JP6927968B2 - Transparent conductive member and organic electroluminescence element - Google Patents

Description

The present invention relates to a transparent conductive member including a light scattering layer and an organic electroluminescence device including the transparent conductive member.

A transparent conductive member provided with a conductive layer formed on a resin film using a conductive substance is a thin type such as an organic electroluminescence (EL) element used for a display or a lighting panel, a solar cell, an electronic paper, or the like. Widely used as a transparent electrode for electronic devices. In particular, large-area electronic devices such as organic EL elements for lighting and solar cells for power generation are required to have high luminous efficiency or power generation efficiency, and therefore, a transparent conductive member having low resistance is desired.

As a low-resistance transparent conductive member, for example, a metal fine wire produced by printing a fine line pattern using a metal ink composition containing metal particles and a solvent for application to an inkjet method and then firing the fine line pattern. (See, for example, Patent Document 1 and Patent Document 2).
Further, in order to improve the luminous efficiency of an organic EL element or the like to which a transparent conductive member is applied, a configuration has been proposed in which a light scattering layer composed of light scattering particles and a binder is provided between the base material and the conductive layer ( For example, see Patent Document 3). In this configuration, by having the light scattering layer, the reflection at the interface between the conductive layer and the substrate is reduced, and the light extraction efficiency is improved.

Japanese Unexamined Patent Publication No. 2007-332347 Japanese Unexamined Patent Publication No. 2010-198935 JP-A-2009-76452

However, a pattern of a metal ink composition is formed on a light scattering layer composed of light scattering particles and a binder by using the above-mentioned metal ink composition, and the pattern of the metal ink composition is fired to form a fine metal wire. Then, the metal particles in the pattern are scattered along with the scattering due to the evaporation of the solvent that is rapidly heated during firing, and the surface of the fine metal wire is defective in unevenness, disconnection, and disappearance (ablation). Therefore, when the fine metal wire is formed on the conventional light scattering layer, a pattern defect of the fine metal wire occurs, so that sufficient reliability cannot be obtained in the transparent conductive member or the organic EL element.

In order to solve the above-mentioned problems, the present invention provides a transparent conductive member capable of improving light extraction efficiency and reliability, and an organic EL element capable of improving luminous efficiency and reliability.

The transparent conductive member of the present invention is formed by covering a resin base material, a light scattering layer containing particles and a binder formed on the resin base material, a metal fine wire formed on the light scattering layer, and a metal fine wire. It is provided with a transparent conductive film. The light scattering layer contains 80% or more of spherical particles having an aspect ratio of 2 or less as particles, and the thickness of the light scattering layer is larger than the average particle diameter of the particles and is 250 nm or more and 1000 nm or less . The particle abundance in the region on the resin substrate side from the center in the thickness direction is larger than the particle abundance in the region on the transparent conductive film side from the center in the thickness direction.
Further, the organic electroluminescence element of the present invention includes a light emitting unit and a second electrode on the transparent conductive member.

According to the present invention, it is possible to provide a transparent conductive member capable of improving light extraction efficiency and reliability, and an organic EL element capable of improving luminous efficiency and reliability.

It is a figure which shows the schematic structure of the transparent conductive member. It is a figure which shows the schematic structure of the modification of the transparent conductive member. It is a figure which shows the schematic structure of the organic EL element.

Hereinafter, examples of embodiments for carrying out the present invention will be described, but the present invention is not limited to the following examples.
The explanation will be given in the following order.
1. 1. Transparent conductive member 2. Deformation example of transparent conductive member 3. Manufacturing method of transparent conductive member 4. Organic electroluminescence element 5. Manufacturing method of organic electroluminescence device

<1. Transparent conductive member>
Hereinafter, embodiments of the transparent conductive member will be described.
FIG. 1 shows a schematic configuration of the transparent conductive member of the present embodiment. The transparent conductive member 10 shown in FIG. 1 includes a resin base material 11, a light scattering layer 15 provided on the resin base material 11, and a conductive layer 12 provided on the light scattering layer 15. The light scattering layer 15 includes particles 16 and a binder 17. The conductive layer 12 is composed of a thin metal wire 13 formed on the light scattering layer 15 and a transparent conductive film 14 provided over the thin metal wire 13.

The transparent conductive member 10 has a total light transmittance of preferably 70% or more, more preferably 80% or more. The total light transmittance can be measured according to a known method using a spectrophotometer or the like. If the total light transmittance is low, it becomes difficult for light to go out of the element, and the brightness is lowered. Further, as the electrical resistance value of the conductive layer of the transparent conductive member 10, the surface resistivity is 100Ω / sq. For use in a large-area organic electronic device. It is preferably 10Ω / sq. More preferably: The surface resistivity can be measured according to, for example, JIS K6911, ASTM D257, etc., and can be easily measured using a commercially available surface resistivity meter.

[Light scattering layer]
In the transparent conductive member 10, the particles 16 contained in the light scattering layer 15 include 80% or more of spherical particles having an aspect ratio of 2 or less. The thickness of the light scattering layer 15 is larger than the particle size of the particles 16. As described above, the particles 16 contain 80% or more of spherical particles having an aspect ratio of 2 or less, and the thickness of the light scattering layer 15 is larger than the particle diameter of the particles 16, so that the particles 16 are light scattering layers in the light scattering layer 15. It tends to be unevenly distributed in the region on the 11 side of the resin base material of 15. As a method of unevenly distributing the particles 16 in the region on the resin substrate 11 side, for example, a means of diluting the liquid concentration from the usual coating concentration and applying the particles 16 thicker by the dilution amount can be used. By doing so, the time from immediately after application to the completion of drying of the coating film can be adjusted, and the particles 16 are likely to sink into the resin base material 11 side, so that the particles of the particles 16 on the resin base material 11 side The abundance rate (uneven distribution rate) of 16 can be adjusted.

By unevenly distributing the spherical particles 16 in the region on the resin base material 11 side in this way, as shown in FIG. 1, the particles 16 are above the surface of the binder 17 on the conductive layer 12 side in the light scattering layer 15. It is easy to form the light scattering layer 15 so that it does not protrude toward (the conductive layer 12 side). Therefore, it is possible to suppress the generation of irregularities on the surface of the light scattering layer 15 due to the protrusion of the particles 16 and improve the flatness of the surface of the light scattering layer 15. The surface roughness of the light scattering layer 15 is better as the Ra is smaller. As a preferable surface roughness, the arithmetic average roughness Ra is 10 nm or less, and more preferably Ra is 5 nm or less.

By increasing the flatness of the surface of the light scattering layer 15, even when the metal fine wire is formed directly above the light scattering layer 15, ablation when the pattern of the metal ink composition is fired to form the metal fine wire. Can be prevented. Therefore, it is not necessary to provide another configuration such as a flattening layer on the light scattering layer 15, and it is possible to suppress a decrease in reliability of the transparent conductive member 10 due to the occurrence of a pattern defect of the fine metal wire.

The uneven distribution of the particles 16 in the light scattering layer 15 means that the light scattering layer 15 is placed on the transparent conductive film 14 side and the resin group from the center in the thickness direction at the thickness at which the binder of the light scattering layer 15 is formed. When divided into both sides of the material 11, the volume ratio of the particles 16 is different between the transparent conductive film 14 side and the resin base material 11. In the transparent conductive member 10, the particle abundance of the particles 16 in the region of the resin base material 11 side from the center in the thickness direction of the light scattering layer 15 is the particles 16 in the region of the transparent conductive film 14 side from the center in the thickness direction. Greater than the particle abundance of. The method of calculating the particle abundance on the resin base material 11 side is to prepare a cross section of the light scattering layer 15 and to prepare each region of the region on the resin base material 11 side and the region on the transparent conductive film 14 side from the center in the thickness direction. In, any five places can be photographed with a transmission electron microscope (TEM) and calculated from the thickness of the light scattering layer 15 and the cross-sectional area of the particles.

The particle abundance on the resin base material 11 side of the light scattering layer 15 preferably exceeds 50%. Further, the particle abundance rate on the resin base material 11 side of the light scattering layer 15 is preferably 65% or more, and preferably 70% or more. The higher the particle abundance rate on the resin base material 11 side of the light scattering layer 15, the easier it is for light extraction to improve and the less ablation occurs.

Hereinafter, the refractive indexes of the binder and the particles are measured values at a wavelength of 633 nm.
The binder 17 preferably has a refractive index nb of 1.50 or more and less than 2.00 in light having a wavelength of 633 nm. The refractive index nb of the binder 17 is the refractive index of the single material when it is formed of a single material, and in the case of a mixed system, it is the total value obtained by multiplying the refractive index peculiar to each material by the mixing ratio. It is a calculated refractive index calculated by.

Further, as a role of the particles 16 in the light scattering layer 15, a scattering function of waveguide light can be mentioned. In order to improve the scattering function of the waveguide light, it is necessary to improve the scattering property of the particles 16. In order to improve the scattering property, methods such as increasing the difference in refractive index between the particles 16 and the binder 17, increasing the layer thickness, and increasing the particle density can be considered. The other method with the least adverse effect on performance is to increase the difference in refractive index between the particles 16 and the binder 17.

The refractive index difference | nb-np | between the refractive index nb of the binder 17 and the refractive index np of the contained particles 16 is preferably 0.2 or more and 1.0 or less. Especially preferably, it is 0.3 or more. When the refractive index difference | nb-np | between the binder 17 and the particles 16 is 0.2 or more, a scattering effect occurs at the interface between the binder 17 and the particles 16. The larger the refractive index difference | nb-np |, the greater the refraction at the interface and the better the scattering effect.

In order to generate the refractive index difference | nb-np |, the refractive index np of the particle 16 is made smaller than the refractive index nb of the binder 17, or the refractive index np of the particle 16 is set from the refractive index nb of the binder 17. Also increase. The refractive index np of the particles 16 is the refractive index of the single material when it is formed of a single material, and in the case of a mixed system, the refractive index peculiar to each material is multiplied by the mixing ratio. It is a calculated refractive index calculated from the total value.

When the refractive index np of the particles 16 is smaller than the refractive index nb of the binder 17, it is preferable to use low refractive index particles having a refractive index np of less than 1.5 as the particles 16. Then, as the binder 17, it is preferable to use a high refractive index binder having a refractive index nb of 1.6 or more. When the refractive index np of the particles 16 is larger than the refractive index nb of the binder 17, it is preferable to use high refractive index particles having a refractive index np of 1.7 or more and 3.0 or less as the particles 16. Then, as the binder 17, it is preferable to use a binder having a refractive index nb smaller than the refractive index np of the particles 16 by 0.2 or more.

As described above, the light scattering layer 15 has an action of diffusing light due to the difference in refractive index between the binder 17 and the particles 16. Therefore, the particles 16 are required to have little adverse effect on other layers and have a high property of scattering light.
The layer thickness of the light scattering layer 15 needs to be thick to some extent in order to secure the optical path length for causing scattering, but on the other hand, it needs to be thin enough not to cause energy loss due to absorption. Therefore, the thickness of the light scattering layer 15 is preferably 250 nm or more and 1000 nm or less.

