JP7066578B2 - Organic electronic devices and substrates for organic electronic devices - Google Patents

Description

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

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

By the way, since organic semiconductors have low charge mobility, they are often used in the form of ultra-thin films, and are generally formed in layers having a thickness of several tens of nm to several μm. Therefore, if the substrate (base material) on which the organic semiconductor is laminated has irregularities, it may cause an element short circuit and reduce the manufacturing yield.

Therefore, in order to flatten the abnormal protrusions on the substrate, an organic EL element in which a resin coating film having a film thickness of 0.1 μm to several tens of μm is coated on a polished glass substrate has been proposed (Japanese Patent Laid-Open No. 2000-21563). See Gazette). 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, a flexible metal plate or metal foil is used as a base material, and an insulating layer made of an organic resin having a film thickness of 1 to 40 μm, a surface roughness Ra ≦ 0.5 μm, and Rmax ≦ 1.5 μm is used as a base material. An insulating substrate for an organic EL element formed on the surface has been proposed (see JP-A-2002-25763). However, according to the verification by the present inventors, even if the surface roughness of the insulating layer is controlled before the formation of the organic EL element, the surface roughness of the insulating layer increases during the formation of the organic EL element, and the element short circuit occurs. It was found that it may occur, and it is not enough to guarantee the flatness of the substrate only by defining the surface roughness of the insulating layer before forming the organic EL element.

Japanese Unexamined Patent Publication No. 2000-21563 Japanese Unexamined Patent Publication No. 2002-25763

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

As a result of diligent studies by the present inventors, when the ratio of uncured carbon-carbon double bonds contained in the synthetic resin which is the main component of the insulating layer is high (the degree of curing is low), insulation is performed during the formation of the organic EL element. It was concluded that the surface roughness of the layer increases and element short circuit is likely to occur. Then, the present inventors have a wave number of 1730 cm ^-1 in the absorption spectrum obtained by measuring with a Fourier transform infrared absorption spectrophotometer as an index for specifying the ratio of carbon-carbon double bonds in the insulating layer, that is, the degree of hardening. We have found that the area ratio of the peak at wave number 910 cm ^-1 to the peak at is effective, and completed the present invention.

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

In the organic electronic device, the area ratio obtained by measuring with a Fourier transform infrared absorption spectrophotometer of the insulating layer of the substrate is set to be equal to or less than the upper limit, so that the uncured synthetic resin contained in the synthetic resin which is the main component of the insulating layer is not cured. The ratio of carbon-carbon double bonds is low, and the insulating layer is moderately cured. Therefore, it is unlikely that a short circuit will occur due to an increase in the surface roughness of the insulating layer during the formation of the organic EL element. Therefore, the organic electronic device is excellent in manufacturing yield.

The area ratio is preferably 0.003 or more. By setting the area ratio to 0.003 or more in this way, it is easy to secure the flexibility of the insulating layer, and the organic electronic device can be easily installed on the curved surface.

The synthetic resin may contain a cured product of a thermosetting acrylic resin or a thermosetting unsaturated polyester. By including the cured product of the thermosetting acrylic resin or the thermosetting unsaturated polyester in the synthetic resin in this way, the insulating layer is prevented from increasing the surface roughness of the insulating layer during the formation of the organic EL element. Can be formed more easily.

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

The insulating layer may contain a pigment. By containing the pigment in the insulating layer in this way, the flattening of the surface can be promoted by suppressing the shrinkage of the resin and the like.

The pigment is preferably an inorganic pigment, and 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 way, the generation of protrusions on the surface of the insulating layer can be suppressed, so that the flattening of the surface can be further promoted.

It is preferable that the metal layer contains iron, titanium, or an alloy thereof as a main component. By using these metals as the main components of the metal layer in this way, it is possible to easily and surely form a base material having excellent strength and resistance.

