JP2020038790A - Organic electronic device and substrate for organic electronic device - Google Patents

Abstract

To provide an organic electronic device which has a superior manufacture yield by suppressing element short-circuiting, and a substrate for the organic electronic device.SOLUTION: The present invention relates to an organic electronic device comprising a substrate and an organic electronic element laminated on one surface of the substrate, in which the substrate has a metal layer and an insulation layer laminated on at least one surface side of the metal layer and consisting principally of synthetic resin, and the area ratio of a peak at a wave number of 910 cmof an absorption spectrum, obtained by measuring the insulation layer by a Fourier transformation infrared absorption spectrophotometer, to a peak at a wave number of 1,730 cmis 0.017 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an organic electronic device and a substrate for an organic electronic device.

  2. Description of the Related Art Organic electronic devices using organic semiconductors are expected to be applied to organic EL (electroluminescence) lighting, solar cells, and the like because they are flexible and thin and can save power. The organic EL lighting requires a light emitting layer containing at least an organic semiconductor, and further includes a charge injection layer, a charge transport layer, and the like in order to increase luminous efficiency. Further, the solar cell includes an electron donor, an electron acceptor, and the like.

  By the way, organic semiconductors are often used in the form of an extremely thin film due to low charge mobility, and are generally formed in a layer having a thickness of several tens nm to several μm. For this reason, if the substrate (base material) on which the organic semiconductor is laminated has irregularities, it causes a short circuit of the element, and lowers the production yield.

  Therefore, in order to flatten abnormal protrusions on the substrate, an organic EL element has been proposed in which a resin film having a thickness of 0.1 μm to several tens μm is applied on a polished glass substrate (Japanese Patent Application Laid-Open No. 2000-21563). Reference). However, an organic electronic device using a glass substrate is not suitable for installation on a curved surface, and its use is limited.

  On the other hand, an insulating layer having a thickness of 1 to 40 μm, a surface roughness Ra ≦ 0.5 μm, and a surface roughness Rmax ≦ 1.5 μm made of an organic resin is used as a base material. An organic EL element insulating substrate formed on the surface has been proposed (see JP-A-2002-25763). However, according to the verification of the present inventors, even if the surface roughness of the insulating layer is controlled before forming the organic EL element, the surface roughness of the insulating layer increases during the formation of the organic EL element, and a short circuit of the element occurs. In some cases, it was found that ensuring the surface roughness of the insulating layer before forming the organic EL element was not enough to ensure the flatness of the substrate.

JP-A-2000-21563 JP-A-2002-25763

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an organic electronic device and an organic electronic device substrate that are excellent in manufacturing yield by suppressing occurrence of element short circuit.

The present inventors have conducted intensive studies and found that when the ratio of uncured carbon-carbon double bonds contained in the synthetic resin as the main component of the insulating layer is high (the degree of curing is low), the insulating during the formation of the organic EL element is performed. It has been concluded that the surface roughness of the layer is increased and the short circuit of the element is likely to occur. The present inventors have determined that the ratio of the carbon-carbon double bond in the insulating layer, that is, as an index for specifying the degree of curing, is a wavenumber of 1730 cm ^{−1 of an} absorption spectrum obtained by measurement with a Fourier transform infrared absorption spectrophotometer. The present inventors have found that the area ratio of the peak at the wave number of 910 cm ^-1 to the peak at the above is effective, and completed the present invention.

That is, the invention made in order to solve the above-mentioned problem is an organic electronic device including a substrate and an organic electronic element laminated on one surface of the substrate, wherein the substrate has a metal layer and a metal layer. A peak at 1730 cm ^-1 of an absorption spectrum obtained by measuring the insulating layer with a Fourier transform infrared absorption spectrophotometer, the insulating layer being laminated on at least one surface side and having an insulating layer mainly composed of a synthetic resin. peak area ratio in the wave number 910 cm ^-1 for is 0.017 or less.

  The organic electronic device, since the area ratio obtained by measuring with a Fourier transform infrared absorption spectrophotometer of the insulating layer of the substrate is not more than the upper limit, uncured contained in the synthetic resin that is the main component of the insulating layer. The ratio of carbon-carbon double bonds is low, and the insulating layer is appropriately cured. For this reason, element short-circuiting due to an increase in the surface roughness of the insulating layer during the formation of the organic EL element is unlikely to occur. Therefore, the organic electronic device is excellent in production yield.