The scattering in the light scattering layer 15 represents a state in which the haze value (ratio of the scattering transmittance to the total light transmittance) in a single layer of the light scattering layer 15 is 20% or more. The haze value of the light scattering layer 15 in a single layer is more preferably 25% or more, and particularly preferably 30% or more. When the haze value is 20% or more, the light scattering property (light extraction efficiency) can be improved.

[particle]
As described above, the light scattering layer 15 contains 80% or more of spherical particles having an aspect ratio of 2 or less as the particles 16. The spherical particles having an aspect ratio of 2 or less preferably have an average particle diameter of 200 to 500 nm, more preferably 200 to 450 nm, and even more preferably less than 250 to 400 nm.
The aspect ratio referred to here is the ratio of the major axis length to the minor axis length of the particles 16. For example, the particles 16 can be randomly photographed with a scanning electron microscope (SEM) to obtain an image, and the major axis length and the minor axis length of the particles 16 can be obtained and calculated from the image. The particles are photographed at a magnification of 100,000, the aspect ratio for 100 particles is confirmed from the image, and the ratio is obtained.

In the light scattering layer 15, for example, the scattering property can be improved by adjusting the average particle size and the aspect ratio of the particles 16. Specifically, it is preferable to use particles that are larger than the region that causes Mie scattering in the visible light region. On the other hand, in order to make the particles 16 unevenly distributed on the base material 11 side and flatten the surface of the light scattering layer 15, it is necessary to make the average particle diameter smaller than the thickness of the light scattering layer 15.
The average particle size of the particles can be measured by image processing of electron micrographs. The particles are photographed at a magnification of 100,000, and the length of the major axis of the particles is measured from the image. The average particle size of 100 particles is taken as the average particle size of the particles.

The particles 16 are not particularly limited, and any of the above-mentioned low refractive index particles and high refractive index particles can be appropriately selected depending on the intended purpose. For example, organic fine particles and inorganic fine particles can be used as the low refractive index particles and high refractive index particles.

In the light scattering layer 15 having a structure in which the refractive index np of the particles 16 is smaller than the refractive index nb of the binder 17, examples of the low refractive index particles include acrylic resin (1.49), PTFE (1.35), and PFA (. 1.35), SiO ₂ (1.46), magnesium fluoride (1.38), lithium fluoride (1.392), calcium fluoride (1.399), silicone rubber (1.40), fluoride Examples thereof include vinylidene (1.42), silicone resin (1.43), polypropylene (1.48), and urethane (1.49). The numbers in parentheses indicate the typical refractive index of the particles made of each material.

In the light scattering layer 15 having a structure in which the refractive index np of the particles 16 is larger than the refractive index nb of the binder 17, the high refractive index particles are described in International Publication No. 2009/014707 and US Pat. No. 6,608,439. Quantum dots can also be preferably used. Of these, inorganic fine particles having a high refractive index are preferable.

Examples of the organic fine particles having a high refractive index include polymethylmethacrylate beads, acrylic-styrene copolymer beads, melamine beads, polycarbonate beads, styrene beads, crosslinked polystyrene beads, polyvinyl chloride beads, and benzoguanamine-melamine formaldehyde beads. And so on.

Examples of the inorganic fine particles having a high refractive index include inorganic oxide particles composed of at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony and the like. Specific examples of the inorganic oxide particles include ZrO ₂ , TiO ₂ , BaTIO ₃ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO, SiO ₂ , ZrSiO ₄ , and zeolite. Among them, TiO ₂ , BaTiO ₃ , ZrO ₂ , ZnO, SnO ₂ are preferable, and TiO ₂ is most preferable. Further, _{among TiO 2,} the rutile type is preferable to the anatase type because the catalytic activity is lower, the weather resistance of the light scattering layer 15 and the adjacent layer is higher, and the refractive index is higher.

Whether the particles 16 are used with surface treatment or without surface treatment in order to be contained in the light scattering layer 15 from the viewpoint of improving dispersibility and stability when used as a dispersion liquid described later. Can be selected.

When surface treatment is performed, specific materials for surface treatment include dissimilar inorganic oxides such as silicon oxide and zirconium oxide, metal hydroxides such as aluminum hydroxide, and organic acids such as organosiloxane and stearic acid. Be done. 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 dissimilar inorganic oxide and / or the metal hydroxide is preferable, and the metal hydroxide is more preferable as the surface treatment material. When surface treatment is performed, the surface treatment portion is also included in the particle volume.

When the inorganic oxide particles are surface-coated with a surface treatment material, the coating amount is preferably 0.01 to 99% by mass. Within this range, the effect of improving the dispersibility and stability of the surface treatment can be sufficiently obtained. Generally, this coating amount is expressed as the mass ratio of the surface treatment material used on the surface of the particles to the mass of the particles.

Further, in the light scattering layer 15, the volume ratio of the above-mentioned particles 16 to the binder 17 (hereinafter referred to as PB ratio) is preferably 5 vol% or more and 40 vol% or less. The volume ratio (PB ratio) is the ratio of the volume of the binder 17 to the volume of the particles 16 in the total volume of the light scattering layer 15 [particle volume / (particle volume + binder volume)]. By setting the PB ratio to 5 vol% or more, the light extraction in the light scattering layer 15 is likely to be improved. It is more preferably 10 vol% or more, still more preferably 20 vol% or more. Further, when the PB ratio is 40 vol% or less, the particle abundance rate on the resin base material 11 side tends to be increased, and the flatness of the surface of the light scattering layer 15 tends to be improved. That is, by setting the volume ratio of the particles 16 to the above range, it is possible to suppress the protrusion of the particles 16 from the surface of the light scattering layer 15 due to the excess of the particles 16, and to improve the light scattering efficiency and the light extraction efficiency. Can be done.

Further, the particle abundance of the particles 16 in the region of the resin base material 11 is preferably 50 vol% or more, more preferably 60 vol% or more, and 70 vol% or more than the center of the light scattering layer 15 in the thickness direction. The above is particularly preferable.

As a result, the light scattering layer 15 can be configured so as not to protrude above the surface of the binder 17 on the conductive layer 12 side (conducting layer 12 side). Therefore, it is possible to suppress the generation of irregularities on the surface of the light scattering layer 15 due to the protrusion of the particles 16 and improve the flatness of the surface of the light scattering layer 15. Further, in the light scattering layer 15, the amount of light scattering can be increased to improve the light extraction efficiency.

[Binder]
The binder 17 of the light scattering layer 15 has either a configuration in which the refractive index np of the particles 16 is smaller than the refractive index nb of the binder 17 or a configuration in which the refractive index np of the particles 16 is larger than the refractive index nb of the binder 17. However, a known binder can be used without particular limitation. Further, a plurality of types of binders can be mixed and used.

In the light scattering layer 15, as a high refractive index binder applied to a configuration in which the refractive index np of the particles 16 is smaller than the refractive index nb of the binder 17, it is preferable to use a binder having a refractive index nb of 1.6 or more. For example, Rio Duras TYZ series, Rio Duras TYT series (manufactured by Toyo Ink Co., Ltd.), _{resin paint containing ZrO 2} fine particles (manufactured by Pixilent Technologies), UR series (manufactured by Nissan Chemical Industries), Organtics series (manufactured by Matsumoto Fine Chemical Co., Ltd.), PIUVO series (KSM), acrylic resin series, epoxy resin series (NTT Advanced Technology), hitaloid series (Hitachi Kasei), etc. can be used.

Further, in the light scattering layer 15 having a structure in which the refractive index np of the particles 16 is larger than the refractive index nb of the binder 17, the refractive index nb of the binder is 0.2 or more smaller than the refractive index np of the particles 16. It is preferable to use a binder having a high refractive index as much as possible, and the above-mentioned high refractive index binder can be used.
This is because, in the case of the low refractive index binder, the light coming from the conductive layer 12 side cannot travel into the low refractive index binder depending on the penetration angle and is reflected.

Further, as the binder 17 of the light scattering layer 15, an inorganic material or a compound capable of forming an oxide, a nitride or an oxide nitride of a metal by irradiation with ultraviolet rays under a specific atmosphere can also be used. .. As such a compound, a compound that can be modified at a relatively low temperature described in JP-A-8-12879 is preferable.
Specifically, polysiloxane (including polysilsesquioxane) having a Si—O—Si bond, polysilazane having a Si—N—Si bond, and both Si—O—Si bond and Si—N—Si bond. Polysilazane and the like containing the above can be mentioned. These can be used by mixing two or more kinds.

(Polysiloxane)
The polysiloxane used in the light scattering layer 15 includes R ₃ SiO _1/2 , R ₂ SiO, RSiO _3/2, and SiO ₂ as general structural units. Here, R is independent of the group consisting of an alkyl group containing a hydrogen atom and 1 to 20 carbon atoms such as methyl, ethyl and propyl, an aryl group such as phenyl, and an unsaturated alkyl group such as vinyl. Is selected. Examples of particular polysiloxane _{groups, PhSiO 3/2, MeSiO 3/2, HSiO} 3/2, MePhSiO, Ph 2 SiO, PhViSiO, ViSiO 3/2, MeHSiO, MeViSiO, Me 2 SiO, Me 3 SiO 1 _{/ 2} etc. can be mentioned. Mixtures and copolymers of polysiloxane can also be used. Vi represents a vinyl group.

(Polysilsesquioxane)
In the light scattering layer 15, it is preferable to use polysilsesquioxane among the above-mentioned polysiloxanes. Polysilsesquioxane is a compound containing silsesquioxane as a structural unit. "Silsesquioxane" is a compound represented by _{RSiO 3/2} , and is usually represented by _{RSiX 3.} R is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an araalkyl group (also referred to as an aralkyl group) and the like, and X is a halogen, an alkoxy group and the like.
The shape of the molecular arrangement of polysilsesquioxane is typically an amorphous structure, a ladder-like structure, a cage-shaped structure, a cage-shaped structure in which one silicon atom is missing, or a cage-shaped structure in which a silicon-oxygen bond is formed. A partially cleaved structure or the like in which is partially cut is known.

Among these polysilsesquioxane, it is preferable to use a so-called hydrogen silsesquioxane polymer. Examples of the hydrogen silsesquioxane polymer include a hydride siloxane polymer represented by _{HSi (OH) x} (OR) _{y Oz / 2.} Each R is an organic group or a substituted organic group, which forms a hydrolyzable substituent when attached to silicon by an oxygen atom. x = 0 to 2, y = 0 to 2, z = 1 to 3, x + y + z = 3. Examples of R include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), an aryl group (for example, a phenyl group, etc.), and an alkenyl group (for example, an allyl group, a vinyl group, etc.). These resins are completely condensed (HSiO _3/2 ) _n , or only partially hydrolyzed (ie, containing some Si-OR) and / or partially condensed (ie, one). (Including Si-OH of the part).

(Polysilazane)
Polysilazane used in the light scattering layer 15 is a polymer having a silicon-nitrogen bond, and is composed of Si—N, Si—H, N—H, etc., SiO ₂ , Si ₃ N _4, and both intermediate solid solutions SiO _x N _y. It is an inorganic precursor polymer such as (x = 0.1 to 1.9, y = 0.1 to 1.3).

As the polysilazane preferably used for the light scattering layer 15, the polysilazane represented by the following general formula (1) can be used.

