JPWO2019138863A1 - Electrode substrate material for organic devices - Google Patents

Abstract

The electrode substrate material for an organic device includes a conductor layer 101 made of a patterned metal foil, and a flattening layer 102 provided around the conductor layer 101. In the first surface 111, the surface of the conductor layer 101 is exposed from the flattening layer 102, and the surface of the conductor layer 101 and the surface of the flattening layer 102 form a continuous flat surface.

Description

The present disclosure relates to electrode substrate materials for organic devices.

In recent years, organic electroluminescence (EL) elements have been attracting attention as a light source for next-generation lighting equipment. The organic EL element is provided with an organic light emitting layer between the anode and the cathode, holes and electrons are recombined in the organic light emitting layer, and light is emitted by the energy generated at this time. In addition, organic solar cells such as perovskite type and dye-sensitized type are attracting attention as next-generation solar cell devices. An organic solar cell has a photoelectric conversion layer between the anode and the cathode, and generates electricity by extracting electrons and holes excited by incident sunlight from the anode and the cathode.

In these devices, there is a demand for an electrode substrate material capable of forming an organic functional layer such as an organic light emitting layer and a photoelectric conversion layer, and capable of taking out and taking in light.

The electrode substrate material is required to have smoothness that allows the organic functional layer to be formed so as not to cause pinholes, and particularly to have no steps or protrusions. In recent years, organic EL elements and organic solar cells are required to have a large area. In order to make a large-area organic EL element emit light uniformly, it is important to be able to supply electric power to the entire surface of the device. In an organic solar cell having a large area, it is important to efficiently transport the excited electrons and holes in the device. Therefore, the electrode substrate material is required to have a low surface resistance. Furthermore, since organic EL elements and organic solar cells are required to be produced by a roll-to-roll process in order to increase productivity and to be molded into a curved surface and used, high flexibility is also required for the electrode substrate material. Be done.

Development of electrode substrate materials for organic devices that meet these requirements is underway. For example, an electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a glass substrate and an electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a gas barrier film are being studied (for example). , Patent Document 1).

Further, an electrode substrate material for an organic device formed by laminating a mesh-shaped metal vapor deposition film on a gas barrier film or the like has also been studied (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2008-031496 Japanese Unexamined Patent Publication No. 2001-0110574

However, the electrode substrate material for an organic device in which indium tin oxide (ITO) is laminated on a glass substrate is not flexible and cannot be bent and cannot be manufactured by roll-to-roll. Furthermore, it takes time for pretreatment to ensure wettability in order to adapt to the coating process.

The electrode substrate material for organic devices in which indium tin oxide (ITO) is laminated on a gas barrier film or the like has considerably higher surface resistance than metals such as silver, aluminum or copper. Although it can be further bent, if the radius of curvature of the bend is reduced, the ITO layer is cracked and the surface resistance is increased.

On the other hand, when the electrode substrate material for an organic device is formed on a gas barrier film or the like with a metal vapor deposition film, the mesh-shaped wiring portion becomes a step. Further, although it can be bent, if the radius of curvature of the bending is small, the metal vapor deposition film is cracked and the surface resistance is increased, so that sufficient flexibility cannot be obtained.

An object of the present disclosure is to make it possible to realize an electrode substrate material for an organic device having high smoothness, low surface resistance, and high flexibility.

One aspect of the electrode substrate material for an organic device of the present disclosure includes a conductor layer made of a patterned metal foil and a flattening layer provided around the conductor layer, and in the first surface, the conductor layer The surface is exposed from the flattening layer, and the surface of the conductor layer and the surface of the flattening layer form a continuous flat surface.

In one aspect of the electrode substrate material for an organic device, the conductor layer may form a pattern having a line width of 20 μm or more and 200 μm or less, and the density of the conductor layer per unit area on the first surface may be 15% or less. it can.

In one aspect of the electrode substrate material for an organic device, the flattening layer includes a gas barrier layer and a transparent resin layer, and the surface of the gas barrier layer and the exposed surface of the conductive layer can form a continuous smooth surface.

In one aspect of the electrode substrate material for an organic device, the gas barrier layer comprises at least one of a layer containing aluminum and oxygen as main components and a layer containing silicon and at least one of nitrogen, oxygen and carbon as main components, and the thickness thereof. The diameter can be 20 nm or more.

In one aspect of the electrode substrate material for an organic device, the flattening layer can have a light transmittance of 85% or more at a wavelength of 400 nm to 800 nm.