  The area ratio is preferably 0.003 or more. When the area ratio is 0.003 or more, the flexibility of the insulating layer can be easily secured, and the organic electronic device can be easily installed on a curved surface.

  It is preferable that the synthetic resin contains a cured product of a thermosetting acrylic resin or a thermosetting unsaturated polyester. As described above, by including a cured product of a thermosetting acrylic resin or a thermosetting unsaturated polyester in the synthetic resin, it is possible to prevent the surface roughness of the insulating layer from increasing during the formation of the organic EL element and to increase the insulating layer. Can be formed more easily.

  The insulating layer may include a synthetic resin cured using a thermosetting agent. By including a synthetic resin cured by using a thermosetting agent in the insulating layer, the controllability of the curing of the insulating layer is enhanced, and the area ratio can be easily controlled.

  The insulating layer preferably contains a pigment. By including the pigment in the insulating layer, flattening of the surface can be promoted by suppressing shrinkage of the resin and the like.

  The pigment is preferably an inorganic pigment. The average particle size of the pigment is preferably 300 nm or less, and the content of the pigment in the insulating layer is preferably 50% by mass or less. By containing 50% by mass or less of the inorganic pigment having an average particle size of 300 nm or less in this manner, the occurrence of protrusions on the surface of the insulating layer can be suppressed, and the surface flattening can be further promoted.

  The metal layer may be mainly composed of iron, titanium, or an alloy thereof. By using these metals as the main components of the metal layer, a substrate having excellent strength and durability can be easily and reliably formed.

  The organic electronic device may be used for organic EL lighting or an organic solar cell. Since the organic electronic device has excellent production yield as described above, it can be suitably used for organic EL lighting or organic solar cells.

Another invention made to solve the above problem has a metal layer, and an insulating layer laminated on at least one surface side of the metal layer and containing a synthetic resin as a main component. peak area ratio in the wave number 910 cm ^-1 to a peak at the wave number 1730 cm ^-1 of the absorption spectrum obtained by measuring with transform infrared absorption spectrometer is an organic electronic device substrate is 0.017 or less.

  The organic electronic device substrate, since the area ratio of the insulating layer obtained by measuring with a Fourier transform infrared absorption spectrophotometer is not more than the upper limit, the uncured non-cured resin contained in the main component of the insulating layer. Low percentage of carbon-carbon double bonds. For this reason, when forming an organic EL element on the organic electronic device substrate, an element short circuit due to an increase in the surface roughness of the insulating layer hardly occurs. Therefore, an organic electronic device using the organic electronic device substrate has an excellent manufacturing yield.

Here, the “main component” is a component contained most, for example, a component contained at 50% by mass or more. The `` peak '' of the absorption spectrum obtained by measuring with a Fourier transform infrared absorption spectrophotometer is due to a specific interatomic bond. There is. Thus, the "peak in the wave number 1730 cm ^-1" and "peak at the wave number 910 cm ^-1" shall each containing a peak wavenumber shifts within ± 10 cm ^-1.

  The “average particle size” is a particle size distribution (D50) of 50% of the volume integrated value from the small particle size calculated based on the measurement result of the particle size distribution of the particles by a general particle size distribution meter. Means Such a particle size distribution can be measured by a diffraction or scattering intensity pattern generated by irradiating the particles with light. Examples of such a particle size distribution meter include “Microtrack 9220FRA” and “Microtrack HRA” manufactured by Nikkiso Co., Ltd. And the like.

  As described above, the organic electronic device and the substrate for an organic electronic device of the present invention are excellent in the production yield by suppressing the occurrence of the element short circuit when forming the organic EL element on the substrate.

1 is a schematic sectional view illustrating an organic electronic device according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view illustrating an organic electronic device according to an embodiment of the present invention, which is different from FIG. 1. FIG. 3 is a schematic cross-sectional view illustrating an organic electronic device according to an embodiment of the present invention, which is different from FIGS. 1 and 2. It is a graph which shows the example of the absorption spectrum obtained by measuring with a Fourier-transform infrared absorption spectrophotometer. 3 is a photograph of the surface of the substrate for an organic electronic device of Example 1 observed with an optical microscope. 5 is a photograph of the surface of the substrate for an organic electronic device of Comparative Example 1 observed by an optical microscope. 9 is a photograph of the surface of the substrate for an organic electronic device of Example 3 observed by ATF. 4 is a photograph of the surface of the substrate for an organic electronic device of Comparative Example 1 observed by ATF.