In the formula, R ¹ , R ² and R ³ 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, respectively.

From the viewpoint of the denseness of the obtained light scattering layer 15 as a film, perhydropolysilazane (PHPS) in which all ^{of R 1} , R ² and R ^{3 of the general formula (1) are hydrogen atoms is particularly preferable.} Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on a 6-membered ring and an 8-membered ring, and its molecular weight is about 600 to 2000 (gel) in terms of number average molecular weight (Mn). It is a polystyrene equivalent by permeation chromatography) and is a liquid or solid substance.

Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating liquid. Examples of commercially available products of the polysilazane solution include NN120-20, NAX120-20, and NL120-20 manufactured by AZ Electronic Materials Co., Ltd.

As the binder 17, an ionizing radiation curable resin composition can be used, but as a curing method of the ionizing radiation curable resin composition, a usual curing method, that is, irradiation with an electron beam or ultraviolet rays can be used.
For example, in the case of electron beam curing, 10 to 1000 keV emitted from various electron beam accelerators such as Koklov Walton type, Van de Graaff 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 of 30 to 300 keV is preferably used. In the case of ultraviolet curing, ultraviolet rays emitted from light rays such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

(Vacuum ultraviolet irradiation device with excimer lamp)
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.
Noble gas atoms such as xenon (Xe), krypton (Kr), argon (Ar), and neon (Ne) are called inert gases because they do not chemically bond to form molecules. However, a noble gas atom (excited atom) that has obtained energy by discharge or the like can be combined with another atom to form a molecule.
For example, when the noble gas is Xe (xenon), 172 nm excimer light is emitted when _{the excited excimer molecule Xe 2} ^{* transitions to the ground state, as shown by the following reaction formula.}

e + Xe → Xe ^*
Xe ^* + 2Xe → Xe ₂ ^* + Xe
Xe ₂ ^* → Xe + Xe + hν (172nm)

A feature of excimer lamps is that they are highly efficient because their radiation is concentrated in one wavelength and almost no light other than the required light is emitted. Moreover, since extra light is not emitted, the temperature of the object can be kept relatively low. Furthermore, since it does not take time to start and restart, it is possible to turn on and blink instantly.

A dielectric barrier discharge lamp is an example of a light source that efficiently irradiates excimer light.
The configuration of the dielectric barrier discharge lamp is to generate a discharge between the electrodes via a dielectric. Generally, at least one electrode is arranged between the discharge container made of the dielectric and the outside thereof. Just do it. As a dielectric barrier discharge lamp, for example, a rare gas such as xenone is sealed in a double-cylindrical discharge container composed of a thick tube and a thin tube made of quartz glass, and a mesh-like electrode is formed outside the discharge container. There is one in which one electrode is provided and another electrode is provided inside the inner tube. The dielectric barrier discharge lamp generates a dielectric barrier discharge inside the discharge container by applying a high-frequency voltage or the like between the electrodes, and generates excimer light when excimer molecules such as xenon generated by the discharge are dissociated. ..

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 irradiated object due to the irradiation light itself can be suppressed.

[Conductive layer]
In the transparent conductive member 10, a pattern is formed on one surface of the resin base material 11 by metal thin wires 13 which are thin wires containing metal. The thin metal wire 13 is formed in a predetermined pattern having an opening on one surface of the resin base material 11. The portion of the resin base material 11 on which the thin metal wire 13 is not formed becomes an opening (translucent window portion). The shape of the thin wire pattern of the metal fine wire 13 is not particularly limited. For example, it may be a striped pattern, a grid pattern, a random mesh pattern, or the like. The thin metal wire 13 is formed so as to be in direct contact with the light scattering layer 15. Further, another layer may be formed between the thin metal wire 13 and the light scattering layer 15.

Then, on the thin metal wire 13, the transparent conductive film 14 is formed as a layer continuous in the plane direction. By coating the thin metal wire 13 to form the transparent conductive film 14, the conductive layer 12 having low resistance and uniform surface resistance can be formed. The transparent conductive film 14 is formed so as to be in direct contact with the light scattering layer 15 except for the portion where the thin metal wire 13 is formed. Further, another layer may be formed between the transparent conductive film 14 and the light scattering layer 15.

[Conductive layer: thin metal wire]
The thin metal wire 13 constituting the conductive layer 12 is formed of a metal as a main component and having 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.

When a transparent substrate is used, the proportion occupied by the openings, that is, the aperture ratio 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 13 is preferably in the range of 10 to 200 μm, and more preferably in the range of 10 to 100 μm. When the line width of the thin metal wire 13 is 10 μm or more, desired conductivity can be obtained, and when it is 200 μm or less, the transparency of the transparent conductive member is improved.
In the striped or grid pattern, the spacing between the thin metal wires is preferably in the range of 0.5 to 4 mm.

The height (thickness) of the thin metal wire 13 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 13 is 0.1 μm or more, the desired conductivity can be easily obtained. Further, by setting the thickness to 5.0 μm or less, it is possible to reduce the influence of the unevenness difference on the layer thickness distribution of the functional layer when used in an organic electronic device.

(Metallic ink composition)
It is preferable that the thin metal wire 13 is formed by preparing a metal or a metal ink composition containing a metal forming material, applying the metal ink composition, and then appropriately selecting a post-treatment such as a drying treatment or a firing treatment.

The metal (elemental metal or alloy) to be blended in the metal ink composition is preferably in the form of particles or fibers (tube-like, wire-like, etc.), and more preferably in the form of metal nanoparticles. Further, it is preferably formed from a metal forming material which has a metal atom (element) and produces a metal by a structural change such as decomposition. The metal and the metal-forming material in the metal ink composition may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and the ratio thereof can be adjusted arbitrarily.

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 luminous efficiency of the obtained organic electronic device. These metals or alloys may be used alone or in combination of two or more.

The metal ink 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 ink 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 diameter in the range of 3 to 300 nm are preferable, and those having an average particle diameter in the range of 5 to 100 nm are more preferably used. In particular, silver nanoparticles having an average particle diameter in the range of 3 to 100 nm are preferable. The metal nanowire is preferably a silver wire having a width of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm.

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

In the metal colloid, when a protective agent that coats the surface of the metal nanoparticles is used, an organic π-bonded ligand is preferable. 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, as the organic π-bonded ligand, an amino group, an alkylamino group, a mercapto group, a hydroxyl group, etc. are used as substituents in order to improve the coordination to the 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 pamphlet 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-bonding ligand of the present embodiment and the preparation of the metal nanoparticle dispersion liquid containing the organic π-bonding ligand are described in paragraphs [0039] to [0060] of International Publication No. 2011/114713. It can be carried out according to the described method.

The average particle size of the metal colloid is usually 3 nm or more and 500 nm or less, preferably 5 nm or more and 50 nm or less. 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 13 can be improved.

When a protective agent that coats the surface of the metal nanoparticles is used in the metal nanoparticle dispersion liquid, it is preferable to use a protective agent that disengages the ligand at a low temperature of 200 ° C. or lower. As a result, the protective agent is peeled off due to 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.

As the material for forming metallic silver, it is preferable to use an organic silver complex compound prepared by reacting a silver compound represented by _{[Ag n X] with an ammonium carbamate-based 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-mentioned ammonium carbamate compounds, the alkylammonium alkylcarbamate 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 compound 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 directly reacted 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 compound 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 compound is well soluble in various solvents including solvents used in the production of organic silver complex compounds, such as alcohols such as methanol, esters such as ethyl acetate, ether solvents such as tetrahydrofuran. Therefore, the organic silver complex compound can be easily applied to the coating and printing steps as a metal ink 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 silver β-ketocarboxylate and silver carboxylate (4) but also silver carboxylate having a group represented by the formula [-COOAg] including these can be used. can.

When the metal ink 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 react with the acid together with the silver carboxylate. It is preferable that one or more nitrogen-containing compounds selected from the group consisting of ammonium salts 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 chain 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.

[Conductive layer: transparent conductive film]
The transparent conductive film 14 constituting the conductive layer 12 is provided on the surface of the light scattering layer 15 so as to cover the surface of the thin metal wire 13. The transparent conductive film 14 is a layer containing a conductive material for conducting electricity in the transparent conductive member 10. Examples of the transparent conductive film 14 include metal thin films such as Au, Ag, Pt, Cu, Rh, Pd, Al, and Cr, In ₂ O ₃ , CdO, CdIn ₂ O ₄ , Cd ₂ SnO ₄ , _{and TIO 2} . SnO ₂ , ZnO, ITO (indium tin oxide), IZO (indium zinc oxide), IGO (indium gallium oxide), IWZO (indium tungsten zinc oxide), AZO (Al-doped zinc oxide) , GZO (Ga-doped zinc oxide), ATO (antimony tin oxide), FTO (F-doped tin oxide), TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, GaN, CuAlO ₂ , CuGaO ₂ , Examples thereof include conductive inorganic compound layers such as SrCu ₂ O ₂ , LaB ₆ , and RuO _2. These compounds may be crystalline or amorphous. Further, a material such as IDIXO (In ₂ O _3- ZnO) capable of producing an amorphous and transparent conductive member 10 may be used. Further, a conductive polymer may be used, and examples thereof include polyacetylene, poly (p-phenylene vinylene), polypyrrole, polythiophene, polyaniline, and poly (p-phenylene sulfide). The transparent conductive film 14 may contain only one kind of these conductive materials, or may contain two or more kinds of these conductive materials.
The method for forming the transparent conductive film 14 is not particularly limited, and conventionally known methods can be used. As a method for forming the transparent conductive film 14, for example, a CVD method by a dry process, a vacuum deposition method, an ion plating method, a sputtering method and the like can be used.

The transparent conductive film 14 is preferably formed by using a conductive metal oxide having ^{a volume resistivity of less than 1 × 10 1 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 of the conductive plastic of JIS K 7194-1994 by the four-probe method. 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).
The transparent conductive film 14 has a sheet resistance of 10000 Ω / sq. From the viewpoint of forming the conductive layer 12 of the transparent conductive member 10. It is preferably 2000Ω / sq. More preferably:

When a metal thin film is used, the thickness of the transparent conductive film 14 is preferably in the range of 5 nm to 15 nm. When a metal oxide or a conductive inorganic compound is used, it can be in the range of 10 to 500 nm. From the viewpoint of increasing conductivity, the thickness is preferably in the range of 100 to 500 nm. From the viewpoint of enhancing the smoothness of the surface, the thickness is preferably 50 nm or more.

Among the above-mentioned materials, it is preferable to select a metal oxide as a material capable of ensuring high transparency even when the thickness of the transparent conductive film 14 is increased. Further, when the transparent conductive film 14 is provided at about 150 nm, it is difficult to secure transparency with the above-mentioned metal and ITO. Therefore, it is preferable to use IZO, AZO, GZO, ATO, ZnO, SnO _{2, and FTO as the transparent conductive film 14.}

In particular, as the metal oxide that can be used for the transparent conductive film 14, IZO, IGO, and IWZO are preferable. Among them, as IZO, _{a composition represented by a weight ratio of In 2} O ₃ : ZnO = 80 to 95: 5 to 20 is preferable. As the IGO, _{a composition represented by a weight ratio of In 2} O ₃ : Ga ₂ O ₃ = 70 to 95: 5 to 30 is preferable. As the IWZO, _{a composition represented by a weight ratio of In 2} O ₃ : WO ₃ : ZnO = 95 to 99.8: 0.1 to 2.5: 0.1 to 2.5 is preferable.

