layer, a thin metal wire and a transparent conductive layer on a transparent resin substrate as an example.

<Formation process of base layer>
The base layer is formed by preparing a dispersion liquid for forming a base layer in which a resin and a thiol group-containing compound or the like (details will be described later) are dispersed in a solvent, and applying this dispersion liquid for forming a base layer onto a substrate. To do.

The dispersion solvent used for the dispersion liquid for forming the base layer is not particularly limited, but it is preferable to select a solvent that does not cause precipitation of the resin and aggregation of the thiol group-containing compound or the like. When oxide particles are contained in the base layer, from the viewpoint of dispersibility, a liquid containing a resin, a thiol group-containing compound, etc., and oxide particles is dispersed by a method such as ultrasonic treatment or bead mill treatment. Filtration with a filter or the like is preferable because it is possible to prevent the formation of oxide agglomerates on the substrate after coating and drying.

Any suitable method can be selected as the method for forming the base layer. For example, as a coating method, various printing methods such as a gravure printing method, a flexo printing method, an offset printing method, a screen printing method, and an inkjet printing method can be used. In addition, various coating methods such as roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, curtain coating method, spray coating method, and doctor coating method can be used. ..
When the base layer is formed into a predetermined pattern, it is preferable to use a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, or an inkjet printing method.

The base layer is formed by forming the above coating method on a substrate and then drying it by a known heat drying method such as warm air drying or infrared drying, or by natural drying. The temperature at which heat drying is performed can be appropriately selected depending on the substrate to be used, but it is preferably performed at a temperature of 200 ° C. or lower.
Further, depending on the resin to be selected, treatments such as curing by light energy such as ultraviolet rays and excimer light and thermosetting with less damage to the substrate may be performed, and in particular, curing by excimer light is a preferable embodiment.

When a polar solvent having a hydroxy group such as water or a low boiling point solvent having a boiling point of 200 ° C. or less is selected as the dispersion solvent used for the dispersion liquid for forming the base layer, a drying treatment by infrared irradiation is performed as a drying method. Is preferable. In particular, it is preferable to selectively irradiate a specific wavelength region with a wavelength-controlled infrared heater or the like. By selectively using a specific wavelength region, the wavelength of the absorption region of the substrate can be cut. With respect to polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) as a substrate, the absorption of a specific wavelength emitted from the infrared heater is small, so that the heat damage to the substrate is small. In particular, it is preferable to use an infrared heater in which the filament temperature of the light source is in the range of 1600 to 3000 ° C. Since the hydroxy group has absorption at a specific wavelength emitted from the infrared heater, the solvent can be dried.

As the polar solvent having a hydroxy group, in addition to water (preferably pure water such as distilled water and deionized water), alcoholic solvents such as methanol and ethanol, glycols, glycol ethers, mixed solvents of water and alcohol, etc. Can be mentioned.
Specific examples of the glycol ether-based organic solvent include ethyl carbitol and butyl carbitol.
Specific examples of the alcohol-based organic solvent include 1-propanol, 2-propanol, n-butanol, 2-butanol, diacetone alcohol, butoxyethanol, and the like, in addition to the above-mentioned methanol and ethanol.

<Printing process of composition containing metal nanoparticles>
In the printing process of the metal nanoparticle-containing composition, the metal nanoparticle-containing composition is printed (coated) in a pattern on the base layer by a printing method.

The metal nanoparticle-containing composition contains at least the metal nanoparticles and the solvent, but may contain additives such as a dispersant, a viscosity modifier, and a binder. The solvent contained in the metal nanoparticle-containing composition is not particularly limited, but a compound having a hydroxy group is preferable, and water, alcohol, and glycol ether are preferable in that the solvent can be efficiently volatilized by irradiation with mid-infrared rays.

Examples of the solvent used in the metal nanoparticles-containing composition include water, methanol, ethanol, propanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, and hexane. Diol, heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalol, geraniol, nerol, heptadienol, tetradecenol, hexadeceneol, phytol, oleyl alcohol, dedecenol, decenol, undecylenel alcohol, nonenol , Citronerol, octenol, heptenol, methylcyclohexanol, menthol, dimethylcyclohexanol, methylcyclohexenol, terpineol, dihydrocarbeol, isopregol, cresol, trimethylcyclohexenol, glycerin, ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, butanediol, pentanediol, heptanediol, propanediol, hexanediol, octanediol, ethylene glycol monoethyl ether, ethylene glycol Examples include monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether. Be done.

A method generally used for electrode pattern formation can be applied to the pattern formation of the metal nanoparticle-containing composition by the printing method. As a specific example, regarding the gravure printing method, the methods described in JP-A-2009-295980, JP-A-2009-259286, JP-A-2009-96189, JP-A-2009-90662, and the like are flexographic methods. The printing method is described in JP-A-2004-268319, JP-A-2003-168560, etc., and the screen printing method is described in JP-A-2010-34161, JP-A-2010-10245, JP-A-2009. Examples of the method described in JP-A-302345 and the like are described in JP-A-2011-180562, JP-A-2000-127410, JP-A-8-238774 and the like for the inkjet printing method.

<Drying process of metal nanoparticle-containing composition>
Next, the metal nanoparticle-containing composition coated on the base layer is dried. The drying treatment can be carried out using a known drying method. Examples of the drying method include air cooling drying, convection heat transfer drying using warm air, radiant electric heat drying using infrared rays, conduction heat transfer drying using a hot plate, vacuum drying, and internal use of microwaves. Heat-generating drying, IPA steam drying, marangoni drying, rotagoni drying, freeze drying and the like can be used.

The drying treatment is preferably carried out in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 5000 parts by volume ppm. By performing the drying treatment with the oxygen (O ₂ ) concentration within the above range, a metal oxide derived from the metal nanoparticle-containing composition material is preliminarily formed on the surface of the metal nanoparticle-containing composition printed in a pattern. can do.
For the adjustment of the above atmosphere, it is preferable to use a dry inert gas, particularly a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by adjusting the flow rate ratio of the oxygen and the inert gas introduced into the room.

The heat drying is preferably performed in a temperature range of 50 to 200 ° C. at a temperature at which the substrate is not deformed. It is more preferable to heat the substrate under the condition that the surface temperature of the substrate is 50 to 150 ° C. When a PET substrate is used as the substrate, it is particularly preferable to heat it in a temperature range of 100 ° C. or lower. The drying time depends on the temperature and the size of the metal nanoparticles used, but is preferably in the range of 10 seconds to 30 minutes, and from the viewpoint of productivity, it is in the range of 10 seconds to 15 minutes. More preferably, it is in the range of 10 seconds to 5 minutes.

In the drying treatment, it is preferable to perform the drying treatment by infrared irradiation. In particular, it is preferable to selectively irradiate a specific wavelength region with a wavelength-controlled infrared heater or the like. By selectively using a specific wavelength region, it is possible to cut the absorption region of the substrate and selectively irradiate the solvent of the metal nanoparticle-containing composition with a specific wavelength effective. In particular, it is preferable to use an infrared heater in which the filament temperature of the light source is in the range of 1600 to 3000 ° C.
Further, it is more preferable to perform the drying treatment by combining the wavelength-controlled infrared heater and the oxygen concentration from the viewpoint of conductivity and rectification characteristics.

<Metal wire forming process (calcination of metal nanoparticles-containing composition)>
Next, the dried metal nanoparticle-containing composition is fired to form fine metal wires. The metal nanoparticle-containing composition is fired by irradiating (flash firing) light (flash light) using a flash lamp. Thereby, the conductivity of the transparent electrode can be improved.
The metal nanoparticle-containing composition is calcined in an atmosphere in which the concentration of the oxygen-containing substance is in the range of 50 to 2000 volume ppm. If the concentration of the oxygen-containing substance is less than 50 volume ppm, it is presumed that the surface of the fine metal wire is not covered with the metal oxide. Therefore, the formation of the transparent conductive layer causes the fine metal wire to be rapidly oxidized or sulfurized. This occurs, and the conductivity of the thin metal wire deteriorates. If the concentration of the oxygen-containing substance is larger than 2000 volume ppm, the crystal growth of the metal oxide generated on the surface of the metal nanoparticle-containing composition cannot be sufficiently suppressed, and the rectification characteristics are deteriorated.
For the adjustment of the above atmosphere, it is preferable to use a dry inert gas, particularly a dry nitrogen gas from the viewpoint of cost. The concentration of the oxygen-containing substance can be adjusted by adjusting the flow rate ratio of the oxygen-containing substance and the inert gas introduced into the room.

Examples of the oxygen-containing substance include oxygen (O ₂ ), water vapor, carbon monoxide, carbon dioxide, nitrogen dioxide (NO ₂ ), dinitrogen pentoxide (N ₂ O ₅ ) and the like.
Further, two or more kinds of oxygen-containing substances may be contained, and in this case, the concentration of the oxygen-containing substances contained in the system may be in the range of 50 to 2000 volume ppm as a whole.
The firing of the metal nanoparticle-containing composition is preferably carried out in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 2000 volume ppm.

As the discharge tube of the flash lamp used in the flash firing, a discharge tube of xenon, helium, neon, argon or the like can be used, but it is preferable to use a xenon lamp.

The preferred spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. Within this range, there is little damage such as thermal deformation of the substrate due to flash firing.

Light irradiation conditions of the flash lamp is arbitrary, it is preferable that total irradiation energy in the range of 0.1~50J / cm ^2, in a range of 0.5~10J / cm ² More preferred. The light irradiation time is preferably in the range of 10 μs to 100 msec, more preferably in the range of 100 μs to 10 msec. The number of times of light irradiation may be once or a plurality of times, and is preferably performed within the range of 1 to 50 times. By irradiating the flash light within these preferable condition ranges, a thin metal wire can be formed without damaging the substrate.

The flash lamp irradiation on the substrate is preferably performed from the side where the pattern of the metal nanoparticle-containing composition of the substrate is formed. When the substrate is transparent, it may be irradiated from the substrate side or from both sides of the substrate.

The surface temperature of the substrate during flash firing includes the heat resistant temperature of the substrate, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the metal nanoparticle-containing composition, the type and pressure of the atmospheric gas, and the metal nanoparticles. It may be determined in consideration of thermal behavior such as dispersibility and oxidative property of the composition, and it is preferably performed at room temperature (25 ° C.) or higher and 200 ° C. or lower.

The light irradiation device of the flash lamp may be any one that satisfies the above irradiation energy and irradiation time. Further, the flash firing can be performed in an atmosphere of an inert gas such as nitrogen, argon or helium as long as the atmosphere is within the concentration range of the oxygen-containing substance.

<Process of forming transparent conductive layer>
The transparent conductive layer according to the present invention is configured as a metal oxide layer or an organic conductive layer, as will be described later.
Hereinafter, the case where the transparent conductive layer is a metal oxide layer and the case where the transparent conductive layer is an organic conductive layer will be described separately.

(1) Formation of Metal Oxide Layer The metal oxide layer can be formed by various sputtering methods, ion plating methods, etc., in the same manner as in the case of forming a conventional metal oxide layer.

Examples of the sputtering method include DC sputtering, RF sputtering, DC magnetron sputtering, RF magnetron sputtering, ECR plasma sputtering, ion beam sputtering and the like.
Further, in the sputtering method, by examining various conditions as shown below, it is possible to adjust the conductivity and the gas barrier property even if the composition is the same as in IZO.

For example, the metal oxide layer is formed by the DC magnetron sputtering method with the distance between the target substrates during sputtering in the range of 50 to 100 mm and the sputtering gas pressure in the range of 0.5 to 1.5 Pa. Can be done.

Regarding the distance between the target substrates, if the distance between the target substrates is shorter than 50 mm, the kinetic energy of the sputter particles to be deposited increases, so that the damage to the substrates increases. In addition, the film thickness becomes non-uniform and the film thickness distribution becomes poor. If the distance between the target substrates is longer than 100 mm, the film thickness distribution is improved, but the kinetic energy of the sputter particles to be deposited becomes too low, densification due to diffusion is unlikely to occur, and the density of the metal oxide layer becomes low, which is not preferable.

Regarding the sputtering gas pressure, if the sputtering gas pressure is lower than 0.5 Pa, the kinetic energy of the deposited sputtering particles becomes large, so that the damage to the substrate becomes large. If the sputtering gas pressure is higher than 1.5 Pa, not only the film formation rate becomes slow, but also the kinetic energy of the deposited sputtering particles becomes too low, densification due to diffusion does not occur, and the density of the metal oxide layer is low. Therefore, it is not preferable.

(2) Formation of Organic Conductive Layer As a method for forming the organic conductive layer, it is preferable to form at least a mixed solution of a conductive polymer and a resin by applying it on a thin metal wire and drying it.
The solid content concentration in the coating liquid is preferably in the range of 0.5 to 30% by mass, and in the range of 1 to 20% by mass, the stagnation stability of the liquid, the smoothness of the coating film and the like. , More preferable from the viewpoint of developing the leak prevention effect.

The coating methods include roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method, and letterpress (letterpress printing). ) Printing method, letterpress (screen) printing method, flat plate (offset) printing method, concave plate (gravure) printing method, spray printing method, inkjet printing method and the like can be used.

Next, the applied coating liquid is appropriately dried. The conditions for the drying treatment are not particularly limited, but it is preferable to carry out the drying treatment at a temperature within a range in which the substrate or the like is not damaged. For example, it can be dried at 80 to 150 ° C. for 10 seconds to 30 minutes.
Further, the methods described in the above-mentioned method for drying the base layer and the method for drying the metal nanoparticle-containing composition can also be preferably used, and it is particularly preferable to perform the drying treatment with a wavelength-controlled infrared heater.

Further, from the viewpoint of wettability, the transparent conductive layer may be subjected to a surface treatment, and a conventionally known technique can be used for the surface treatment. For example, examples of the surface treatment include surface activation treatments such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

<< Manufacturing equipment for transparent electrodes >>
Examples of the transparent electrode manufacturing apparatus include a single-wafer type and a roll-to-roll method, but from the viewpoint of productivity, the roll-to-roll method is preferable.
Hereinafter, a manufacturing apparatus adopting a roll-to-roll method will be described as a manufacturing apparatus applicable to the transparent electrode manufacturing method described above, but the present invention is not particularly limited thereto.

The manufacturing apparatus 100 shown in FIG. 3 includes a delivery roller 20, a first film forming chamber 30, a second film forming chamber 40, a third film forming chamber 50, and a winding roller 60, and the transparent resin substrate 1 is , In this order, they are conveyed from the delivery roller 20 to the take-up roller 60.