  Hereinafter, embodiments of an organic electronic device and a substrate for an organic electronic device of the present invention will be described in detail with reference to the drawings as appropriate.

  The organic electronic device shown in FIG. 1 includes a substrate 1 and an organic electronic element 2 laminated on one surface of the substrate 1.

<Substrate>
The substrate 1 is a substrate for an organic electronic device according to an embodiment of the present invention, and includes a metal layer 1a and an insulating layer 1b laminated on at least one surface (the organic electronic element laminated surface) of the metal layer 1a. And

(Metal layer)
The metal layer 1a is a layer containing a metal as a main component, and as the metal, iron, titanium, or an alloy thereof is used. Specifically, as the metal layer 1a, a cold-rolled steel sheet, a hot-dip galvanized steel sheet (GI), an alloyed hot-dip Zn-Fe coated steel sheet (GA), an alloyed hot-dip Zn-5% Al-plated steel sheet (GF), Metal plates such as electric pure galvanized steel plate (EG), electric Zn-Ni plated steel plate, titanium plate, and galvalume steel plate (registered trademark) can be used.

  The metal plate is preferably a non-chromate-treated one, but a chromate-treated one or an untreated one can also be used.

As shown in FIG. 2, a reaction layer 1c formed by a phosphoric acid-based chemical conversion treatment may be laminated on the metal layer 1a side of the organic electronic element lamination surface, that is, between the metal layer 1a and the insulating layer 1b. In particular, in the case of a galvanized metal plate, the reaction layer 1c formed by performing a chemical conversion treatment with an acidic aqueous solution containing colloidal silica and an aluminum phosphate compound is preferable. When an acidic aqueous solution containing colloidal silica and an aluminum phosphate compound is used as a chemical conversion treatment solution, the surface of the zinc-based plating layer is etched by the acidic aqueous solution. At the same time, a reaction layer 1c mainly composed of AlPO ₄ or Al ₂ (HPO ₄ ) _{3 which} is hardly soluble in aluminum phosphate (slightly soluble in water or an alkaline aqueous solution) is formed on the surface of the zinc-based plating layer. By depositing and incorporating silica fine particles into the reaction layer 1c, aluminum phosphate and silica fine particles are combined and integrated. Further, a dense reaction layer 1c is formed between the zinc-based plating layer roughened by etching, and the bonding with the insulating layer 1b formed on the reaction layer 1c is also dense and strong. . When the acidic aqueous solution contains a water-soluble resin such as polyacrylic acid, the deposition state of the silica fine particles in the obtained reaction layer 1c can be further strengthened.

  Further, as shown in FIG. 3, rust prevention layers 1d may be provided on both surfaces of the metal layer 1a. By providing the rust prevention layer 1d in this way, the durability of the substrate 1 is improved, and the substrate 1 can be used for a long time. When the rust-proof layer 1d is provided on the organic electronic element laminated surface side of the metal layer 1a, the reaction layer 1c is laminated on the organic electronic element laminated surface side of the rust-proof layer 1d. The rust prevention layer 1d may be laminated on one side of the metal layer 1a, especially on only the organic electronic element laminated surface side.

  The average thickness of the metal layer 1a is not particularly limited, but can be 0.3 mm or more and 2.0 mm or less.

(Insulating layer)
The insulating layer 1b is a layer having an insulating property, and has a synthetic resin as a main component. The insulating layer 1b can be a cured product such as a thermosetting resin or a photocurable resin or a thermoplastic resin. In addition, the said thermoplastic resin may be crosslinked.

  Among these, a cured product of a thermosetting resin is preferable. By using the thermosetting resin as the main component of the insulating layer 1b as described above, the controllability of curing when forming the insulating layer 1b is enhanced, and the insulating layer 1b can be formed more easily. The thermosetting resin is not particularly limited, and examples thereof include an acrylic resin, a polyester, a phenol resin, an epoxy resin, a urea resin, a melamine resin, and a diallyl phthalate resin. The resin preferably contains a cured product of a thermosetting acrylic resin and a thermosetting unsaturated polyester. As described above, by including the cured product of the thermosetting acrylic resin or the thermosetting unsaturated polyester in the synthetic resin of the insulating layer 1b, it is possible to prevent the surface roughness of the insulating layer 1b from increasing during the formation of the organic EL element. In addition, the insulating layer 1b can be formed more easily.