The transparent conductive film 14 preferably has an arithmetic average roughness Ra of 5 nm or less. Further, Ra is preferably 3 nm or less. The arithmetic mean roughness Ra is measured using, for example, an atomic force microscope (manufactured by Digital Instruments).

[Resin base material]
The resin base material 11 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 resin base material 11 is not particularly limited. For example, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, and polystyrene Resins, polyolefin resins such as cyclic olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resin, polysalphon (PSF) resin, polyether salphon (PES) resin, polycarbonate Examples thereof include (PC) resin, polyamide resin, polyimide resin, acrylic resin, and triacetyl cellulose (TAC) resin. These resins may be used alone or in combination of two or more.
Further, the resin base material 11 may be an unstretched film or a stretched film.

When the resin base material 11 has high transparency, the transparent conductive member 10 can be used as a transparent electrode of an 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 resin base material 11 may be subjected to a surface activation treatment in order to improve the adhesion with the light scattering layer 15 formed on the resin base material 11. Further, a 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 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. The light scattering layer 15 may be a single layer, but if it has a multi-layer structure, the adhesion is further improved.

<2. Deformation example of transparent conductive member>
Next, a modification of the transparent conductive member described in the above-described embodiment will be described.
FIG. 2 shows a schematic configuration of a modified example of the transparent conductive member. The transparent conductive member 10A shown in FIG. 2 includes a resin base material 11, a light scattering layer 15 provided on the resin base material 11, an ablation prevention layer 18 provided on the light scattering layer 15, and an ablation prevention layer 18. It is provided with a conductive layer 12 provided above. The transparent conductive member 10A having this configuration is different from the transparent conductive member of the above-described embodiment only in that it has an ablation prevention layer 18, and has the same configuration as the transparent conductive member of the above-described embodiment in other configurations. Therefore, in the following description, only the configuration related to the ablation prevention layer 18 will be described, and the description of the other configurations will be omitted.

In the transparent conductive member 10A shown in FIG. 2, an ablation prevention layer 18 is provided between the light scattering layer 15 and the conductive layer 12. The ablation prevention layer 18 is provided so as to be in direct contact with the light scattering layer 15. Further, a thin metal wire 13 is formed directly above the ablation prevention layer 18, and the ablation prevention layer 18 is formed so as to be in direct contact with the thin metal wire 13. Further, the transparent conductive film 14 is formed so as to be in direct contact with the ablation prevention layer 18 except for the portion where the thin metal wire 13 is formed. Other layers may be formed between the light scattering layer 15 and the ablation prevention layer 18 and between the ablation prevention layer 18 and the conductive layer 12.

[Ablation prevention layer]
The ablation prevention layer 18 is a layer for suppressing penetration of a solvent or the like in the metal ink composition into the light scattering layer 15 when the metal ink composition for forming the metal fine wire 13 is applied and patterned. be. When the solvent or the like in the metal ink composition permeates the light scattering layer 15, the solvent is vaporized by heating at the time of forming the metal fine wire, causing ablation of the metal fine wire. Therefore, the structure of the ablation prevention layer 18 is not particularly limited as long as it is a layer having a high solvent barrier property. Further, it is preferable that the film is a uniform film without breakage such as pinholes so that the solvent in the metal ink composition does not come into contact with the light scattering layer 15. Further, since the ablation prevention layer 18 only needs to have a solvent barrier property, it does not need to have flatness or other functions. Therefore, the ablation prevention layer may have a sufficient thickness to realize the solvent barrier property, and is preferably 10 nm or more and 100 nm or less, for example.

Further, in general, in a light scattering layer having a conventional structure in which particles protrude from the surface, the flatness of the light scattering layer is low and the surface unevenness is high, so that a thin film of about 10 to 100 nm is formed on the light scattering layer. Then, the material for forming the film tends to gather in the concave portion, and it is difficult for the material for forming the film to be arranged on the convex portion. Therefore, it is difficult to form a film on the convex portion, and a pinhole or the like breaks down on the convex portion, so that a uniform film cannot be formed. In a film having such a broken portion, a solvent or the like of the metal ink composition permeates the light scattering layer 15 from the broken portion of the film, and ablation occurs during firing.

On the other hand, in the transparent conductive member 10A, since the light scattering layer 15 has high flatness, even if the thickness of the ablation prevention layer 18 is as thin as about 10 nm, the material for forming the film is light. A film that is uniformly arranged on the scattering layer 15 and does not break down is likely to be formed. Therefore, in the transparent conductive member 10A, the ablation prevention layer 18 that does not break even if it is thin can be formed.

The ablation prevention layer 18 can be applied without particular limitation as long as it is a material having a solvent barrier property. For example, polyethylene, polypropylene, ethylene-vinyl alcohol copolymer resin, polyvinylidene chloride, fluororesin, polysiloxane, polysilazane, polysiloxazan, silicon dioxide, silicon nitride compound, silicon nitride compound, niobide pentoxide, etc. are applied. be able to. A silicon compound is particularly preferable because of its luminous efficiency. The material of the ablation prevention layer 18 is preferably a material having a refractive index close to that of the light scattering layer material.

<3. Manufacturing method of transparent conductive member>
Next, a method of manufacturing the transparent conductive member 10 having the above-described configuration will be described.
In the production of the transparent conductive member 10, the resin base material 11 is first prepared. As the resin base material 11, a gas barrier film having a gas barrier layer formed in advance may be prepared as the resin base material 11, if necessary. Further, if necessary, a particle-containing layer is formed on the resin base material 11, or a resin base material 11 on which the particle-containing layer is formed in advance is prepared.

[Formation of light scattering layer]
Next, the light scattering layer 15 is formed on the prepared resin base material 11. The light scattering layer 15 is formed by dispersing the binder 17 and the particles 16 in a solvent to prepare a dispersion liquid for forming a light scattering layer, and applying this dispersion liquid onto a resin base material.

The dispersion solvent used for the dispersion liquid is not particularly limited, but it is preferable to select a solvent that does not cause precipitation of the binder 17 and aggregation of the particles 16. From the viewpoint of dispersibility, a method in which a liquid obtained by mixing the binder 17 and the particles 16 is dispersed by a method such as ultrasonic treatment or bead mill treatment and then filtered through a filter or the like is preferable.

Any suitable method can be selected as the coating method of the dispersion liquid for forming the light scattering layer. For example, 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 selected. In addition to the method, use 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 done.
When the light scattering layer 15 is formed in 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.

Further, the light scattering layer 15 is coated with a dispersion liquid for forming a light scattering layer, and then the formed coating film is dried 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 according to the resin base material 11 to be used. The heat drying is preferably performed at a temperature of 200 ° C. or lower. Further, depending on the material of the binder 17 to be used, treatments such as curing by light energy such as ultraviolet rays and heat curing with less damage to the resin base material 11 may be performed.

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 light scattering layer, the filament temperature of the light source is 1600 as a drying method. It is preferable to use an infrared heater in the range of ~ 3000 ° C. Since the hydroxy group has absorption at a specific wavelength emitted from the infrared heater, the solvent can be dried. On the other hand, with respect to polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) as the resin base material 11, heat damage to the resin base material 11 is small because absorption of a specific wavelength emitted from the infrared heater is small.

The polar solvent having a hydroxy group includes water (preferably pure water such as distilled water and deionized water), alcohol solvents such as methanol and ethanol, glycols, glycol ethers, and a mixture of water and alcohol. Examples include solvents. 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. ..

[Formation of anti-ablation layer]
Next, the ablation prevention layer 18 is formed on the light scattering layer 15. The ablation prevention layer 18 may be formed as needed. The method for forming the ablation prevention layer 18 is not particularly limited. For example, when forming a resin film such as polyethylene or polypropylene, a liquid composition containing these resins is prepared, the liquid composition is applied onto the light scattering layer 15, and then dried to prevent the ablation prevention layer 18. Can be formed. Further, after preparing the liquid composition containing the precursor, the liquid composition can be applied onto the light scattering layer 15 and reacted by heating, energy ray irradiation or the like to form the ablation prevention layer 18.

Further, when forming an inorganic film such as silicon dioxide or a silicon nitride compound, the ablation prevention layer 18 can be formed by using a vacuum deposition method, a sputtering method or the like. Examples of applicable vapor deposition methods include resistance heating vapor deposition, electron beam deposition, ion plating, ion beam deposition, and the like. As the vapor deposition apparatus, for example, a BMC-800T vapor deposition machine manufactured by Syncron Co., Ltd. can be used.

[Metal wire formation process: pattern formation]
Next, the thin metal wire 13 is formed on the light scattering layer 15 or the ablation prevention layer 18. The method for forming the thin metal wire 13 is not particularly limited, and a conventionally known method can be used. As the conventionally known method for forming the thin metal wire 13, for example, a method using a metal ink composition and applying a photolithography method, a coating method, a printing method, or the like can be used.

The metal ink composition contains the above-mentioned metal nanoparticles or metal colloid and a solvent, and may contain additives such as a dispersant, a viscosity modifier, and a binder. The solvent contained in the composition containing metal nanoparticles or metal colloid is not particularly limited, but a compound having an OH group is preferable in that the solvent can be efficiently volatilized by irradiation with mid-infrared rays, and water, alcohol, etc. Glycol ether is preferred.

Examples of the solvent used in the composition containing metal nanoparticles and metal colloids include water, methanol, ethanol, propanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, Hexadecanol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalol, geraniol, nerol, heptadienol, tetradecenol, hexadeceneol, phytol, oleyl alcohol, dedecenol, desenol, unde Sirenyl alcohol, nonenol, citronellol, 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 mono Ethyl ether, ethylene glycol 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, tripropylene glycol Examples thereof include monomethyl ether.

When forming a pattern of a composition containing metal nanoparticles or metal colloids by a printing method, a method generally used for forming an electrode pattern can be applied. As a specific example, regarding the gravure printing method, the methods described in JP-A-2009-295980, JP-A-2009-259826, JP-A-2009-96189, JP-A-2009-90662, and the like are used for flexographic printing. Regarding the method, the methods described in JP-A-2004-268319 and JP-A-2003-168560 are used. For the screen printing method, JP-A-2010-34161, JP-A-2010-10245, and JP-A-2009-302345 are used. Examples of the method described in Japanese Patent Application Laid-Open No. 11-180562, Japanese Patent Application Laid-Open No. 2000-127410, and Japanese Patent Application Laid-Open No. 8-238774 are examples of the inkjet printing method.

When forming a pattern of a composition containing metal nanoparticles or metal colloids by the photolitho method, specifically, a metal ink composition is formed on the entire surface of the light scattering layer 15 by printing or coating. After performing the drying treatment and the firing treatment described later, the pattern is processed into a desired pattern by etching using a known photolitho method.

[Metal wire forming process: drying]
Next, the composition containing the applied metal nanoparticles and metal colloid 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 heat drying is preferably performed in a temperature range of 50 to 200 ° C. at a temperature at which the resin base material 11 is not deformed. It is more preferable to heat the resin base material 11 under the condition that the surface temperature 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 firing 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 resin base material 11 and selectively irradiate a specific wavelength effective for the solvent of the metal ink composition. 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.