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

Another invention made to solve the above-mentioned problems 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, and the above-mentioned insulating layer is obtained by Fourier. This is a substrate for an organic electronic device in which the area ratio of the peak having a wave number of 910 cm ^-1 to the peak having a wave number of 1730 cm ^-1 in the absorption spectrum obtained by measuring with a converted infrared absorption spectrophotometer is 0.017 or less.

Since the area ratio of the substrate for an organic electronic device obtained by measuring with a Fourier transform infrared absorption spectrophotometer of the insulating layer is not more than the upper limit, the uncured synthetic resin contained in the synthetic resin which is the main component of the insulating layer is not cured. The ratio of carbon-carbon double bonds is low. Therefore, when the organic EL element is formed on the substrate for the organic electronic device, the element short circuit due to the increase in the surface roughness of the insulating layer is unlikely to occur. Therefore, the organic electronic device using the substrate for the organic electronic device is excellent in the manufacturing yield.

Here, the "main component" is a component contained most, for example, a component contained in an amount of 50% by mass or more. Further, the "peak" of the absorption spectrum obtained by measuring with the Fourier transform infrared absorption spectrophotometer is caused by a specific interatomic bond, but the wave number shift of the peak occurs depending on the type of the insulating layer or the like. There is. Therefore, the "peak at wave number 1730 cm ^-1 " and "peak at wave number 910 cm ^-1 " are assumed to include peaks whose wave numbers are shifted within ± 10 cm ^-1 , respectively.

The "average particle size" is a particle size (D50) of 50% of the volume integrated value from the small particle size side calculated based on the measurement result of measuring the particle size distribution of the particles with a general particle size distribution meter. Means. Such a particle size distribution can be measured by the intensity pattern of diffraction and scattering 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. ] Etc. are exemplified.

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 circuit when forming an organic EL element on the substrate.

It is a schematic sectional drawing which shows the organic electronic device of one Embodiment of this invention. FIG. 3 is a schematic cross-sectional view showing 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 showing 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 the Fourier transform infrared absorption spectrophotometer. It is a photograph of the substrate surface for an organic electronic device of Example 1 observed with an optical microscope. It is a photograph of the substrate surface for an organic electronic device of Comparative Example 1 observed with an optical microscope. It is a photograph of the substrate surface for an organic electronic device of Example 3 observed by ATF. It is a photograph of the substrate surface for an organic electronic device of Comparative Example 1 observed by ATF.

Hereinafter, embodiments of the organic electronic device and the substrate for the 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.

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

(Metal layer)
The metal layer 1a is a layer containing a metal as a main component, and iron, titanium, or an alloy thereof is used as the metal. Specifically, the metal layer 1a includes a cold-rolled steel sheet, a hot-dip galvanized steel sheet (GI), an alloyed hot-dip Zn-Fe-plated steel sheet (GA), an alloyed hot-dip Zn-5% Al-plated steel sheet (GF), and the like. 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.

As the metal plate, a non-chromate-treated one is preferable, but a chromate-treated one or an unchromated one can also be used.

As shown in FIG. 2, the reaction layer 1c formed by the phosphoric acid-based chemical conversion treatment may be laminated on the organic electronic device laminated surface side of the metal layer 1a, that is, between the metal layer 1a and the insulating layer 1b. In particular, in the case of a zinc-plated metal plate, the reaction layer 1c formed by chemical conversion treatment with an acidic aqueous solution containing colloidal silica and an aluminum phosphate salt compound is preferable. When an acidic aqueous solution containing colloidal silica and an aluminum phosphate salt 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 ) _, which is sparingly soluble in aluminum phosphate (difficult to dissolve in water or an alkaline aqueous solution), is formed on the surface of the zinc-based plating layer. When the silica fine particles are deposited and incorporated into the reaction layer 1c, the aluminum phosphate and the silica fine particles are compositely integrated. Further, a dense reaction layer 1c is formed between the zinc-based plating layer roughened by etching, and the bond with the insulating layer 1b formed on the reaction layer 1c is also dense and strong. .. Further, when a water-soluble resin such as polyacrylic acid is contained in the acidic aqueous solution, the deposited state of the silica fine particles in the obtained reaction layer 1c can be further strengthened.