In one aspect of the electrode substrate material for organic devices, the transparent resin layer is polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC). , Fluororesin, indium tin oxide (ITO), and polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS), which may be one or more.

In one aspect of the electrode substrate material for an organic device, the conductor layer can be an aluminum foil having a thickness of 6 μm or more and 30 μm or less.

In one aspect of the electrode substrate material for organic devices, the conductor layer may include a substrate pattern and a peripheral pattern that is provided outside the substrate pattern and can be connected to an external device.

In one aspect of the surface electrode material for an organic electroluminescence device, the surface of the conductor layer may be exposed from the flattening layer on the second surface opposite to the first surface, and on the second surface, the conductor. The surface of the layer may be covered with a flattening layer.

According to the electrode substrate material for an organic device of the present disclosure, high smoothness, low surface resistance and high flexibility can be realized.

It is sectional drawing which shows the organic EL element which used the surface electrode material for organic EL element of one Embodiment. It is a perspective view which shows the surface electrode material for an organic EL element which concerns on one Embodiment. FIG. 3 is a cross-sectional view taken along the line III-III of FIG. It is a top view which shows the modification of the pattern of a conductor layer. It is sectional drawing which shows the modification of the surface electrode material for an organic EL element. It is sectional drawing which shows the modification of the surface electrode material for an organic EL element. It is sectional drawing which shows the modification of the surface electrode material for an organic EL element. It is sectional drawing which shows the modification of the surface electrode material for an organic EL element. It is a perspective view which shows one step of the manufacturing method of the surface electrode material for an organic EL element. It is a perspective view which shows one step of the manufacturing method of the surface electrode material for an organic EL element. It is a perspective view which shows one step of the manufacturing method of the surface electrode material for an organic EL element. It is a perspective view which shows one step of the manufacturing method of the surface electrode material for an organic EL element. It is sectional drawing which shows one step of the manufacturing method of the surface electrode material for an organic EL element. It is sectional drawing which shows one step of the manufacturing method of the surface electrode material for an organic EL element.

The electrode substrate material for an organic device of the present embodiment has a conductor layer 101 and a flattening layer 104, and can be used as an anode (front electrode) 202 of the organic EL element 200 as shown in FIG. In the organic EL element 200, the light emitting layer 201 is provided between the anode 202 and the cathode 203. The light generated in the light emitting layer 201 is output from the anode 202 side.

In the present embodiment, the light emitting layer 201 includes a cathode 203 and an anode 202 including a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a charge confinement layer, and the like in addition to the organic light emitting layer. It means the entire layer formed by vapor deposition or coating between them.

As shown in FIGS. 2 and 3, the electrode substrate material 100 for an organic device of the present embodiment includes a conductor layer 101 made of a patterned metal foil and a flattening layer 104 provided around the conductor layer 101. It has. In the first surface 111, the surface of the conductor layer 101 is exposed from the flattening layer 104, and the surface of the conductor layer 101 and the surface of the flattening layer 104 form a continuous flat surface. Therefore, an organic functional layer or the like can be easily formed on the first surface.

The electrode substrate material for an organic device of the present embodiment is composed of a conductor layer 101 whose surface is made of a metal foil and a flattening layer 102, and since the ITO layer does not exist, the coatability can be easily improved. Therefore, when the organic device is manufactured by the coating method, there is an advantage that the time for pretreatment such as UV ozone cleaning can be shortened.

<Conductor layer>
The conductor layer 101 of the present embodiment is made of a metal foil patterned in a predetermined shape. Unlike the conductor layer made of a metal vapor-deposited film or the like, the conductor layer 101 made of a metal foil is unlikely to break even when bent, so that sufficient flexibility can be realized. When the electrode substrate material 100 for an organic device is used as the electrode 202 of the organic device, the conductor layer 101 comes into contact with the light emitting layer 201 of the organic EL element and applies a voltage to the light emitting layer 201.

The metal foil used as the conductor layer 101 is not particularly limited, and may be, for example, an aluminum foil, a copper foil, a gold foil, a silver foil, or the like. Of these, an aluminum foil that is lightweight, less likely to cause deep oxidation, and has high light reflectivity is preferable.

Further, the metal foil used as the conductor layer 101 may have a metal thin film made of at least one kind such as nickel, copper, silver, platinum, and gold formed on the surface by plating or vapor deposition.