[Metal wire forming process: firing]
Next, the pattern of the dried metal ink composition is fired. Depending on the type of metal composition contained in the metal ink composition (for example, the silver colloid having the above-mentioned π-bonded organic ligand), sufficient conductivity is exhibited by the drying treatment, so that the firing step is not performed. You may.

(Baking by irradiation with flash light)
It is preferable that the pattern of the metal ink composition is fired by light irradiation (flash firing) using a flash lamp in order to improve the conductivity of the transparent conductive member 10. 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 resin base material 11 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 in 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 resin base material 11.

It is preferable that the flash lamp irradiation of the resin base material 11 is performed from the side where the pattern of the metal ink composition of the resin base material 11 is formed. When the resin base material 11 is transparent, it may be irradiated from the resin base material 11 side or from both sides of the resin base material 11.

The surface temperature of the resin base material 11 during flash firing includes the heat resistant temperature of the resin base material 11, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the metal ink composition, the type and pressure of the atmospheric gas, and the like. It may be determined in consideration of the dispersibility of the metal ink composition, thermal behavior such as oxidative property, and the like, and it is preferably performed at room temperature 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 may be carried out in the atmosphere, but if necessary, it may be carried out in an atmosphere of an inert gas such as nitrogen, argon or helium.

[Process of forming transparent conductive film]
Next, the transparent conductive film 14 is formed on the entire surface of the formed region of the conductive layer 12 by covering the thin metal wire 13. The transparent conductive film 14 can be formed by a sputtering method using the above-mentioned metal oxide sputtering target, an ion plating method, or the like.

For example, the transparent conductive film 14 is subjected to various sputtering methods, ion plating methods, etc. in the same manner as in the case of forming a conventional metal oxide layer, except that the temperature inside the film forming apparatus is set to 200 ° C. or lower. A film can be formed. By setting the temperature in the film forming apparatus to 200 ° C. or lower, the crystal phase is not generated in the metal oxide layer, and the transparent conductive film 14 can be produced.

In particular, it is preferable that the substrate temperature at the time of film formation is 90 ° C. or lower, particularly 70 ° C. or lower. By setting the substrate temperature at the time of film formation to 90 ° C. or lower, preferably 70 ° C. or lower, a transparent conductive film can be produced without generating a crystal phase, and deformation of the resin base material 11 can be prevented. In order to set the substrate temperature at the time of film formation to 70 ° C. or lower, the temperature inside the film forming apparatus is set to, for example, 70 ° C. or lower. Alternatively, a cooling mechanism is attached to the substrate side to reduce the substrate temperature to 70 ° C. or lower.

As the sputtering method for forming the transparent conductive film 14, for example, DC sputtering, RF sputtering, DC magnetron sputtering, RF magnetron sputtering, ECR plasma sputtering, ion beam sputtering and the like can be used.

The transparent conductive film 14 can be formed by a DC magnetron sputtering method, for example, when the distance between target substrates during sputtering is 50 to 100 mm and the sputtering gas pressure is 0.5 to 1.5 Pa.

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 resin base material 11 increases. In addition, the film thickness becomes non-uniform and the film thickness distribution becomes poor. When 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 transparent conductive film 14 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 resin base material 11 becomes large. When the sputtering gas pressure is higher than 1.5 Pa, not only the film forming speed 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 transparent conductive film 14 is low. Therefore, it is not preferable.

<4. Organic electroluminescence element>
Next, an embodiment of an organic electroluminescence device (organic EL device) using the above-mentioned transparent conductive member will be described. The organic EL element of the present embodiment has a configuration in which the conductive layer of the above-mentioned transparent conductive member is used as a first electrode (transparent electrode), and a light emitting unit and a second electrode (counter electrode) are provided on the first electrode. Is. Therefore, in the following description of the organic EL element, detailed description of the same configuration as the above-mentioned transparent conductive member will be omitted.

[Structure of organic EL element]
The configuration of the organic EL element of this embodiment is shown in FIG. The organic EL element 20 shown in FIG. 3 includes a conductive layer 12 (first electrode) of the transparent conductive member 10A and a second electrode 22, and a light emitting unit 21 is provided as an organic functional layer between the electrodes. The transparent conductive member 10A 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.

Only the portion where the light emitting unit 21 is sandwiched between the conductive layer 12 and the second electrode 22 of the transparent conductive member 10A is the light emitting region in the organic EL element 20. The organic EL element 20 is configured as a bottom emission type that extracts the generated light (hereinafter referred to as emission light h) from at least the resin base material 11 side of the transparent conductive member 10A. 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 20, take-out electrodes (not shown) are provided at the ends of the conductive layer 12 and the second electrode 22 of the transparent conductive member 10A. The conductive layer 12 and the second electrode 22 of the transparent conductive member 10A and the external power supply (not shown) are electrically connected via a take-out electrode.

The layer structure of the organic EL element 20 is not limited, and may be a general layer structure. For example, when the conductive layer 12 of the transparent conductive member 10A functions as an anode (that is, an anode) and the second electrode 22 functions as a cathode (that is, a cathode), the light emitting unit 21 starts from the conductive layer 12 side of the transparent conductive member 10A. An example is a configuration in which a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer are laminated in this order, but it is essential to have at least a light emitting layer constructed by using an organic material. Is. 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 21, for example, the electron injection layer may be made of an inorganic material.

In addition to these layers, the light emitting unit 21 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 second electrode 22 which is a cathode may also have a laminated structure if necessary.

Further, the organic EL element 20 may be an element having a so-called tandem structure in which a plurality of light emitting units 21 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 21 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 insulating layer, and has electrons in the adjacent layer on the anode side and holes 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 the above. Examples of the material used for the intermediate connector layer include ITO (indium / tin oxide), IZO (inorganic / zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiO _x , VO _x , CuI, InN, and GaN. , CuAlO ₂ , CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ , Al and other conductive inorganic compound layers, Au / Bi ₂ O _{3 and} other bilayer films, SnO ₂ / Ag / SnO ₂ and 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 such oligothiophene Examples thereof include, but are not limited to, a sex organic substance layer, a metal phthalocyanine, a metal-free phthalocyanine, a metal porphyrin, a conductive organic compound layer such as a metal-free porphyrin, and the like.

Preferred configurations in the light emitting unit 21 include, but are not limited to, for example, configurations in which the anode and the cathode are excluded 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. Japanese Patent No. 6337492, International Publication No. 2005/09087, Japanese Patent Application Laid-Open No. 2006-228712, Japanese Patent Application Laid-Open No. 2006-24791, Japanese Patent Application Laid-Open No. 2006-49393, Japanese Patent Application Laid-Open No. 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. Japanese Patent Application Laid-Open No. 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 20 has a light emitting unit 21 sandwiched between a pair of electrodes of a first electrode and a second electrode 22 made of a conductive layer 12 of a transparent conductive member 10A. One of the conductive layer 12 (first electrode) and the second electrode 22 of the transparent conductive member 10A serves as an anode of the organic EL element 20, and the other serves as a cathode.

Further, in the organic EL element 20 shown in FIG. 3, the conductive layer 12 of the transparent conductive member 10A is made of a transparent conductive material, and the second electrode 22 is made of a highly reflective material. When the organic EL element 20 is a double-sided light emitting type, the second electrode 22 is also made of a transparent conductive material.

[Second electrode]
In the organic EL element 20, when the second electrode 22 is used as an anode, 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, indium tin oxide (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 (100 μm or more). The 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 increase the transmittance to more than 10%. The sheet resistance as an anode is several hundred Ω / sq. The following is preferable. The film thickness depends on the material, but is usually selected within the range of 10 to 1000 nm, preferably within the range of 10 to 200 nm.

When the second electrode 22 is used as a cathode in the organic EL element 20, 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 electrodes. Used as a substance.
The cathode is an electrode film that functions as a cathode that supplies electrons to the light emitting unit 21. The cathode can be produced by forming a thin film of these electrode substances 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 film 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 film 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 12 of the transparent conductive member 10A and an external power source, and the material thereof is not particularly limited, and a known material can be preferably used. A metal film such as a MAM electrode (Mo / Al / Nd alloy / Mo) having a three-layer structure can be used.

[Sealing member]
The organic EL element 20 may be sealed with a sealing member (not shown) for the purpose of preventing deterioration of the light emitting unit 21 made of 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 20, and is fixed to the resin base material 11 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 20 and at least cover the light emitting unit 21. Further, an electrode may be provided on the sealing member so that the electrode terminal portion of the organic EL element 20 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, polysulfone and the like. 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, the oxygen permeability was measured by the method based on JIS K 7126-1987 is ^{1 × 10 -3 ml / (m} 2 · 24h · atm) or less, to JIS K 7129-1992 measured in compliance with the method, the water vapor transmission rate (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably at ^{1 × 10 -3 g / (m} 2 · 24h) or less ..

Further, the adhesive portion for fixing the sealing member to the resin base material 11 side is used as a sealing agent for sealing the organic EL element 20. 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 coating the adhesive portion on the adhesive portion between the sealing member and the transparent conductive member 10A, 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 conductive member 10A, the gas phase or liquid phase of the gap includes an inert gas such as nitrogen or argon, fluorinated hydrocarbon, or silicon. It is preferable to inject an inert liquid such as oil. It is also possible to create a vacuum. Further, a hygroscopic compound can be enclosed inside.

Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide, etc.) and sulfates (for example, 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) Barium, 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 placed on the transparent conductive member 10A in a state where the light emitting unit 21 of the organic EL element 20 is completely covered and the electrode terminal portion of the organic EL element 20 is exposed. Is provided.

Such a sealing film is constructed by using an inorganic material or an organic material. In particular, it is made 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 21 in the organic EL element 20. 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 20, 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 20 and the sealing member are sandwiched between the transparent conductive member 10A. In particular, when the sealing member is a sealing film, mechanical protection against the organic EL element 20 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 thinner polymer film, a metal plate, a thinner metal film, 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.

<5. Manufacturing method of organic electroluminescence device>
Next, an example of a method for manufacturing the organic EL element 20 shown in FIG. 3 will be described.
First, the transparent conductive member 10A is manufactured by the above-mentioned manufacturing method.
Next, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer are formed in this order on the transparent conductive member 10A to form the light emitting unit 21. 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. 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 21, the second electrode 22 is formed on the upper portion by an appropriate film forming method such as a vapor deposition method or a sputtering method. At this time, the second electrode 22 has a shape in which the terminal portion is pulled out from above the light emitting unit 21 to the peripheral edge of the resin base material 11 while maintaining the insulating state with respect to the conductive layer 12 of the transparent conductive member 10A by the light emitting unit 21. Form a pattern. As a result, the organic EL element 20 is obtained. Further, after that, a sealing member is provided which covers at least the light emitting unit 21 in a state where the take-out electrode and the terminal portion of the second electrode 22 in the organic EL element 20 are exposed.

As described above, the desired organic EL element 20 can be obtained on the transparent conductive member 10A. In the production of such an organic EL element 20, it is preferable to consistently produce the light emitting unit 21 to the second electrode 22 by one evacuation, but the resin base material 11 is taken out from the vacuum atmosphere in the middle and is different. A film forming method may be applied. 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.