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

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

(Insulation layer)
The insulating layer 1b is a layer having an insulating property, and contains 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. The thermoplastic resin may be crosslinked.

Among these, a cured product of a thermosetting resin is preferable. By using the cured product of the thermosetting resin as the main component of the insulating layer 1b in this way, the controllability of curing at the time of 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 acrylic resin, polyester, phenol resin, epoxy resin, urea resin, melamine resin, diallyl phthalate resin, and the like, but synthesis of the insulating layer 1b. The resin preferably contains a cured product of a thermosetting acrylic resin and a thermosetting unsaturated polyester. By including the cured product of the thermosetting acrylic resin or the thermosetting unsaturated polyester in the synthetic resin of the insulating layer 1b in this way, it is possible to prevent the surface roughness of the insulating layer 1b from increasing during the formation of the organic EL element. At the same time, the insulating layer 1b can be formed more easily.

The thermosetting acrylic resin is obtained by a polymerization reaction of an acrylic acid ester or a methacrylic acid ester. Examples of the raw material of the thermosetting acrylic resin include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate and the like. Be done. Further, as the thermosetting acrylic resin, various commercially available products can be preferably used, and examples thereof include a 4times level coat manufactured by Kuboko Paint Co., Ltd.

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 for the heat-curable unsaturated polyester include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. .. Examples of polyhydric alcohols used as a raw material for the heat-curable 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. Be done. Further, as the thermosetting unsaturated polyester, various commercially available products can be suitably used, for example, Byron (registered trademark) 23CS, Byron (registered trademark) 29CS, Byron (registered trademark) 29XS, Byron (registered trademark). Examples thereof include 20SS (trademark) and 29SS (registered trademark) 29SS (all manufactured by Toyobo Co., Ltd.).

The lower limit of the content of the synthetic resin in the insulating layer 1b is preferably 50.0% by mass, 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, more preferably 56.3% by mass. By setting the content of such a synthetic resin, an insulating layer 1b suitable for the substrate 1 can be formed. The content of the synthetic resin refers to the ratio of the content of the synthetic resin to the total mass of the solid content (synthetic resin, thermosetting agent, pigment, etc.) in the insulating layer 1b. The same applies to the content of the thermosetting agent and the like described later.

The insulating layer 1b is preferably cured by containing a thermosetting agent. That is, it is preferable that the insulating layer 1b contains a synthetic resin cured by using a thermosetting agent. The insulating layer 1b is considered to be insoluble in an organic solvent, but the solvent used during molding may infiltrate into the layer and cause deterioration such as swelling. In order to suppress this, it is effective to increase the degree of curing (crosslinking density) of the insulating layer 1b by containing a predetermined amount of the thermosetting agent. In addition, since the degree of curing can be easily controlled by the heat curing agent, the area of the peak having a wave number of 910 cm ^-1 with respect to the peak having a wave number of 1730 cm ^-1 in the absorption spectrum obtained by measuring with a Fourier transform infrared absorption spectrophotometer described later. Easy to control the ratio.

The thermosetting agent is not particularly limited, but a thermosetting agent having good compatibility with the thermosetting resin, being able to crosslink the thermosetting resin, and having good liquid stability is preferable.

The lower limit of the content of the thermosetting agent in the insulating layer 1b before curing is preferably 10.0% by mass, more preferably 20.0% by mass. On the other hand, the upper limit of the content of the thermosetting agent is preferably 50.0% by mass. By setting the content of such a thermosetting agent, the insulating layer 1b can be easily and surely formed.

The lower limit of the mass ratio of the heat curing 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. If the mass ratio is less than the lower limit, the effect of the thermosetting agent may not be sufficiently obtained. On the contrary, when the mass ratio exceeds the upper limit, curing may occur rapidly and cracks or cracks may occur in the insulating layer 1b, or the thermosetting agent may be excessive and the manufacturing cost may increase.