In the first film forming chamber 30, a base layer is formed on the transparent resin substrate 1 carried in from the delivery roller 20. The first film forming chamber has a coating portion 31, a drying portion 32, and a curing portion 33 from the upstream side to the downstream side. The base layer forming coating liquid is applied onto the transparent resin substrate 1 in the coating portion 31, and the base layer forming coating liquid is dried and cured in the drying portion 32 and the curing portion 33 to form the base layer. The cured portion 33 is preferably cured by excimer light.

A partition wall may be appropriately provided between the coating portion 31, the drying portion 32, and the curing portion 33.

Next, a thin metal wire is formed on the base layer in the second film forming chamber 40. The second film forming chamber 40 has a printing unit 41, a drying unit 42, and a firing unit 43 from the upstream side to the downstream side. The printing unit 41 prints the metal nanoparticle-containing composition on the base layer in a pattern. The metal nanoparticle-containing composition printed in this pattern is dried in the drying section 42. At this time, it is preferable to dry in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 5000 volume ppm. Finally, the metal nanoparticles-containing composition dried in the firing unit 42 is irradiated with flash light and fired to form fine metal wires. As described above, the firing of the metal nanoparticle-containing composition is carried out in an atmosphere in which the concentration of the oxygen-containing substance is in the range of 50 to 2000 volume ppm.

A partition wall, a pressure adjusting chamber, or the like may be appropriately provided between the printing unit 41, the drying unit 42, and the firing unit 43, and in particular, the oxygen (or oxygen-containing substance) concentration differs between the drying unit 42 and the firing unit 43. When drying and firing in the above, it is preferable to provide at least a partition wall or the like between the drying portion 42 and the firing portion 43.

Next, a transparent conductive layer is formed in the third film forming chamber 50. The third film forming chamber 50 has at least a film forming portion 51, and when the transparent conductive layer is a metal oxide layer, the transparent conductive layer is formed on the thin metal wire by a sputtering method or the like in the film forming section 51. In the case of an organic conductive layer, a transparent conductive layer is formed on a thin metal wire by a coating method at the film forming portion 51, and then the coating liquid is dried at a drying portion (not shown).

The transparent resin substrate 1 that has undergone the above steps is wound by a take-up roller 60 to produce a transparent electrode having a transparent conductive layer formed on the transparent resin substrate 1.

<< Constructible sheaf of transparent electrode >>
Hereinafter, each member constituting the transparent electrode according to the present invention will be described.

<Thin metal wire (2)>
The thin metal wire according to the present invention is mainly composed of a metal and is formed with a metal content ratio to the extent that conductivity can be obtained. The ratio of the metal in the thin metal wire is preferably 50% by mass or more.

The fine metal wire contains a metal material and is formed in a pattern so as to have an opening on the base layer. The opening is a portion having no thin metal wire and is a translucent portion of the transparent electrode.

The pattern shape of the thin metal wire is not particularly limited. Examples of the pattern shape of the fine metal wire include a striped shape (parallel line shape), a lattice shape, a honeycomb shape, a random mesh shape, and the like, and from the viewpoint of transparency, the striped shape is particularly preferable.

Further, the ratio (opening ratio) occupied by the openings is preferably 80% or more from the viewpoint of transparency. For example, the aperture ratio of a striped pattern having a line width of 100 μm and a line spacing of 1 mm is about 90%.

The line width of the thin metal wire is preferably in the range of 10 to 200 μm, more preferably in the range of 10 to 100 μm. When the line width of the thin metal wire is 10 μm or more, the desired conductivity can be obtained, and when it is 200 μm or less, the transparency of the transparent electrode is improved. Further, in the striped or lattice-shaped pattern, the interval between the fine metal wires is preferably in the range of 0.5 to 4 mm.

The height (thickness) of the thin metal wire is preferably in the range of 0.1 to 5.0 μm, and more preferably in the range of 0.1 to 2.0 μm. When the height of the thin metal wire is 0.1 μm or more, the desired conductivity can be obtained, and when it is 5.0 μm or less, the difference in unevenness affects the layer thickness distribution of the functional layer when used in an organic electronic device. Can be reduced.

(1) Metal Nanoparticle-Containing Composition As described above, the metal nanoparticle-containing composition is prepared by preparing a metal or a metal nanoparticle-containing composition containing a metal-forming material, applying the mixture, and then drying or firing. The treatment is appropriately performed to form.
Examples of the metal used for the metal nanoparticles include metals such as gold, silver, copper and platinum, and alloys containing these as main components. Among these, gold and silver are preferable from the viewpoint of having excellent light reflectance and further improving the efficiency of the obtained organic electronic device. Any one of these metals or alloys may be used alone, or two or more thereof may be used in combination as appropriate.

The metal nanoparticle-containing composition is preferably a metal colloid or a metal nanoparticle dispersion liquid having a structure in which the surface of the metal nanoparticles is coated with a protective agent and stably and independently dispersed in a solvent.

As the average particle size of the metal nanoparticles in the metal nanoparticle-containing composition, those having an atomic scale of 1000 nm or less can be preferably applied. In particular, as the metal nanoparticles, those having an average particle size in the range of 3 to 300 nm are preferable, and those having an average particle size in the range of 5 to 100 nm are more preferably used. In particular, silver nanoparticles having an average particle size in the range of 3 to 100 nm are preferable.

Here, the average particle size of the metal nanoparticles and the metal colloid can be determined by measuring the particle size of the metal nanoparticles in the dispersion using a transmission electron microscope (TEM). For example, among the particles observed in the TEM image, the particle diameter of 300 independent metal nanoparticles that do not overlap can be measured to calculate the average particle diameter.

In the metal colloid, the organic π-bonded ligand is preferable as the protective agent for coating the surface of the metal nanoparticles. Conductivity is imparted to the metal colloid by π-bonding the organic π-conjugated ligand to the metal nanoparticles.

As the organic π-bonded ligand, one or more compounds selected from the group consisting of phthalocyanine derivatives, naphthalocyanine derivatives and porphyrin derivatives are preferable.
Further, the organic π-bonded ligand includes an amino group, an alkylamino group, a mercapto group, a hydroxyl group as substituents in order to improve the coordination to metal nanoparticles and the dispersibility in the dispersion medium. At least one selected from a carboxyl group, a phosphine group, a phosphonic acid group, a sulfonic acid group, a halogen group, a selenol group, a sulfide group, a selenoether group, an amide group, an imide group, a cyano group, a nitro group, and salts thereof. It is preferable to have a substituent of.

Further, as the organic π-bonded ligand, the organic π-conjugated ligand described in International Publication No. 2011/114713 can be used.

As a specific compound of the organic π-bonded ligand, one or more selected from the following OTAN, OTAP and OCAN are preferable.
OTAN: 2,3,11,12,20,21,29,30-octakis [(2-N, N-dimethylaminoethyl) thio] naphthalocyanine OTAP: 2,3,9,10,16,17,23 , 24-octakis [(2-N, N-dimethylaminoethyl) thio] phthalocyanine OCAN: 2,3,11,12,20,21,29,30-naphthalocyanine octacarboxylic acid

As a method for preparing a metal nanoparticle dispersion liquid containing an organic π-bonded ligand, a liquid phase reduction method can be mentioned. Further, the production of the organic π-bonded ligand of the present embodiment and the preparation of the metal nanoparticle dispersion liquid containing the organic π-bonded ligand are described in the methods described in paragraphs 0039 to 0060 of International Publication No. 2011/114713. It can be done according to the same procedure.

The average particle size of the metal colloid is usually in the range of 3 to 500 nm, preferably in the range of 5 to 50 nm. When the average particle size of the metal colloid is within the above range, fusion between the particles is likely to occur, and the conductivity of the obtained fine metal wire can be improved.

In the metal nanoparticle dispersion liquid, as the protective agent for coating the surface of the metal nanoparticles, it is preferable to use a protective agent from which the ligand is released at a low temperature of 200 ° C. or lower. As a result, the protective agent is removed by low temperature or low energy, metal nanoparticles are fused, and conductivity can be imparted.
Specific examples thereof include the metal nanoparticle dispersions described in JP2013-142173, JP2012-162767, JP2014-139343, and Patent No. 5606439.

Examples of the metal forming material include metal salts, metal complexes, organometallic compounds (compounds having a metal-carbon bond), and the like. The metal salt and the metal complex may be either a metal compound having an organic group or a metal compound having no organic group. By using a metal-forming material in the metal nanoparticle-containing composition, a metal is generated from the material, and a metal fine wire containing this metal is formed.

As the material for forming metallic silver, it is preferable to use an organic silver complex prepared by reacting a silver compound represented by "Ag _n X" with an ammonium carbamate compound. In "Ag _n X", n is an integer of 1 to 4, where X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrite, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, It is a substituent selected from the group composed of acetylacetonate and carboxylate.

Examples of the silver compound include silver oxide, silver thiocyanate, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoride, and acetylacetate. Examples thereof include silver nitrate, silver acetate, silver lactate, and silver oxalate. As the silver compound, it is preferable to use silver oxide or silver carbonate in terms of reactivity and post-treatment.

Examples of the ammonium carbamate compound include ammonium carbamate, ethyl ammonium ethyl carbamate, isopropylammonium isopropyl carbamate, n-butylammonium n-butyl carbamate, isobutylammonium isobutyl carbamate, t-butylammonium t-butyl carbamate, and 2-ethylhexyl ammonium 2. -Ethylhexyl ammonium carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutylammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl decyl carbamate, hexamethylene Examples thereof include iminium hexamethyleneimine carbamate, morphorium morpholin carbamate, pyridinium ethylhexyl carbamate, triethylenediaminium isopropyl bicarbamate, benzylammonium benzyl carbamate, triethoxysilylpropylammonium triethoxysilylpropyl carbamate and the like. Among the above ammonium carbamate compounds, the alkylammonium alkyl carbamate substituted with the primary amine is preferable because it is superior to the secondary or tertiary amine in terms of reactivity and stability.

The organic silver complex can be produced by the method described in JP-A-2011-48795. For example, one or more of the silver compounds and one or more of the ammonium carbamate compounds can be synthesized by directly reacting them under normal pressure or pressure in a nitrogen atmosphere without using a solvent. Also, alcohols such as methanol, ethanol, isopropanol and butanol, glycols such as ethylene glycol and glycerin, acetates such as ethyl acetate, butyl acetate and carbitol acetate, ethers such as diethyl ether, tetrahydrofuran and dioxane. , Methyl ethyl ketone, ketones such as acetone, hydrocarbons such as hexane and heptane, aromatics such as benzene and toluene, and solvents such as halogen-substituted solvents such as chloroform, methylene chloride and carbon tetrachloride. Can be reacted.

The structure of the organic silver complex can be represented by "Ag [A] _m ". In "Ag [A] _m ", A is the above-mentioned ammonium carbamate compound, and m is 0.7 to 2.5.

The organic silver complex is well soluble in a variety of solvents, including solvents for producing organic silver complexes, such as alcohols such as methanol, esters such as ethyl acetate, and ether solvents such as tetrahydrofuran. Therefore, the organic silver complex can be easily applied to a coating or printing step as a metal nanoparticle-containing composition.

Further, as a material for forming metallic silver, silver carboxylate having a group represented by the formula "-COOAg" can be exemplified. The silver carboxylate is not particularly limited as long as it has a group represented by the formula "-COOAg". For example, the number of groups represented by the formula "-COOAg" may be only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

The silver carboxylate is preferably one or more selected from the group consisting of silver β-ketocarboxylate described in JP-A-2015-66695 and silver carboxylate (4). As the material for forming metallic silver, not only β-ketosilver carboxylate and silver carboxylate (4) but also silver carboxylate having a group represented by the formula "-COOAg" including these can be used. it can.

When the metal nanoparticles-containing composition contains the silver carboxylate as a metal-forming material, the amine compound having 25 or less carbon atoms, the quaternary ammonium salt, ammonia, and the amine compound or ammonia are acids together with the silver carboxylate. It is preferable that one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting with the above are blended.

The amine compound has 1 to 25 carbon atoms and may be any of a primary amine, a secondary amine and a tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain-like or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or the ammonium salt moiety (for example, the nitrogen atom constituting the amino group "-NH ₂ " of the primary amine) may be one or two or more.

<Transparent conductive layer (3)>
The transparent conductive layer according to the present invention is provided on the thin metal wire, and it is preferable that the transparent conductive layer is provided so as to cover the entire surface of the thin metal wire.
The transparent conductive layer is configured as a metal oxide layer or an organic conductive layer.

The thickness of the transparent conductive layer according to the present invention is in the range of 30 to 300 nm. The transparent electrode produced by the production method of the present invention can sufficiently exhibit conductivity even if the thickness of the transparent conductive layer is within the above range. The thickness of the transparent conductive layer is more preferably in the range of 50 to 150 nm.

The metal oxide layer and the organic conductive layer are preferably formed by using a highly conductive metal oxide having a volume resistivity in the range of 1 × ^10-5 to 1 × 10 ^-2 Ω · cm. The volume resistivity can be obtained by measuring the sheet resistance and the film thickness measured in accordance with the resistivity test method by the four-probe method of conductive plastic of JIS K 7194: 1994. The film thickness can be measured using a contact type surface shape measuring device (for example, DECTK) or a light interference surface shape measuring device (for example, WYKO).
Further, the metal oxide layer and the organic conductive layer have a sheet resistance of 10000 Ω / sq. From the viewpoint of ensuring conductivity. It is preferably 2000Ω / sq. More preferably:

(1) Metal Oxide Layer The metal oxide that can be used for the metal oxide layer is not particularly limited as long as it is a material having excellent transparency and conductivity. Examples of the metal oxide that can be used in the metal oxide layer include ITO (tin-doped indium oxide), IZO (indium oxide / zinc oxide), IGO (gallium-doped indium oxide), IWZO (indium oxide / tin oxide), and ZnO (znO). Zinc oxide), GZO (Ga-doped zinc oxide), IGZO (indium, gallium, zinc oxide) and the like.

In particular, as the metal oxide that can be used in the metal oxide layer, IZO, IGO, and IWZO are preferable. Above all, as IZO, a composition represented by a mass ratio of In ₂ O ₃ : ZnO = 80 to 95: 20 to 5 is preferable. As the IGO, a composition represented by a mass ratio of In ₂ O ₃ : Ga ₂ O ₃ = 70 to 95:30 to 5 is preferable. As the IWZO, a composition represented by a mass ratio of In ₂ O ₃ : WO ₃ : ZnO = 95 to 99.8: 2.5 to 0.1: 2.5 to 0.1 is preferable.