The pattern of the conductor layer 101 can be designed according to the characteristics required for the electrode substrate material 100 for an organic device. For example, known surface electrode patterns used as electrodes for organic devices, such as grids, meshes, spirals, stripes, meandering shapes, and other indefinite shapes, can be employed.

As shown in FIG. 4, the pattern of the conductor layer 101 can include not only the substrate pattern 121 which is one electrode of the organic device but also the peripheral pattern 122 provided outside the substrate pattern 121. The peripheral pattern 122 is a second peripheral pattern that connects the first peripheral pattern 122A that connects the substrate pattern and the terminal 124 and the electrode 123 and the terminal 124 that are provided on the surface opposite to the substrate pattern 121 of the organic device. 122B and can be included. The terminal 124 can be connected to an external device or the like. Further, the peripheral pattern 122 can be directly connected to an external device or the like without going through the terminal 124. The external device can be, for example, a power supply unit that supplies power to the organic device.

The thickness of the conductor layer 101 is not particularly limited, but is preferably 6 μm or more from the viewpoint of ensuring flexibility and reducing surface resistance. Further, from the viewpoint of improving the light transmittance, it is preferably 30 μm or less.

The line width of the conductor layer 101 is not particularly limited, but is preferably 20 μm or more from the viewpoint of reducing surface resistance, and is preferably 200 μm or less from the viewpoint of reducing light emission unevenness. From the viewpoint of ensuring light transmission, the density of the conductor layer per unit area on the first surface 111 is preferably 15% or less.

<Flat layer>
The flattening layer 102 is provided around the conductor layer 101 so as to fill the opening of the patterned conductor layer 101. At least on the first surface 111, the flattening layer 102 does not cover the conductor layer 101, and the surface of the conductor layer 101 is exposed.

At least on the first surface 111, the surface of the conductor layer 101 and the surface of the flattening layer 102 form a continuous flat surface. Specifically, the surface of the conductor layer 101 and the surface of the flattening layer 102 are continuous surfaces having no step at the boundary portion thereof, and the first surface 111 as a whole is a flat surface. Since the first surface 111 is such a continuous flat surface, a uniform light emitting layer 201 can be formed on the surface of the electrode substrate material for an organic device of the present embodiment. The first surface 111 may be in close contact with the entire surface of the light emitting layer 201, but the level difference at the boundary between the surface of the conductor layer 101 and the surface of the flattening layer 102 is preferably 300 nm or less.

The flattening layer 102 may be visually transparent, but it is preferable that the transmittance at a wavelength of 400 nm to 800 nm is 85% or more. Luminous efficiency can also be improved by setting the transmittance of the flattening layer within this range.

If the flattening layer 102 can be made transparent, its composition is not limited. For example, transparent resins such as polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC) and fluororesin can be used. These resins can be used alone or in combination of two or more. Further, a transparent conductive material such as indium tin oxide (ITO) or polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS) can also be used.

The flattening layer 102 may be one layer or a plurality of layers. By forming the flattening layer 102 into a plurality of layers having different refractive indexes, it is possible to control the diffusion of light, reduce total reflection, and improve the light extraction efficiency.

As shown in FIG. 3, when the conductor layer 101 is not covered by the flattening layer 102 also on the second surface 112 opposite to the first surface 111, there is an advantage that the degree of freedom of the feeding point is increased. can get. However, as shown in FIG. 5, on the second surface 112, the flattening layer 102 may cover the conductor layer 101. Further, the second surface 112 is preferably a flat surface from the viewpoint of light extraction, but may have irregularities. For example, as shown in FIG. 6, it is possible to have a configuration in which irregularities corresponding to the pattern of the conductor layer 101 exist on the second surface 112.

The thickness of the flattening layer 102 is the same as the thickness of the conductor layer 101 when the conductor layer 101 is exposed even on the second surface 112. When the conductor layer 101 is to be covered by the second surface, it may be thicker than the conductor layer 101, but it is preferably 60 μm or less from the viewpoint of flexibility and light transmission.

As shown in FIG. 7, the transparent support 105 can be attached to the second surface 112 side. By laminating the transparent support 105, the strength of the surface electrode material 100 for the organic EL element can be increased. The transparent support 105 is not particularly limited, and includes, for example, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), glass, and the like. can do. The transparent support can also be a layer having an antireflection function.

