JP4508219B2 - Organic electroluminescence display device and organic electroluminescence display element sealing method - Google Patents

Description

  The present invention relates to a sealing method in which an electronic device such as an organic electroluminescence (EL) display element is hermetically sealed and sealed from moisture contained in the outside air so as to have a long life. The present invention relates to an electroluminescence (EL) display device or an electronic device.

  Conventionally, glass has been used as a substrate for display devices such as liquid crystal display devices and organic electroluminescence display devices, or as a substrate for electronic devices such as CCD and CMOS sensors due to its high thermal stability and transparency. I came.

  In recent years, with the widespread use of portable information terminal devices such as mobile phones, display devices and electro-optical devices that can also be received by these terminal devices are easy to break and are more flexible and hard to break than glass. Adoption is being considered.

  However, plastic substrates that are normally produced contain moisture inside. For example, when this is used in an organic electroluminescence display device, the moisture gradually diffuses into the display device, and the influence of the diffused moisture is present. As a result, the durability of the display device or the like is lowered. For example, there is a problem that a dark spot which is a non-light emitting region is generated in the light emitting region.

  However, since the plastic substrate has moisture permeability, a metal oxide film such as silica having low moisture permeability is directly formed on the plastic substrate by vapor deposition. For example, in WO0036665, a monomer containing acrylate is used. By vapor deposition, polymerization, vapor deposition of silica, further vapor deposition of a monomer containing acrylate and polymerization to form a sealing film, or a method of forming a film having a lower moisture permeability on the resin substrate, Various attempts have been made to reduce the moisture permeability of the resin substrate.

  In general, display elements and electronic devices are formed on these substrates, and in order to seal them from the outside air, the display elements and electronic devices are formed on these substrates, and then the moisture permeability of the water is reduced. A method is generally used in which the surroundings are further closed and the periphery is closed with a sealing material having low moisture permeability to form a sealed container.

  However, the low moisture-permeable film formed on the resin substrate can block the entry of moisture from the substrate plane side, but water from the cross-sectional side of the plastic substrate cut according to the size of the device. As permeation cannot be prevented, for example, the above-mentioned failure due to moisture permeation occurs particularly in the region near the outer periphery of the display element, and the polymer film or inorganic film is easily peeled off during handling from the cut surface. There is a problem in that it further allows the permeation of moisture from the portion, and further, how to completely seal is a problem.

  The present invention is to seal an organic electroluminescence display element and seal it from moisture contained in the outside air to obtain a long-life organic EL display device. Also, an organic EL display element or other electronic device is provided. The object is to obtain an excellent sealing method capable of sealing and suppressing the permeation of moisture into the sealed space.

  The above object of the present invention is achieved by the following means.

  1. In an organic electroluminescence display device comprising an organic electroluminescence display element and a sealed container that houses the organic electroluminescence display element and blocks outside air, the sealed container is provided on the upper surface and the lower surface of the organic electroluminescence display element, respectively. Two opposing resin substrates that are superimposed, and the organic electroluminescence that is provided between the two resin substrates and surrounds the outer periphery of the organic electroluminescence display element, and bonds the two resin substrates together It is formed of a sealing material for shielding the display element from the outside air, and the cut surfaces of the two resin substrates are cut so as to form a taper, and at least the cut surfaces of the two resin substrates are subjected to metal oxidation. At least one layer containing an oxide or nitride is formed. The organic electroluminescence display device characterized by comprising.

  2. 2. The organic electroluminescence according to 1 above, wherein at least one layer containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Display device.

  3. An organic electroluminescence display element, two opposing resin substrates respectively superimposed on the upper and lower surfaces of the organic electroluminescence display element, and an outer periphery of the organic electroluminescence display element between the opposing resin substrates In a sealed container that is provided to surround and seals the organic electroluminescence display element from the outside air that bonds the opposing resin substrates together, the cut surfaces of the two resin substrates are tapered. The organic electroluminescence display element is characterized in that at least one layer containing a metal oxide or nitride is formed on at least a cut surface of the two resin substrates. Stop method.

  4). 4. The organic electroluminescence display element according to 3 above, wherein at least one film containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Sealing method.

  5. At least one film containing the metal oxide or nitride and having a film thickness of 100 nm or more is formed by an atmospheric pressure plasma method using a reactive gas containing an organosilicon compound. 5. The method for sealing an organic electroluminescence display element according to 3 or 4 above.

  6). By exposing at least the resin substrate cut surface to a plasma flow generated by bringing a reactive gas containing an organosilicon compound into a plasma state by discharge between opposing electrodes under atmospheric pressure or pressure near atmospheric pressure 6. The method for sealing an organic electroluminescence display element according to 5 above, wherein at least one film containing a metal oxide or nitride is formed on at least a cut surface of the resin substrate.

  7). 7. The organic electroluminescence display element according to 6 above, wherein at least one layer containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Sealing method.

  8). The film containing the metal oxide or nitride has a film thickness of 100 nm or more, further contains a metal oxide or nitride on the outermost surface of the film, and the film thickness does not exceed 70 nm. The method for sealing an organic electroluminescence display element as described in 6 or 7 above, wherein a film having a carbon content of 0.2% or less is formed.

9. The method for sealing an organic electroluminescence display element according to any one of 5 to 8 above, wherein a high frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more are supplied and discharged. .

  An excellent method of sealing and sealing various electronic devices such as organic EL display elements and protecting them from the influence of moisture is obtained, and a long-life organic EL display device having excellent scratch resistance is obtained by this method. I was able to.

  As a result of various studies, we have been able to obtain a long-life display element by using a resin substrate having a moisture sealing film that has overcome the above-described problems with the above-described configuration, and a sealed container manufactured using the resin substrate.

  A resin substrate such as a polyethylene terephthalate film is used as a substrate for an electronic device such as the organic EL display element, and the resin film itself has sufficient moisture permeability to seal it from the outside and remove the influence of moisture. In order to seal water vapor by reducing the water permeability sufficiently without being at a low level, the resin film is sealed with a low water permeability, for example, having a certain thickness such as 100 nm or more, preferably 500 nm or more. It is necessary to combine the membranes. By sealing the organic EL display element or the like using a resin substrate having these sealing films, the moisture sealing performance is improved. In the present invention, an electronic device such as the organic EL display element is externally provided. In order to seal and remove the influence of moisture, the sealing film is not only applied to the surface of the resin substrate but also to the cut surface of the substrate that constitutes the formed sealed container. It is also found that forming the film has a higher sealing effect.

  Embodiments of the present invention will be described below with reference to the drawings.

  As described above, in order to block the display element and the electronic device from the outside air using the resin substrate having the sealing film, the display element and the electronic device are formed on the resin substrate having low moisture permeability, and then the moisture In general, a resin substrate with reduced moisture permeability is further overlapped and the periphery is closed with a sealing material having low moisture permeability to form a sealed container.

  FIG. 1 shows a sealing film containing, for example, vapor deposition of silica disclosed in, for example, WO0036665, and vapor deposition of a monomer containing acrylate, or metal oxide or nitride such as silica described later. A resin substrate such as polyethylene terephthalate (PET) is formed (resin constituting the substrate will be described later). In FIG. 1, S represents a resin substrate, and 11 represents the sealing film.

  In order to form a sealed container using a resin substrate having these sealing films, first, an organic EL display element that is intended to create a resin substrate having a sealing film formed on a resin film such as polyethylene terephthalate or the like The size is adjusted to the size of the electronic device, and this is used as a substrate, and the organic EL display element and the electronic device are formed on the substrate.

  In order to hermetically seal the organic EL display element, the electronic device, etc., after forming the element on such a substrate, these substrates are stacked as a substrate facing the upper part of the element, and further, moisture is surrounded around the element. It arrange | positions so that the sealing material with low permeability | transmittance may be surrounded, both the board | substrate with which the element was formed, and the board | substrate piled up on the upper part are bonded together, and an element | device is interrupted | blocked from external air.

  An example of the organic EL display device in which the organic EL display element having such a configuration is sealed in a sealed container is shown in FIG. Here, 1 is a substrate comprising a resin substrate S and the sealing film 11, 2 is a sealing material, and 3 is an organic EL display element. Here, the same substrates are used, but different substrates may be used as long as the substrates have low moisture permeability.

  FIG. 3 shows another example of an organic EL display device configured using substrates having sealing films (11 and 12 respectively) on both sides of the resin substrate S. The sealing films 11 and 12 may be different from each other or the same.