  The thermosetting acrylic resin is obtained by a polymerization reaction of an acrylic ester or a methacrylic ester. Examples of the raw material of the thermosetting acrylic resin include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, ethyl hexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, and the like. Can be Further, as the thermosetting acrylic resin, various commercially available products can be suitably used, and for example, 4-times level coat manufactured by Takashi Kubo Paint Co., Ltd. can be mentioned.

  The thermosetting unsaturated polyester is obtained by a condensation reaction between a polybasic acid such as a dibasic acid and a polyhydric alcohol. Examples of the polybasic acid used as a raw material of the thermosetting unsaturated polyester include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride. . Examples of the polyhydric alcohols used as a raw material of the thermosetting unsaturated polyester include ethylene glycols such as ethylene glycol, diethylene glycol and polyethylene glycol, and propylene glycols such as propylene glycol, dipropylene glycol and polypropylene glycol. Can be Various commercially available products can be suitably used as the thermosetting unsaturated polyester. For example, Byron (registered trademark) 23CS, Byron (registered trademark) 29CS, Byron (registered trademark) 29XS, and Byron (registered trademark) Trademark) 20SS, Byron (registered trademark) 29SS (all manufactured by Toyobo Co., Ltd.) and the like.

  The lower limit of the content of the synthetic resin in the insulating layer 1b is preferably 50.0% by mass, and more preferably 60.0% by mass. On the other hand, the upper limit of the content of the synthetic resin is preferably 80.0% by mass, and more preferably 56.3% by mass. With such a content of the synthetic resin, the insulating layer 1b suitable for the substrate 1 can be formed. Note that the content of the synthetic resin indicates a ratio of the content of the synthetic resin to the total mass of the solid components (synthetic resin, thermosetting agent, pigment, and the like) in the insulating layer 1b. The same applies to the content of a later-described thermosetting agent and the like.

It is preferable that the insulating layer 1b be cured by containing a thermosetting agent. That is, the insulating layer 1b preferably contains a synthetic resin cured using a thermosetting agent. Although the insulating layer 1b does not dissolve in the organic solvent, there is a possibility that the solvent used during molding may enter the layer and deteriorate such as swelling. In order to suppress this, it is effective to increase the degree of curing (crosslink density) of the insulating layer 1b by including a predetermined amount of a thermosetting agent. Further, it becomes easy to control the degree of curing by heat curing agent, the area of the peak in the wave number 910 cm ^-1 to a peak at the wave number 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrometer to be described later The ratio can be easily controlled.

  The thermosetting agent is not particularly limited, but is preferably one that has good compatibility with the thermosetting resin, can crosslink the thermosetting resin, and has good liquid stability.

  As a minimum of content of a thermosetting agent in insulating layer 1b before hardening, 10.0 mass% is preferred and 20.0 mass% is more preferred. On the other hand, the upper limit of the content of the thermosetting agent is preferably 50.0% by mass. With such a content of the thermosetting agent, the insulating layer 1b can be easily and reliably formed.

  The lower limit of the mass ratio of the thermosetting agent to the synthetic resin in the insulating layer 1b before curing is preferably 0.3, more preferably 0.4, and even more preferably 0.65. On the other hand, the upper limit of the mass ratio is preferably 1.0. When the mass ratio is less than the lower limit, the effect of the thermosetting agent may not be sufficiently obtained. Conversely, if the mass ratio exceeds the upper limit, curing may occur rapidly, causing cracks or cracks in the insulating layer 1b, or an excessive amount of the thermosetting agent may increase the production cost.

  Further, the insulating layer 1b preferably contains a pigment. In the insulating layer 1b containing a synthetic resin as a main component, volume shrinkage may occur at the time of curing, or the surface shape may be largely undulated or uneven due to the influence of a solvent volatile gas component. Therefore, by containing the pigment in the insulating layer 1b, the shrinkage of the synthetic resin can be suppressed and the solvent gas desorption can be promoted, so that the surface shape can be flattened. On the other hand, due to the inclusion of the pigment, the surface roughness increases, and many protrusions can be formed on the surface. In order to suppress the formation of the protrusions, the type, particle size, and content of the pigment to be added may be adjusted.