Further, as shown in FIG. 8, a black protective layer 106 may be provided on the second surface 112 side so as to hide the conductor layer 101. By providing the black protective layer 106 on the back surface of the conductor layer 101, the pattern of the conductor layer 101 becomes difficult to see when the organic device is viewed from the front surface side, and the design is improved. Both the transparent support 105 and the protective layer 106 can also be provided.

The protective layer 106 can be formed, for example, by using a black dry film resist used in the etching step described later, and using the dry film resist remaining after exposure and development without peeling after etching.

When the electrode substrate material 100 for an organic device has the above configuration, the surface resistance can be lowered and the flexibility can be increased as compared with the conventional electrode substrate material for an organic device. In addition, it is possible to improve the luminous efficiency when it is made into a device.

The flattening layer 102 may be configured to include the gas barrier layer 103 and the transparent resin layer 104. The organic light emitting layer and the photoelectric conversion layer of an organic device are vulnerable to water vapor, and even a small amount of water vapor deteriorates. Therefore, the organic light emitting layer and the photoelectric conversion layer are sealed with glass, metal, a gas barrier film, or the like. However, the blocking of water vapor on the electrode substrate side may not be sufficient. Since the electrode substrate material has the water vapor barrier property 103, it is possible to prevent water vapor from entering from the electrode substrate side and suppress deterioration of the organic functional layer.

The gas barrier layer 103 may be formed of any material as long as it has high transparency and water vapor barrier properties. For example, a layer containing aluminum and oxygen as main components can be formed by an atomic deposition method. In addition, a layer containing silicon, nitrogen, oxygen and carbon as main components can be formed by a chemical vapor deposition (CVD) method. The gas barrier layer 103 is not limited to one layer, and may be a laminated body of a plurality of layers. The thickness of the gas barrier layer 103 is preferably 20 nm or more from the viewpoint of blocking water vapor.

When the gas barrier layer 103 is provided, the surface of the conductor layer 101 and the surface of the gas barrier layer 103 can form a continuous flat surface. The level difference at the boundary between the surface of the conductor layer 101 and the surface of the gas barrier layer 103 is preferably 300 nm or less. The thickness of the transparent resin layer 104 can be made thinner than the thickness of the conductor layer 101.

<Manufacturing method>
The electrode substrate material 100 for an organic device of the present embodiment can be formed, for example, as follows.

First, as shown in FIG. 9A, a metal foil 302 to be a conductor layer is laminated on a base material 301 having a smooth surface and poor adhesion to resin and metal. The base material having poor adhesion refers to a base material having a performance that can be easily separated even if a resin or a metal comes into contact with the base material. The base material itself may be formed of a material having poor adhesion, or a coating layer having poor adhesion may be provided on the surface. For example, one or more of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic and polyvinyl chloride (PVC) are used as the base material. be able to.

As the metal foil 302, a material and thickness capable of forming the conductor layer 101 described above is used. From the viewpoint of improving the adhesion between the conductor layer 101 formed by the metal foil 302 and the light emitting layer 201, it is preferable that the surface of the metal foil 302 to be bonded to the base material 301 is smooth, and specifically, the arithmetic mean roughness. (Ra) is preferably 50 nm or less. When laminating the metal foil 302 on the base material 301, a poorly adherent or slightly adherent adhesive or the like can be applied to at least one surface of the base material 301 and the metal foil 302. In this way, laminating becomes easy.

Next, as shown in FIG. 9B, the metal foil 302 laminated on the surface of the base material 301 is patterned to form the conductor layer 101. The patterning of the metal foil 302 can be performed by a known method such as wet etching or dry etching. As the pattern formed by etching, a known electrode pattern adopted as an electrode of an organic device can be adopted as described above. Further, a pattern having the base pattern 121 and the peripheral pattern 122 as shown in FIG. 4 can be used.

Next, as shown in FIG. 9C, a transparent material is applied to form the flattening layer 102. As the transparent material, the material described above can be used, and in the case of a material having fluidity at room temperature, coating can be performed using, for example, a coater. Materials that are fluid at room temperature include, for example, resins that are fluid when dissolved in a solvent, resins that are fluid under specific temperature conditions, and resins that are fluid at room temperature and curable by heat or light. And so on.

Next, as shown in FIG. 9D, the base material 301 is peeled off. By making the base material resistant to adhesion, it can be easily peeled off. In the first surface formed by peeling the base material 301, the conductor layer 101 is not covered by the flattening layer 102 and is exposed. Further, the first surface is a surface to which the surface state of the base material 301 is transferred. By using the base material 301 having a smooth surface, a smooth first surface can be obtained.