  Referring to FIG. 2, the organic EL display element 3 is sealed in a space cut off from the outside air by the two substrates 1 and the sealing material 2, and is sealed in the direction of arrow A, ie, organic Invasion of moisture or water vapor from a direction perpendicular to the substrate of the EL element or another substrate overlaid on the display element can be sufficiently suppressed by the presence of the sealing film. There is no sealing film against moisture permeation from the cut surface of the substrate indicated by B, that is, from a direction parallel to the substrate surface, which is quite defenseless. Although the area of the cross section is not so large, the display device in which the organic EL display element is sealed still has a relatively large water penetration from the cross section of the substrate constituting the hermetic container. It causes a failure such as a dark spot in an area close to the cross section. Even in the vicinity of the display device, this failure affects the image quality and is fatal in the display device.

  When the substrate 1 having the sealing films 11 and 12 on both sides of the resin substrate S as shown in FIG. 3 is used, the organic EL display element uses a material with low moisture permeability for the sealing material 2. As long as this sealing material and the respective sealing films 11 formed on the adhesive surfaces of the upper and lower substrates are completely sealed from the outside air and sealed.

  However, when moisture penetrates into the resin film from the cross section (cut surface) of the substrate 1 on which the metal oxide film, for example, used for the sealing film is not formed (also indicated by arrow B), the cross section There is a phenomenon in which a part of the near sealing film is broken by penetration of moisture from the inside of the resin film, thereby promoting cracking and peeling, although not as remarkable as in the case of FIG. Of course, the peripheral portion of the display device is more likely to deteriorate than the central portion. In addition, when the adhesion with the sealing material is uniform and not perfect, the life is further deteriorated. Therefore, in order to further improve the life of the organic EL display element, moisture permeation from the cross section of the substrate can also be prevented. is necessary.

  Therefore, the present invention uses such a composite substrate made of a resin substrate such as a plastic film and a sealing film, and seals an organic EL display element or the like (although it may be another electronic device) from the outside. It provides a method for complete sealing from influences.

  According to the present invention, a liquid crystal display element, an organic electroluminescence display element, or an electronic device such as a CCD or CMOS sensor is formed from a resin container, and a sealed container that is blocked from outside air is formed. A low film containing a metal oxide or nitride can be formed as a sealing film, and an internal display element can be shielded from external moisture.

  The present invention relates to an electronic device such as an organic EL display element, which is cut off from the outside by a sealed container formed using at least a resin substrate, and then a sealing material that forms a cut surface of the substrate constituting the sealed container and at least the substrate cutting By forming a film containing metal oxide or nitride with low water permeability on the surface (cross section) as a sealing film, deterioration of electronic devices such as organic EL display elements due to moisture is prevented and the life is improved. Or an organic EL display device formed by the method.

  Accordingly, as one aspect of the present invention, after forming a sealed container for sealing the display element or the like with a plastic substrate and a sealing material previously formed with a sealing film as shown in FIG. An embodiment in which a sealing film is formed on the cut surface is available.

  Further, as another aspect, without using a resin substrate on which a sealing film is formed from the beginning, for example, a resin substrate itself such as plastic, for example, polyethylene phthalate, and a sealing material (described later, for example, a thermosetting epoxy type resin) Organic EL display elements or other electronic devices are sealed in advance in a sealed container composed of a resin, an ultraviolet curable epoxy resin, or a room temperature curable epoxy resin using a reaction initiator. After that, a sealing film is formed on the entire outer surface of the hermetic container, such as a resin substrate surface, a cutting surface, and a sealing material for blocking the display element from the outside at the same time as bonding each resin substrate. The mode which forms after can be mention | raise | lifted.

  In addition, the present invention provides a sealing film having a low moisture permeability, particularly used for a cross section of a substrate (and a substrate) for constituting a sealed container that shields these display elements from moisture and seals them inside. It is to provide.

  As a material for the sealing film having low water permeability, a metal oxide or nitride is suitable for forming a relatively hard and dense film.

  A film containing a metal oxide or nitride may be formed by any method such as a method of applying a solution called a sol-gel method, vacuum deposition, sputtering, CVD method (chemical vapor deposition), etc. In order to form a film on the cut surface of the substrate, a vapor deposition method or a plasma treatment method is suitable. Particularly, a formation method by plasma treatment at or near atmospheric pressure, which will be described in detail later, is particularly suitable. By blowing a plasma flow using an organometallic compound as a reactive gas and causing a plasma state by discharge between opposing electrodes to at least the substrate cutting surface of the sealed container in which the display element is sealed, at least the cutting surface ( The method of forming the cross section) directs the surface on which the film is to be formed (surface treatment) in the direction of the plasma flow regardless of the shape or size of the formed display element, etc. Can form a film (surface treatment) at any site, can form a dense film that is characteristic of plasma discharge treatment, can select the reactive gas, and can control the physical properties of the film according to the plasma generation conditions. Etc. are preferable. Incidentally, the atmospheric pressure or the vicinity of the atmospheric pressure refers to a pressure close to the atmospheric pressure, and is a pressure of 20 kPa to 110 kPa, preferably a pressure of 93 kPa to 104 kPa.

  As a compound used as a reactive gas for forming a film containing the metal oxide or nitride of the present invention used in the atmospheric pressure plasma method as a sealing film, there is an organometallic compound.

  In the film containing the metal oxide or nitride in the present invention, the phrase “containing” means that the main component and 90% or more of the total constituent components are occupied by the metal oxide or nitride.

  Examples of the metal oxide or nitride include silicon oxide, titanium oxide, indium oxide, tin oxide, ITO (indium tin oxide), alumina, and other metal oxides, metal nitrides such as silicon nitride, silicon oxynitride, and titanium oxynitride. And metal oxynitrides.

Although silicon oxide has high transparency, it preferably contains nitrogen atoms because it has a slightly lower gas barrier property and allows water to pass through a little. In the case of silicon oxynitride or titanium oxynitride, it is expressed by the composition of SiO _x N _y and TiO _x N _y , and increasing the nitrogen ratio enhances the gas barrier property, but conversely reduces the light transmittance. Therefore, when the substrate needs to have light transparency, it is even more preferable in terms of light transmittance if x and y are values that satisfy the following expression.

0.4 ≦ x / (x + y) ≦ 0.8
For example, when x = 0, that is, SiN hardly transmits light. The ratio of oxygen atoms and nitrogen atoms can be measured in the same manner as the carbon content described later using XPS (ESCACAB-200R manufactured by VG Scientific).

  In the present invention, silicon oxide and tin oxide are particularly preferable as the main component of the film containing metal oxide or nitride because of its low moisture permeability.

  In addition, as the reactive gas for forming these metal oxides or nitrides, for example, an organometallic compound or a metal hydride compound can be used, and the compound can be any of gas, liquid, and solid at normal temperature and pressure. Although it may be in a state, in the case of gas, it can be introduced into the discharge space as it is, and in the case of liquid or solid, it is vaporized by means such as heating, decompression or ultrasonic irradiation. Moreover, you may dilute and use it with a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents as a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.

  In order to form a silicon oxide film as an organometallic compound, there is no generation of corrosive and noxious gases, and there is little contamination in the process. For example, it is represented by the following general formulas (1) to (5). Compounds are preferred.

In the formula, R ₂₁ to R ₂₆ represent a hydrogen atom or a monovalent group. n1 represents a natural number.

  Examples of the compound represented by the general formula (1) include hexamethyldisiloxane (HMDSO), tetramethyldisiloxane (TMDSO), 1,1,3,3,5,5-hexamethyltrisiloxane and the like. It is done.

In the formula, R ₃₁ and R ₃₂ represent a hydrogen atom or a monovalent group. n2 represents a natural number.

  Examples of the compound represented by the general formula (2) include hexamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and the like.

General formula (3)
(R ₄₁ ) _n Si (R ₄₂ ) _4-n
In the formula, R ₄₁ and R ₄₂ represent a hydrogen atom or a monovalent group. n represents an integer from 0 to 3.

  Examples of the organosilicon compound represented by the general formula (3) include tetraethoxysilane (TEOS), methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, and ethyltrisilane. Methoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, vinyl Examples include trimethoxysilane and vinyltriethoxysilane.

In the formula, A represents a single bond or a divalent group. R _{51 to} R ₅₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, an amino group, or a silyl group. R ₅₁ and R ₅₂ , R ₅₄ and R ₅₅ may be condensed to form a ring.

In the general formula (4), A is preferably a single bond or a divalent group having 1 to 3 carbon atoms. R ₅₄ and R ₅₅ may be condensed to form a ring, and examples of the ring formed include a pyrrole ring, a piperidine ring, a piperazine ring, and an imidazole ring. R _{51 to} R ₅₃ are preferably a hydrogen atom, a methyl group or an amino group.