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 during curing, the surface shape may be greatly undulated or uneven may be formed due to the influence of the solvent volatile gas component. Therefore, by incorporating the pigment in the insulating layer 1b, it is possible to suppress the shrinkage of the synthetic resin and promote the desorption of the solvent gas, so that the surface shape can be flattened. On the other hand, the inclusion of the pigment may increase the surface roughness and form many protrusions on the surface. In order to suppress the formation of these protrusions, it is advisable to adjust the type, particle size and content of the pigment to be added.

Examples of the pigment include organic pigments and inorganic pigments. 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. When the average particle size of the pigment is less than the above lower limit, or when the content of the pigment is less than the above lower limit, the effect of flattening the surface of the insulating layer 1b by adding the pigment may be insufficient. On the contrary, 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 increase due to the inclusion of the pigment.

As the pigment, a commercially available product may be used as long as the above-mentioned preferable average particle size is satisfied. For example, JR-806 (average particle size 250 nm) manufactured by Teika Co., Ltd. and Typake (registered trademark) manufactured by Ishihara Sangyo Co., Ltd. Examples thereof include CR-50 (average particle size 250 nm) and R930 (average particle size 250 nm).

In addition, in order to suppress the 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.

As the lower limit of the average thickness of the insulating layer 1b, 5 μm is preferable, and 10 μm is more preferable. On the other hand, the upper limit of the average thickness of the insulating layer 1b is preferably 30 μm, more preferably 20 μm. If 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. On the contrary, 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 in accordance with JIS-K-7194 (1994).

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

Here, as shown in FIG. 4, the “peak area” is described as an example of a peak having a wave number of 1730 cm ^-1 in the absorption spectrum, and is an absorption spectrum obtained by measuring with a Fourier transform infrared absorption spectrophotometer. The area of the shaded area surrounded by the waveform forming the peak at the wave number of 1730 cm ^-1 and the baseline B.

Among the above-mentioned peaks, the peak having a wave number of 910 cm ^-1 is derived from the out-of-plane eccentric vibration of the olefin CH group without branching in the chemical structure of the synthetic resin, and the area of this peak is the constitution of the insulating layer 1b. 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 expansion and contraction vibration of the ester bond (double bond of C and O) and is invariant to the progress of the curing reaction. That is, the area of the peak at the wave number 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 it is, the more the curing is progressing.

The upper limit of the area ratio of the peak is 0.017, more preferably 0.010. On the other hand, as the lower limit of the area ratio of the peak, 0.003 is preferable, and 0.005 is more preferable. If the area ratio of the peak exceeds the upper limit, the synthetic resin is not sufficiently cured, so that deformation may occur during the formation of the organic electronic device 2 and the surface roughness of the insulating layer 1b may increase. On the contrary, when the area ratio of the peak is less than the above lower limit, the synthetic resin may be cured too much and the flexibility of the substrate 1 may be lowered, or the synthetic resin may be excessively shrunk and the insulating layer 1b may be cracked. It 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, an electronic paper element, and the like.

Examples of the organic EL element include those in which an anode, an organic light emitting layer, and a cathode are laminated in this order. In the organic EL element, other electron injection layers, electron transport layers, hole transport layers, and the like may be laminated in a timely manner. 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 a metal or indium zinc oxide (IZO) can be used. A naphthyl-substituted diamine derivative (α-NPD) can be used as the main component of the organic light emitting layer.

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

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

(Board preparation process)
In this step, the insulating layer 1b is laminated and the substrate 1 is formed by applying and heating the composition for forming the insulating layer on the organic electronic device laminated surface side of the metal layer 1a. The composition for forming an insulating layer is preferably liquid. That is, it is preferable that the composition for forming an insulating layer contains a solvent.