The transparent electrode may be provided with a plurality of metal oxide layers.

(2) Organic Conductive Layer The organic conductive layer is mainly composed of a conductive polymer and a binder. As the conductive polymer and the binder, the compounds described in Japanese Patent No. 5750908 and Japanese Patent No. 5782855 can be used. In addition, the preparation (method) of the organic conductive composition for forming the organic conductive layer, the formation (method) of the organic conductive layer, etc. shall be carried out according to the methods described in Japanese Patent No. 5750908 and Japanese Patent No. 5782855. Can be done.

<Underground layer (4)>
The base layer according to the present invention is a layer that serves as a base for forming a thin metal wire or a transparent conductive layer, and improves the adhesion between the substrate and the thin metal wire or the transparent conductive layer.
The base layer preferably contains a compound having a thiol group and a compound selected from poly (meth) acrylate and poly (meth) acrylamide having an aminoethyl group, and two or more of them are used in combination. You may.

Further, the underlying layer may contain inorganic particles in addition to the above compounds, and is particularly preferably formed containing oxide particles. Since the base layer contains oxide particles, the adhesion to the fine metal wire and the transparent conductive layer is improved.

Further, the base layer can be provided with a function other than improving the adhesion to the thin metal wire or the transparent conductive layer. As a function other than adhesion, it is preferable to have a light extraction function. In order to impart a light extraction function to the base layer, it is preferable to include oxide particles having a higher refractive index than the resin together with the resin constituting the base layer. Oxide particles having a higher refractive index than this resin function as light scattering particles in the base layer, so that light scattering occurs in the base layer and a light extraction function is imparted to the base layer.

The thickness of the base layer is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 100 nm. When the thickness of the base layer is 10 nm or more, the base layer itself becomes a continuous film and the surface becomes smooth, and the influence on the organic electronic device is small. On the other hand, when the thickness of the base layer is 1000 nm or less, the transparency of the transparent electrode due to the base layer can be reduced and the adsorption gas derived from the base layer can be reduced, and the deterioration of the resistance of the thin metal wire can be suppressed. it can. Further, when the thickness of the base layer is 1000 nm or less, damage to the base layer when the transparent electrode is bent can be suppressed.

The transparency of the base layer can be arbitrarily selected depending on the application, but the higher the transparency, the better the application to the transparent electrode, which is preferable from the viewpoint of expanding the application. The total light transmittance of the base layer is at least 40% or more, preferably 50% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like.

(Compound with thiol group)
The compound having a thiol group (also referred to as a mercapto group) (hereinafter, also referred to as a thiol group-containing compound) is not particularly limited as long as the effect of the present invention is not impaired.
The thiol group-containing compound according to the present invention is preferably a polyfunctional thiol group-containing compound having two or more thiol groups. As a result, it is possible to achieve adhesion with a fine metal wire containing a more metallic material.

The thiol group-containing compound is preferably a condensate of a compound having a structure represented by the following general formula (I) and a monohydric or polyhydric alcohol or an amine.

In the general formula (I), R ¹ and R ² independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them is an alkyl group having 1 to 10 carbon atoms. m is an integer from 0 to 2, and n is 0 or 1.

The alkyl group having 1 to 10 carbon atoms in R ¹ and R ² may be linear or branched, and specifically, a methyl group, an ethyl group, an n-propyl group, or iso-. Examples thereof include a propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, an n-octyl group and the like, and a methyl group or an ethyl group is preferable.

m is an integer from 0 to 2, but is preferably 0 or 1.
n is 0 or 1, but preferably 0.

Examples of the compound having the structure represented by the general formula (I) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, 3-mercaptoisobutyric acid and the like.

As monohydric alcohols, methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-Methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2 -Pentanol, 1-heptanol, 2-heptanol, 2-methyl-2-heptanol, 2-methyl-3-heptanol and the like can be mentioned.

Examples of the polyhydric alcohol include glycols (however, the alkyllen group preferably has 2 to 10 carbon atoms, and the carbon chain may be branched), for example, ethylene glycol, diethylene glycol, 1,2-propylene. Glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane , Dipentaerythritol and the like.
Of these, ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane and pentaerythritol are preferable.

As the alcohol that condenses with the compound having the structure represented by the general formula (I), a polyfunctional thiol group-containing compound can be obtained, and thus a polyhydric alcohol is preferable.

The amine is not particularly limited and may be any of primary to primary amines, but for example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine and dimethyl. Amine, diethylamine, dipropylamine, dibutylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylene diamine, tolylene diamine, paraxylylene diamine, phenylenediamine, isophoronediamine And so on.

Specific examples of the thiol group-containing compound applicable to the underlying layer according to the present invention are exemplified compounds SH-1 to SH-155, SE-1 to SE-84 and SA-1 to SA-34.

In addition, as the thiol group-containing compound, the compounds described in Japanese Patent No. 4911666 and Japanese Patent No. 4917294 can also be preferably used.

The above-exemplified compounds SH-1 to SH-155, SE-1 to SE-84 and SA-1 to SA-34 can be synthesized by a known method.

Further, as the thiol group-containing compound, a silsesquioxane derivative having a thiol group (hereinafter, also simply referred to as a silsesquioxane derivative) can be used.
The silsesquioxane derivative is not particularly limited, but is preferably a compound having a cage-type siloxane structure represented by the following general formula (A).

In the general formula (A), X ^A represents the following X ¹ or X ² , but at least one of X ^A is X ² .

In X ¹ and X ² , R ^{1 to} R ⁵ independently represent an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon ring group. A represents a divalent hydrocarbon group having 1 to 8 carbon atoms.

The alkyl group having 1 to 8 carbon atoms represented by R ^{1 to} R ⁵ in X ¹ and X ² may be linear or branched, and specifically, a methyl group. Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like can be mentioned.

Examples of the aromatic hydrocarbon ring group represented by R ^{1 to} R ⁵ in X ¹ and X ² include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms represented by A in X ² include a linear or branched alkylene group having 1 to 8 carbon atoms. Among these, linear alkylene groups having 2 or 3 carbon atoms such as −CH ₂ CH ₂ − and −CH ₂ CH ₂ CH ₂ − are preferable because the silsesquioxane derivative can be easily synthesized.

Further, as a commercially available silsesquioxane derivative, composelan (registered trademark) SQ100 series manufactured by Arakawa Chemical Industries, Ltd. can also be used.

In addition, JP-A-2015-59108, JP-A-2012-180464 and the like can be referred to as a silsesquioxane derivative having a thiol group applicable to the present invention and a method for synthesizing the derivative.

(Poly (meth) acrylate having aminoethyl group and poly (meth) acrylamide)
The poly (meth) acrylate and poly (meth) acrylamide having an aminoethyl group are not particularly limited as long as they do not inhibit the effect of the present invention, but are preferably having a partial structure represented by the following general formula (II). ..

In general formula (II), R ³ represents a hydrogen atom or a methyl group. Q represents −C (= O) O− or −C (= O) NRa−. Ra represents a hydrogen atom or an alkyl group. A is a substituted or unsubstituted alkylene group, or _{- (CH 2 CHRbNH) x -CH} 2 CHRb- represent, Rb represents a hydrogen atom or an alkyl group, x represents the average number of repeating units, and a positive integer Is.

As the alkyl group in Ra, for example, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable.

Moreover, these alkyl groups may be substituted with a substituent. Examples of these substituents include alkyl group, cycloalkyl group, aryl group, heterocycloalkyl group, heteroaryl group, hydroxy group, halogen atom, alkoxy group, alkylthio group, arylthio group, cycloalkoxy group, aryloxy group, Acyl group, alkylcarboxylic amide group, arylcarboxylic amide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulfonyl group, arylsulfonyl group, alkyloxysulfonyl group, aryloxysulfonyl group, alkylsulfonyloxy group, arylsulfonyl It may be substituted with an oxy group or the like. Of these, a hydroxy group and an alkyloxy group are preferable.

The alkyl group as the substituent may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, and even more preferably 1 to 8. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group and the like.
The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
The number of carbon atoms of the heterocycloalkyl group is preferably 2 to 10, and more preferably 3 to 5. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, a 2-morpholinyl group and the like.
The number of carbon atoms of the heteroaryl group is preferably 3 to 20, and more preferably 3 to 10. Examples of the heteroaryl group include a thienyl group and a pyridyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkoxy group may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, further preferably 1 to 6, and 1 to 4. Is the most preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group, an octyloxy group and the like, and an ethoxy group is preferable.
The alkylthio group may be branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 12, further preferably 1 to 6, and 1 to 4. Is the most preferable. Examples of the alkylthio group include a methylthio group and an ethylthio group.
The arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group and a naphthylthio group.
The cycloalkoxy group preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutyloxy group, a cyclopentyroxy group, a cyclohexyloxy group and the like.
The aryloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
The acyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, a benzoyl group and the like.
The alkylcarboxylic amide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarboxylic amide group include an acetamide group.
The arylcarboxylic amide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarboxylic amide group include a benzamide group.
The alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the sulfonamide group include a methane sulfonamide group.
The arylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylsulfonamide group include a benzenesulfonamide group and a p-toluenesulfonamide group.
The carbon number of the aralkyl group is preferably 7 to 20, and more preferably 7 to 12. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
The alkoxycarbonyl group preferably has 1 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
The aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
The aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms. Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
The acyloxy group preferably has 1 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, an isopropenyl group and the like.
The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 12 carbon atoms. Examples of the alkynyl group include an ethynyl group and the like.
The alkylsulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.
The arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
The alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkyloxysulfonyl group include a methoxysulfonyl group and an ethoxysulfonyl group.
The aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.
The alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylsulfonyloxy group include a methylsulfonyloxy group and an ethylsulfonyloxy group.
The arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group.
The substituents may be the same or different, and these substituents may be further substituted.

The alkylene group in A preferably has 1 to 5 carbon atoms, and more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the above-mentioned substituents.
As the alkyl group in Rb, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable. These alkyl groups may be substituted with the above-mentioned substituents.

The average number of repeating units x is not particularly limited as long as it is a positive integer, but is preferably an integer of 1 to 20.

The weight average molecular weight (Mw) of the poly (meth) acrylate and the poly (meth) acrylamide is preferably in the range of 10,000 to 500,000, more preferably in the range of 30,000 to 200,000. When the weight average molecular weight (Mw) is 10,000 or more, the underlying layer containing poly (meth) acrylate and poly (meth) acrylamide is hard, so that the film thickness changes over time, changes in film thickness under forced deterioration conditions, and interface deterioration with other layers. No electrical or optical defects occur without causing. Further, if it is 500,000 or less, the solubility in the coating solution for forming the base layer and the compatibility with other compounds are good, and further, there is a problem of peeling from other layers having different hardness in a low temperature or high temperature environment. It does not occur.

(1) Poly (meth) acrylate having an aminoethyl group Examples of the poly (meth) acrylate having an aminoethyl group include a polymer or a copolymer of a (meth) acrylate having an aminoethyl group.
Examples of the (meth) acrylate include a monofunctional or bifunctional (meth) acrylate having one or two (meth) acryloyl groups and a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups. ..

Examples of the monofunctional (meth) acrylate include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl. (Meta) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate , C _1-24 alkyl (meth) acrylate such as stearyl (meth) acrylate, cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Bridge ring type (meth) acrylate such as dicyclopentenyloxyethyl (meth) acrylate, Bornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenyl (meth) acrylate, nonylphenyl ( Aryl (meth) acrylate such as meta) acrylate, aralkyl (meth) acrylate such as benzyl (meth) acrylate, hydroxy C _2- such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate. Fluoro C _1-10 alkyl such as ₁₀ alkyl (meth) acrylate or C _2-10 alcandiol mono (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate Alkoxyalkyl (meth) acrylates such as (meth) acrylates and methoxyethyl (meth) acrylates, aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylates and phenoxypropyl (meth) acrylates, and phenylcarbitol (meth) acrylates. , Aryloxy (poly) alkoxyalkyl (meth) acrylates such as nonylphenylcarbitol (meth) acrylates and nonylphenoxy polyethylene glycol (meth) acrylates, polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylates, Glycerin mono (meta) ) Alcan polyol such as acrylate Mono (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-t-butylaminoethyl (meth) acrylate and other amino groups or substituted amino groups (Meta) acrylate having, glycidyl (meth) acrylate and the like can be mentioned.

Examples of the bifunctional (meth) acrylate include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, and 1,4-butane. Alkane diol di (meth) acrylate such as diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, alkane polyol di (meth) acrylate such as glycerin di (meth) acrylate. ) Polyalkylene glycol di () acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. Meta) acrylate, 2,2-bis (4- (meth) acryloxiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxidiethoxyphenyl) propane, 2,2-bis (4-( Di (meth) acrylate of C _2-4 alkylene oxide adduct of bisphenols (bisphenol A, bisphenol S, etc.) such as meta) acryloxipolyethoxyphenyl) propane, di (meth) acrylate of acid-modified alkane polyol such as fatty acid-modified pentaerythritol. Examples thereof include a bridging ring-type di (meth) acrylate such as a meta) acrylate, a tricyclodecanedimethanol di (meth) acrylate, and an adamantandi (meth) acrylate.

Further, examples of the bifunctional (meth) acrylate include epoxy di (meth) acrylate (bisphenol A type epoxy di (meth) acrylate, novolak type epoxy di (meth) acrylate, etc.) and polyester di (meth) acrylate (for example, aliphatic polyester). Type di (meth) acrylate, aromatic polyester type di (meth) acrylate, etc.), (poly) urethane di (meth) acrylate (polyester type urethane di (meth) acrylate, polyether type urethane di (meth) acrylate, etc.), silicone (meth) ) Also examples include oligomers or resins such as acrylate.

Examples of the polyfunctional (meth) acrylate include an esterified product of a polyhydric alcohol and a (meth) acrylic acid, for example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolethane tri (meth) acrylate. Examples thereof include pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. Furthermore, in these polyfunctional (meth) acrylates, the polyhydric alcohol may be an adduct of an alkylene oxide (eg, C _2-4 alkylene oxide such as ethylene oxide or propylene oxide).

Among these polyfunctional (meth) acrylates, 3 to 6-functional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable, and pentaerythritol is preferable. 3-4 functional (meth) acrylates such as tri (meth) acrylate are more preferred.
Further, as the polyfunctional (meth) acrylate, a polyfunctional (meth) acrylate not modified with an amine (an unmodified polyfunctional (meth) acrylate to which amines are not added by Michael addition or the like) is preferable.