  Examples of the compound represented by the general formula (4) include aminomethyltrimethylsilane, dimethyldimethylaminosilane, dimethylaminotrimethylsilane, allylaminotrimethylsilane, diethylaminodimethylsilane, 1-trimethylsilylpyrrole, 1-trimethylsilylpyrrolidine, isopropylamino. Methyltrimethylsilane, diethylaminotrimethylsilane, anilinotrimethylsilane, 2-piperidinoethyltrimethylsilane, 3-butylaminopropyltrimethylsilane, 3-piperidinopropyltrimethylsilane, bis (dimethylamino) methylsilane, 1-trimethylsilylimidazole Bis (ethylamino) dimethylsilane, bis (dimethylamino) dimethylsilane, bis (butylamino) dimethylsilane, 2-amino Tylaminomethyldimethylphenylsilane, 3- (4-methylpiperazinopropyl) trimethylsilane, dimethylphenylpiperazinomethylsilane, butyldimethyl-3-piperazinopropylsilane, dianilinodimethylsilane, bis (dimethylamino) And diphenylsilane.

  In the general formula (4), particularly preferred compounds are those represented by the general formula (5).

In the formula, R ₆₁ to R ₆₆ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aromatic heterocyclic group.

In the general formula (5), R ₆₁ to R ₆₆ are preferably a hydrocarbon group having 1 to 10 carbon atoms from the viewpoint of easiness of vaporization, more preferably at least two of R ₆₁ to R ₆₃ and R _64. At least two of R ₆₆ are methyl groups.

  Examples of the compound represented by the general formula (5) include 1,1,3,3-tetramethyldisilazane and 1,3-bis (chloromethyl) -1,1,3,3-tetramethyldisilazane. Hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, and the like.

  In addition, for example, dibutyltin diacetate can be used to form tin oxide.

  Further, a film containing at least one of an oxygen atom and a nitrogen atom and a metal atom such as silicon or tin can be obtained by combining oxygen gas or nitrogen gas with the organometallic compound at a predetermined ratio.

  Further, as described later, hydrogen gas or the like may be mixed in the mixed gas as described above in order to adjust the carbon content in the film.

  For these reactive gases, Group 18 atoms of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc., particularly helium and argon are preferably used. A film is formed by mixing and supplying a mixed gas to a plasma discharge generator (plasma generator). Although the ratio of the inert gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the inert gas being 90.0 to 99.9% with respect to the entire mixed gas.

  By using these organometallic compounds as reactive gases and controlling the plasma generation conditions, the flexibility of the film containing metal oxide or nitride can be controlled. That is, by controlling the plasma generation conditions to form a film, carbon atoms can be contained in the film containing metal oxide or nitride (the carbon content can be changed), The flexibility of the film varies depending on the content value.

  Compared with vacuum plasma method, sputtering method, etc., atmospheric pressure plasma method has high density of particles such as ions derived from reaction gas existing between electrodes. This is because carbon tends to remain. The carbon in the film is preferably contained in a slight amount because it gives the film flexibility and scratch resistance is improved, and specifically, it is preferably contained in an amount of 0.2 to 5% by mass. If the content exceeds 5% by mass, the physical properties such as the refractive index of the film may change over time, which is not preferable.

In order to set the carbon content in the film to 0.2 to 5% by mass, plasma discharge is caused by supplying a high frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more as described later. It is preferable that the high-frequency voltage has a continuous sine waveform.

  This carbon content depends mainly on the frequency of the power supply and the supply power, and decreases as the frequency of the high frequency of the voltage applied to the electrode increases and the supply power increases. Further, when hydrogen gas is injected into the mixed gas, carbon atoms are easily consumed, and the content in the film can be reduced, which can also be controlled.

  A film containing metal oxide or nitride having a film thickness of 100 nm or more, preferably 500 nm or more, which is formed in order to improve the sealing property of water vapor, causes cracks by forming a flexible film. Peeling is prevented by stress relaxation. Further, in the present invention, the cross-sectional shape reduces peeling and cracking from the cut surface of the substrate when it is bent due to roughness or the like when viewed from a microscopic viewpoint.

  Specific examples of the mixed gas for forming a film containing, for example, Si, O, N and C in a predetermined ratio as described above will be described below.

  A case where a silicon oxynitride (SiON) film having x / (x + y) of 0.80 or less and further containing 0.2 to 5% by mass of carbon is formed from a reaction gas of silazane and oxygen gas will be described. In this case, Si and N in the film are all derived from silazane.

  The oxygen gas is preferably 0.01 to 5% by volume of the mixed gas, more preferably 0.05 to 1% by volume. Further, from the reaction efficiency of oxygen and silazane, it is preferable to mix in a volume such that the molar ratio of oxygen gas to silazane is 1 to 4 times the composition ratio (molar ratio) of the desired film. In this way, the ratio of the oxygen gas to the entire mixed gas and the ratio to the silazane are set.

  Further, when the SiN film is formed from silazane without introducing oxygen gas, the vaporized silazane may be 0.2 to 1.5% by volume with respect to the entire mixed gas. If this is the case, carbon will remain in the film considerably, so that the hydrogen gas of 2% by volume or less of the mixed gas at the maximum can be mixed to reduce the carbon in the formed film.

  As the Si source, not only the organic silicon compound as described above but also an inorganic silicon compound may be used.

  In addition to oxygen gas, ozone, carbon dioxide, water (water vapor) or the like may be used as the oxygen source, and ammonia, nitrogen oxide or the like may be used as the nitrogen source in addition to silazane or nitrogen gas.

  In the present invention, the resin substrate that can be used to form a sealed container is preferably a flexible resin film having a thickness of 50 to 500 μm, and is not particularly limited. Polyesters such as terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetates such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, Polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyester Teruketon, polyimides, polyethersulfones, polysulfones, polyether ketones, polyamide, fluorine resin, nylon, polymethyl methacrylate, can be mentioned a film made of a resin such as an acrylic or polyarylates. In particular, cycloolefin resins such as Arton (trade name, manufactured by JSR Corporation) or Apel (trade name, manufactured by Mitsui Chemicals, Inc.) are also preferable.

  After forming the sealing film on these substrates using these resin substrates, or using these resin substrates as they are, a display device in which an organic EL display element or the like is sealed in a sealed container is first constructed. In any case, after sealing, in the above case, at least on the cut surface of the resin substrate constituting the sealed container in which the sealing film is not formed, and in the latter case, A film containing the metal oxide or nitride having a low water permeability is later applied to the resin substrate surface and the back surface of the resin substrate and the cut surface serving as a display portion, and the plasma at the atmospheric pressure to the vicinity of the atmospheric pressure. It is formed by a processing method. In particular, a mixed gas in which a reactive gas and an inert gas are mixed by a discharge under atmospheric pressure, which will be described later, is used as a discharge plasma, and this is used as a plasma flow to easily form a film ( It is preferable to use an apparatus capable of performing surface treatment.

  It is necessary to form a metal oxide or nitride-containing film having a certain thickness in order to reduce the water permeability, even on the resin substrate cross section or the resin base material surface, preferably 100 nm or more Further, it is necessary to form at least one layer of the material film having a thickness of 200 nm or more (preferably 1000 nm or less). In particular, since the resin film used as the resin substrate has a thickness of 50 μm to 500 μm, the area of the cross section (cut surface) of the substrate is compared with the thickness of the film (100 nm to 1000 nm) obtained by the plasma discharge treatment of the present invention. large.

  In the present invention, the carbon content in the film containing the metal oxide or nitride is not particularly selected. However, in order to provide flexibility, the carbon content with high flexibility is 0.2 to 5%. It is preferable to use a metal oxide or nitride film in the above range.

  On the other hand, the surface of the sealing film is preferably a relatively hard film from the viewpoint of improving scratch resistance, and the carbon content of the outermost surface is preferably 0.2% or less.

  Therefore, it is preferable to stack a hard film having a low carbon content on the surface of a metal oxide or nitride film having a carbon content in the range of 0.2 to 5%. Having a high hardness film on the surface makes it difficult for scratches and cracks to enter, and at the same time makes the surface film difficult to break due to stress relaxation of the soft film with a large film thickness formed adjacent to it. Is preferable. If the thickness of the film formed on the surface is too large, the film itself is low in flexibility and cracks easily occur, so a film thickness of 70 nm or less is preferable. Moreover, if it is at least 5 nm or more, the effect is small.

  FIG. 4 shows an example of a plasma film forming apparatus for performing discharge plasma processing used in the present invention. When a film is formed on a substrate 101 having a property that cannot be placed between electrodes, for example, a thick substrate 101, A reactive gas in a plasma state is jetted onto a substrate as a plasma wind to form a thin film.