After forming the flattening layer 102 and before peeling off the base material 301, a step of laminating the transparent support 105 may be provided. By providing the transparent support 105, the base material 301 can be easily peeled off even when the flattening layer 102 is thin. After the base material 301 is peeled off, the transparent support 105 can be attached.

The flattening layer 102 may be included in the gas barrier layer 103 and the transparent resin layer 104. In this case, as shown in FIG. 10A, the gas barrier layer 103 covers both the portion where the metal foil 302 is removed and the portion where the metal foil 302 remains on the surface of the base material 301 after the conductor layer 101 is formed. To form. The gas barrier layer 103 can be formed of a material having a high water vapor barrier property. For example, an atomic deposition method or the like may be used to form a layer containing aluminum and oxygen as main components (for example, a layer composed of Al ₂ O ₃ or the like), or a chemical vapor deposition (CVD) method may be used to form a layer with silicon. A layer containing at least one of nitrogen, oxygen and carbon as a main component (for example, a layer composed of SiOx, SiN, SiON, SiONC or the like) may be formed. It is also possible to form a laminate in which these layers are combined. As shown in FIG. 10B, after the gas barrier layer 103 is formed, a transparent material is applied to the surface of the gas barrier layer 103 to form the transparent resin layer 104. Although FIG. 10B shows an example in which the transparent resin layer 104 completely fills the recess, the recess may not be completely filled. Further, the transparent resin layer 104 can completely cover the gas barrier layer 103. When the base material 301 is peeled off, the first surface, which is a continuous flat surface between the surface of the conductor layer 101 and the surface of the gas barrier layer 103, is exposed.

The method for producing the electrode substrate material for an organic device is not limited to such a method, and can be formed by another method as long as the first surface can be made flat.

The electrode substrate material for an organic device of the present disclosure will be described in more detail with reference to Examples. The following examples are exemplary and are not intended to limit the invention.

<Evaluation of smoothness>
To evaluate the smoothness of the electrode substrate material for organic devices, observe the uneven shape of the surface with a field of view of 2.2 mm x 2.2 mm using the ultra-high resolution non-contact three-dimensional surface shape measurement system BW-D500 manufactured by Nikon Corporation. , The maximum in-plane height Sz was measured. It is a value calculated by expanding the maximum height Rz defined in JIS-B0601-2001 to three dimensions so that it can be applied to the entire observed surface. Those having a smoothness of Sz of 200 nm or less were regarded as good (◯), and those having a smoothness of more than 200 nm were regarded as poor (x).

<Evaluation of water vapor barrier property>
The evaluation of the water vapor barrier property of the electrode substrate material for organic devices is the water vapor permeability defined in JIS K 7129-7: 2016. The sample was placed on the vapor-deposited metallic calcium, and after 100 hours had passed in an environment of 40 ° C. and 90%, it was calculated from the area of corroded calcium.

<Evaluation of surface resistance>
The surface resistance of the electrode substrate material for organic devices is measured by measuring the resistance value between two diagonal points of a 50 mm × 50 mm sample using an ohmmeter (RD701 DIGITAL MULTIMETER, manufactured by Sanwa Electric Instrument Co., Ltd.). I asked for it. Those having a surface resistance of 10 Ω / cm or less were regarded as good (◯), and those having a surface resistance of more than 10 Ω / cm ² were regarded as defective (x).

<Evaluation of flexibility>
The surface resistance of the target sample before and after the bending test was measured, and the rate of decrease in surface resistance was determined. The bending test was performed 50 times with a 10 mmφ mandrel using a coating film bending tester. Those having a reduction rate of surface resistance of 5% or less were regarded as having good flexibility (◯), and those having a reduction rate of more than 5% were regarded as defective (x).

(Example 1)
A hard-to-adhere adhesive is applied to one surface (main surface) of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) measuring 3 cm x 3 cm and having a thickness of 15 μm (arithmetic mean roughness Ra: 7 nm), and at 100 ° C. After drying, the base material was attached to the coated surface on the adhesive side and aged at 50 ° C. for 4 days. The base material was a 38 μm-thick PET film (manufactured by Teijin Film Solutions Co., Ltd.).