These (meth) acrylates can be used alone or in combination of two or more.

Hereinafter, exemplary compounds PE-1 to PE-9 are shown as specific examples of the poly (meth) acrylate having an aminoethyl group applicable to the underlying layer according to the present invention. In addition, x and y in the following exemplified compounds represent the polymerization ratio of the copolymer. The polymerization ratio can be appropriately adjusted according to the solubility, electrode performance, etc., and can be, for example, x: y = 10: 90 or the like.

The above-exemplified compounds PE-1 to PE-9 can be synthesized by a known method. More specifically, (i) a method of aminoethylating (meth) acrylate and then polymerizing or copolymerizing, and (ii) a method of polymerizing (meth) acrylate and then aminoethylating it can be mentioned.
The method for synthesizing the exemplary compound PE-7 is shown below as an example.

[Synthesis Example] Synthesis of Exemplified Compound PE-7 80 parts by mass of toluene was charged into a glass reactor equipped with a thermometer, a stirrer, and a reflux condenser, and the internal temperature was heated to 110 ° C. 1.2 parts by mass of 2,2-azobis- (2-methylbutyronitrile) was added as an initiator, and a mixed solution consisting of 100 parts by mass of methyl methacrylate and 18 parts by mass of acrylic acid was added dropwise over 3 hours, and further 4 Continued heating for hours. After completion of the reaction, toluene was added to obtain a carboxy group-containing polymer solution.

120 parts by mass of the above carboxy group-containing polymer solution and 60 parts by mass of toluene were charged, and a mixed solution of 53.8 parts by mass of ethyleneimine and 30 parts by mass of toluene was added dropwise at 40 ° C. over 30 minutes. After the dropping, the reaction was carried out at 40 ° C. for 2 hours, the internal temperature was raised to 70 ° C., and the mixture was further stirred for 5 hours for aging to obtain an exemplary compound PE-7.
The conversion rate of the carboxy group to the amino group was 100% when calculated from the amount of ethyleneimine consumed calculated from the analysis of gas chromatography.
Subsequently, unreacted ethyleneimine was removed by distillation under reduced pressure. When the polymer solution after distillation under reduced pressure was analyzed by gas chromatography having a detection limit of 1 ppm or less, ethyleneimine was not detected.

In addition, the methods described in JP-A-4-356448, JP-A-2003-41000 and the like can also be referred to.

(2) Poly (meth) acrylamide having an aminoethyl group Examples of the poly (meth) acrylamide having an aminoethyl group include a polymer or a copolymer of (meth) acrylamide having an aminoethyl group.

Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-benzyl (meth). Acrylamide, N-hydroxyethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N- (hydroxyphenyl) (meth) acrylamide, N- (sulfamoylphenyl) (meth) acrylamide , N- (phenylsulfonyl) (meth) acrylamide, N- (trillsulfonyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl- Examples thereof include N-methyl (meth) acrylamide.

Hereinafter, exemplary compounds PA-1 to PA-12 are shown as specific examples of poly (meth) acrylamide having an aminoethyl group applicable to the underlying layer according to the present invention. In addition, x and y in the following exemplified compounds represent the polymerization ratio of the copolymer. The polymerization ratio can be, for example, x: y = 10: 90 or the like.

The above-exemplified compounds PA-1 to PA-12 can be synthesized by a known method. Aminoethylation of (meth) acrylamide or aminoethylation of poly (meth) acrylamide (homopolymer) can be carried out in the same manner as the aminoethylation of (meth) acrylate or poly (meth) acrylate described above.

(resin)
The resin constituting the base layer is not particularly limited as long as it can form the base layer.
For example, a known natural polymer material having a repeating structure of a monomer or a synthetic polymer material can be used. For these, an organic polymer material, an inorganic polymer material, an organic-inorganic hybrid polymer material, a mixture thereof, and the like can be used. Two or more of these resins can be mixed and used.

The resin can be synthesized by a known method. Natural polymer materials can be extracted from natural raw materials or synthesized by microorganisms such as cellulose. The synthetic polymer can be obtained by radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, ring-opening polymerization, polycondensation, addition polymerization, addition condensation, living polymerization thereof and the like.

Further, these resins may be homopolymers or copolymers, and when a monomer having asymmetric carbon is used, they can have a regularity of any one of random, syndiotackic, and isotackic. Further, in the case of a copolymer, it can take the form of random copolymerization, alternate copolymerization, block copolymerization, graft copolymerization and the like.

As for the form of the resin, the resin itself may be a liquid or a solid. Further, it is preferable that the resin is dissolved in a solvent or uniformly dispersed in the solvent. Further, the resin may be a water-soluble resin or a water-dispersible resin.

Further, the resin may be an ionizing radiation curable resin that is cured by ultraviolet rays or an electron beam, a thermosetting resin that is cured by heat, or a resin produced by a sol-gel method. Further, the resin may be crosslinked.

In the above-mentioned resins, natural polymers and synthetic polymers are described in the respective sections of "Chemical Encyclopedia" (Tokyo Kagaku Dojin, 1989), pages 1551 and 769, edited by Michinori Oki, Toshiaki Osawa, Motoharu Tanaka, and Hideaki Chihara. Can be used as an example.

Specifically, as the natural polymer material, a natural organic polymer material is preferable, and natural fibers such as cotton, hemp, cellulose, silk and wool, proteins such as gelatin, and natural rubber can be mentioned. Synthetic polymer materials include polyolefin resin, polyacrylic resin, polyvinyl resin, polyether resin, polyester resin, polyamide resin, polyurethane resin, polyphenylene resin, polyimide resin, polyacetal resin, polysulfone resin, fluororesin, epoxy resin, and silicone resin. , Phenolic resin, melamine resin, polyurethane resin, polyurea resin, polycarbonate resin, polyketone resin and the like.

Examples of the polyolefin resin include polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), and polyisoprene. , Polybutadiene, polycyclopentene, polynorbornene and the like.
Examples of the polyacrylic resin include polymethacrylate, polyacrylate, polyacrylamide, polymethacrylamide, polyacrylonitrile and the like.
Examples of the polyvinyl resin include polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polymethyl vinyl ether, polyethyl vinyl ether, polyisobutyl vinyl ether and the like.
Examples of the polyether resin include polyalkylene glycols such as polyethylene oxide and polypropylene oxide.
Examples of the polyester resin include polyalkylene phthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyalkylene naphthalates such as polyethylene naphthalate.
Examples of the polyamide resin include polyamide 6, polyamides 6 and 6, polyamide 12, and polyamide 11.
Examples of the fluororesin include polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene and the like.

The above-mentioned water-soluble resin means a resin that dissolves 0.001 g or more in 100 g of water at 25 ° C. The degree of dissolution can be measured with a haze meter, a turbidity meter, or the like. The color of the water-soluble resin is not particularly limited, but it is preferably transparent. The number average molecular weight of the water-soluble resin is preferably in the range of 3000 to 20000000, more preferably in the range of 4000 to 500000, and further preferably in the range of 5000 to 100,000.

The number average molecular weight and molecular weight distribution of the water-soluble resin can be measured by generally known gel permeation chromatography (GPC). The solvent used is not particularly limited as long as the binder is dissolved, but tetrahydrofuran (THF), dimethylformamide (DMF) and dichloromethane (CH ₂ Cl ₂ ) are preferable, THF and DMF are more preferable, and DMF is further preferable. Is. The measurement temperature is also not particularly limited, but is preferably 40 ° C.

Specific examples of the water-soluble resin include natural polymer materials and synthetic polymer materials such as acrylic, polyester, polyamide, polyurethane, and fluorine-based resins, and examples thereof include casein, starch, and agar. , Carrageenan, sesulose, hydroxylethyl cellulose, carboxylmethylcellulose, hydroxylethylcellulose, dextran, dextrin, purulan, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly (2-hydroxyethyl acrylate), poly ( 2-Hydroxyethyl methacrylate), polyacrylamide, polymethacrylicamide, polystyrene sulfonic acid, water-soluble polyvinyl butyral and other polymers can be mentioned.

The above-mentioned water-dispersible resin means a resin that can be uniformly dispersed in an aqueous solvent and in which colloidal particles made of the resin are dispersed without agglomerating in the aqueous solvent. The size (average particle size) of the colloidal particles is generally in the range of 1 to 1000 nm. The average particle size of the above colloidal particles can be measured with a light scattering photometer.

The aqueous solvent is not only pure water such as distilled water and deionized water, but also an aqueous solution containing acids, alkalis, salts and the like, a water-containing organic solvent, and a solvent such as a hydrophilic organic solvent. An alcohol-based solvent such as methanol or ethanol, a mixed solvent of water and alcohol, or the like can be mentioned. The water-dispersible resin is preferably transparent. The water-dispersible resin is not particularly limited as long as it is a medium for forming a film. Examples of the water-dispersible resin include water-based acrylic resin, water-based urethane resin, water-based polyester resin, water-based polyamide resin, water-based polyolefin resin and the like.

Examples of the aqueous acrylic resin include a polymer of vinyl acetate, acrylic acid, acrylic acid-styrene, or a copolymer with other monomers. In addition, the acid moiety responsible for imparting dispersibility in an aqueous solvent is composed of a copolymer of an anionic and nitrogen atom-containing monomers formed with ions such as lithium, sodium, potassium, and ammonium, and nitrogen. There is a cationic system in which an atom forms a hydrochloride or the like, or a nonionic system in which a site such as a hydroxy group or an ethylene oxide is introduced, but it is preferably anionic.

Examples of the water-based urethane resin include water-dispersed urethane resin and ionomer-type water-based urethane resin (anionic). Examples of the water-dispersible urethane resin include a polyether urethane resin and a polyester urethane resin, and a polyester urethane resin is preferable. Further, for use in optical applications, it is preferable to use non-yellowing isocyanate having no aromatic ring.

Examples of the ionomer type water-based urethane resin include polyester-based urethane resin, polyether-based urethane resin, and polycarbonate-based urethane resin, and polyester-based urethane resin and polyether-based urethane resin are preferable.

The aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
Examples of the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalindicarboxylic acid, adipic acid, succinic acid, sebatic acid, dodecanedioic acid and the like, and these may be used alone. However, two or more kinds may be used in combination, and as a polybasic acid component that can be particularly preferably used, terephthalic acid and isophthalic acid are produced in large quantities industrially and are inexpensive. Is particularly preferable.
Examples of the polyol component include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol, and bisphenol, and these are used alone. As a polyol component that can be used in combination or in combination of two or more, it is industrially mass-produced, inexpensive, and has solvent resistance of the resin film. Ethylene glycol, propylene glycol, or neopentyl glycol is particularly preferable because it has a good balance of various performances such as improved weather resistance.

Examples of the inorganic polymer material include polysiloxane, polyphosphazene, polysilane, polygerman, polystanan, borazin-based polymer, polymetalloxane, polysilazane, titanium oligomer, silane coupling agent and the like. Specific examples of the polysiloxane include silicone, silsesquioxane, and silicone resin.

Organic-inorganic hybrid polymer materials include polycarbosilane, polycilylene allylene, polysilol, polyphosphine, polyphosphine oxide, poly (ferrocenylsilane), and silsesquioxane derivatives based on silsesquioxane. , Resin in which silica is compounded with resin, and the like can be mentioned.

Specific examples of silsesquioxane derivatives based on silsesquioxane include photocurable SQ series (Toagosei Co., Ltd.), composelan SQ (Arakawa Chemical Co., Ltd.), and Sila-DEC (Chisso Co., Ltd.). And so on. Further, as a resin in which silica is compounded with a resin, a component series (Arakawa Chemical Co., Ltd.) and the like can be specifically mentioned.

Further, as the resin, a curable resin such as an ionizing radiation curable resin or a thermosetting resin can be used. The ionizing radiation curable resin is a resin that can be cured by a usual curing method of an ionizing radiation curable resin composition, that is, irradiation with an electron beam or ultraviolet rays.

For example, in the case of electron beam curing, 10 to 1000 keV emitted from various electron beam accelerators such as Koklov Walton type, Bandegraph type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam or the like having an energy in the range of, preferably in the range of 30 to 300 keV is used.

In the case of ultraviolet curing, ultraviolet rays emitted from light rays such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps can be used. Specific examples of the ultraviolet irradiation device include a rare gas excimer lamp that emits vacuum ultraviolet rays in the range of 100 to 230 nm. Since the excimer lamp has a high light generation efficiency, it can be turned on with a low power input. Further, since light having a long wavelength that causes a temperature rise is not emitted and energy is irradiated at a single wavelength in the ultraviolet region, it has a feature that the temperature rise of the object to be irradiated by the irradiation light itself can be suppressed.

The thermosetting resin is a resin that is cured by heating, and it is more preferable that the resin contains a cross-linking agent. As a heating method for the thermosetting resin, a conventionally known heating method can be used, and heater heating, oven heating, infrared heating, laser heating, and the like can be used.

Further, a surface energy adjusting agent may be added to the resin used for the base layer. By adding a surface energy adjusting agent, the adhesion between the fine metal wire and the base layer, the line width of the fine metal wire, and the like can be adjusted.

(Oxide particles)
The oxide particles that can be added to the base layer are not particularly limited as long as they can be applied to a transparent electrode. By adding the oxide particles to the resin, the physical properties such as the film strength, elasticity, and refractive index of the underlying layer can be appropriately adjusted, and the adhesion to the fine metal wire is also improved. Examples of the oxide particles include oxides of metals such as magnesium, aluminum, silicon, titanium, zinc, yttrium, zirconium, molybdenum, tin, barium, and tantalum. In particular, the oxide particles are preferably any of titanium oxide, aluminum oxide, silicon oxide or zirconium oxide.

The average particle size of the oxide particles is preferably in the range of 5 to 300 nm, and particularly preferably in the range of 5 to 100 nm because it can be suitably used for a transparent electrode. When oxide particles having an average particle size within the above range are used, sufficient unevenness can be formed on the surface of the base layer, and the adhesion to the fine metal wire is improved. When the average particle size is 100 nm or less, the surface becomes smooth and the influence on the organic electronic device is small.

The average particle size of the oxide particles can be easily measured by using a commercially available measuring device using a light scattering method. Specifically, a value measured by a laser Doppler method at 25 ° C. and 1 ml of a sample diluent can be used using a Zetasizer 1000 (manufactured by Malvern).
The oxide particles are preferably contained in the base layer in the range of 10 to 70 vol%, and more preferably in the range of 20 to 60 vol%.