  Examples of the pigment include an organic pigment and an inorganic pigment. However, since the purpose of adding the pigment in the present invention is to control the surface shape, it is preferable to use an inorganic pigment. Examples of the inorganic pigment include white pigments such as titanium oxide, calcium carbonate, zinc oxide, barium sulfate, lithopone, and lead white, and black pigments such as carbon black and iron black.

  The average particle size of the pigment is preferably 100 nm or more and 300 nm or less. The content of the pigment in the insulating layer 1b is preferably 30% by mass or more and 50% by mass or less. If the average particle size of the pigment is less than the lower limit, or if the content of the pigment is less than the lower limit, the effect of adding the pigment to the surface of the insulating layer 1b may not be sufficient. Conversely, when the average particle size of the pigment exceeds the upper limit or when the content of the pigment exceeds the upper limit, the surface roughness of the insulating layer 1b may be increased due to the pigment.

  As the pigment, a commercially available product may be used as long as it satisfies the preferable average particle size described above. For example, JR-806 (average particle size: 250 nm) manufactured by Teica Co., Ltd .; CR-50 (average particle diameter 250 nm), R930 (average particle diameter 250 nm) and the like.

  In order to suppress segregation of the pigment, the insulating layer 1b may contain a pigment dispersant. Suitable pigment dispersants are water-soluble acrylic resins, water-soluble styrene acrylic resins, nonionic surfactants, or combinations thereof.

  The lower limit of the average thickness of the insulating layer 1b is preferably 5 μm, more preferably 10 μm. On the other hand, the upper limit of the average thickness of the insulating layer 1b is preferably 30 μm, more preferably 20 μm. When the average thickness of the insulating layer 1b is less than the above lower limit, the insulating property of the substrate 1 may be insufficient. Conversely, if the average thickness of the insulating layer 1b exceeds the above upper limit, the flexibility of the substrate 1 may be insufficient.

The resistivity of the insulating layer 1b is preferably 10 ¹⁰ Ωcm or more. The “resistivity” is a value measured according to JIS-K-7194 (1994).

(Peak area ratio)
In the organic electronic device, the peak area ratio in the wave number 910 cm ^-1 to a peak at the wave number 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrophotometer of the insulating layer 1b of the substrate for the electronic device 1 (Hereinafter, also simply referred to as “peak area ratio”) is set to a predetermined value or less.

Here, as shown in FIG. 4, the term “peak area” refers to, for example, a peak at a wave number of 1730 cm ⁻¹ of an absorption spectrum, and an absorption spectrum obtained by measurement with a Fourier transform infrared absorption spectrophotometer. Of the waveform forming a peak at the wave number of 1730 cm ^-1 and the area of the hatched portion surrounded by the base line B.

Among the above-mentioned peaks, the peak at the wave number of 910 cm ⁻¹ is derived from out-of-plane bending vibration of an unbranched olefin CH group in the chemical structure of the synthetic resin, and the area of this peak depends on the configuration of the insulating layer 1 b. Of the components, it corresponds to the total amount of uncured carbon-carbon double bonds involved in the curing reaction. On the other hand, the peak at the wave number of 1730 cm ⁻¹ is derived from the stretching vibration of the ester bond (double bond between C and O) and is invariant to the progress of the curing reaction. That is, the area of the peak at the wave number of 1730 cm ^-1 corresponds to the total amount of the insulating layer 1b. Therefore, the area peak ratio functions as an index indicating the degree of curing of the synthetic resin in the insulating layer 1b, and the smaller the value, the more the curing progresses.

  The upper limit of the peak area ratio is 0.017, more preferably 0.010. On the other hand, the lower limit of the peak area ratio is preferably 0.003, and more preferably 0.005. If the area ratio of the peaks exceeds the upper limit, the synthetic resin is insufficiently cured, so that deformation may occur during the formation of the organic electronic element 2 and the surface roughness of the insulating layer 1b may increase. Conversely, if the peak area ratio is less than the lower limit, the curing of the synthetic resin proceeds excessively, and the flexibility of the substrate 1 may be reduced, or the insulating layer 1b may be cracked due to excessive shrinkage of the synthetic resin. May occur.

<Organic electronic device>
Examples of the organic electronic element 2 include an organic EL element, a solar cell element, a liquid crystal display element, a thin film transistor, a touch panel element, and an electronic paper element.