Next, an alkali-developed dry film resist having a thickness of 15 μm was attached to the back surface of the aluminum foil, exposed and developed by ultraviolet rays (UV) using a mesh-shaped photomask, and the portion where the dry film resist did not remain was chloride. Etching was performed using an aqueous iron (II) solution to form a conductor layer. The line width of the conductor layer was 75 μm, the pitch was 1500 μm, and the wiring density was 10%.

Next, a SiN film was formed at 150 nm by the plasma CVD method on both the portion where the aluminum foil was removed by etching and the remaining portion, and then an Al ₂ O ₃ film was formed at 20 nm by the atomic deposition method. A gas barrier layer was formed.

Next, an epoxy resin having an average transmittance of 90% at a wavelength of 400 to 800 nm is applied to the surface of the formed gas barrier layer so that the film thickness from the surface on which the gas barrier layer is formed on the adhesive is 20 μm. A flattening layer was formed by coating so that the unevenness of the conductor layer was embedded. A commercially available antireflection film having a thickness of 30 μm was attached to the surface of the flattening layer as a transparent support and dried at 100 ° C. After that, the base material was peeled off to obtain an electrode substrate material for an organic device.

The smoothness of the obtained electrode substrate material for organic devices is Rz 127 nm, the water vapor barrier property is ^10-5 g / m ² / day or less, the surface resistance is 0.02 Ω / cm 2, and after the bending test. The surface resistance did not change.

An organic EL light emitting device having the target sample as an anode was formed. The element was formed as follows. First, polyethylene dixithiophene-polystyrene sulfonate (PEDOT / PSS, manufactured by sigma aldrich) was spin-coated on the target sample using a spin coater (Mikasa Co., Ltd., SpinCoater MS-A150) at 3000 rpm, and dried in the air. It was. Subsequently, Poly [(9,9-dioctylfluorenyl-2,7-diyl) -co- (4,4'-(N- (4-sec-butylphenyl) diphenylamine)]] (TFB, manufactured by sigma aldrich) was added to toluene. It was spin-coated at 3000 rpm and dried in a nitrogen atmosphere. After that, poly (9,9-dioctylfluorene-alt-benzothiadiazole) F8BT, manufactured by sigma aldrich) was dissolved in toluene. The one was spin coated at 2000 rpm. Next, lithium fluoride was vacuum-deposited using a vacuum vapor deposition apparatus (JEE-4X, manufactured by JEOL Ltd.), and aluminum was vacuum-deposited as an anode.

A voltage of 7V is applied to the obtained element to emit light, and the brightness with respect to the current and voltage is measured using a luminance meter (Konica Minolta, color luminance meter CS-200), and the brightness per 1A is obtained as the luminous efficiency. As a result, it was 0.9 cd / A.

Using the UV / O ₃ cleaning and reforming device SKB401Y-02 manufactured by Sun Energy Co., Ltd., for the electrode substrate material for organic devices at a wavelength of 254 nm and an illuminance of 10.0 mW / cm ² for 1 minute, 5 minutes, and 3/10 levels. UV ozone cleaning was performed, and each was evaluated by the wetting tension test method defined in JIS-K-6768-1999. As a result, it was 63 mN / m in 1 minute, 73 mN / m in 5 minutes, and 73 mN / m in 10 minutes. there were.

(Example 2)
The same as in Example 1 was carried out except that the aluminum foil was a copper foil (purity 99.96%) having a thickness of 15 μm and the epoxy resin was an acrylic resin.

The smoothness of the obtained electrode substrate material for organic devices is Rz 72 nm, the water vapor barrier property is 10 ^-5 g / m ² / day or less, the surface resistance is 0.01 Ω / cm ² , and after the bending test. The surface resistance of was not changed.

Further, as in Example 1, an organic EL light emitting device having the target sample as an anode was formed, and the luminous efficiency was measured and found to be 1.4 cd / A. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 67 mN / m at 1 minute, 73 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

(Example 3)
The same as in Example 1 except that the line width of the conductive layer was 100 μm, the pitch was 2000 μm, and the wiring density was 9%.

The smoothness of the obtained electrode substrate material for organic devices is Rz 158 nm, the water vapor barrier property is 10 ^-5 g / m ² / day or less, the surface resistance is 0.01 Ω / cm ² , and after the bending test. The surface resistance of was not changed.
Further, as in Example 1, an organic EL light emitting device having the target sample as an anode was formed, and the luminous efficiency was measured and found to be 1.0 cd / A. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 63 mN / m at 1 minute, 73 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

(Example 4)
An electrode substrate material for an organic device was obtained in the same manner as in Example 1 except that the gas barrier layer was not formed, that is, the portion where the aluminum foil was removed by etching and the surface with the conductor layer were directly filled with the epoxy resin.