<Manufacturing of transparent conductive member and organic EL element of sample 100>
[Transparent conductive member: resin base material]
(Preparation of base material)
As a resin base material, a polyethylene terephthalate (PET) film having a thickness of 100 μm (Lumirror (registered trademark) U48 manufactured by Toray Industries, Inc.) was prepared.

(Preparation of primer layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation is applied to the easily adhesive surface of the resin base material with a wire bar so that the layer thickness after coating and drying is 4 μm, and then drying conditions: After drying at 80 ° C. for 3 minutes, the primer layer was prepared by curing under an air atmosphere using a high-pressure mercury lamp under curing conditions of 1.0 J / cm ^2.

[Transparent conductive member: Fabrication of conductive layer (thin metal wire)]
A silver nanoparticle dispersion (Flow Metal SR6000, manufactured by Bando Chemical Co., Ltd.) is applied as a metal ink composition on a resin base material on which a primer layer is prepared in a grid pattern with a width of 50 μm and a pitch of 1 mm using an inkjet printing method. To form a pattern of the metal ink composition. The area for forming the pattern of the metal ink composition was 30 mm × 40 mm. As an inkjet printing method, an inkjet head having an ink droplet ejection amount of 4 pl was used, and a pattern was printed by adjusting the coating speed and the ejection frequency. 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 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 flowed between the glass plates. The pattern of the formed metal ink composition was dried using a heater.

Next, using a xenon flash lamp 2400WS (manufactured by COMET) equipped with a short wavelength cut filter of 250 nm or less, ^{a flash light with a total light irradiation energy of 3.5 J / cm 2} was applied to a metal ink with an irradiation time of 2 msec. Irradiation was performed once from the pattern side of the composition. As a result, the pattern of the metal ink composition after drying was fired to produce fine metal wires.

[Transparent conductive member: Fabrication of conductive layer (transparent conductive film)]
The resin base material (50 mm × 50 mm) prepared up to the fine metal wire was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and the compound (1-6) was placed in a tantalum resistance heating boat. These substrate holders and resistance heating boats were attached to the first vacuum chamber of the vacuum deposition apparatus. Further, silver (Ag) was put into a tungsten resistance heating boat and installed in the second vacuum chamber.

Next, after the first vacuum chamber ^{was depressurized to 4 × 10 -4} Pa, a resistance heating boat containing the compound (1-6) was energized and heated, and the vapor deposition rate was 0.1 to 0.2 nm / sec. An underlayer made of the compound (1-6) was prepared on the substrate within the range of. The layer thickness of the base layer was 50 nm.

Next, the substrate prepared up to the base layer was transferred to the second vacuum chamber under a vacuum state. After depressurizing the second vacuum chamber to 4 × 10 ^-4 Pa, a resistance heating boat containing silver is energized to heat it, and it is placed on the base layer within a vapor deposition rate of 0.1 to 0.2 nm / sec. A conductive layer made of silver having a layer thickness of 8 nm was prepared, and a transparent conductive film having a laminated structure of a base layer and a silver thin film was prepared.
The transparent conductive member of the sample 100 was produced by the above method.

[Organic EL element: Fabrication of light emitting unit]
The vapor deposition crucible in the vacuum vapor deposition apparatus was filled with the constituent materials of each layer of the light emitting unit in an optimum amount for producing an organic EL element. As the crucible for vapor deposition, a crucible made of a resistance heating material such as molybdenum or tungsten was used.

As the constituent materials of each layer of the light emitting unit, the following compounds α-NPD, BD-1, GD-1, RD-1, H-1, H-2 and E-1 were used.

First, the vacuum is ^{reduced to 1 × 10 -4} Pa, the crucible for vapor deposition filled with the compound α-NPD is energized and heated, and the film is vapor-deposited on a transparent electrode at a vapor deposition rate of 0.1 nm / sec to form a layer. A hole injection transport layer having a thickness of 40 nm was prepared.

Similarly, the compounds BD-1 and H-1 are co-deposited at a vapor deposition rate of 0.1 nm / sec so that the concentration of the compound BD-1 becomes 5%, and a fluorescent light emitting layer having a layer thickness of 15 nm and exhibiting a blue color is exhibited. Was produced.
Next, the compounds GD-1, RD-1 and H-2 were deposited at 0.1 nm / sec so that the concentration of the compound GD-1 was 17% and the concentration of the compound RD-1 was 0.8%. Co-deposited at a rate to produce a phosphorescent light emitting layer exhibiting yellow light emission with a layer thickness of 15 nm.

Then, compound E-1 was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to prepare an electron transport layer having a layer thickness of 30 nm.

[Organic EL element: Fabrication of second electrode]
Further, lithium fluoride (LiF) was prepared with a layer thickness of 1.5 nm, and aluminum 1 nm and silver 150 nm were vapor-deposited to prepare a second electrode (cathode). The second electrode was manufactured in a shape in which the terminal portion was pulled out from the peripheral edge of the substrate in a state of being insulated by the organic functional layer from the hole injection transport layer to the electron transport layer.

A vapor deposition mask was used to prepare each layer, and the 4.5 cm × 4.5 cm region located in the center of the 5 cm × 5 cm substrate was set as the light emitting region, and the width was 0.25 cm over the entire circumference of the light emitting region. A non-emission region was provided.

[Organic EL element: Sealing]
(Preparation of adhesive composition)
100 parts by mass of Opanol B50 (BASF, Mw: 340,000) as a polyisobutylene resin, 30 parts by mass of Nisseki polybutene grade HV-1900 (Mw: 1900) as a polybutene resin, hindered amine light stabilizer TINUVIN765 (manufactured by Ciba Japan, having a tertiary hindered amine group) 0.5 parts by mass, IRGANOX1010 (manufactured by Ciba Japan, β-position of hindered phenol group) as a hindered phenolic antioxidant 0.5 parts by mass (having a butyl group) and 50 parts by mass of Eastocac H-100L Resin (manufactured by Eastman Chemical Co., Inc.) as a cyclic olefin polymer are dissolved in toluene, and a stickiness having a solid content concentration of about 25% by mass is dissolved. The agent composition was prepared.

(Preparation of adhesive sheet for sealing)
A pressure-sensitive adhesive layer prepared by using a polyethylene terephthalate film Alpet 12/34 (manufactured by Asia Aluminum Co., Ltd.) on which aluminum (Al) is vapor-deposited as a gas barrier layer and drying a solution of the above-mentioned pressure-sensitive adhesive composition. The aluminum side (gas barrier layer side) was coated so that the layer thickness was 20 μm, and dried at 120 ° C. for 2 minutes to prepare 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 produced pressure-sensitive adhesive layer surface to prepare a sealing pressure-sensitive adhesive sheet.

(Sealing)
It was confirmed that the sealing adhesive sheet prepared by the above method was cooled to room temperature (25 ° C.) after removing the release sheet in a nitrogen atmosphere and drying on a hot plate heated to 120 ° C. for 10 minutes. Then, it was laminated so as to completely cover the cathode, and heated at 90 ° C. for 10 minutes. In this way, the organic EL element of the sample 100 was produced.

<Manufacturing of transparent conductive member and organic EL element of sample 101>
On a resin substrate on which a primer layer was prepared in the same manner as in Sample 100, rod-shaped particles having a refractive index of 2.3, a particle ratio of 2 or less, a particle ratio of 65%, and a particle diameter of 350 nm were formed by the following method, and the refractive index was 1. A light scattering layer having a particle abundance of 40% on the resin substrate side and a PB ratio of 45%, which was composed of a binder of .807, was prepared with a thickness of 350 nm. Then, the transparent conductive film was produced and sealed on the light scattering layer in the same manner as in the sample 100 to produce the transparent conductive member of the sample 101 and the organic EL element.

[Preparation of light scattering layer]
Titanium oxide particles (Titanics JR-808, manufactured by Teika) and binder (PCPM-47-BPA, manufactured by Pixilent Technologies) with a PB ratio of 45%, 2-propanol, propylene glycol monomethyl ether (PGME) and 2- The solvent ratio with methyl-2,4-pentanediol (PD) was 20% by mass / 40% by mass / 40% by mass, and the solid content concentration in the organic solvent was 12% by mass.
To the above solid content (effective mass component), 0.4% by mass of an additive (Disperbyk-2096 manufactured by Big Chemie Japan Co., Ltd.) was added, and a formulation was designed in a ratio of 10 ml to form a dispersion liquid for forming a light scattering layer. Was prepared.

Specifically, the the TiO ₂ particles and a solvent and additives were mixed with 10% by weight ratio with respect to TiO ₂ particles, while cooling at room temperature (25 ° C.), an ultrasonic dispersing machine (manufactured by SMT Co. UH- 50) was dispersed for 10 minutes under the standard conditions of a microchip step (MS-3 3 mmφ manufactured by SMT Co., Ltd.) to prepare a dispersion liquid of _{TiO 2.}
Next, _{while stirring the TiO 2} dispersion at 100 rpm, the resin solution was mixed and added little by little, and after the addition was completed, the stirring speed was increased to 500 rpm and mixed for 10 minutes, and then the hydrophobic PVDF 0.45 μm filter (manufactured by Watman). ) To obtain the desired dispersion liquid for forming a light scattering layer.

After applying the above dispersion liquid on a resin base material by an inkjet coating method, it is simply dried (70 ° C., 2 minutes), and further, it is used for 5 minutes under output conditions where the base material temperature is less than 80 ° C. by wavelength control IR described later. A drying process was performed.

Next, the curing reaction was promoted under the following modification treatment conditions.
(Modification processing equipment)
Equipment: Excimer irradiation device MODEL MECL-M-1-200 manufactured by MD.com Co., Ltd.
Irradiation wavelength: 172 nm
Lamp-filled gas: Xe

(Modification treatment conditions)
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 irradiator: 20.0%
Irradiation energy: 8J / cm ²

<Manufacturing of transparent conductive member of sample 102 and organic EL element>
The transparent conductive member of the sample 102 and the organic EL element are prepared in the same manner as the above-mentioned sample 101 except that the solid content concentration of the dispersion liquid for forming the light scattering layer of the light scattering layer is adjusted to 10% by mass. Was produced.