The solvent used in the insulating layer forming composition is not particularly limited as long as it can dissolve or disperse each component to be contained in the insulating layer forming composition. 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 and xylene. Aromatic hydrocarbons such as Solbesso® 100 (registered trademark) 100 (manufactured by Exxon Mobile), Solvesso® 150 (manufactured by Exxon Mobile); aliphatic hydrocarbons such as hexane, heptane, octane; ethyl acetate, acetate Examples thereof include esters such as butyl. The solid content of the insulating layer forming composition can be adjusted by using such a solvent.

The lower limit of the solid content concentration of the insulating layer forming composition is preferably 20% by mass, more preferably 40% by mass. On the other hand, the upper limit of the solid content concentration of the insulating layer forming composition is preferably 80% by mass, more preferably 70% by mass. If the solid content concentration is less than the above lower limit, that is, if the amount of solvent is too large, a large amount of solvent evaporates during heating, and as a result, convection due to the vaporized solvent is likely to occur near the surface of the metal layer 1a, and the insulating layer 1b The smoothness of the surface of the surface may be impaired. On the contrary, if the solid content concentration exceeds the above upper limit, it may be difficult to apply the composition for forming an insulating layer.

The method of applying and heating (drying and baking) the composition for forming an insulating layer is not particularly limited, and a known method can be appropriately adopted. 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. And the spray ringer method is preferred.

The lower limit of the heating temperature of the insulating layer forming composition 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 less than the above lower limit, the strength of the insulating layer 1b may be insufficient. On the contrary, when the heating temperature exceeds the above upper limit, the solvent may evaporate violently, and as a result, the smoothness of the surface of the insulating layer 1b may be impaired. The heating temperature refers to the ultimate plate temperature (Peek Metal Temperature: PMT).

The lower limit of the heating time of the insulating layer forming composition is preferably 3.0 minutes, more preferably 3.5 minutes, still 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, still more preferably 10 minutes. If the heating time of the insulating layer forming composition is less than the above lower limit, the synthetic resin tends to be insufficiently cured, deformation occurs during the formation of the organic electronic device 2, and the surface roughness of the insulating layer 1b increases. There is a risk. On the contrary, if the heating time of the composition for forming the insulating layer exceeds the above upper limit, the synthetic resin may be cured too much and the flexibility of the substrate 1 may be lowered, or the synthetic resin may be excessively shrunk to cause the insulating layer 1b. There is a risk of cracking. After the composition for forming an insulating layer is applied and heated, the substrate 1 once returned to room temperature may be heated again to promote 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 heating time of the insulating layer forming composition. Therefore, the heating temperature and heating time of the insulating layer forming composition are determined so that the peak area ratio is 0.017 or less.

As described above, the reaction layer 1c may be formed before the insulating layer forming composition is applied to the metal layer 1a. Further, the rust preventive layer 1d may be provided on the surface of the metal layer 1a.

Further, in order to improve the flatness, the organic electronic element laminated surface (the surface of the insulating layer 1b) of the substrate 1 may be polished. 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 laminating process)
In this step, the organic electronic element 2 is laminated on the organic electronic element laminated surface of the substrate 1. As the laminating method, a conventionally known method can be used.

<Advantage>
The organic electronic device and the substrate for the electronic device have a peak with a wave number of 910 cm ^-1 with respect to a peak with a wave number of 1730 cm ^-1 in the absorption spectrum obtained by measuring with a Fourier transform infrared absorption spectrophotometer of the insulating layer 1b of the substrate 1. Since the area ratio of the above is 0.017 or less, the ratio of the uncured carbon-carbon double bond contained in the synthetic resin which is the main component of the insulating layer 1b is low, and the insulating layer 1b is appropriately cured. Therefore, it is unlikely that a short circuit will occur due to an increase in the surface roughness of the insulating layer 1b during the formation of the organic EL element. Therefore, the organic electronic device using the substrate for the electronic device is excellent in manufacturing yield.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

(Example 1)
As the 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 per surface on both sides of the metal plate was prepared. A thermosetting acrylic resin paint (4times level coat manufactured by Kuboko Paint Co., Ltd., standard type / clear) is spray-coated on one surface of this metal plate so that the reached plate temperature (PMT) becomes 220 ° C. After heating for 2 minutes, an insulating layer having an average thickness of 15 μm was formed to obtain a substrate.