  In the plasma film-forming apparatus 100 of FIG. 4, 35a is a dielectric, 35b is a metal base material, and 105 is a power supply. A mixed gas composed of an inert gas and a reactive gas is introduced into the slit-shaped discharge space of two electrodes (one electrode is grounded to the ground) in which a metal base material 35b is coated with a dielectric 35a, A high frequency voltage is applied from the power source 105 to discharge in the discharge space, the reactive gas is changed to a plasma state, and a plasma flow composed of the reactive gas in the plasma state is jetted onto the base material 101 to be applied to the surface of the base material 101. A film derived from a reactive gas is formed.

In order to obtain a high plasma density between the electrodes, it is preferable to supply a certain amount of power at a high frequency voltage. Specifically, it is preferable to apply a high frequency voltage of 100 kHz or more and 150 MHz or less, and even more preferably 200 kHz or more. The lower limit value of the power supplied between the electrodes is preferably 1 W / cm ² or more and 50 W / cm ² or less, and more preferably ² W / cm ² or more.

The voltage application area (cm ² ) in the electrode is the area where discharge occurs.

  The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave, but a sine wave is preferable because the film forming speed increases.

  Such an electrode is preferably one in which a dielectric is coated on a metal base material as described above. Either one of the electrodes is coated with a dielectric, and preferably both are coated with a dielectric. The dielectric is preferably an inorganic substance having a non-dielectric constant of 6 to 45.

  When the dielectric is placed on one of the electrodes, the shortest distance between the dielectric and the electrode, and as the distance between the solid dielectrics when the solid dielectric is placed on both of the electrodes, uniform discharge is performed in either case. From the viewpoint, 0.5 mm to 20 mm is preferable, and 1 mm ± 0.5 mm is particularly preferable. The distance between the electrodes is determined in consideration of the thickness of the dielectric around the electrodes and the magnitude of the applied voltage.

  In addition, the dielectric surface is polished and the electrode surface roughness Rmax (JIS B 0601) is set to 10 μm or less, so that the thickness of the dielectric and the gap between the electrodes can be kept constant, and the discharge state is stabilized. I can do it. Furthermore, the durability can be greatly improved by eliminating the distortion and cracking due to the difference in thermal shrinkage and residual stress of the dielectric and coating the non-porous high-precision inorganic dielectric.

  In addition, in manufacturing electrodes with a dielectric coating on a metal base material, as described above, it is necessary to polish the dielectric and to minimize the difference in thermal expansion between the metal base material of the electrode and the dielectric. Therefore, it is preferable to line the inorganic material on the surface of the base material by controlling the amount of bubbles mixed as a layer capable of absorbing stress. In particular, the material is preferably a glass obtained by a melting method known as cocoon, and the amount of bubbles mixed in the lowermost layer in contact with the conductive metal base material is 20-30% by volume, and the subsequent layers are 5% by volume. By setting it as the following, the favorable electrode which does not generate | occur | produce dense and a crack will be made.

  As another method for coating the base material of the electrode with a dielectric, ceramic spraying is performed precisely to a porosity of 10 vol% or less, and further, a sealing treatment is performed with an inorganic material that is cured by a sol-gel reaction. It is done. Here, in order to promote the sol-gel reaction, heat curing or UV curing is good. Further, when the sealing liquid is diluted, and coating and curing are repeated several times in succession, the mineralization is further improved and a dense electrode without deterioration. Can do.

  The electrode is composed of a combination in which a ceramic is thermally sprayed on a conductive base material 35b such as a metal and then a ceramic coating treatment dielectric 35a sealed with an inorganic material is coated. As the ceramic material used for thermal spraying, alumina, silicon nitride or the like is preferably used. Among these, alumina is more preferably used because it is easy to process.

  Or you may comprise from the combination which coat | covered the lining process dielectric material 35a which provided the inorganic material by lining to the electroconductive base materials 35b, such as a metal. As the lining material, silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, and vanadate glass are preferably used. Of these, borate glass is more preferred because it is easy to process.

  Examples of the conductive base material 35b such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  In the present embodiment, the electrode may have a cooling means using cooling water (not shown).

  Moreover, in order to suppress the bad influence by the high temperature at the time of discharge, the temperature of the base material to be surface-treated (film formation) is suppressed from room temperature (15 ° C. to 25 ° C.) to less than 200 ° C., more preferably from room temperature to 100 ° C. If necessary, it is cooled by an electrode cooling unit (not shown).

  The power source of the plasma film forming apparatus used for forming the film of the present invention such as the power source 105 of FIG. 4 is not particularly limited, but is an impulse high frequency power source (100 kHz used in continuous mode) manufactured by HEIDEN Laboratory, a high frequency power source manufactured by PEARL INDUSTRY CO., LTD. (200 kHz), high frequency power source (800 kHz) manufactured by Pearl Industry, high frequency power source (13.56 MHz) manufactured by JEOL, high frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be used.

  Using such a plasma film forming apparatus, a sealing film containing a metal oxide or nitride according to the present invention can be formed.

  Next, a preferred example in which the organic EL display element according to the present invention is sealed in a sealed container made of a resin substrate and a sealing material will be described below.

  FIG. 5 is a cross-sectional view and a top view illustrating an example of an organic EL display device in which an organic EL display element is sealed with a resin substrate and a sealing material. This organic EL display element is composed of a transparent substrate 1, an opposing substrate 4, and a sealing material 2 which is arranged so as to surround the periphery of the organic EL display element and which bonds the substrates together to block the organic EL display element from the outside air. Thus, a hermetic container for shielding the EL display element laminate from the outside air is constituted. The transparent substrate 1 and the substrate 4 are plastic sheets made of a resin such as polyester, polyacrylate, polycarbonate, polysulfone, or polyetherketone, and are not particularly coated with the sealing film. In the figure, the area of the substrate on which the organic EL layer is formed is increased, and a pattern such as a lead wire for establishing electrical connection between the electrode of the organic EL display element sealed inside and the outside is sealed on the substrate. It is formed out of the container.

  Referring briefly to the configuration of FIG. 5, the organic EL display element 3 formed on the substrate 1 first has a thin film made of a desired electrode material, for example, an anode material, on the substrate 1 of 1 μm or less, preferably An anode (anode) is formed by a method such as vapor deposition or sputtering so as to have a film thickness in the range of 10 nm to 200 nm. Further, although not shown here, a hole injection layer, a light emitting layer, A thin film made of a material such as an electron injection layer is formed, and a thin film such as a cathode (cathode) is laminated thereon by a method such as vapor deposition or sputtering (illustrated in detail in FIG. 5). Absent). In order to transmit light emission, it is sufficient that either one of the anode and the cathode is transparent or translucent.

A resin substrate such as a polyethylene terephthalate film is also stacked as the substrate 4 on the upper surface of the organic EL display element 3, in the drawing, on the cathode side. The substrate 4 and the transparent substrate 1 are bonded to each other via a substantially frame-shaped sealing material 2 provided on the periphery of the substrate by a coating method, a transfer method or the like so as to surround the periphery of the organic EL display element 3. Done in A substrate 4 having an area smaller than that of the substrate 1 is selected for connection to the outside by the lead wire or the like. The sealing material 2 is made of a thermosetting epoxy resin, an ultraviolet curable epoxy resin, a room temperature curable epoxy resin in which a reaction is started by microencapsulating and pressurizing a reaction initiator. In this case, an air escape opening or the like is provided at a predetermined location of the sealing material 2 (not shown) to complete the sealing. The air escape opening is either one of the above curable epoxy resins in a reduced pressure atmosphere (preferably with a degree of vacuum of 1.33 × 10 ⁻² MPa or less) in a vacuum apparatus, or in a nitrogen gas or inert gas atmosphere, or Sealed with an ultraviolet curable resin or the like.

  The epoxy resins in this case are bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, xylenol type, phenol novolac type, cresol novolac type, polyfunctional type, tetraphenylolmethane type, polyethylene glycol type, polypropylene A glycol type, hexanediol type, trimethylolpropane type, propylene oxide bisphenol A type, hydrogenated bisphenol A type, or a mixture thereof is mainly used. When the sealing material 2 is formed by a transfer method, a film is preferable.

The counter substrate 4 may be formed of glass, resin, ceramic, metal, metal compound, or a composite thereof. In a test in accordance with JIS Z-0208, the thickness is preferably 1 μm or more and the water vapor transmission rate is preferably 1 g / m ² · 1 atm · 24 hr (25 ° C.) or less. It is preferable to use a flexible resin substrate.