  Examples of the organic EL element include an element in which an anode, an organic light emitting layer, and a cathode are laminated in this order. In the organic EL element, an electron injection layer, an electron transport layer, a hole transport layer, and the like other than the above may be appropriately laminated. Known elements can be used as the elements constituting the organic EL element. As the anode, for example, a transparent electrode using indium tin oxide (ITO) can be used. As the cathode, for example, an electrode using metal or indium zinc oxide (IZO) can be used. As a main component of the organic light emitting layer, a naphthyl-substituted diamine derivative (α-NPD) can be used.

  By using the organic EL element as described above as the organic electronic element 2, the organic electronic device can be suitably used for organic EL lighting.

  Further, by using a solar cell element in which an anode, an electron donor, an electron acceptor, and a cathode are stacked in this order, for example, as the organic electronic element 2, the organic electronic device can be suitably used for an organic solar cell.

<Production method>
The organic electronic device can be obtained by a manufacturing method including, for example, a step of preparing the substrate 1 and a step of laminating the organic electronic element 2 on one surface of the substrate 1.

(Substrate preparation process)
In this step, the insulating layer 1b is laminated by applying and heating the composition for forming an insulating layer on the side of the metal layer 1a on which the organic electronic element is laminated, and the substrate 1 is formed. The composition for forming an insulating layer is preferably in a liquid state. That is, the composition for forming an insulating layer preferably contains a solvent.

  The solvent used for the composition for forming an insulating layer is not particularly limited as long as it can dissolve or disperse each component to be contained in the composition for forming an insulating layer. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; toluene, benzene, xylene, Aromatic hydrocarbons such as Solvesso (registered trademark) 100 (manufactured by ExxonMobil) and Solvesso (registered trademark) 150 (manufactured by ExxonMobil); aliphatic hydrocarbons such as hexane, heptane, and octane; ethyl acetate, acetic acid And esters such as butyl. The solid content of the insulating layer forming composition can be adjusted using such a solvent.

  As a minimum of solid concentration of a constituent for insulating layer formation, 20 mass% is preferred and 40 mass% is more preferred. On the other hand, the upper limit of the solid concentration of the composition for forming an insulating layer is preferably 80% by mass, and more preferably 70% by mass. If the solid concentration is less than the lower limit, that is, if the amount of the solvent is too large, a large amount of the solvent evaporates at the time of heating. The surface smoothness may be impaired. Conversely, if the solid content exceeds the upper limit, application of the composition for forming an insulating layer may be difficult.

  The method for applying and heating (drying and baking) the composition for forming an insulating layer is not particularly limited, and a known method can be appropriately employed. Examples of the coating method include a bar coater method, a roll coater method, a curtain flow coater method, a spray method, a spray ringer method, and the like. Among these, from the viewpoint of cost and the like, a bar coater method, a roll coater method, And the spray ringer method are preferred.

  The lower limit of the heating temperature of the composition for forming an insulating layer is preferably 200 ° C, more preferably 210 ° C. On the other hand, the upper limit of the heating temperature is preferably 250 ° C, more preferably 240 ° C. If the heating temperature is lower than the above lower limit, the strength of the insulating layer 1b may be insufficient. Conversely, when the heating temperature exceeds the upper limit, the solvent evaporates violently, and as a result, the surface smoothness of the insulating layer 1b may be impaired. Note that the heating temperature refers to a peak metal temperature (PMT).

  The lower limit of the heating time of the composition for forming an insulating layer is preferably 3.0 minutes, more preferably 3.5 minutes, and even more preferably 4.0 minutes. On the other hand, the upper limit of the heating time of the composition for forming an insulating layer is preferably 20 minutes, more preferably 15 minutes, and still more preferably 10 minutes. If the heating time of the composition for forming an insulating layer is less than the above lower limit, the curing of the synthetic resin is likely to be insufficient, and deformation occurs during the formation of the organic electronic element 2, and the surface roughness of the insulating layer 1b increases. There is a risk. Conversely, if the heating time of the composition for forming an insulating layer exceeds the above upper limit, the curing of the synthetic resin proceeds excessively, and the flexibility of the substrate 1 may be reduced, or the insulating layer 1b may be excessively shrunk by the synthetic resin. Cracks may occur. After the composition for forming an insulating layer is applied and heated, the substrate 1 that has once returned to room temperature may be heated again to advance the curing of the synthetic resin. In this case, the heating time of the insulating layer forming composition refers to the total heating time including the heating time at the time of applying the insulating layer forming composition.