Examples of the above-mentioned titanium oxide fine particles include JP-A-59-223231, JP-A-10-265223, JP-A-2009-179497, JP-A-2010-058047, JP-A-2008-303126, International. It can be synthesized by referring to the synthesis method described in Publication No. 2001/016027 and "Titanium oxide-Physical properties and applied technology" (written by Manabu Kiyono, Gihodo Publishing Co., Ltd., p.255-258).

Further, as the oxide particles, those subjected to surface treatment may be used from the viewpoint of improving dispersibility and stability when used as a dispersion liquid. When surface-treating oxide particles, specific materials for surface-treatment include dissimilar inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, organosiloxane, and stearic acid. Examples include organic acids. One of these surface treatment materials may be used alone, or a plurality of types may be used in combination. Among them, from the viewpoint of the stability of the dispersion liquid, the surface treatment material is preferably at least one of a dissimilar inorganic oxide and a metal hydroxide, and a metal hydroxide is more preferable.

Further, the base layer may contain an inorganic compound other than oxide particles. As is generally understood, an inorganic compound is a compound other than an organic compound, and specifically, a simple part of a carbon compound and a compound composed of an element other than carbon. Typical examples of the inorganic compounds constituting the underlayer include metals, carbides, nitrides, borides and the like, in addition to the above-mentioned metal oxides.
Further, as the base layer, the base layer itself may be provided with a function as an optical scattering layer, or an optical scattering layer may be provided as upper and lower layers of the base layer. Thereby, the efficiency of the organic electronic device can be improved.

<Transparent resin substrate (1)>
The transparent resin substrate according to the present invention is not particularly limited as long as it has high light transmittance. For example, a resin substrate, a resin film, and the like are preferably used, but it is preferable to use a transparent resin film from the viewpoint of productivity and performance such as light weight and flexibility.

The resin that can be used as the substrate is not particularly limited, and is, for example, a polyester resin such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene resin, or ring. Polyolefin resins such as olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyetheretherketone (PEEK) resins, polysulfone (PSF) resins, polyethersulfon (PES) resins, polycarbonates (PC) Examples thereof include resins, polyamide resins, polyimide resins, acrylic resins, and triacetyl cellulose (TAC) resins. These resins may be used alone or in combination of two or more.
Further, the substrate may be an unstretched film or a stretched film.

When the substrate has high transparency, the transparent electrode can be used as the transparent electrode of the organic electronic device, which is preferable. High transparency means that the total light transmittance in the visible light wavelength region measured by a method based on JIS K 7361-1: 1997 (test method for total light transmittance of plastic-transparent material) is 50% or more. That is, 80% or more is more preferable.

The substrate may be subjected to a surface activation treatment in order to improve the adhesion to the base layer formed on the substrate, the gas barrier layer described later, and the like. Further, a clear hard coat layer may be provided in order to enhance impact resistance. Examples of the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment and the like.
Examples of the material of the clear hard coat layer include polyester, polyamide, polyurethane, vinyl-based copolymer, butadiene-based copolymer, acrylic-based copolymer, vinylidene-based copolymer, epoxy-based copolymer, and the like. An ultraviolet curable resin can be preferably used.

<Gas barrier layer (5)>
The performance of an organic electronic device such as an organic EL element to which a transparent electrode is applied easily deteriorates when a small amount of water or oxygen is present inside the device. Therefore, in order to prevent moisture and oxygen from entering the inside of the device through the substrate, it is preferable to provide a gas barrier layer having a high shielding ability against moisture and oxygen. Further, a gas barrier film having a gas barrier layer formed on the substrate in advance can be used as a substrate for a transparent electrode.

The composition and structure of the gas barrier layer and the method for forming the gas barrier layer are not particularly limited, and a layer made of an inorganic compound such as silica can be formed by vacuum deposition or a CVD method. For example, the following silicon-containing polymer modification layer, silicon compound layer, and transition metal oxide layer can be used alone or in combination to form a gas barrier layer.

(Silicon-containing polymer modified layer)
The silicon-containing polymer modification layer applied to the gas barrier layer is a modification treatment of a silicon-containing polymer having a bond of silicon and oxygen (Si—O), silicon and nitrogen (Si—N), etc. in a repeating structure. Formed by. Although the silicon-containing polymer is converted to silica or the like by the modification treatment, it is not necessary to modify all of the silicon-containing polymer, and at least a part thereof, for example, the ultraviolet irradiation surface side may be modified.

The thickness of the silicon-containing polymer modified layer can be appropriately set depending on the intended purpose, but is generally in the range of 10 nm to 10 μm.

Specific examples of the silicon-containing polymer include polysiloxane having a Si—O bond (including polysilsesquioxane), polysilazane having a Si—N bond, and Si—O bond and Si—N bond in the repeating structure. Polysilazane and the like containing both of the above can be mentioned. These can be used by mixing two or more kinds. It is also possible to laminate layers of different types of silicon-containing polymers.

The polysiloxane contains- [RaSiO _1/2 ]-,-[RbSiO]-,-[RcSiO _3/2 ]-,-[SiO ₂ ]-and the like in the repeating structure. Ra, Rb and Rc are independently an alkyl group containing a hydrogen atom and 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) and an aryl group (for example, a phenyl group and an unsaturated alkyl group). Etc.) and other substituents.
Polysilsesquioxane is a compound among the above polysiloxanes that has the same structure as silsesquioxane in its repeating structure. Silsesquioxane is a compound having a structure represented by the above- [RcSiO _3/2 ]-.

The structure of polysilazane can be represented by the following general formula (B).

General formula (B)
-[Si (R ¹ ) (R ² ) -N (R ³ )]-

In the general formula (B), R ¹ , R ² and R ³ independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

Polysilazane in which all of R ¹ , R ² and R ^{3 in} the above general formula (B) are hydrogen atoms is perhydropolysilazane. Perhydropolysilazane is preferable because a dense film can be obtained.
Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring. Its molecular weight is about 600 to 2000 (in terms of polystyrene) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and their states differ depending on the molecular weight.

On the other hand, in the above general formula (B), the polysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like is an organopolysilazane. Organopolysilazane has improved adhesion to the underlying substrate due to alkyl groups such as methyl groups, and can impart toughness to polysilazane, which has hard and brittle properties, so cracks occur even when the film is thickened. It has the advantage of being suppressed. Therefore, perhydropolysilazane and organopolysilazane are appropriately selected depending on the intended use, or both are mixed and used.

Polysiloxazan contains, in its repeating structure, structures represented by-[(SiH ₂ ) _n (NH) _r ]-and-[(SiH ₂ ) _m O]-. n, m and r independently represent 1-3.

As another example of polysilazane that is ceramicized at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a polysilazane having a main skeleton composed of a unit represented by the above general formula (B) with a silicon alkoxide (for example, JP-A-P). 5-238827 (see JP-A-5238827), glycidol-added polysilazane obtained by reacting glycidol (see, for example, JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (see, for example, JP-A-6-). 240208), metal carboxylate-added polysilazane obtained by reacting metal carboxylate (see, for example, JP-A-6-299118), and acetylacetonate complex containing metal. Examples thereof include polysilazane with an acetylacetonate complex (see, for example, JP-A-6-306329), polysilazane with metal fine particles added by adding metal fine particles (see, for example, JP-A-7-196986), and the like.

The silicon-containing polymer modified layer can be formed by forming a coating film using the coating liquid containing the silicon-containing polymer described above and subjecting the coating film to a modification treatment.
Examples of the coating film forming method include a roll coating method, a flow coating method, a spray coating method, a printing method, a dip coating method, a bar coating method, a cast film forming method, an inkjet method, and a gravure printing method.

For the preparation of the coating liquid, it is preferable to avoid the use of an alcohol-based organic solvent that easily reacts with polysilazane or an organic solvent containing water. Therefore, examples of the organic solvent that can be used for preparing the coating liquid include hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers. Etc., such as ethers. Specific examples thereof include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, sorbesso and terben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to the characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.

As the coating liquid, a commercially available product in which polysilazane is dissolved in an organic solvent can be used. Examples of commercially available products that can be used include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials.

The coating liquid may also contain a catalyst from the viewpoint of accelerating the reforming treatment.
The catalyst is preferably a basic catalyst, for example, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N', N'-tetra. Amine catalysts such as methyl-1,3-diaminopropane, N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, Pd compounds such as propionic acid Pd, Examples thereof include metal catalysts such as Rh compounds such as Rh acetylacetonate, N-heterocyclic compounds and the like.

The content of the silicon-containing polymer in the coating liquid varies depending on the thickness of the silicon-containing polymer modifying layer to be formed and the pot life of the coating liquid, but is preferably in the range of 0.2 to 35.0% by mass.

The formed coating film can be dried by heating from the viewpoint of removing the organic solvent in the coating film.
The temperature at the time of heating can be in the range of 50 to 200 ° C. The heating time is preferably set to a short time in order to prevent deformation of the substrate and the like. For example, when polyethylene terephthalate having a glass transition temperature of 70 ° C. is used for the substrate, the temperature during the drying process can be set to 150 ° C. or lower in order to prevent deformation of the resin film.

Further, the formed coating film may be subjected to a drying treatment for dehumidifying while maintaining a low humidity environment from the viewpoint of removing water in the coating film.
Since the humidity in a low humidity environment changes with temperature, the relationship between temperature and humidity can be determined by the dew point temperature regulation. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is -8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./25%). Humidity is 1%) or less. To facilitate the removal of moisture, it may be dried under reduced pressure. The pressure for drying under reduced pressure can be selected in the range of normal pressure to 0.1 MPa.

As a method for modifying the coating film, a known method with less damage to the substrate can be used, and plasma treatment, ozone treatment, ultraviolet ray or vacuum ultraviolet irradiation treatment, etc., which can perform low temperature treatment, can be used. it can. Of these, the vacuum ultraviolet irradiation treatment is preferable because the gas barrier property is unlikely to decrease due to the influence of the environment between the formation of the silicon-containing polymer modified layer and the formation of the transition metal oxide layer.

The vacuum ultraviolet irradiation treatment uses the light energy of vacuum ultraviolet light in the wavelength range of 100 to 200 nm, which is larger than the interatomic bonding force constituting the silicon-containing polymer, and the interatomic bonding is performed by the action of only photons, which is called the photon process. It is a process of converting to silica or the like in a relatively low temperature environment of about 200 ° C. or lower by directly cutting and advancing an oxidation reaction with active oxygen or ozone.

The light source of the vacuum ultraviolet light may be one that generates light having a wavelength of 100 to 200 nm, and a rare gas excimer lamp having an irradiation wavelength of about 172 nm (for example, Xe excimer lamp MODEL manufactured by MD.com). : MECL-M-1-200), low-pressure mercury steam lamps of about 185 nm, medium-pressure and high-pressure mercury steam lamps of 200 nm or less, and the like.

The features of the Exima lamp are that it emits light of a single wavelength and has extremely high luminous efficiency, that the emitted light has a short wavelength and the temperature of the irradiation target can be kept low, and that it can be turned on and blinked instantly. It is a light source that can be easily applied to substrates that are easily affected by heat.
In particular, the short single-wavelength vacuum ultraviolet light of 172 nm emitted by the Xe excimer lamp has a large oxygen absorption coefficient, generates high-concentration active oxygen or ozone from a small amount of oxygen, and has a high ability to dissociate organic bonds. Therefore, the reforming process can be performed in a short time.

The irradiation conditions of the vacuum ultraviolet rays may be set within a range that does not deteriorate the substrate and the like below the silicon-containing polymer modified layer.
For example, the irradiation time of ultraviolet rays is generally in the range of 0.1 seconds to 10 minutes and in the range of 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate and the coating liquid. preferable.
From the viewpoint of uniformly irradiating the ultraviolet rays, it is preferable to irradiate the coating film of the silicon-containing polymer modified layer with the reflected light obtained by reflecting the ultraviolet rays from the light source by the reflector.

The illuminance of the vacuum ultraviolet rays can be in the range of 1 mW / cm ^{2 to} 10 W / cm ² . When it is 1 mW / cm ² or more, the reforming efficiency is improved, and when it is 10 W / cm ² or less, ablation that may occur in the coating film, damage to the substrate, and the like can be reduced.
The irradiation energy amount (irradiation amount) of the vacuum ultraviolet rays can be in the range of 0.1 to 10.0 J / cm ² . Within this range, it is possible to prevent cracks from being excessively modified, thermal deformation of the substrate, and the like, and productivity is also improved.

The vacuum ultraviolet irradiation treatment may be a batch treatment or a continuous treatment. In the case of batch processing, the processing can be performed in an ultraviolet firing furnace provided with a light source of vacuum ultraviolet rays (for example, an ultraviolet firing furnace manufactured by Igraphics Co., Ltd.). In the case of continuous processing, the substrate may be conveyed and the ultraviolet rays may be continuously irradiated in the zone provided with the light source of vacuum ultraviolet rays.

Oxygen is required for the reaction during vacuum ultraviolet irradiation, but since vacuum ultraviolet is absorbed by oxygen and the reforming efficiency tends to decrease, irradiation of vacuum ultraviolet in an atmosphere with as low oxygen concentration and water vapor concentration as possible. It is preferable to carry out. For example, the oxygen concentration during vacuum ultraviolet irradiation can be in the range of 10 to 20000 volume ppm (0.001 to 2% by volume). The water vapor concentration is preferably in the range of 1000-4000 volume ppm.
For the adjustment of the above atmosphere, it is preferable to use a dry inert gas, particularly a dry nitrogen gas from the viewpoint of cost. The oxygen concentration can be adjusted by adjusting the flow rate ratio of the oxygen gas and the inert gas introduced into the room.

(Silicon compound layer)
As the gas barrier layer, a silicon compound layer containing a silicon compound such as silicon oxide, silicon nitride, silicon nitride, silicon carbide, etc. is further arranged under the silicon-containing polymer modified layer from the viewpoint of further enhancing the gas barrier property. You can also do it.

If the layer adjacent to the transition metal oxide layer is a silicon-containing polymer modified layer, the layer below the silicon-containing polymer modified layer may have a multilayer structure of a silicon compound layer and a silicon-containing polymer modified layer. it can. Due to the multilayer structure, the gas barrier property against the gas entering the transparent electrode can be further enhanced, and the stability of the conductive performance can be further enhanced.