  In these organic EL display devices, in order to efficiently form a film containing the metal oxide or nitride on the cut surface of the substrate, the plasma state is applied to the cut surface using the device shown in FIG. A mixed gas (plasma wind) containing a reactive gas must be injected. In order to do this continuously, as shown in FIG. 5 (a), the mixed gas formed into plasma using the plasma film forming apparatus 100 shown in FIG. preferable. For example, using a plasma generator having an electrode width (width in the depth direction in the figure) larger than the width of the organic EL display device on which a film containing metal oxide or nitride is to be formed, the electrode or processing is to be performed. The organic EL display device is moved relative to the plasma film forming device (for example, the organic EL device is moved in the direction of the arrow by a conveying means such as a belt). Surface processing (film formation) can be simultaneously performed on the cut surface. Further, if necessary, the display device to be further processed is rotated 90 degrees (or 45 degrees if necessary) to rotate the display device, and the first time it is on the side of the belt. A film containing a metal oxide or nitride can be simultaneously formed on each substrate cross-section and on the substrate surface by carrying the cross-section once again at a position in the direction of travel and further performing a film forming process. it can. FIG. 5B shows an organic EL display device in which a film is formed on the substrate surface and the cut surface.

  Although not shown, these organic EL display devices have a structure in which a part of the formed transparent electrode and aluminum cathode can be taken out as a terminal outside the sealing material, and the substrate cross section and other surfaces of the substrate. When the terminal is covered by forming a film on the substrate 1, the outer side of the sealing material (on the substrate 1 as shown in FIGS. 5A and 5B) Therefore, for the terminals and lead wires drawn out to the outside of the formed sealed container), after forming the sealing film, using a mask, a resist is formed, and the lead wires or terminal portions that are connected to the outside, It is necessary to expose the lead wire or the terminal portion except the film containing metal oxide or nitride by plasma etching or etching by a conventional method such as RIE.

  Further, as a resist suitable for these purposes, there is, for example, a negative type or a positive type photosensitive resin. A mask is overlaid thereon and irradiated with radiation to cause a necessary structural change in the resist material to form a resist pattern similar to a photomask.

  After the resist pattern is formed, plasma etching using a halogenated hydrocarbon, reactive ion etching (RIE), or the like is used to remove a film containing a metal oxide such as silicon oxide or nitride by etching. .

  In addition, when the lead wire is completely drawn out from the substrate in the form of a lead wire, there is no need to expose the surface of the substrate or the pattern of the lead wire or the terminal. Can be formed.

  As described above, after the plasma treatment is performed on one surface of the substrate and the four cut surfaces of both substrates, or the surface of the substrate 1 on which the lead wires are formed, the plasma is again applied to the opposite side of the substrate. By performing the treatment, as shown in FIG. 5C, a film containing a metal oxide or nitride is completely formed on the entire surface of each display device. Next, the sealing film covering the lead wire is removed by plasma etching, the conductive pattern of the lead wire or terminal on the substrate 1 is exposed, and the organic EL display element is sealed in the sealed container. A device can be obtained.

  FIG. 6 shows an example of an apparatus in which two plasma film forming apparatuses 100 are arranged at angles of θ and θ ′ with respect to a direction perpendicular to the substrate surface of the organic EL display device to be processed. A method for efficiently performing plasma treatment on the cut surface of the substrate by using such an apparatus will be described. θ is preferably an angle of 5 to 60 degrees. According to this method, a film containing metal oxide or nitride can be formed on each surface more uniformly by plasma treatment than the above method.

  FIG. 7 shows an example of an apparatus that efficiently forms a film by plasma on the substrate cross section of the organic EL display device. When a composite resin substrate having a film containing a metal oxide or nitride as shown in FIG. 2 is used for both substrates 1 and 4, the processing on both substrate surfaces can be omitted, so that the substrate cross section Only a film containing metal oxide or nitride may be formed. In this case, (a) in FIG. 7 and a top view when viewed from above are shown in (b). Two plasma film forming apparatuses 100 are arranged on both sides of the belt, and the gap between the two electrode plates (plasma flow). Is arranged so as to be parallel to the belt so that the plasma flow is just injected onto the cut surface of the substrate along the gap (plasma flow is injected) between the two electrode plates of the apparatus. The organic EL display element can be enclosed by moving the belt, transporting the display device (in the direction indicated by arrow C), and forming a film on both cut surfaces.

  When a film containing a metal oxide or nitride is formed on the cross section of a sealed container formed using a resin substrate, the cut surface of the resin substrate is previously tapered (θ is 5). When the organic EL display element is sealed using a cut substrate and an organic EL display device is formed (FIG. 8), the plasma is efficiently ejected from above as shown in FIG. A film can be formed on the cut surface of the substrate. Of course, two plasma film forming apparatuses may be used as in FIG.

  The film containing the metal oxide or nitride according to the present invention needs to have a certain thickness in order to reduce the water permeability, and as described above, the water vapor transmission is reduced. Therefore, a metal oxide or nitride film having a thickness of 100 nm or more and a film thickness smaller than this, that is, a film not exceeding 70 nm, which is resistant to scratches, is relatively hard, that is, has a carbon content. It is preferable to form a film containing a metal oxide or nitride having a low thickness as the outermost surface layer. For a metal oxide or nitride film having a thickness of 100 nm or more, a film that is resistant to bending and has some flexibility, that is, a metal oxide or nitride that has a carbon content of 0.2 to 5%. A film containing a product is preferable. As a result, a sealing film that suppresses the occurrence of film peeling and cracks and has a low moisture permeability that hardly damages the surface can be obtained.

  Therefore, the formation of the film containing a metal oxide or nitride having low water permeability formed by the plasma treatment is preferably performed in at least two stages, each with different formation conditions.

  These films do not necessarily need to be one layer at a time. The surface layer may be a film that is relatively hard, that is, a film containing a metal oxide or nitride having a low carbon content. These layers may be arranged alternately.

  Therefore, when viewed from another viewpoint, the present invention is a resin substrate having a resin film as a base material and having a composite film laminate in which water permeability is suppressed, and an organic EL display device and various electronic devices. It can be suitably used as a substrate for use.

  That is, one embodiment of the present invention contains a metal oxide or nitride, has a carbon content of 0.2% or less, contains a film with a thickness not exceeding 70 nm, and a metal oxide or nitride. The moisture sealing film is characterized in that at least one film having a thickness of 100 nm or more is laminated.

  With the sealing method using the metal oxide-containing film having low moisture permeability according to the present invention, while maintaining the flexibility characteristic of the resin substrate, the moisture in the resin substrate and the external Therefore, moisture such as water vapor that permeates through the resin base material can be blocked, so that the sealed internal space can be kept at a low humidity, and the lifetime as an organic electroluminescence display element can be greatly increased.

  Next, an organic electroluminescence display element sealed with these sealing films according to the present invention will be described.

  In the present invention, an organic electroluminescence display element (also referred to as an organic EL display element) has a structure in which a light emitting layer is held between a pair of electrodes of an anode and a cathode. In the broad sense, the light emitting layer referred to in this specification refers to a layer that emits light when a current is passed through an electrode composed of a cathode and an anode. Specifically, it refers to a layer containing an organic compound that emits light when an electric current is passed through an electrode composed of a cathode and an anode. The organic EL display device according to the present invention may have a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer in addition to the light emitting layer as necessary, and is sandwiched between a cathode and an anode. Take the structured. Moreover, you may have a protective layer.

In particular,
(I) Anode / light emitting layer / cathode (ii) Anode / hole injection layer / light emitting layer / cathode (iii) Anode / light emitting layer / electron injection layer / cathode (iv) Anode / hole injection layer / light emitting layer / electron There are structures such as injection layer / cathode (v) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode.

  Furthermore, a cathode buffer layer (for example, lithium fluoride) may be inserted between the electron injection layer and the cathode. Further, an anode buffer layer (for example, copper phthalocyanine) may be inserted between the anode and the hole injection layer.

  The light emitting layer may be provided with a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, and the like on the light emitting layer itself. That is, (1) an injection function capable of injecting holes from an anode or a hole injection layer and applying electrons from a cathode or an electron injection layer when an electric field is applied, and (2) injection At least one of a transport function that moves electric charges (electrons and holes) by the force of an electric field, and (3) a light-emitting function that provides a field for recombination of electrons and holes inside the light-emitting layer and connects it to light emission. In this case, it is not necessary to provide at least one of a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer separately from the light emitting layer. . In addition, a function as a light emitting layer may be imparted by adding a compound that emits light to the hole injection layer, the electron injection layer, the hole transport layer, the electron transport layer, and the like. The light emitting layer may have a difference in the ease of hole injection and the ease of electron injection, and the transport function represented by the mobility of holes and electrons may be large or small. The one having a function of moving at least one of the charges is preferable.