  The degree of curing of the synthetic resin is mainly determined by the heating temperature and the heating time of the composition for forming an insulating layer. Therefore, the heating temperature and the heating time of the composition for forming an insulating layer are determined so that the peak area ratio is 0.017 or less.

  As described above, the reaction layer 1c may be formed before applying the composition for forming an insulating layer to the metal layer 1a. Further, a rust prevention layer 1d may be provided on the surface of the metal layer 1a.

  Further, in order to enhance the flatness, the surface of the substrate 1 on which the organic electronic elements are laminated (the surface of the insulating layer 1b) may be subjected to polishing. Examples of the polishing method include chemical polishing (CMP), electrolytic polishing, mechanical polishing, and the like. Among these, from the viewpoint of removing fine irregularities, a chemical electrolytic polishing method using, for example, silica, alumina, ceria, titania, zirconia, germania, or the like as an abrasive is preferable.

(Organic electronic device lamination process)
In this step, the organic electronic element 2 is laminated on the organic electronic element laminated surface of the substrate 1. As the lamination method, a conventionally known method can be used.

<Advantages>
The organic electronic device and the substrate for the electronic device, a peak in the wave number 910 cm ^-1 to a peak at the wave number 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrophotometer of the insulating layer 1b of the substrate 1 Is 0.017 or less, the ratio of uncured carbon-carbon double bonds contained in the synthetic resin that is the main component of the insulating layer 1b is low, and the insulating layer 1b is appropriately cured. For this reason, element short-circuiting due to an increase in the surface roughness of the insulating layer 1b during the formation of the organic EL element is unlikely to occur. Therefore, the organic electronic device using the electronic device substrate has an excellent manufacturing yield.

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

(Example 1)
As a metal layer, an electrogalvanized metal plate (EG) having a plate thickness of 0.8 mm and a zinc plating adhesion amount of 20 g / m ^{2 on} both surfaces of the metal plate was prepared. On one surface of this metal plate, a thermosetting acrylic resin paint (4times level coat, standard type / clear, manufactured by Takashi Kubo Paint Co., Ltd.) is applied by spraying so that the ultimate plate temperature (PMT) becomes 220 ° C. Heating was performed for 2 minutes to form an insulating layer having an average thickness of 15 μm, thereby obtaining a substrate.

  As post-curing, the substrate was further heated in the atmosphere at 240 ° C. for 1.5 minutes to cure the insulating layer. Therefore, the total heating time is 3.5 minutes.

Next, the surface of the insulating layer was smoothed by subjecting the substrate to chemical mechanical polishing. Specifically, the substrate was set on a holder of the polishing apparatus to which a suction pad for mounting a substrate was attached, and was set on a polishing pad mounted on a surface plate of the polishing apparatus with the insulating layer facing downward. Granular alumina (average particle size: about 100 nm) is used as an abrasive, pressure is 65 g / cm ² , rotation speed per rotation is 1 m, each rotation speed between the substrate and the platen is 50 rpm, and chemical mechanical polishing is performed for 10 minutes. Was done. The polishing depth was 6 μm in terms of polishing amount.

  Thus, a substrate for an organic electronic device of Example 1 was obtained.

(Example 2)
A substrate for an organic electronic device of Example 2 was obtained in the same manner as in Example 1, except that the post-curing conditions were set to 3 minutes in the air at 230 ° C.

(Example 3)
A substrate for an organic electronic device of Example 3 was obtained in the same manner as in Example 1 except that the post-curing conditions were set to 6 minutes in the air at 220 ° C.

(Comparative Example 1)
A substrate for an organic electronic device of Comparative Example 1 was obtained in the same manner as in Example 1 except that post-curing was not performed.

<Peak area ratio>
To the organic electronic device substrate of Example 1 to Example 3 and Comparative Example 1, in the wave number 910 cm ^-1 to a peak at the wave number 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrometer The area ratio of the peak was determined.

As a Fourier transform infrared absorption spectrophotometer, a 3100FT-IR / 600UMA microscope infrared microscope system manufactured by Varian was used, and measurement was performed in a micro ATR mode at a resolution of 4 cm ^-1 . Table 1 shows the results.