The smoothness of the obtained electrode substrate material for organic devices was Rz 127 nm, the surface resistance was 0.02 Ω / cm ² , and the surface resistance after the bending test did not change. The water vapor barrier property was 5.68 g / m ² / day.

An organic EL light emitting device having the target sample as an anode was formed in the same manner as in Example 1, and the luminous efficiency was measured and found to be 0.9 cd / A. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 68 mN / m at 1 minute, 68 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

(Example 5)
The part where the gas barrier layer was not formed, that is, the part where the aluminum foil was removed by etching and the surface with the conductor layer were directly filled with epoxy resin, and the transparent support was 75 μm thick and the water vapor transmission rate was 4 × 10 ^-4 g /. An electrode substrate material for an organic device was obtained in the same manner as in Example 1 except that a commercially available gas barrier film of m ² / day was used.

The smoothness of the obtained electrode substrate material for organic devices was Rz 142 nm, the surface resistance was 0.02 Ω / cm ² , and the surface resistance after the bending test did not change. The water vapor barrier property was 3 × ^10-2 g / m ² / day.

An organic EL light emitting device having the target sample as an anode was formed in the same manner as in Example 1, and the luminous efficiency was measured and found to be 0.5 cd / A. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 66 mN / m at 1 minute, 73 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

(Comparative Example 1)
An electrode substrate material for an organic device was obtained by laminating indium tin oxide (ITO) on a glass substrate with a film thickness of 155 nm by a sputtering method.

The smoothness of the obtained electrode substrate material for organic devices was Rz: 17 nm, the water vapor barrier property was 10 ^-5 g / m ² / day or less, but the surface resistance was 0.68 Ω / cm ² . The glass substrate broke when bent even slightly.

Further, as in Example 1, an organic EL light emitting device having the target sample as an anode was formed, and the luminous efficiency was measured and found to be 5.2 cd / A. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 48 mN / m at 1 minute, 61 mN / m at 5 minutes, and 67 mN / m at 10 minutes.

(Comparative Example 2)
An electrode substrate for organic devices by laminating indium tin oxide (ITO) at a film thickness of 120 nm on a commercially available gas barrier film having a thickness of 75 μm and a water vapor transmittance of 4 × 10 ^-4 g / m ² / day by a sputtering method. Obtained the material.

The smoothness of the obtained electrode substrate material for organic devices was Rz: 58 nm, the water vapor barrier property was 1 × 10 ^-4 g / m ² / day, but the surface resistance was 9.40 Ω / cm ² . The resistance value after the bending test increased sharply to 2296.00Ω / cm ² .

Further, as in Example 1, an organic EL light emitting device having the target sample as an anode was formed, but no light was emitted. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 52 mN / m at 1 minute, 58 mN / m at 5 minutes, and 62 mN / m at 10 minutes.

The crystallinity of the ITO film formed on the film was poor, and the surface resistance was increased. Since it is a film, it can be bent, but when it is bent with a small radius of curvature, cracks occur in the ITO film and resistance increases. In addition, a long pretreatment time was required to improve the wetting tension.

(Comparative Example 3)
A commercially available acrylic adhesive is applied to one surface (main surface) of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30) having a thickness of 15 μm (Ra: 7 nm) of 3 cm × 3 cm, and the coated surface on the adhesive side. A commercially available gas barrier film having a thickness of 75 μm and a water vapor transmission rate of 4 × 10 ^-4 g / m ² / day was attached to the film.

Next, a commercially available dry film was attached to the back surface of the aluminum foil, exposed and developed under UV conditions using a mesh-shaped photomask, and the portion where the dry film did not remain was exposed to an aqueous iron (II) chloride solution. A fine wire was formed by etching, and a dry film was peeled off with an aqueous sodium hydroxide solution to obtain a surface electrode material for an organic EL element.

The water vapor barrier property of the obtained electrode substrate material for organic devices was 4 × 10 ^-4 g / m ² / day, but the surface resistance was 0.04 Ω / cm ² , and the resistance value changed after the bending test. Although not, the smoothness was Rz: 1621 nm.

An organic EL light emitting device having the target sample as an anode was formed in the same manner as in Example 1, but no light was emitted. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 70 mN / m at 1 minute, 73 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

Since the conductor layer was formed of aluminum foil, there was no problem in surface resistance and flexibility, but since the flattening layer was not formed, a step was generated and the smoothness was poor.