  There is no restriction | limiting in particular about the kind of luminescent material used for this light emitting layer, A well-known thing can be used as a luminescent material in a conventional organic EL display element. Such a light-emitting material is mainly an organic compound, and may have a desired color tone, for example, Macromol. Symp. 125, pages 17 to 26, and the like.

  The light emitting material may have a hole injection function and an electron injection function in addition to the light emission performance, and most of the hole injection material and the electron injection material can be used as the light emitting material.

  The light emitting material may be a polymer material such as p-polyphenylene vinylene or polyfluorene, and further using a polymer material in which the light emitting material is introduced into a polymer chain or the light emitting material is a polymer main chain. Also good.

  Further, a dopant (guest material) may be used in combination with the light emitting layer, and an arbitrary one can be selected from known ones used as a dopant for an organic EL display element.

  Specific examples of the dopant include quinacridone, DCM, coumarin derivatives, rhodamine, rubrene, decacyclene, pyrazoline derivatives, squarylium derivatives, europium complexes and the like. In addition, iridium complexes (for example, those described in JP-A No. 2001-247859, or expressed by the formulas described in WO0070655, pages 16-18, for example, tris (2-phenylpyridine) iridium, etc.) Examples of the dopant include osmium complexes or platinum complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphyrin platinum complexes.

  In order to form a light emitting layer using the above-mentioned material, there is a method of forming a thin film by a known method such as a vapor deposition method, a spin coat method, a cast method, or an LB method. It is preferable. Here, the molecular deposition film refers to a thin film formed by deposition from the gas phase state of the compound or a film formed by solidification from the molten state or liquid phase state of the compound. Usually, this molecular deposited film can be distinguished from a thin film (molecular accumulated film) formed by the LB method, a difference in aggregation structure and higher order structure, and a functional difference resulting therefrom.

  Further, as described in JP-A-57-51781, this light-emitting layer is obtained by dissolving the light-emitting material in a solvent together with a binder such as a resin and then forming a thin film by spin coating or the like. Can be formed. There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, Usually, it is the range of 5 nm-5 micrometers.

  The hole injection material, which is a material of the hole injection layer, has either hole injection or electron barrier properties, and may be either organic or inorganic. Examples of the hole injection material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl; N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; Bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N′-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) biphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole and two condensations described in US Pat. No. 5,061,569 Having an aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (MTDATA) in which three triphenylamine units are linked in a starburst type. Can be mentioned.

  In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material. The hole injection layer can be formed by thinning the hole injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole injection layer, Usually, it is about 5 nm-5 micrometers. The hole injection layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

  The electron injecting layer only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material can be selected from conventionally known compounds. Examples of materials used in this electron injection layer (hereinafter referred to as electron injection materials) include heterocyclic tetracarboxylic anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene, carbodiimide, Examples include fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, and oxadiazole derivatives. In addition, a series of electron transfer compounds described in Japanese Patent Application Laid-Open No. 59-194393 is disclosed as a material for forming a light emitting layer in the publication. It was found that it can be used as a material. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material. In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as the electron injecting material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron injection material. Further, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as the electron injecting material, and similarly to the hole injecting layer, inorganic semiconductors such as n-type-Si and n-type-SiC are also used as the electron injecting material. be able to.

  This electron injection layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although the film thickness as an electron injection layer does not have a restriction | limiting in particular, Usually, it selects in 5 nm-5 micrometers. This electron injection layer may have a single layer structure composed of one or two or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

  Furthermore, a buffer layer (electrode interface layer) may be present between the anode and the light emitting layer or hole injection layer and between the cathode and the light emitting layer or electron injection layer.

  The buffer layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the light emission efficiency. “The organic EL element and the forefront of its industrialization (issued on November 30, 1998 by NTS Corporation) 2) Chapter 2 “Electrode Materials” (pages 123 to 166) in detail, and includes an anode buffer layer and a cathode buffer layer.

  The details of the anode buffer layer are also described in JP-A-9-45479, 9-260062, and 8-288069. Specific examples thereof include a phthalocyanine buffer layer represented by copper phthalocyanine, vanadium oxide. And an oxide buffer layer, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

  The details of the cathode buffer layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, a metal buffer layer represented by strontium, aluminum and the like, Examples thereof include an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, and an oxide buffer layer typified by aluminum oxide.

  The buffer layer is preferably a very thin film, and depending on the material, the film thickness is preferably in the range of 0.1 to 100 nm.

  Further, in addition to the basic constituent layer, a layer having other functions may be laminated as required. For example, JP-A-11-204258, JP-A-11-204359, and “Organic EL device and its industrialization front line ( It may have a functional layer such as a hole blocking layer described on page 237 of "November 30, 1998, NTS Corporation").

  The buffer layer may function as a light emitting layer when at least one of the compounds of the present invention is present in at least one of the cathode buffer layer and the anode buffer layer.

As the anode in the organic EL display element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO.

  The anode may be formed by forming a thin film by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method. As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 nm to 200 nm.

As the cathode of the organic EL display element, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this from the viewpoint of durability against electron injecting and oxidation, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Further, the sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In order to transmit light, if either the anode or the cathode of the organic EL display element is transparent or translucent, the light emission efficiency is improved, which is convenient.

  Preferred examples of organic EL display elements comprising an anode / hole injection layer / light emitting layer / electron injection layer / cathode according to the present invention sealed in a sealed container using a resin substrate such as a resin film Will be explained.

  FIG. 9 is a cross-sectional view showing an example of the organic EL display device of the present invention in which the organic EL display element 3 is formed on the substrate 1. The substrate 1 may be a sheet base material made of a resin such as polyester, polyacrylate, polycarbonate, polysulfone, polyether ketone, or a plurality of films containing metal oxide or nitride on the base material. The substrate according to the present invention shown in FIG. 1 as a film may be used.

First, a plurality of anodes (anodes) 301 are provided on the substrate 1 in parallel with each other. A thin film made of a desired electrode material, for example, a material for an anode is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in a range of 10 nm to 200 nm, and an anode (anode) 301 is manufactured. . As an anode in an organic EL display element, a metal, an alloy, an electrically conductive compound and a mixture thereof having a large work function (4 eV or more), such as a metal such as Au, CuI, indium tin oxide (ITO), indium zinc A conductive transparent material such as oxide (IZO), SnO ₂ , or ZnO is used.

  Next, the organic EL layer 302 is formed thereon. That is, although not shown here, an organic EL layer thin film made of each of the above materials such as a hole injection layer, a light emitting layer, and an electron injection layer is formed.

  Next, a cathode (cathode) 303 selected from the materials described above is formed on the organic EL layer 302 by forming a thin film by a method such as vapor deposition or sputtering. In addition, as described above, in order to transmit light emission, if either one of the anode or the cathode of the organic EL display element is transparent or translucent, the light emission efficiency is advantageously improved.

As described above, there are spin coating method, casting method, vapor deposition method and the like as a method for manufacturing each layer of the organic EL layer 302. However, vacuum is easy because a homogeneous film is easily obtained and pinholes are not easily generated. Vapor deposition is preferred. When a vacuum deposition method is employed for thinning, the deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally a boat heating temperature of 50 to 450 ° C., vacuum It is desirable to select appropriately within a range of a degree of 10 ⁻⁶ to 10 ⁻³ Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 5 nm to 5 μm.

  After forming these layers, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL display element can be obtained.

  The laminate of the organic EL display element 3 is preferably produced from the hole injection layer to the cathode consistently by a single evacuation, but the production order is reversed so that the cathode, the electron injection layer, and the light emission. It is also possible to produce a layer, a hole injection layer, and an anode in this order. In the case of applying a DC voltage to the organic EL display element thus obtained, light emission can be observed by applying a voltage of about 5 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

Further, a protective film may be provided on the entire surface of the organic EL display element 3 including the cathode (cathode) 303. For example, the inorganic protective layer is made from those dispersed SiO ₂ in CeO _2. The inorganic protective film 5 is formed by a sputtering method, an ion plating method, a vapor deposition method, or the like, and has a film thickness of 1 to 100,000, preferably 500 to 10,000. In this case, after forming the cathode (cathode) 303, the inorganic protective film can be continuously formed in vacuum without being returned to the atmosphere, or can be transported in a nitrogen gas or inert gas atmosphere. It can be formed in a vacuum again by being conveyed by a simple conveying system.

  On the upper surface of the cathode (cathode) 303, an opposing substrate 4 is overlaid, whereby the organic EL display element is cut off and sealed from the outside. Needless to say, a film containing a metal oxide or nitride having a low moisture permeability may be formed on the substrate 4 in advance.