<Manufacturing of transparent conductive member of sample 103 and organic EL element>
The particles used to prepare the light scattering layer were changed to MP-6035 (manufactured by Soken Kagaku Co., Ltd.), and the refractive index was 1.48, the proportion of particles with an aspect ratio of 2 or less was 100%, and the refractive index was 450 nm. A light scattering layer having a particle abundance rate of 40% on the resin substrate side and a PB ratio of 45% was prepared with a thickness of 400 nm, which was composed of a binder of 1.807, in the same manner as in Sample 101 described above. A transparent conductive member of sample 103 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 104 and organic EL element>
The particles used to prepare the light scattering layer were changed to SG-TO100 (manufactured by Sugarung AT), and the refractive index was 2.3, the proportion of particles with an aspect ratio of 2 or less was 100%, spherical particles with a particle diameter of 100 nm, and the refractive index. A light scattering layer having a particle abundance of 75% on the resin substrate side and a PB ratio of 45% was prepared with a thickness of 300 nm, which was composed of a binder of 1.807, in the same manner as the above-mentioned sample 102. A transparent conductive member of sample 104 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 105 and organic EL element>
The particles used to prepare the light scattering layer were changed to SG-TO100 (manufactured by Sugarung AT), and the refractive index was 2.3, the proportion of particles with an aspect ratio of 2 or less was 100%, spherical particles with a particle diameter of 100 nm, and the refractive index. A light scattering layer having a particle abundance of 75% on the resin substrate side and a PB ratio of 4%, which comprises a binder of 1.807, was prepared in the same manner as in the above-mentioned sample 102 except that a light scattering layer having a thickness of 300 nm was prepared. A transparent conductive member of sample 105 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 106 and organic EL element>
The particles used to prepare the light scattering layer were changed to B-30 (manufactured by Sakai Chemical Industry Co., Ltd.), and the refractive index was 2.0, the proportion of particles with an aspect ratio of 2 or less was 15%, and spherical particles with a particle diameter of 300 nm were refracted. A light scattering layer having a particle abundance rate of 60% on the resin substrate side and a PB ratio of 20%, which is composed of a binder having a refractive index of 1.807, was prepared with a thickness of 500 nm in the same manner as in the sample 102 described above. , A transparent conductive member of sample 106, and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 107 and organic EL element>
In the preparation of the light scattering layer, the sample 107 was prepared in the same manner as the above-mentioned sample 104 except that the light scattering layer having a particle abundance rate of 80% on the resin substrate side and a PB ratio of 30% was prepared with a thickness of 260 nm. A transparent conductive member and an organic EL element were manufactured.

<Manufacturing of transparent conductive member of sample 108 and organic EL element>
The particles used to prepare the light scattering layer were changed to SG-TO200 (manufactured by Sugarung AT), and the refractive index was 2.3, the proportion of particles with an aspect ratio of 2 or less was 100%, spherical particles with a particle diameter of 210 nm, and the refractive index. A light scattering layer having a particle abundance rate of 55% on the resin substrate side and a PB ratio of 30% was prepared with a thickness of 230 nm, which was composed of a binder of 1.807, in the same manner as the above-mentioned sample 102. A transparent conductive member of sample 108 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 109 and organic EL element>
The particles used to prepare the light scattering layer were changed to SG-TO200 (manufactured by Sugarung AT), and the refractive index was 2.3, the proportion of particles with an aspect ratio of 2 or less was 100%, spherical particles with a particle diameter of 210 nm, and the refractive index. A light scattering layer having a particle abundance rate of 60% on the resin substrate side and a PB ratio of 30%, which comprises a binder of 1.807, was prepared in the same manner as in Sample 102 described above, except that a light scattering layer having a thickness of 300 nm was prepared. A transparent conductive member of sample 109 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 110 and organic EL element>
The particles used to prepare the light scattering layer were changed to R-42 (manufactured by Sakai Chemical Industry Co., Ltd.), and the refractive index was 2.3, the proportion of particles with an aspect ratio of 2 or less was 85%, and spherical particles with a particle diameter of 290 nm were refracted. A light scattering layer having a particle abundance rate of 65% on the resin substrate side and a PB ratio of 20%, which is composed of a binder having a refractive index of 1.807, was prepared with a thickness of 500 nm in the same manner as in the sample 102 described above. , A transparent conductive member of sample 110 and an organic EL element were produced.

<Manufacturing of transparent conductive member and organic EL element of sample 111>
In the preparation of the light scattering layer, the solid content ratio of the solution particles to be prepared and the resin is set to 20% by volume (particles) / 80% by volume (resin), the particle abundance on the resin base material side is 65%, and the PB ratio is 20. The transparent conductive member of the sample 111 and the organic EL element are formed by the same method as the above-mentioned sample 110 except that the scattering layer is prepared with a thickness of 500 nm and the transparent conductive film made of ITO is prepared by the following method. Made.

[Preparation of transparent conductive film (ITO)]
The base material prepared up to the fine metal wire is transferred to a commercially available parallel plate sputtering device equipped with an ITO target, the inside of the sputtering device chamber is ^{depressurized to 5 × 10 -3} Pa, and then nitrogen gas and oxygen gas are flowed while flowing. A transparent conductive film of ITO having a film thickness of 150 nm was produced by discharging at a DC output of 500 W and having a film forming rate of 10 nm / sec.

<Manufacturing of transparent conductive member of sample 112 and organic EL element>
In the preparation of the light scattering layer, the solid content ratio of the solution particles to be prepared and the resin is set to 5% by volume (particles) / 95% by volume (resin), the particle abundance ratio on the resin base material side is 70%, and the PB ratio is 5%. The transparent conductive member of sample 112 and the organic EL element are formed by the same method as that of sample 107 described above, except that the light scattering layer is prepared with a thickness of 500 nm and a transparent conductive film made of IZO is prepared by the following method. Was produced.

[Preparation of transparent conductive film (IZO)]
The base material prepared up to the thin metal wire is transferred to a commercially available parallel plate sputtering device equipped with an IZO target, the inside of the sputtering device chamber is ^{depressurized to 5 × 10 -3} Pa, and then nitrogen gas and oxygen gas are flowed while flowing. A transparent conductive film of IZO having a film thickness of 250 nm was produced by discharging at a DC output of 500 W and having a film formation rate of 10 nm / sec.

<Manufacturing of transparent conductive member of sample 113 and organic EL element>
In the preparation of the light scattering layer, the sample 113 was prepared in the same manner as the above-mentioned sample 112 except that the light scattering layer having a particle abundance ratio of 65% on the resin substrate side and a PB ratio of 10% was prepared with a thickness of 500 nm. A transparent conductive member and an organic EL element were manufactured.

<Manufacturing of transparent conductive member of sample 114 and organic EL element>
In the preparation of the light scattering layer, the sample 114 was prepared in the same manner as the above-mentioned sample 112 except that the light scattering layer having a particle abundance rate of 70% on the resin substrate side and a PB ratio of 20% was prepared with a thickness of 600 nm. A transparent conductive member and an organic EL element were manufactured.

<Manufacturing of transparent conductive member of sample 115 and organic EL element>
In the preparation of the light scattering layer, the sample 115 was prepared in the same manner as the above-mentioned sample 114 except that the light scattering layer having a particle abundance rate of 85% on the resin substrate side and a PB ratio of 20% was prepared with a thickness of 800 nm. A transparent conductive member and an organic EL element were manufactured.

<Preparation of sample 116 transparent conductive member and organic EL element>
In the preparation of the light scattering layer, the sample 116 was prepared in the same manner as the above-mentioned sample 114 except that the light scattering layer having a particle abundance rate of 95% on the resin substrate side and a PB ratio of 20% was prepared with a thickness of 1200 nm. A transparent conductive member and an organic EL element were manufactured.

<Manufacturing of transparent conductive member and organic EL element of sample 117>
The particles used to prepare the light scattering layer were changed to BT-HPS500 (manufactured by Toa Synthetic Co., Ltd.), and the refractive index was 2.42, the proportion of particles with an aspect ratio of 2 or less was 90%, and the refractive index was 400 nm. A light scattering layer having a particle abundance rate of 60% on the resin substrate side and a PB ratio of 20% was prepared with a thickness of 700 nm, which was composed of a binder of 1.807, in the same manner as the above-mentioned sample 114. A transparent conductive member of sample 117 and an organic EL element were produced.

<Manufacturing of transparent conductive member of sample 118 and organic EL element>
The transparent conductive member of sample 118 is the same method as that of sample 117 described above, except that the binder used for producing the light scattering layer is changed to 230La (refractive index 1.5, organic-inorganic hybrid resin, manufactured by Rasa Industries, Ltd.). , And an organic EL element was manufactured.

<Manufacturing of transparent conductive member and organic EL element of sample 119>
In the production of the light scattering layer, a light scattering layer having a particle abundance rate of 65% on the resin substrate side and a PB ratio of 20 was produced with a thickness of 500 nm, and an ablation prevention layer was further formed on the light scattering layer by the following method. The transparent conductive member of sample 119 and the organic EL element were produced in the same manner as in sample 114 described above, except that the conductive layer was produced on the anti-ablation layer.

[Preparation of anti-ablation layer]
Saran Resin R204 (vinylidene chloride; PVDC) manufactured by Asahi Kasei Co., Ltd. was dissolved in THF (tetrahydrofuran) / TOR (toluene) as a coating liquid for preparing an ablation prevention layer, and the solid content concentration became 5% by mass. Adjusted to be.

The prepared solution is applied onto the light scattering layer to a thickness such that the dry film thickness is 5 nm by an inkjet coating method, then simply dried (70 ° C., 3 minutes), and further, 50 ° C. 48 using a dryer. The drying treatment was carried out under the condition of time.

<Manufacturing of transparent conductive member of sample 120 and organic EL element>
The transparent conductive member of sample 120 and the organic EL element were prepared in the same manner as the above-mentioned sample 119 except that the ablation prevention layer was prepared by the following method using polysilazane.

[Preparation of anti-ablation layer]
A catalyst-free perhydropolysilazane 20% by mass dibutyl ether solution (Aquamica NN120-20, manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst containing 5% by mass of a solid content are contained as a coating solution for preparing an anti-ablation layer. It was mixed with a 20% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NAX120-20, manufactured by AZ Electronic Materials), and the amine catalyst was further adjusted to 1% by mass of the solid content, and then further diluted with dibutyl ether. A 5% by mass dibutyl ether solution was prepared.

Next, the prepared solution was applied on the light scattering layer to a thickness such that the dry layer thickness was 5 nm. Further, the coating film was subjected to a drying treatment under the conditions of a drying temperature of 80 ° C., a drying time of 300 seconds, and a dew point of 5 ° C. in a dry atmosphere.

After the drying treatment, the substrate temperature was cooled to 25 ° C., and the coating film was modified by vacuum ultraviolet irradiation in a vacuum ultraviolet irradiation device. As the light source of the vacuum ultraviolet irradiation device, an Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays having a wavelength of 172 nm was used. After the reforming treatment, the substrate on which the gas barrier layer was formed was dried under the same drying conditions as described above. After drying, a second modification treatment was performed to form an ablation-preventing layer having a layer thickness of 5 nm after drying. In each step of coating, drying, and reforming, a uniform tension was applied to the substrate by the tension control mechanism.

<Manufacturing of transparent conductive member and organic EL element of sample 121>
The transparent conductive member of sample 121 and the organic EL element were prepared in the same manner as the above-mentioned sample 119 except that the ablation prevention layer was prepared of silicon nitride (SiN) by the following method.

[Preparation of anti-ablation layer]
In the chamber of the magnetron sputtering apparatus (manufactured by Anerva, SPF-730H), the base material prepared up to the light scattering layer was mounted. Next, the inside of the chamber of the magnetron sputtering apparatus was depressurized to an ^{ultimate vacuum degree of 3.0 × 10 -4 Pa by an oil rotary pump and a cryopump.} Si is used as a target, argon gas 7 sccm and nitrogen gas 26 sccm are introduced, high frequency power (input power 1.2 kW) having a frequency of 13.56 MHz is applied, a film formation pressure is 0.4 Pa, and a film thickness is 300 nm. A silicon nitride film was formed. As a result, an ablation prevention layer made of silicon nitride (SiN) was produced with a film thickness of 5 nm.