(Comparative Example 4)
Aluminum was vapor-deposited on a commercially available gas barrier film having a thickness of 75 μm and a water vapor transmittance of 4 × 10 ^-4 g / m ² / day to form an aluminum-deposited film having a thickness of 300 nm. Next, a commercially available dry film is attached to the surface of the aluminum vapor-deposited film, exposed and developed by UV using a mesh-shaped photomask, and the portion where the dry film does not remain is etched with an aqueous iron (II) chloride solution. And patterned. Then, the dry film was peeled off with an aqueous sodium hydroxide solution to obtain an electrode substrate material for an organic device.

The obtained electrode substrate material for organic devices had a water vapor barrier property of 4 × 10 ^-4 g / m ² / day and a surface resistance of 0.42 Ω / cm 2, but the resistance value after the bending test was 12.6 Ω. In addition to increasing to / cm ² , the smoothness was Rz: 343 nm.

An organic EL light emitting device having the target sample as an anode was formed in the same manner as in Example 1, but no light was emitted. When the wetting tension after UV ozone cleaning was evaluated in the same manner as in Example 1, it was 50 mN / m at 1 minute, 73 mN / m at 5 minutes, and 73 mN / m at 10 minutes.

Since the conductor layer is formed of an aluminum-deposited film, the conductor layer is cracked after 50 bending tests, and the surface resistance is increased. In addition, the smoothness was poor due to the step caused by the conductor layer.

Table 1 summarizes the results of each example and comparative example.

The electrode substrate material for organic devices of the present disclosure can realize high smoothness, gas barrier property, light transmittance, low surface resistance and high flexibility, and shorten the pretreatment in the coating process, and can realize the electrode substrate material for organic devices. It is useful as a material.

100 Electrode substrate material for organic devices 101 Conductor layer 102 Flattening layer 103 Gas barrier layer 104 Transparent resin layer 105 Transparent support 106 Protective layer 111 First surface 112 Second surface 121 Base pattern 122 Peripheral pattern 122A First peripheral pattern 122B Second peripheral pattern 123 Electrode 124 Terminal 200 Organic EL element 201 Light emitting layer 202 Electrode 203 Electrode 301 Base material 302 Metal leaf

Claims (10)

A conductor layer made of patterned metal leaf and
A flattening layer provided around the conductor layer is provided.
In the first surface, the surface of the conductor layer is exposed from the flattening layer, and the surface of the conductor layer and the surface of the flattening layer form a continuous flat surface for an organic device. Electrode substrate material. The organic device according to claim 1, wherein the conductor layer forms a pattern having a line width of 20 μm or more and 200 μm or less, and the density of the conductor layer per unit area on the first surface is 15% or less. Electrode substrate material. The flattening layer includes a gas barrier layer and a transparent resin layer.
The electrode substrate material for an organic device according to claim 1 or 2, wherein the surface of the gas barrier layer and the exposed surface of the conductor layer form a continuous smooth surface. 3. The gas barrier layer includes at least one of a layer containing aluminum and oxygen as main components and a layer containing silicon and at least one of nitrogen, oxygen and carbon as main components, and has a thickness of 20 nm or more. The electrode substrate material for an organic device described in 1. The electrode substrate material for an organic device according to any one of claims 1 to 4, wherein the flattening layer has a light transmittance of 85% or more at a wavelength of 400 nm to 800 nm. The flattening layer is made of polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), polystyrene (PS), polycarbonate (PC), acrylic, polyvinyl chloride (PVC), fluororesin, indium tin oxide (ITO). The electrode substrate material for an organic device according to claim 5, which is one or more of polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT / PSS). The electrode substrate material for an organic device according to any one of claims 1 to 6, wherein the conductor layer includes a substrate pattern and a peripheral pattern provided outside the substrate pattern and connectable to an external device. The electrode substrate material for an organic device according to any one of claims 1 to 7, wherein the conductor layer is an aluminum foil having a thickness of 6 μm or more and 30 μm or less. The electrode substrate material for an organic device according to any one of claims 1 to 8, wherein the surface of the conductor layer is exposed from the flattening layer on the second surface opposite to the first surface. .. The electrode substrate material for an organic device according to any one of claims 1 to 9, wherein the surface of the conductor layer is covered with the flattening layer on the second surface opposite to the first surface. ..

Images