The silicon compound layer includes a vacuum vapor deposition method using silicon oxide as a raw material, a magnetron sputtering method using a target containing silicon, an ion plating method, and a silicon-containing polymer (for example, a silicon-containing polymer used for a silicon-containing polymer modification layer such as polysilazane). , Hexamethyldisiloxane, perhydropolysilazane, etc.), silicon dioxide, etc. as raw materials, and can be formed by a plasma CVD (Chemical Vapor Deposition) method or the like.

(Transition metal oxide layer)
The transition metal oxide layer is formed on the silicon-containing polymer modified layer by using the transition metal oxide. Since the transition metal oxide layer is adjacent to the silicon-containing polymer modified layer, oxidation of the silicon-containing polymer modified layer can be suppressed, and a very high gas barrier property can be exhibited together with the silicon-containing polymer modified layer.

The transition metal oxides used in the transition metal oxide layer are oxides of metals from Group 3 to Group 12 in the Periodic Table of the Elements, and one of them may be used alone or a plurality of them. Seeds may be used together.
From the viewpoint of obtaining higher stability, the transition metal oxide is preferably an oxide of a Group 5 metal in the Periodic Table of the Elements. Examples of Group 5 metals include vanadium (V), niobium (Nb), tantalum (Ta) and the like.

Above all, it is preferable that the transition metal oxide is niobium oxide. A transparent electrode that combines a transition metal oxide layer using niobium oxide and a silicon-containing polymer modified layer not only improves the stability of conductive performance, but also reduces the angle dependence of the transmittance of incident light. Can be done. This is because the low refractive index layer and the high refractive index layer are laminated to cause multiple interference of light, the reflectance is reduced, and the optical behavior is changed due to the difference in refractive index. It is presumed to be a factor.

The content of the transition metal oxide in the transition metal oxide layer is preferably in the range of 50 to 100% by mass. Within this range, a sufficient gas barrier property can be obtained by the interaction of the transition metal in the transition metal oxide layer with the silicon-containing polymer modified layer.

As a method for forming the transition metal oxide layer, since it is easy to adjust the composition ratio of the transition metal and oxygen, physical vapor deposition (PVD: Physical Vapor Deposition) such as a vapor deposition method, a sputtering method, and an ion plating method. Examples include a method, a CVD method such as a plasma CVD method, and an atomic layer deposition (ALD) method. Above all, a sputtering method that does not damage the lower layer and has high productivity is preferable.

As the sputtering method, a bipolar sputtering method, a magnetron sputtering method, a dual magnetron (DM: Dual Magnetron) sputtering method, a reactive sputtering method, an ion beam sputtering method, an electron cyclotron resonance (ECR: Electron Cycloron Resonance) sputtering method and the like are used. One of them may be used alone, or two or more of them may be used in combination.
The target application method can be appropriately selected according to the target type. In the case of the DC (direct current) method or the DM method, a thin film of the transition metal oxide can be formed by using a transition metal as the target and introducing oxygen as a raw material gas. In the case of the RF (radio frequency) method, a transition metal oxide target can be used. As the inert gas, He, Ne, Ar, Kr, Xe and the like can be used, and among them, Ar is preferable.

The transition metal oxide layer may be a single layer or may have a multi-layer structure of two or more layers. In the case of a multi-layer structure, the transition metal oxide used for each layer may be the same or different. The thickness of the transition metal oxide layer is preferably in the range of 1 to 200 nm from the viewpoint of exhibiting a uniform gas barrier property regardless of the position.

(Gas barrier layer forming process)
In the production of the transparent electrode of the present invention, a gas barrier layer may be formed on the substrate, if necessary. The gas barrier layer is formed before the above-mentioned thin metal wire, transparent conductive layer, and base layer are formed.

The gas barrier layer is preferably formed by vacuum vapor deposition or a CVD method in which the above-mentioned silicon-containing polymer modification layer, silicon compound layer, and transition metal oxide layer are formed alone or in combination. As the method for forming the silicon-containing polymer modification layer, the silicon compound layer, and the transition metal oxide layer, the above-mentioned methods and conditions can be used, respectively.

<Particle-containing layer (6)>
The particle-containing layer is provided on the surface (back surface) opposite to the surface (front surface) on which the fine metal wire is formed in the substrate. When the transparent electrodes are in direct contact with each other, such as when the transparent electrodes are stacked or when a long transparent electrode is wound in a roll shape, the transparent electrodes have a particle-containing layer. It is possible to suppress charging and sticking of transparent electrodes to each other.

The particle-containing layer is composed of particles and a binder resin. The particle-containing layer preferably contains particles in the range of 1 to 900 parts by mass with respect to 100 parts by mass of the binder resin.

(particle)
The particles constituting the particle-containing layer are preferably inorganic fine particles, inorganic oxide particles, conductive polymer particles, conductive carbon fine particles, and the like. Of these, oxide particles such as ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₂ , V ₂ O ₅ and inorganic oxide particles such as SiO ₂ are preferable. In particular, SnO ₂ and SiO ₂ are preferable.

(Binder resin)
Examples of the binder resin constituting the particle-containing layer include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polyvinyl terephthalate, and copolybutylene. / Tele / Isophthalate and other polyesters, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl benzal and other polyvinyl alcohol derivatives, norbornene polymers containing norbornene compounds, polymethylmethacrylate, polyethylmethacrylate, polypropyltylmethacrylate , Polybutyl methacrylate, polymethyl acrylate and other acrylic resins or copolymers of acrylic resins and other resins can be used, but the resin materials are not particularly limited. Among these, cellulose derivatives and acrylic resins are preferable, and acrylic resins are most preferably used.

As the binder resin, the thermoplastic resin having a weight average molecular weight (Mw) of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. is preferable in terms of optical properties and the quality of the particle-containing layer to be formed. ..

The glass transition temperature can be determined by the method described in JIS K 7121. The binder resin used here is 60% by mass or more, more preferably 80% by mass or more, based on the total mass of the resin constituting the particle-containing layer, and an active ray-curable resin or a thermosetting resin is applied as necessary. You can also do it.

(Method of forming particle-containing layer)
In the production of the transparent electrode, a particle-containing layer may be formed on the substrate (back surface side), if necessary. The particle-containing layer is formed before the above-mentioned thin metal wire, transparent conductive layer, base layer and gas barrier layer are formed.

In the formation of the particle-containing layer, the above-mentioned particles and the binder resin are dissolved in an appropriate organic solvent to prepare a coating liquid for forming the particle-containing layer in a solution state, and the coating liquid is applied onto the substrate by these wet coating methods. Dry to form a particle-containing layer.

As the organic solvent used for preparing the coating liquid for forming the particle-containing layer, hydrocarbons, alcohols, ketones, esters, glycol ethers and the like can be appropriately mixed and used, and the organic solvent is particularly used. It is not limited to these.

Examples of hydrocarbons include benzene, toluene, xylene, hexane, cyclohexane and the like, and examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert. -Butanol, pentanol, 2-methyl-2-butanol, cyclohexanol and the like can be mentioned. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and examples of esters include formic acid. Examples thereof include methyl, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, ethyl lactate, methyl lactate, and examples of glycol ethers (1 to 4 carbon atoms) include methyl cell solve, ethyl cell solve, and the like. Propylene glycol monomethyl ether (abbreviation: PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol mono (1 to 4 carbon atoms) alkyl ether esters Examples of the solvent include propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and examples of other solvents include N-methylpyrrolidone. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.

As a method of applying the coating liquid for forming a particle-containing layer on a substrate, doctor coat, extrusion coat, slide coat, roll coat, gravure coat, wire bar coat, reverse coat, curtain coat, extrusion coat, or US Pat. Examples thereof include an extrusion coating method using the hopper described in the specification. By appropriately using these wet coating methods, a particle-containing layer having a dry film thickness in the range of 0.1 to 20 μm, preferably 0.2 to 5 μm can be formed on the substrate.

<< Organic electronic device (organic EL element) >>
Next, an embodiment of an organic electroluminescence device (organic EL device) will be described as an example of an organic electronic device using the above-mentioned transparent electrode.
The organic EL element has a configuration in which the above-mentioned transparent electrode is used as one electrode (transparent electrode), and a light emitting unit and the other electrode (counter electrode) are provided on the transparent electrode. Therefore, in the following description of the organic EL element, detailed description of the same configuration as the above-mentioned transparent electrode will be omitted.

<Structure of organic EL element>
The configuration of the organic EL element is shown in FIG. The organic EL element 200 shown in FIG. 4 includes a transparent electrode 10 and a counter electrode 220, and a light emitting unit 210 is provided as an organic functional layer between the transparent electrodes 10. The transparent electrode 10 has the same configuration as that of FIG. 2 described above.

Here, the "light emitting unit" refers to a light emitting body (unit) containing at least various organic compounds and mainly composed of organic functional layers such as a light emitting layer, a hole transport layer, and an electron transport layer. The illuminant is sandwiched between a pair of electrodes consisting of an anode and a cathode, and holes supplied from the anode and electrons supplied from the cathode recombine in the illuminant. It emits light. The organic EL element may include a plurality of the light emitting units according to the desired light emitting color.

In the organic EL element 200, only the portion where the light emitting unit 210 is sandwiched between the thin metal wire 2 of the transparent electrode 10 and the transparent conductive layer 3 and the counter electrode 220 is the light emitting region in the organic EL element 200. The organic EL element 200 is configured as a bottom emission type that takes out the generated light (hereinafter, also referred to as emitted light) from at least the transparent resin substrate 1 side of the transparent electrode 10. In addition, transparency (translucency) means that the light transmittance at a wavelength of 550 nm is 50% or more. The principal component is the component having the highest proportion in the entire composition.

Further, in the organic EL element 200, a take-out electrode (not shown) is provided at the end of the thin metal wire 2 (or the transparent conductive layer 3) of the transparent electrode 10 and the counter electrode 220. The thin metal wire 2 (or the transparent conductive layer 3) of the transparent electrode 10 and the counter electrode 220 and the external power supply (not shown) are electrically connected via the take-out electrode.

The layer structure of the organic EL element 200 is not limited, and may be a general layer structure. For example, when the metal wire 2 of the transparent electrode 10 functions as an anode (that is, an anode) and the counter electrode 220 functions as a cathode (that is, a cathode), the light emitting unit 210 has holes in order from the metal wire 2 side of the transparent electrode 10. An example is a configuration in which an injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer is laminated, but it is essential to have at least a light emitting layer constructed by using an organic material. The hole injection layer and the hole transport layer may be provided as the hole transport injection layer. The electron transport layer and the electron injection layer may be provided as an electron transport injection layer. Further, among these light emitting units 210, for example, the electron injection layer may be made of an inorganic material.

In addition to these layers, the light emitting unit 210 may have a hole blocking layer, an electron blocking layer, and the like laminated at necessary locations. Further, the light emitting layer may have each color light emitting layer that generates light emitted in each wavelength region, and each of these color light emitting layers may be laminated via a non-light emitting auxiliary layer. The auxiliary layer may function as a hole blocking layer and an electron blocking layer. Further, the counter electrode 220, which is a cathode, may also have a laminated structure as required.

Further, the organic EL element 200 may be an element having a so-called tandem structure in which a plurality of light emitting units 210 including at least one light emitting layer are laminated. As a typical element configuration of the tandem structure, for example, the following configuration can be mentioned.

Anode / 1st light emitting unit / intermediate connector layer / 2nd light emitting unit / intermediate connector layer / 3rd light emitting unit / cathode

Here, the first light emitting unit, the second light emitting unit, and the third light emitting unit may all be the same or different. Further, the two light emitting units may be the same, and the remaining one may be different. The plurality of light emitting units 210 may be directly laminated or may be laminated via an intermediate connector layer.

The intermediate connector layer is also generally called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulation layer, and has electrons in the adjacent layer on the anode side and positive in the adjacent layer on the cathode side. A known material composition can be used as long as the layer has a function of supplying holes. Materials used for the intermediate connector layer include, for example, ITO, IZO (inorganic zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, GaN, CuAlO ₂ , CuGaO ₂ , Conductive inorganic compound layers such as SrCu ₂ O ₂ , LaB ₆ , RuO ₂ , Al, two-layer films such as Au / Bi ₂ O ₃ , SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi _{2 O 3 / Au / Bi 2 O} 3, TiO 2 / TiN / TiO 2, TiO 2 / ZrN / TiO 2 or the like multilayer film, also fullerenes such as _{C 60,} conductive organic material layer such as oligothiophene, metal phthalocyanines , Metal-free phthalocyanines, metal porphyrins, conductive organic compound layers such as metal-free porphyrins, and the like, but are not limited thereto.

Preferred configurations in the light emitting unit 210 include, but are not limited to, for example, configurations in which the anode and the cathode are removed from the configurations described in the above typical element configurations.
Specific examples of the tandem organic EL element include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, and US Pat. No. 6,107,734. Specification, US Pat. No. 6,337,492, International Publication No. 2005/09087, JP-A-2006-228712, JP-A-2006-24791, JP-A-2006-49393, JP-A-2006-49394. , Japanese Patent Application Laid-Open No. 2006-49396, Japanese Patent Application Laid-Open No. 2011-96679, Japanese Patent Application Laid-Open No. 2005-340187, Japanese Patent No. 4711424, Japanese Patent No. 3496681, Japanese Patent No. 3884564, Japanese Patent No. 4213169, Japanese Patent Publication No. Kai 2010-192719, Japanese Patent Application Laid-Open No. 2009-0762929, Japanese Patent Application Laid-Open No. 2008-0784414, Japanese Patent Application Laid-Open No. 2007-059848, Japanese Patent Application Laid-Open No. 2003-272860, Japanese Patent Application Laid-Open No. 2003-045676, International Publication No. Examples thereof include the element configuration and constituent materials described in 2005/094130 and the like.

(electrode)
The organic EL element has a light emitting unit sandwiched between a pair of electrodes including a conductive layer of a transparent electrode and a counter electrode. One of the conductive layer and the counter electrode of the transparent electrode serves as an anode of the organic EL element, and the other serves as a cathode.

Further, in the organic EL element 200 shown in FIG. 4, the transparent conductive layer 3 of the transparent electrode 10 is made of a transparent conductive material, and the counter electrode 220 is made of a highly reflective material. When the organic EL element 200 is a double-sided light emitting type, the counter electrode 220 is also made of a transparent conductive material.