  In Table 1, Reference Example 1 is the result of measuring the thermosetting acrylic resin paint used.

<Evaluation>
An ITO film (average film thickness: 200 nm) was formed on the organic electronic device substrates of Examples 1 to 3 and Comparative Example 1 by a sputtering method, and the surface was observed.

The formation of the ITO film was performed using HSM-542 manufactured by Shimadzu Corporation with the target used as the ITO target. The introduced gas at the time of sputtering was a mixed gas of Ar gas 20 sccm and O ₂ gas 0.5 sccm, the gas pressure was 1.34 mTorr (0.179 Pa), and the film formation power was 150 W.

  The surface of the organic electronic device substrate on which the ITO film was formed was observed at a magnification of 10 times with an optical microscope. As a result, the substrates for organic electronic devices of Examples 1 to 3 were flat with no wrinkles observed on the surface. FIG. 5 shows a photograph of the surface of the substrate for an organic electronic device of Example 1 observed by an optical microscope. On the other hand, in the organic electronic device substrate of Comparative Example 1, wrinkles were observed on the surface as shown in FIG.

  Further, the surfaces of the organic electronic device substrates of Example 3 and Comparative Example 1 were observed using an AFM (atomic force microscope), and the surface roughness was calculated. The measurement was performed on a square having a side of 100 μm. FIGS. 7 and 8 show photographs of the surface of the substrate for an organic electronic device of Example 3 and photographs of the surface of the substrate for an organic electronic device of Comparative Example 1 observed by AFM, respectively. The surface roughness of Example 3 was 3.4 nm, and the surface roughness of Comparative Example 1 was 121 nm.

  From the above results, in Examples 1 to 3 in which the peak area ratio of the absorption spectrum obtained by measurement with a Fourier transform infrared absorption spectrophotometer was 0.017 or less, the surface of the insulating layer was formed even after the ITO film was formed. Low roughness. On the other hand, in Comparative Example 1, since the peak area ratio was more than 0.017, it is considered that the surface roughness of the insulating layer increased during the formation of the ITO film. Therefore, by setting the peak area ratio to 0.017 or less, it can be said that short-circuiting of the device due to an increase in surface roughness of the insulating layer during formation of the organic EL device can be suppressed.

  As described above, the organic electronic device and the substrate for an organic electronic device of the present invention are excellent in manufacturing yield by suppressing the occurrence of element short-circuiting when forming an organic EL element on the substrate, and thus are suitable for various uses. Can be used.

DESCRIPTION OF SYMBOLS 1 Substrate 1a Metal layer 1b Insulation layer 1c Reaction layer 1d Rust prevention layer 2 Organic electronic element

Claims (9)

An organic electronic device comprising a substrate and an organic electronic element laminated on one surface of the substrate,
The substrate, a metal layer, laminated on at least one surface side of the metal layer, having an insulating layer mainly composed of synthetic resin,
The organic electronic device area ratio of peaks at a wavenumber of 910 cm ^-1 to a peak in the insulating layer at a wavenumber of 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrometer is 0.017 or less.   The organic electronic device according to claim 1, wherein the area ratio is 0.003 or more.   3. The organic electronic device according to claim 1, wherein the synthetic resin includes a cured product of a thermosetting acrylic resin or a thermosetting unsaturated polyester.   The organic electronic device according to claim 1, wherein the insulating layer includes a synthetic resin cured using a thermosetting agent.   The organic electronic device according to claim 1, wherein the insulating layer contains a pigment.   The organic electronic device according to claim 5, wherein the pigment is an inorganic pigment, the average particle size of the pigment is 300 nm or less, and the content of the pigment in the insulating layer is 50% by mass or less.   The organic electronic device according to any one of claims 1 to 6, wherein the metal layer contains iron, titanium, or an alloy thereof as a main component.   The organic electronic device according to any one of claims 1 to 7, which is used for organic EL lighting or an organic solar cell. A metal layer, having an insulating layer laminated on at least one surface side of the metal layer and containing a synthetic resin as a main component,
The organic electronic device substrate area ratio of the peaks in the wave number 910 cm ^-1 to a peak in the insulating layer at a wavenumber of 1730 cm ^-1 of the absorption spectrum obtained by measuring Fourier transform infrared absorption spectrometer is 0.017 or less .

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