The blocking / sealing from the outside is performed by connecting the counter substrate and the transparent substrate 1 to each other through a substantially frame-shaped sealing material 2 provided by a coating method, a transfer method, or the like around the surface of the substrate 4 facing the substrate 1. It is done by pasting together. The sealing material 2 is made of a thermosetting epoxy resin, an ultraviolet curable epoxy resin, a room temperature curable epoxy resin whose reaction starts by microencapsulating and pressurizing a reaction initiator. In this case, an air escape opening or the like is provided at a predetermined location of the sealing material 2 (not shown) to complete the sealing. The air escape opening is either one of the above curable epoxy resins in a reduced pressure atmosphere (preferably with a degree of vacuum of 1.33 × 10 ⁻² MPa or less) in a vacuum apparatus, or in a nitrogen gas or inert gas atmosphere, or Sealed with an ultraviolet curable resin or the like.

  The epoxy resins in this case are bisphenol A type, bisphenol F type, bisphenol AD type, bisphenol S type, xylenol type, phenol novolac type, cresol novolac type, polyfunctional type, tetraphenylolmethane type, polyethylene glycol type, polypropylene A glycol type, hexanediol type, trimethylolpropane type, propylene oxide bisphenol A type, hydrogenated bisphenol A type, or a mixture thereof is mainly used. When the sealing material is formed by a transfer method, a film is preferable.

About the board | substrate 4 which opposes, you may form with glass, resin, a ceramic, a metal, a metal compound, or these composites. In a test according to JIS Z-0208, the thickness is preferably 1 μm or more and the water vapor transmission rate is preferably 1 g / m ² · 1 atm · 24 hr (25 ° C.) or less, and may be selected from these substrates. However, it is preferable to have the sealing film, and it is preferable to use a flexible resin substrate.

  In addition, this sealing material needs to be a structure which can take out a part of transparent electrode and aluminum cathode as a terminal and a lead wire. In FIG. 9 as well, a seal is provided from an anode (anode) 301 provided on the substrate, and a cathode 303 comprising a thin film pattern of a cathode material formed on the anode and the organic EL layer 302. A terminal and a lead wire are formed and can be taken out from a sealed container sealed through the material through the sealing material, but this is omitted in FIG.

  In the present invention, a material that absorbs moisture or reacts with moisture (for example, barium oxide) may be formed in a layer on the substrate and enclosed in a sealed container.

  In the organic EL display device configured as described above, since the transparent substrate 1 and the counter substrate 4 are bonded to each other via the frame-shaped sealing material 2, the organic EL display element is completely sealed by these. By forming a container and forming a film containing the metal oxide and nitride on the container, an anode (anode) 301, a cathode (cathode) provided on the transparent substrate 1 by the counter substrate 4 and the sealing material 2 are formed. ) The organic EL display element including 303 and the like can be completely sealed from the outside, in particular, moisture penetration from the cut surface of the substrate can be suppressed, and the inside can be maintained in a low humidity state. The moisture resistance is further improved, and the generation and growth of dark spots can be further suppressed.

  In addition, the said structure which encloses the base material of this invention and the said organic EL display element is one aspect of this invention, and the structure containing the organic EL display element structure and the base material of this invention is not restricted to these. Absent.

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

Example 1
Each substrate shown below was produced. In the example shown below, when plasma discharge treatment is performed, the plasma film forming apparatus 100 shown in FIG. 4 is used, and for generation of plasma, a high frequency power source JRF-10000 manufactured by JEOL Ltd. is used as a power source. In addition, a stainless steel electrode base material was used, and ceramic (alumina) was sprayed thereon, and then an alumina coating treated dielectric material sealed with an inorganic material was used as an electrode. As the reactive gas, a gas having the following composition was used.

(Reactive gas for silicon oxide film formation)
Inert gas: argon 98.25% by volume
Reactive gas 1: 1.5% by volume of hydrogen gas
Reactive gas 2: Tetramethoxysilane vapor (bubbled with argon gas) 0.25% by volume
(Substrate A)
The plasma film-forming apparatus is used on one side of a 100 μm-thick PET film, the power source is a high-frequency power source JRF-10000 manufactured by JEOL Ltd., a frequency of 13.56 MHz, and a power of 20 W / cm ² . Was supplied to generate plasma. The generated plasma flow was sprayed onto the film surface, and a silicon oxide film 11a was formed to a thickness of 500 nm to obtain a substrate A.

(Substrate K)
On the substrate A, the plasma discharge device 100 is used, and a high frequency power supply JRF-10000 manufactured by JEOL Ltd. is used to supply a voltage of 13.56 MHz and a power of 40 W / cm ^2. Then, plasma was generated, the generated plasma flow was sprayed onto the film surface, and a silicon oxide film 11b was formed to a thickness of 70 nm to obtain a substrate K.

  In the substrate K, the high-frequency supply power applied at the time of forming the outermost surface layer was changed so that the carbon content was smaller than the adjacent silicon oxide layer (0.1%).

  The carbon content of the silicon oxide film on each of the substrates was measured using an XPS surface analyzer at the stage where the film was formed. The XPS surface analysis apparatus is not particularly limited, and any model can be used. In this example, ESCALAB-200R manufactured by VG Scientific, Inc. was used. Mg was used for the X-ray anode, and measurement was performed at an output of 600 W (acceleration voltage: 15 kV, emission current: 40 mA). The energy resolution was set to be 1.5 to 1.7 eV when defined by the half width of a clean Ag3d5 / 2 peak. Before performing the measurement, it is necessary to etch away a surface layer corresponding to a thickness of 10 to 20% of the thickness of the thin film in order to eliminate the influence of contamination. For the removal of the surface layer, it is preferable to use an ion gun that can use rare gas ions, and He, Ne, Ar, Xe, Kr, and the like can be used as ion species. In this measurement, the surface layer was removed using Ar ion etching.

  First, the range of the binding energy from 0 eV to 1100 eV was set at a data acquisition interval of 1.0 eV, and what elements were detected were determined. Next, with respect to all the detected elements except the etching ion species, the data capture interval was set to 0.2 eV, and a narrow scan was performed on the photoelectron peak giving the maximum intensity, and the spectrum of each element was scheduled. The obtained spectrum is transferred on COMMON DATA PROCESSING SYSTEM (Ver. 2.3 or later is preferable) manufactured by VAMAS-SCA-JAPAN in order to eliminate the difference in the content calculation result due to the difference in the measuring apparatus or the computer. After that, processing was performed with the same program, and the value of the carbon content was determined as the atomic concentration.

  Further, before performing the quantitative processing, the count scale was calibrated for each element, and a 5-point smoothing processing was performed. In the quantitative process, the peak area intensity (cps * eV) from which the background was removed was used. For the background treatment, the method by Shirley was used. For the Shirley method, see D.C. A. Shirley, Phys. Rev. , B5, 4709 (1972).

  Table 1 shows the results of the following scratch resistance test performed on the substrates A and K.

<Measurement of scratch resistance>
A probe with steel wool attached to a 1 × 1 cm surface was pressed against the thin film surface of each substrate by applying a load of 250 g and reciprocated 10 times, and then the number of scratches was measured.

  Compared to a substrate having only a silicon oxide film having a film thickness of 500 nm with a carbon content of 0.2% on the outermost surface, the substrate further formed with a silicon oxide film having a smaller carbon content on the outermost surface is scratch resistant. It turns out that it is excellent.

Example 2
Production of Organic EL Display Device An organic EL display device 1 having a sectional view shown in FIG. First, using the substrate K produced in Example 1 as the substrate 1, a mixture of indium oxide and zinc oxide (In In) as a sputtering target on the surface of the substrate K opposite to the surface having the silicon oxide films 11a and 11b. Using a sintered body having an atomic ratio In / (In + Zn) = 0.80), an IZO (Indium Zinc Oxide) film, which is a transparent conductive film, was formed by a DC magnetron sputtering method. That is, the inside of the vacuum apparatus of the sputtering apparatus is depressurized to 1 × 10 ⁻³ Pa or less, and a mixed gas of 1000: 2.8 in terms of volume ratio of argon gas and oxygen gas is 1 × 10 ⁻¹ Pa inside the vacuum apparatus. Then, an IZO film having a thickness of 250 nm was formed as a transparent conductive film by a DC magnetron method at a target applied voltage of 420 V and a substrate temperature of 60 ° C. After patterning the IZO film to form an anode (anode) 301, the transparent support substrate provided with the transparent conductive film is ultrasonically cleaned with i-propyl alcohol, dried with dry nitrogen gas, and UV ozone cleaned. Went for a minute.