(Counter electrode)
When a counter electrode is used as an anode in an organic EL element, a metal having a large work function (4 eV or more), an electrically conductive compound, or a mixture thereof as an electrode material is preferably used. Specific examples of the electrode material that can form the anode include metals such as Au and Ag, and conductive transparent materials such as CuI, ITO, SnO ₂ , and ZnO. Further, a material such as IDIXO (In ₂ O _3- ZnO) which is amorphous and can produce a transparent conductive film may be used.

For the anode, a thin film may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not required so much (about 100 μm or more). ), A pattern may be formed through a mask having a desired shape during vapor deposition or sputtering of the electrode material.

When a coatable substance such as an organic conductive compound is used, a wet film forming method such as a printing method or a coating method can also be used. When the light emission is taken out from the anode side, it is desirable to make the light transmittance larger than 10%. The sheet resistance as an anode is several hundred Ω / sq. The following is preferable. The thickness depends on the material, but is usually selected in the range of 10 to 1000 nm, preferably in the range of 10 to 200 nm.

When a counter electrode is used as a cathode in an organic EL element, a metal having a small work function (4 eV or less) (referred to as an electron-injectable metal), an alloy, an electrically conductive compound, and a mixture thereof are used as the electrode material. Used.
The cathode is an electrode film that functions as a cathode that supplies electrons to the light emitting unit. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

Specific examples of the electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture. , Indium, lithium / aluminum mixture, rare earth metals and the like.

Among these, from the viewpoint of electron injectability and durability against oxidation and the like, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture. Magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture, aluminum and the like are suitable.

Sheet resistance as a cathode is several hundred Ω / sq. The following is preferable, and the thickness is usually selected in the range of 10 nm to 5 μm, preferably in the range of 50 to 200 nm. Further, a transparent or translucent cathode can be produced by producing the above metal as a cathode having a thickness of 1 to 20 nm and then producing the conductive transparent material mentioned in the description of the anode on the metal. By applying this, it is possible to manufacture an element in which both the anode and the cathode are transparent.

(Take-out electrode)
The take-out electrode electrically connects the conductive layer of the transparent electrode and the external power source, and the material thereof is not particularly limited, and a known material can be preferably used. For example, a three-layer structure can be used. A metal film such as a MAM electrode (Mo / Al / Nd alloy / Mo) made of the above can be used.

(Sealing member)
The organic EL element may be sealed with a sealing member for the purpose of preventing deterioration of the light emitting unit constructed by using an organic material or the like. The sealing member is a plate-shaped (film-shaped) member that covers the upper surface of the organic EL element, and is fixed to the substrate side by an adhesive portion. Further, the sealing member may be a sealing film. Such a sealing member is provided so as to expose the electrode terminal portion of the organic EL element and at least cover the light emitting unit. Further, the sealing member may be provided with an electrode so that the electrode terminal portion of the organic EL element and the electrode of the sealing member are made conductive.

Specific examples of the plate-shaped (film-shaped) sealing member include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrates may be used in the form of a thinner film. Examples of the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal substrate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium and tantalum.
In particular, since the element can be thinned, it is preferable to use a polymer substrate or a metal substrate as a sealing member in the form of a thin film.
Further, the substrate material may be processed into an intaglio shape and used as a sealing member. In this case, the above-mentioned substrate member is subjected to processing such as sandblasting and chemical etching to form a concave shape.

Furthermore, the polymer substrate having a film shape, JIS K 7126: oxygen permeability measured in compliance with the method 1987 is ^{1 × 10 -3 ml / (m} 2 · 24h · atm) or less, JIS K 7129: 1992 measured in compliance with the method, the water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)%) is preferably at ^{1 × 10 -3 g / (m} 2 · 24h) or less.

Further, the adhesive portion for fixing the sealing member to the substrate side is used as a sealing agent for sealing the organic EL element. Specific examples of the adhesive portion include acrylic acid-based oligomers, photocurable and thermosetting adhesives having a reactive vinyl group of methacrylic acid-based oligomers, and moisture-curable adhesives such as 2-cyanoacrylic acid ester. Can be mentioned.

Further, as the adhesive portion, a heat and chemical curing type (two-component mixture) such as an epoxy type can be mentioned. Further, hot melt type polyamide, polyester and polyolefin can be mentioned. In addition, a cation-curable type ultraviolet-curable epoxy resin adhesive can be mentioned.

A commercially available dispenser may be used for applying the adhesive portion to the adhesive portion between the sealing member and the transparent electrode, or printing may be performed as in screen printing.
The organic material constituting the organic EL element may be deteriorated by heat treatment. Therefore, it is preferable that the adhesive portion can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Further, the desiccant may be dispersed in the adhesive portion.

When a gap is formed between the plate-shaped sealing member and the transparent electrode, the gap is filled with an inert gas such as nitrogen or argon, fluorinated hydrocarbon, or silicone oil in the gas phase and liquid phase. It is preferable to inject such an inert liquid. It is also possible to create a vacuum. It is also possible to enclose a hygroscopic compound inside.

Examples of the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.) and sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchlorates (eg, perchloric acid) (Valium, magnesium perchlorate, etc.) and the like, and anhydrous salts are preferably used for sulfates, metal halides and perchlorates.

On the other hand, when a sealing film is used as the sealing member, the sealing film is provided on the transparent electrode in a state where the light emitting unit in the organic EL element is completely covered and the electrode terminal portion of the organic EL element is exposed.

Such a sealing film is constructed by using an inorganic material or an organic material. In particular, it is composed of a material having a function of suppressing the intrusion of substances such as water and oxygen that cause deterioration of the light emitting unit in the organic EL element. 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 film made of an organic material may be used together with the film made of these inorganic materials to form a laminated structure.

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

(Protective member)
Further, in order to mechanically protect the organic EL element, a protective member (not shown) such as a protective film or a protective plate may be provided. The protective member is arranged at a position where the organic EL element and the sealing member are sandwiched between the transparent electrode and the protective member. In particular, when the sealing member is a sealing film, mechanical protection against the organic EL element is not sufficient, so it is preferable to provide such a protective member.

As the protective member as described above, a glass plate, a polymer plate, a polymer film thinner than this, a metal plate, a metal film thinner than this, or a polymer material film or a metal material film is applied. Of these, it is particularly preferable to use a polymer film because it is lightweight and thin.

In the above description, as an example of an organic electronic device to which a transparent electrode is applied, an organic EL device to which the transparent electrode of the present invention is applied as a transparent electrode is described, but the transparent electrode is an organic photoelectric conversion element or the like. It can also be applied as a transparent electrode to organic electronic devices.

<Manufacturing method of organic electronic devices>
Next, an example of a method for manufacturing an organic EL element will be described.
First, a transparent electrode is manufactured by the above-mentioned manufacturing method.
Next, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are formed in this order on the conductive layer of the transparent electrode to form a light emitting unit. Examples of the film forming method for each of these layers include a spin coating method, a casting method, an inkjet method, a vapor deposition method, a printing method, etc., but from the viewpoint that a homogeneous film can be easily obtained and pinholes are difficult to be formed. The vacuum deposition method or the spin coating method is particularly preferable. Further, a different film forming method may be applied for each layer. The case of employing an evaporation method in the deposition of these layers, the depositing conditions thereof are varied according to kinds of materials used, generally boat temperature 50 to 450 ° C., vacuum ¹ × 10 -6 ~1 × 10 ^-2 It is preferable to appropriately select each condition within the range of Pa, the vapor deposition rate of 0.01 to 50 nm / sec, the substrate temperature of -50 to 300 ° C., and the layer thickness of 0.1 to 5 μm.

After forming the light emitting unit, a counter electrode is formed on the upper part by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the counter electrode is patterned in a shape in which the terminal portion is pulled out from above the light emitting unit to the peripheral edge of the substrate while maintaining the insulating state with respect to the conductive layer of the transparent electrode by the light emitting unit. As a result, an organic EL element can be obtained. Further, after that, a sealing member that covers at least the light emitting unit is provided in a state where the terminal portions of the take-out electrode and the counter electrode of the organic EL element are exposed.

From the above, a desired organic EL element can be obtained. In the production of such an organic EL element, it is preferable to consistently produce from the light emitting unit to the counter electrode by one vacuum drawing, but even if the substrate is taken out from the vacuum atmosphere and a different film forming method is applied in the middle. I do not care. At that time, consideration must be given to performing the work in a dry inert gas atmosphere.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. Although the display of "%" is used in the examples, it represents "mass%" unless otherwise specified.

[Example 1]
<< Fabrication of transparent electrode >>
Transparent electrodes 101 to 133 were produced as follows.

<Manufacturing of transparent electrode 101>
(1) Preparation of Transparent Resin Substrate A polyethylene terephthalate (PET / CHC) film (G1SBF, thickness 125 μm, refractive index 1.59) with a clear hard coat layer manufactured by Kimoto Co., Ltd. was prepared as a transparent resin substrate.

(2) Formation of Gas Barrier Layer Next, a gas barrier layer was formed on the surface of the substrate (the surface on the side where the thin metal wire is formed).
Specifically, the substrate was set in a discharge plasma chemical vapor deposition apparatus (Plasma CVD apparatus Precision 5000 manufactured by Applied Materials), and the substrate was continuously conveyed by roll-to-roll. Next, a magnetic field was applied between the film forming rollers, and electric power was supplied to each film forming roller to generate plasma between the film forming rollers to form a discharge region. Next, a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas), which is a reaction gas, is applied to the formed discharge region from the gas supply pipe as a film-forming gas. A gas barrier layer having a thickness of 120 nm was formed under the following conditions.

(Film formation conditions)
Supply amount of raw material gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of reaction gas (O ₂ ): 500 sccm
Vacuum degree in vacuum chamber: 3Pa
Power applied from the plasma generation power supply: 0.8 kW
Frequency of power supply for plasma generation: 70kHz
Film transport speed: 0.8 m / min

(3) Formation of fine metal wire A silver nanoparticle dispersion liquid (FlowMetal SR6000, manufactured by Bando Chemical Co., Ltd.) as a metal nanoparticle-containing composition is latticed on a gas barrier layer using an inkjet printing method with a width of 50 μm and a pitch of 1 mm. It was applied in a shape to form a pattern. As an inkjet printing method, an inkjet head having an injection amount of 4 pl of ink droplets was used, and the coating speed and the injection frequency were adjusted to print a pattern. As the inkjet printing apparatus, a desktop robot Shotmaster-300 (manufactured by Musashi Engineering Co., Ltd.) equipped with an inkjet head (manufactured by Konica Minolta) was used, and the operation was controlled by an inkjet evaluation apparatus EB150 (manufactured by Konica Minolta).

Next, two quartz glass plates that absorb infrared rays with a wavelength of 3.5 μm or more are attached to an infrared irradiation device (Ultimate Heater / Carbon, manufactured by Akira Kogyo Co., Ltd.), and wavelength-controlled infrared rays are passed between the glass plates. Using a heater, the pattern of the formed metal nanoparticles-containing composition was dried in the air (oxygen concentration of about 210,000 volume ppm).

Next, using a xenon flash lamp 2400WS (manufactured by COMET) equipped with a short wavelength cut filter of 250 nm or less, in an atmosphere of an oxygen concentration of 20 volume ppm and a water vapor concentration of 20 volume ppm (oxygen-containing substance concentration of 40 volume ppm). , A flash light having a total light irradiation energy of 3.5 J / cm ² is irradiated once from the pattern side of the metal nanoparticle-containing composition with an irradiation time of 2 msec, and the pattern of the metal nanoparticle-containing composition after drying is performed. Was fired to form fine metal wires.

(4) Formation of Transparent Conductive Layer An IZO (mass ratio In ₂ O ₃ : ZnO = 90: 10) film as a metal oxide layer was formed on a thin metal wire with a thickness of 100 nm to prepare a transparent electrode 101.
For the IZO film, an L-430S-FHS sputtering device manufactured by Anerva was used, Ar: 20 sccm, O ₂ : 3 sccm, sputtering pressure: 0.25 Pa, room temperature (25 ° C.), target side power: 1000 W, target-board distance. It was produced by RF sputtering at 86 mm.

<Manufacturing of transparent electrodes 102 to 115>
In the production of the transparent electrode 101, the transparent electrodes 102 to 115 were produced in the same manner except that the oxygen concentration and the water vapor concentration at the time of firing the metal nanoparticle-containing composition were changed as shown in Table 1.

<Manufacturing of transparent electrodes 116 to 120>
In the production of the transparent electrode 107, the transparent electrodes 116 to 120 were produced in the same manner except that the oxygen concentration of the metal nanoparticle-containing composition during the drying treatment was changed as shown in Table 1.

<Manufacturing of transparent electrode 121>
In the preparation of the transparent electrode 107, the transparent electrode 121 was produced in the same manner except that the metal nanoparticle-containing composition was dried on a hot plate at 80 ° C. for 30 minutes.

<Manufacturing of transparent electrode 122>
In the production of the transparent electrode 107, the transparent electrode 122 was produced in the same manner except that the metal nanoparticle-containing composition was dried using an infrared irradiation device (Ultimate Heater / Carbon, manufactured by Akira Kogyo Co., Ltd.).

<Manufacture of transparent electrodes 123 to 126>
In the production of the transparent electrodes 117, the transparent electrodes 123 to 126 were produced in the same manner except that the thickness of the transparent conductive layer was changed as shown in Table 2.

<Manufacturing of transparent electrodes 127 and 128>
In the preparation of the transparent electrode 117, the transparent electrodes 127 and 128 were prepared in the same manner except that IZO in the transparent conductive layer was changed to GZO (Ga-doped zinc oxide) and IGZO (indium gallium zinc oxide), respectively.

<Manufacturing of transparent electrode 129>
In the production of the transparent electrode 117, the transparent electrode 129 was produced in the same manner except that the transparent conductive layer was formed as follows.

(Formation of transparent conductive layer)
The following coating liquid A is applied onto the fine metal wire by adjusting the slit gap of the extrusion head so that the dry film thickness is 300 nm by using an extrusion method, and is heated and dried at 110 ° C. for 5 minutes to obtain a conductive polymer. A transparent conductive layer made of water-soluble polymer P-1 (poly (2-hydroxyethyl acrylate)) was formed. The water-soluble polymer P-1 was synthesized by the method described in paragraph 0156 of Japanese Patent No. 5750908.
The coating liquid A was prepared by mixing a separately prepared solution A and a solution B.