For post-curing, the substrate was further heated in the air 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 performing chemical mechanical polishing on the substrate. Specifically, the substrate was set in the holder to which the suction pad for mounting the substrate of the polishing apparatus was attached, and was set on the polishing pad attached to the surface plate of the polishing apparatus with the insulating layer facing down. Granular alumina (average particle size is about 100 nm) is used as an abrasive, the pressure is 65 g / cm ² , the rotation distance per circumference is 1 m, the rotation speed between the substrate and the surface plate 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.

In this way, the substrate for the 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 condition was set to 230 ° C. in the air for 3 minutes.

(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 condition was set to 220 ° C. in the air for 6 minutes.

(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>
For the substrates for organic electronic devices of Examples 1 to 3 and Comparative Example 1, the wave number of the absorption spectrum obtained by measuring with the Fourier transform infrared absorption spectrophotometer is 910 cm ^-1 with respect to the peak at the wave number of 1730 cm ^-1 . The area ratio of the peak was calculated.

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

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

<Evaluation>
An ITO film (average film thickness of 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.

For the film formation of the ITO film, HSM-542 manufactured by Shimadzu Corporation was used, and the utilization target was an ITO target. The gas introduced during 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 forming power was 150 W.

The surface of the substrate for an organic electronic device on which an ITO film was formed was observed with an optical microscope at a magnification of 10 times. 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 substrate for an organic electronic device of Comparative Example 1, wrinkles were observed on the surface as shown in FIG.

Further, the surfaces of the substrates for organic electronic devices 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. A photograph of the surface of the substrate for an organic electronic device of Example 3 and a photograph of the surface of the substrate for an organic electronic device of Comparative Example 1 observed by AFM are shown in FIGS. 7 and 8, 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 measuring with the Fourier transform infrared absorption spectrophotometer is 0.017 or less, the surface of the insulating layer is formed even after the ITO film is formed. The roughness is low. On the other hand, in Comparative Example 1, since the peak area ratio is 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 the device short circuit due to the increase in the surface roughness of the insulating layer during the 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 suitable for various applications because they are excellent in manufacturing yield by suppressing the occurrence of element short circuit when forming an organic EL element on the substrate. Can be used for.

1 Substrate 1a Metal layer 1b Insulation layer 1c Reaction layer 1d Anti-corrosion layer 2 Organic electronic device

Claims (8)

An organic electronic device including a substrate and an organic electronic element laminated on one surface of the substrate.
The substrate 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.
The area ratio of the peak at wave number 910 cm ^-1 to the peak at wave number 1730 cm ^-1 in the absorption spectrum obtained by measuring the insulating layer with a Fourier transform infrared absorption spectrophotometer is 0.003 or more and 0.017 or less. Electronic device. The organic electronic device according to claim 1, wherein the synthetic resin contains a cured product of a thermosetting acrylic resin or a thermosetting unsaturated polyester. The organic electronic device according to claim 1 or 2 , wherein the insulating layer contains a synthetic resin cured with a thermosetting agent. The organic electronic device according to claim 1 , claim 2 or claim 3 , wherein the insulating layer contains a pigment. The organic electronic device according to claim 4 , 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 5 , 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 6 , which is used for organic EL lighting or an organic solar cell. It 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.
The area ratio of the peak at wave number 910 cm ^-1 to the peak at wave number 1730 cm ^-1 in the absorption spectrum obtained by measuring the insulating layer with a Fourier transform infrared absorption spectrophotometer is 0.003 or more and 0.017 or less. Substrate for electronic devices.

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