<Manufacturing of transparent conductive member of sample 122 and organic EL element>
The particles used to prepare the light scattering layer were changed to MP-6035 (manufactured by Soken Kagaku Co., Ltd.), and the binder was changed to Organtics PC-250 (manufactured by Matsumoto Fine Chemical Co., Ltd.), with a refractive index of 1.48 and an aspect ratio. A light scattering layer having a particle abundance rate of 60% on the resin substrate side and a PB ratio of 20 consisting of spherical particles having a particle ratio of 2 or less and a particle diameter of 450 nm and a binder having a refractive index of 1.91 is 500 nm. The transparent conductive member of sample 122 and the organic EL element were produced in the same manner as in sample 121 described above except that they were produced in thickness.

<Manufacturing of transparent conductive member of sample 123 and organic EL element>
The transparent conductive member of sample 123 and the organic EL element were produced in the same manner as in sample 121 described above except that the ablation prevention layer was set to 120 nm.

<Manufacturing of transparent conductive member and organic EL element of sample 124>
The transparent conductive member of sample 124 and the organic EL element were produced in the same manner as in sample 121 described above except that the ablation prevention layer was set to 50 nm.

Table 1 below shows the main configurations of the transparent conductive members of the samples 101 to 124.

<Evaluation method>
The device characteristics of the produced transparent conductive members of Samples 100 to 124 and the organic EL device were evaluated as follows.

[Ablation]
In the production of the transparent conductive member, the ablation of the thin metal wire was evaluated. As an evaluation method of ablation, visual observation was performed using an optical microscope to determine whether or not the thin metal wire was damaged, and B or higher was regarded as acceptable.
S: Ablation does not occur at all.
A: In rare cases, slight ablation occurs at the edge of the thin metal wire. No actual harm.
B: Slight ablation occurs at the edge of the thin metal wire, but there is no actual damage.
C: There is a place where the thin metal wire is broken due to ablation.
D: Most of the thin metal wires are broken due to ablation.

[Luminous efficiency]
(Total luminous flux)
For each sample prepared, the luminous flux at a constant current was measured using an integrating sphere. Specifically, the total luminous flux was measured at a constant current density of 20 A / m ^2. The luminous efficiency of each sample was determined by a relative value with the luminous efficiency of sample 100 as 1.00, and 1.2 times or more was regarded as acceptable.

[Voltage rise]
Each sample was placed in a constant temperature bath at 85 ° C. (dry), and the voltage increase rate before and after storage at a constant current density similar to the above-mentioned luminous efficiency evaluation was evaluated every 24 hours. Elements whose voltage rise exceeded 1.0 V from the start of the evaluation were disabled, and the period (days) until the voltage rise was disabled was evaluated. The evaluation of each sample was determined as a relative value with respect to the sample 100. Then, the relative value of each sample was evaluated according to the following criteria, and A was regarded as acceptable.
A: Relative value is equal to or higher than sample 100 B: Relative value is 0.5 times or more and less than 1.0 times C: Relative value is less than 0.5 times

[Abnormal light emission]
Each sample was placed in a constant temperature bath at 85 ° C. (dry), elements having dark spots of 0.5 mm or more were disabled, and the period (days) until the dark spots were disabled was evaluated. The evaluation of each sample was determined as a relative value with respect to the sample 100. Then, the relative value of each sample was evaluated according to the following criteria, and A was regarded as acceptable.
A: Relative value is equal to or higher than sample 100 B: Relative value is 0.5 times or more and less than 1.0 times C: Relative value is less than 0.5 times

Table 2 shows the evaluation results of the transparent conductive members of Samples 100 to 124 and the organic EL element.

As shown in Table 2, the transparent conductive member of the sample 101 using rod-shaped particles containing only 65% of particles having an aspect ratio of 2 or less (65% of particles having an aspect ratio of 2 or less) in the light scattering layer is a light scattering layer. The evaluation of ablation is worse than that of the sample 100 which does not have the above and the samples 104 to 124 which use spherical particles containing 80% or more of particles having an aspect ratio of 2 or less in the light scattering layer. Further, the organic EL element of the sample 101 has a large voltage increase and a large dark spot generation as compared with the sample 100 and the samples 104 to 124. In the organic EL element of sample 102, the uneven distribution of particles on the substrate side of the light diffusion layer is 55%, but since the number of spherical particles having an aspect ratio of 2 or less is as small as 65%, voltage rise and abnormal light emission occur. It's getting easier.

Since the sample 101 uses rod-shaped particles, the surface flatness of the light scattering layer is poor. Further, since the rod-shaped particles are used, the particles are not unevenly distributed on the base material side of the light diffusion layer, and many particles are also arranged on the conductive layer side of the light diffusion layer. As described above, when the particle abundance on the substrate side of the light diffusion layer is small and the surface flatness of the light scattering layer is low, ablation occurs when firing the thin metal wire and the flatness is low. The occurrence of element defects is likely to occur.

Further, the sample 103 in which the particle size of the particles used in the light scattering layer is larger than the thickness of the light scattering layer has a poorer ablation evaluation than the sample 100 and the samples 104 to 124. Further, the organic EL element of the sample 103 has a larger voltage rise than the sample 100 and the samples 104 to 124 in which the particle size of the particles used for the light scattering layer is smaller than the thickness of the light scattering layer, and the dark spot The outbreak is also large.

In the sample 103, since the particle size of the particles is larger than the thickness of the light scattering layer, the particles protrude on the surface of the light scattering layer, and the surface flatness of the light scattering layer is poor. Further, since the particle size of the particles is larger than the thickness of the light scattering layer, the volume ratio of the particles on the conductive layer side of the light diffusion layer is high, and the particle abundance ratio on the resin base material side of the light diffusion layer is as small as 40%. Become. As described above, in the light scattering layer, when the particle abundance on the resin base material side is low and the surface flatness is low, ablation occurs when firing the thin metal wire, and the device is caused by the low flatness. Defects are more likely to occur.

Therefore, in the light scattering layer, by using spherical particles having a particle diameter smaller than the thickness of the light scattering layer and containing 80% or more of particles having an aspect ratio of 2 or less, the particles can be unevenly distributed on the substrate side. The flatness of the surface of the light scattering layer can be improved, and the occurrence of ablation can be suppressed. Further, by increasing the flatness of the surface of the light scattering layer, the occurrence of element defects due to the low flatness is less likely to occur.

Further, the sample 109 using particles having a light scattering layer thickness of 300 nm and a particle size of 210 nm emits more light than the samples 104 and 107 using particles having a particle size of 100 nm and having a light scattering layer thickness of 300 nm. Efficiency is improving. Therefore, the luminous efficiency of the organic EL element is improved by using particles having a particle diameter of 200 nm or more. Further, the thickness of the light scattering layer may be 250 nm or more because the flatness of the surface of the light scattering layer cannot be ensured unless the thickness of the light scattering layer is made larger than that of the particles having a particle size of 200 nm or more. preferable.

In the evaluation of samples 112 to 116 designed so that the thickness, uneven distribution, and PB ratio of the light scattering layer are different, the luminous efficiency of the organic EL element tends to be improved by setting the PB ratio to 5 or more. Was done. Further, by increasing the thickness of the light scattering layer and increasing the degree of uneven distribution, the luminous efficiency of the organic EL element tends to be improved easily. Therefore, in the light scattering layer, it is preferable that the PB ratio is 5 or more and the thickness is increased to increase the uneven distribution of particles.

In the samples 119 to 124 having the ablation prevention layer, as in the samples 104 to 118 without the ablation prevention layer, no ablation occurs, and the voltage rise and the evaluation of the dark spot are also good. Furthermore, the luminous efficiency is also good. Therefore, even if a thin film of about 5 to 100 nm such as an ablation prevention layer is provided, a highly reliable transparent conductive member or organic EL element can be formed without deteriorating reliability and light extraction. ..

Further, the sample 122, in which the refractive index of the particles is lower than the refractive index of the binder, has high luminous efficiency as in the samples 119 to 121. Therefore, the light scattering layer may have a high refractive index of either the particle or the binder as long as there is a difference in the refractive index between the particle and the binder, and the light scattering layer is not limited to the combination of the high refractive index particle and the low refractive index binder. It is also possible to combine low refractive index particles and high refractive index binders.

The sample 117 having a refractive index difference of 0.613 has improved luminous efficiency as compared with the sample 110 having a refractive index difference of 0.493 at the same PB ratio of 20. Therefore, the luminous efficiency of the organic EL element is likely to be improved by increasing the difference in refractive index between the particles and the binder. However, the sample 118 having a large refractive index difference of 0.92 has a lower luminous efficiency than the sample 117 having a refractive index difference of 0.613. Therefore, it is preferable that the upper limit of the difference in refractive index between the particles and the binder is about 1. Further, it is preferable that the refractive index of the binder is 1.5 or more.

Further, from the results of Samples 104 to 124, the type of conductive material such as metal or metal oxide is not particularly limited as the transparent conductive film, and various highly translucent conductive materials can be used. Further, the thickness of the transparent conductive member is not particularly limited as long as it does not reduce the transparency of the transparent conductive film and does not reduce the luminous efficiency of the organic EL element.

The present invention is not limited to the configuration described in the above-described embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

10, 10A ... Transparent conductive member, 11 ... Resin base material, 12 ... Conductive layer, 13 ... Metal wire, 14 ... Transparent conductive film, 15 ... Light scattering layer, 16. .. Particles, 17 ... Binder, 18 ... Ablation prevention layer, 20 ... Organic EL element, 21 ... Light emitting unit, 22 ... Second electrode

Claims (7)

With resin base material
A light scattering layer containing particles and a binder formed on the resin base material,
The thin metal wire formed on the light scattering layer and
With a transparent conductive film formed on the thin metal wire,
The light scattering layer contains 80% or more of spherical particles having an aspect ratio of 2 or less as the particles.
The thickness of the light scattering layer is larger than the average particle size of the particles , and is 250 nm or more and 1000 nm or less.
In the light scattering layer, the particle abundance of the particles in the region on the resin substrate side from the center in the thickness direction is larger than the particle abundance of the particles in the region on the transparent conductive film side from the center in the thickness direction. Large transparent conductive member. The transparent conductive member according to claim 1, wherein the volume ratio of the particles in the light scattering layer is 5 vol% or more and 40 vol% or less. The transparent conductive member according to claim 1 or 2, wherein the difference in refractive index between the particles and the binder is 0.2 or more and 1.0 or less. The transparent conductive member according to any one of claims 1 to 3 , wherein the average particle size of the particles having an aspect ratio of 2 or less is 200 nm or more and 500 nm or less. The transparent conductive member according to any one of claims 1 to 4 , wherein an ablation prevention layer is provided on the light scattering layer, and the thin metal wire is formed directly above the ablation prevention layer. The transparent conductive member according to claim 5 , wherein the thickness of the ablation prevention layer is 10 nm or more and 100 nm or less. An organic electroluminescence device using the transparent conductive member according to any one of claims 1 to 6.

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