[Solution A]
Polythiophene: PEDOT-PSS CLEVIOS PH510 (solid content concentration 1.89%, manufactured by HC Starck) 1.59 g
P-1 (20% solid content aqueous solution) 0.35 g
[Solution B]
Dimethyl sulfoxide (DMSO, 1/10 of the mass of conductive polymer solution) 0.16 g
Compound 1 (1/20 mol of the number of hydroxy groups of P-1) 0.008 g

<Manufacturing of transparent electrode 130>
In the production of the transparent electrode 117, the transparent electrode 130 was produced in the same manner except that the base layer was formed between the gas barrier layer and the thin metal wire as follows.

(Formation of base layer)
Hi-Ceratech IR (manufactured by Ube Nitto Kasei Co., Ltd.), 1 equivalent of A-TMM-3LM-N (pentaerythritol triacrylate (triester 57%), Shin Nakamura Chemical Industry Co., Ltd.) on the surface on which the gas barrier layer of the substrate was formed. (Made by Co., Ltd.), and the polymerization initiator Irgacure 184 (manufactured by BASF) in an amount that makes the solid content 0.2% by mass is mixed, and the solid content is 3% by mass with methyl isobutyl ketone (MIBK). Diluted solution of was prepared. This was formed into a film at 2000 rpm using a spin coater, and then dried by the above-mentioned infrared irradiation device. After that, the outer peripheral portion was wiped off so that the base layer fits within the sealing during the production of the organic EL element described later, and cured with an excimer lamp (apparatus: excimer irradiation device MODEL MECL-M-1 manufactured by MD.com Co., Ltd.). -200, irradiation wavelength: 172 nm, lamp encapsulation gas: Xe, excimer lamp light intensity: 130 mW / cm ² (172 nm), distance between sample and light source: 2 mm, stage heating temperature: 70 ° C, oxygen concentration in the irradiation device: 20.0%, irradiation energy: 1 J / cm ² ) was carried out to form a base layer having a thickness of 100 nm.

<Manufacturing of transparent electrodes 131 to 133>
In the production of the transparent electrode 130, the base layer material, Hyceratec IR, was used as Karenz MTBD1 (Showa Denko KK, Exemplified Compound SE-20) and Karenz MTPE1 (Showa Denko KK, Exemplified Compound SE-20), respectively. The transparent electrodes 131 to 133 were produced in the same manner except that they were changed to Karenz MTNR1 (manufactured by Showa Denko KK, Exemplified Compound SE-71).

<< Fabrication of organic EL element >>
Organic EL elements 101 to 133 for evaluation were manufactured as follows.

<Manufacturing of organic EL element 101>
(1) Formation of Light Emitting Unit and Counter Electrode First, each of the crucibles for vapor deposition in the vacuum vapor deposition apparatus was filled with the following materials constituting each layer of the organic functional layer in the optimum amount for manufacturing the device. As the crucible for vapor deposition, a crucible made of molybdenum or tungsten made of a resistance heating material was used.

After depressurizing to a vacuum degree of 1 × 10 ^-4 Pa, the crucible for vapor deposition containing compound M-2 is energized and heated, and vapor deposition is performed on the transparent electrode 101 (transparent conductive layer side) at a vapor deposition rate of 0.1 nm / sec. Then, a hole injection transport layer having a thickness of 40 nm was formed.
Next, compound BD-1 and compound H-1 are co-deposited at a vapor deposition rate of 0.1 nm / sec so that compound BD-1 has a concentration of 5% by mass, and fluorescent emission having a thickness of 15 nm is exhibited. A layer was formed.
Next, the vapor deposition rate of compound GD-1, compound RD-1 and compound H-2 was 0.1 nm / sec so that the concentration of compound GD-1 was 17% by mass and that of RD-1 was 0.8% by mass. To form a phosphorescent light emitting layer having a thickness of 15 nm and exhibiting yellow color.
Then, compound E-1 was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to form an electron transport layer having a thickness of 30 nm.
From the above, an organic functional layer was prepared.

Further, after forming LiF at a thickness of 1.5 nm, aluminum was vapor-deposited at 110 nm to form a counter electrode and a take-out electrode thereof, thereby producing an organic EL element 101.

(2) Sealing (2.1) Preparation of Adhesive Composition As the polyisobutylene resin (A), 100 parts by mass of "Opanol B50 (manufactured by BASF, weight average molecular weight (Mw) = 340000)", polybutene resin (B) As "Nisseki Polybutene Grade HV-1900 (manufactured by Shin Nihon Petroleum Co., Ltd., weight average molecular weight (Mw) = 1900)" 30 parts by mass, as a hindered amine light stabilizer (C) "TINUVIN765 (manufactured by BASF Japan, grade 3) It has a hindered amine group.) ”0.5 parts by mass, as a hindered phenol-based antioxidant (D),“ IRGANOX1010 (manufactured by BASF Japan, β-position of both hindered phenol groups has a tertiary butyl group. ) ”0.5 parts by mass and 50 parts by mass of“ Eastocac H-100L Resin (manufactured by Eastman Chemical Co., Inc.) ”as the cyclic olefin polymer (E) in toluene, and the solid content concentration is about 25 mass. % Adhesive composition was prepared.

(2.2) Preparation of Sealing Member First, a polyethylene terephthalate film having a thickness of 50 μm to which an aluminum (Al) foil having a thickness of 100 μm was bonded was prepared and used as a sealing member. Next, the prepared solution of the adhesive composition is applied to the aluminum side (gas barrier layer side) of the sealing member so that the thickness of the adhesive layer formed after drying is 20 μm, and 2 at 120 ° C. It was dried for minutes to form an adhesive layer.
Next, as a release sheet, a release-treated surface of a polyethylene terephthalate film having a thickness of 38 μm was attached to the formed adhesive layer surface to prepare a sealing member.

The sealing member produced by the above method was left to stand in a nitrogen atmosphere for 24 hours or more.
After being left to stand, the release sheet was removed, and a vacuum laminator heated to 80 ° C. was used to laminate the organic EL element 101 so as to cover the counter electrode. Further, it was heated at 120 ° C. for 30 minutes, and the organic EL element 101 was sealed with a sealing member.

<Manufacturing of organic EL elements 102 to 133>
In the production of the organic EL element 101, the organic EL elements 102 to 133 were produced in the same manner except that the transparent electrode 101 was changed to the transparent electrodes 102 to 133.

《Evaluation》
The following evaluations were performed on the produced transparent electrodes 101 to 133 and the organic EL elements 101 to 133.
The evaluation results are shown in Tables 1 and 2.

<Evaluation of conductivity>
For each of the manufactured transparent electrodes, the surface resistance was measured using a resistivity meter (Loresta GP (MCP-T610 type): manufactured by Dia Instruments Co., Ltd.) in accordance with JIS K 7194: 1994 to determine the conductivity. evaluated.

<Measurement of rectification ratio>
For each of the manufactured organic EL elements, 10 pieces were manufactured by the same manufacturing procedure, the rectification ratio was measured, the average value was obtained, and the rectification ratio was evaluated by the following index.

Rectification ratio = current value when + 4V is applied / current value when -4V is applied 5: Rectification ratio is 1.0 × 10 ⁵ or more 4: Rectification ratio is 1.0 × 10 ⁴ or more and less than 1.0 × 10 ⁵ 3: Rectification ratio is 1.0 × 10 ³ or more and less than 1.0 × 10 ⁴ 2: Rectification ratio is 1.0 × 10 ² or more and less than 1.0 × 10 ³ 1: Rectification ratio is 1.0 × 10 or more and 1.0 Less than x10 ² 0: Rectification ratio is less than 1.0 x10

<Summary>
As is clear from Tables 1 and 2, the transparent electrode manufactured by the method for manufacturing a transparent electrode of the present invention and the organic EL device provided with the transparent electrode have more conductive and rectifying characteristics than the transparent electrode as a comparative example. It was confirmed to be excellent.
From the above, a step of printing the metal nanoparticle-containing composition in a pattern to form a metal thin wire, a step of drying the metal fine wire, a step of irradiating a flash light to fire the metal fine wire, and a step of firing the metal fine wire on the metal fine wire. In the step of forming a transparent conductive layer having a thickness in the range of 30 to 300 nm and firing the thin metal wire, the concentration of the oxygen-containing substance is in the range of 50 to 2000 volume ppm in an atmosphere. It can be seen that the method for producing a transparent electrode to be fired is useful for providing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device.

Further, when comparing the organic EL elements 107, 121 and 122, the organic EL element 107 subjected to wavelength control IR drying has the highest rectification ratio as compared with the organic EL elements 121 and 122 subjected to hot plate drying and IR drying. It was an excellent result. Although the detailed reason is unknown, it is presumed that the fine metal wire produced by using wavelength-controlled IR drying can suppress the growth of minute crystals of metal oxides and metal sulfides on the fine metal wire and has excellent surface smoothness. doing.

Further, when the strength of the fine metal wire (adhesion between the substrate and the fine metal wire) was evaluated by the tape peeling method at the stage where the fine metal wire was manufactured for the organic EL elements 117 and 130 to 133, the organic EL provided with the base layer was provided. The elements 130 to 133 had less peeling of the metal fine wire pattern as compared with the organic EL element 117, and had excellent adhesion between the substrate and the metal fine wire.
Specifically, the adhesion was evaluated by repeating crimping / peeling 10 times using an ST film (Panac 0.1N / 25 mm) on the thin metal wire and visually observing the detachment of the fine metal wire pattern. .. In addition, when the adhesion evaluation was performed on the organic EL elements 117 and 130 to 133 manufactured up to the transparent conductive layer, the same result was obtained, the peeling of the metal fine wire pattern was small, and the adhesion between the substrate and the metal fine wire was improved. It was excellent.

[Example 2]
In the production of the transparent electrodes 101 to 133 of Example 1, a sample in which the particle-containing layer was formed as follows on the surface opposite to the surface on which the gas barrier layer was formed was prepared before the gas barrier layer was formed. Each was prepared.
When the conductivity and rectification characteristics of each sample were evaluated in the same manner as in Example 1, the same results as in Example 1 could be obtained.
It was also confirmed that when the same samples are stacked and the transparent electrodes are in direct contact with each other, charging and sticking between the transparent electrodes can be suppressed.

(Formation of particle-containing layer)
(1) Preparation of colloidal silica-containing monomer 2-methacryloyl in 130 parts by mass of colloidal silica (SiO ₂ component 30% by mass, average particle size 20 nm, manufactured by Nissan Chemical Co., Ltd.) dispersed using ethyl acetate as a solvent. Add 30 parts by mass of oxyethyl isocyanate (MOI, molecular weight 155, manufactured by Showa Denko Co., Ltd.) and 0.1 part by mass of di-n-butyltin dilaurate (DBTDL) as a catalyst, and add 24 at room temperature (25 ° C.). Stirred for hours. The reaction of the isocyanate group was confirmed by infrared spectroscopy (IR), and ethyl acetate as a solvent was removed by an evaporator to obtain a colloidal silica-containing monomer.

(2) Preparation of particle-containing layer preparation solution To 100 parts by mass of the colloidal silica-containing monomer (nonvolatile content: 36% by mass) produced above, a methyl ethyl ketone solution of Li ⁺ / CF ₃ SO ₃ ⁻ (nonvolatile content: 50% by mass) %, 5 parts by mass of Sanko Chemical Industry Co., Ltd.) was mixed and stirred. As an initiator, 1 part by mass of Irgacure 907 (manufactured by BASF Japan Ltd.) was added to prepare a particle-containing layer preparation solution.

(3) Formation of Particle-Containing Layer Next, the prepared particle-containing layer preparation liquid was applied and dried on a resin substrate under the condition that the thickness after curing was 10 μm. After that, an ultraviolet irradiation treatment was carried out under the condition of 300 mJ using an 80 W / cm mercury lamp to form a particle-containing layer.

The present invention can be particularly preferably used to provide a method for producing a transparent electrode having excellent conductivity and excellent rectifying characteristics when applied to an organic electronic device.

1 Transparent resin substrate 2 Metal thin wire 3 Transparent conductive layer 4 Underlayer 5 Gas barrier layer 6 Particle-containing layer 10 Transparent electrode 20 Sending roller 30 First film forming chamber 31 Coating part 32 Drying part 33 Hardened part 40 Second film forming chamber 41 Printing section 42 Drying section 43 Burning section 50 Third film forming chamber 51 Film forming section 60 Winding roller 100 Manufacturing equipment 200 Organic EL element 210 Light emitting unit 220 Opposite electrode

Claims (8)

A method for manufacturing a transparent electrode having a metal fine wire formed in a pattern on a transparent resin substrate and a transparent conductive layer formed on the metal fine wire.
The process of printing the metal nanoparticle-containing composition in a pattern,
A step of drying the metal nanoparticle-containing composition printed in a pattern, and
A step of irradiating the dried metal nanoparticle-containing composition with flash light and firing it to form a fine metal wire.
A step of forming a transparent conductive layer having a thickness in the range of 30 to 300 nm on the thin metal wire, and
Have,
The step of forming the metal fine wire is characterized in that the metal nanoparticle-containing composition is fired in an atmosphere in which the concentration of the oxygen-containing substance is in the range of 50 to 2000 volume ppm to form the metal fine wire. A method for manufacturing a transparent electrode. The step of forming the metal fine wire is characterized in that the metal nanoparticle-containing composition is fired in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 2000 volume ppm to form the metal fine wire. The method for manufacturing a transparent electrode according to claim 1. The step according to claim 1 or 2, wherein in the step of drying the metal nanoparticle-containing composition, the composition is dried in an atmosphere in which the oxygen (O ₂ ) concentration is in the range of 50 to 5000 volume ppm. A method for manufacturing a transparent electrode. The method for producing a transparent electrode according to any one of claims 1 to 3, wherein the thickness of the transparent conductive layer is in the range of 50 to 150 nm. The method for producing a transparent electrode according to any one of claims 1 to 4, wherein the transparent conductive layer contains a metal oxide. The method for manufacturing a transparent electrode according to any one of claims 1 to 5, wherein a base layer is formed between the transparent resin substrate and the thin metal wire. The transparency according to claim 6, wherein the base layer contains a compound having a thiol group and a compound selected from poly (meth) acrylate and poly (meth) acrylamide having an aminoethyl group. Method of manufacturing electrodes. The seventh aspect of claim 7, wherein the compound having a thiol group is a condensate of a compound having a structure represented by the following general formula (I) and a monohydric or polyhydric alcohol or an amine. Manufacturing method of transparent electrode.

(In the general formula (I), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, but at least one of them is an alkyl group having 1 to 10 carbon atoms. Is an integer from 0 to 2, and n is 0 or 1.)

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