The organic EL layer 302 is deposited on the transparent conductive film to be the anode 301 through a square perforated mask, the α-NPD layer (film thickness: 25 nm), and the ratio of the deposition rate of CBP and Ir (ppy). A 100: 6 co-deposited layer (film thickness 35 nm), a BC layer (film thickness 10 nm), an Alq ₃ layer (film thickness 40 nm), and a lithium fluoride layer (film thickness 0.5 nm) were sequentially stacked ( This is not shown in detail in FIG. Furthermore, a cathode (cathode) 303 made of aluminum having a thickness of 100 nm was formed through a mask on which another pattern was formed.

  The organic EL display element was sealed by stacking the substrate K as a substrate 4 on the laminate thus obtained so that the sealing films 11 a and 11 b were on the surface as a substrate 4.

  The substrates 1 and 4 are attached to the surface of the substrate 4 facing the substrate 1 by a substantially frame-shaped sealing material 2 provided so as to surround the periphery of the organic EL layer (by a coating method, a transfer method or the like). The organic EL display element 3 was sealed and sealed in the internal space. As the sealing material, a photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) was used. The organic EL display device 1 has a structure in which lead wires and terminals that are electrically connected to a part of the transparent electrode and the aluminum cathode are drawn on a substrate 1 outside the sealing material. In this way, an organic EL display device 1 was produced ((a) of FIG. 10).

  Next, by the method shown in FIG. 7 using two plasma film forming apparatuses (each apparatus is set to 45 degrees at θ in FIG. 7), each plasma film forming apparatus is the same as when each substrate A was produced. Plasma flow is formed under conditions, jetted, and the produced organic EL device 1 is conveyed by a belt, while the substrate 1 and the substrate 4 of the organic EL display device 1 have two cross sections on the side of the plasma film forming device, a sealing material A silicon oxide film was formed on the surface of the substrate and the outer surface of the sealing material of the substrate 1. Next, the installation position is changed by rotating the organic EL display device by 90 degrees with respect to the moving direction of the belt, and similarly on the unprocessed cut surface, the surface of the sealing material, the outer surface of the sealing material of the substrate 1, and the like. A silicon oxide film was further formed. The conveyance time was adjusted so that the formed silicon oxide film had a thickness of 500 nm.

  Next, using the same apparatus, plasma generation conditions are the same as those when the outermost silicon oxide film 11b of the substrate K is formed, and a silicon oxide film having a thickness of 70 nm is further formed on each cut surface, etc. Silicon oxide films 11a and 11b were formed on each of the upper and lower surfaces and all four side surfaces (cut surfaces) to produce an organic EL display device 2 (shown in FIG. 10B).

Note that an etching resist ER-235N (manufactured by Toyobo Co., Ltd.) is applied as a resist material to a region having a terminal and a lead wire pattern that conducts to the electrode outside the sealing material of the substrate 1 of the organic EL display device 1, and a transparent electrode and aluminum After exposing through the terminal and lead pattern mask which conducts to the electrode, and forming a resist in a portion other than the terminal and lead pattern by a conventional method, a material gas mainly composed of C ₄ F ₈ is also used. The terminals and the lead wire portions were exposed by plasma etching using the.

  These two organic EL display devices 1 and 2 were evaluated as follows.

<Evaluation item 1>
Immediately after the encapsulation, an enlarged photograph of 50 times the display part was taken. Under the conditions of 80 ° C. and 80% relative humidity, a 50-fold magnified photograph was taken after storage for 300 hours, and the area increase rate of the observed dark spots was evaluated.

<< Evaluation item 2 >>
Immediately after encapsulation, a 50x magnified photograph was taken. The bending test for bending the display element to 45 ° and returning it to the original was repeated 1000 times, and then the same storage test as in Evaluation Item 1 was performed to evaluate the increase rate of the dark spot area.

  The area increase rate was evaluated according to the following criteria for both evaluation items 1 and 2.

  These enlarged photographs were compared, and the rate of increase in the area of the dark spot after storage was evaluated for the organic EL display device 2 with the organic EL display device 1 being 100. The result was less than 10%. An organic EL display device 2 in which a silicon oxide film is formed on a cut surface around a sealed container formed by a resin substrate (substrate K) having a sealing film and a sealing material, and the periphery is completely covered with a silicon oxide film, It is clear that the area increase rate of the dark spot is small as compared with the organic EL display device 1 using the substrate K in which the silicon oxide films are formed only on the upper and lower substrate surfaces. In particular, the increase in dark spots was remarkable in the area around the display device. Further, when the bending test was repeated, the difference was further remarkable.

  In this embodiment, a material that adsorbs moisture or reacts with moisture (for example, barium oxide) is not enclosed in the display element, but this does not prevent the inclusion of these materials in the display element.

Example 3
Similar to the organic EL display device 1 of Example 2, except that a 100 μm thick polyethylene terephthalate film is used as the substrates 1 and 4 instead of the substrate K, and the four sides are sealed with two polyethylene terephthalate films and a sealing material. An organic EL display device similar to that shown in FIG. 5A in which the organic EL display element was sealed in a container was produced. Similarly, as shown in FIG. 6, two plasma film forming apparatuses 100 shown in FIG. 4 are used, a high frequency power supply JRF-10000 manufactured by JEOL Ltd. is used as a power source, and a mother is used as an electrode. The material is stainless steel, ceramic (alumina) is sprayed on this, and an electrode coated with an alumina-coated dielectric material sealed with an inorganic material is used. As the reactive gas, a gas having the following composition is used and a frequency of 13. A plasma is generated by supplying a power of 20 W / cm ² at a voltage of 56 MHz, and in the same manner, an oxidation with a film thickness of 500 nm is simultaneously formed on the substrate surface and the four cross-sections as shown in FIG. A tin film 11a was formed.

(Reactive gas for tin oxide film formation)
Inert gas: argon 98.25% by volume
Reactive gas 1: 1.5% by volume of hydrogen gas
Reactive gas 2: 0.25% by volume of dibutyltin diacetate (Bubbling argon gas into liquid heated to 60 ° C)
Further, in the same apparatus, the conditions of the plasma discharge apparatus are changed at the same time, and the same condition as when the second layer film is formed on the substrate K, that is, the frequency (13.56 MHz) and (40 W). / Cm ² ) was supplied to form a silicon oxide film 11b with a thickness of 70 nm (FIG. 11B).

Next, with the same apparatus, on the opposite substrate surface, the same 500 nm tin oxide film 11a and 70 nm silicon oxide film 11b as those formed on the above substrate and the four cut surfaces were respectively used under the same conditions as above. An organic EL display device 3 was produced which was continuously formed so that the surface of the sealed container was completely covered with a sealing film made of a tin oxide film and a silicon oxide film ((c) of FIG. 11).
When this organic EL display device 3 was evaluated in the same manner as described above, as with the organic EL display device 2, the area increase rate of the dark spot was small (5% or less), and it was dark even when the bending test was repeated. It was confirmed that there were few spots.

It is a figure which shows the resin substrate in which the sealing film was formed. It is a figure which shows an example of the organic electroluminescence display which sealed the organic electroluminescence display element in the airtight container. It is a figure which shows another example of the organic electroluminescence display which sealed the organic electroluminescence display element in the airtight container. It is a figure which shows an example of a plasma film forming apparatus. It is sectional drawing and an upper side figure which show an example of the organic electroluminescence display which sealed the organic electroluminescence display element. It is a figure which shows an example of the apparatus which has arrange | positioned two plasma film forming apparatuses. It is a figure which shows an example of the apparatus which performs film | membrane formation efficiently on the board | substrate cross section of an organic electroluminescence display. It is a figure which shows an example of the organic electroluminescence display which sealed the organic electroluminescence display element using the board | substrate cut | disconnected so that a cut surface might form a taper. It is sectional drawing which shows an example of an organic electroluminescent display apparatus. It is sectional drawing of the produced organic electroluminescent display apparatus. It is sectional drawing of the produced organic electroluminescent display apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,4 Board | substrate 2 Sealing material 3 Organic EL display element 301 Anode 302 Organic EL layer 303 Cathode 100 Plasma film-forming apparatus 101 Base material 105 Power supply 35a Dielectric 35b Metal base material S Resin substrate 11, 11a, 11b, 12 Sealing film

Claims (9)

In an organic electroluminescence display device comprising an organic electroluminescence display element and a sealed container that houses the organic electroluminescence display element and blocks outside air, the sealed container is provided on the upper surface and the lower surface of the organic electroluminescence display element, respectively. Two opposing resin substrates that are superimposed, and the organic electroluminescence that is provided between the two resin substrates and surrounds the outer periphery of the organic electroluminescence display element, and bonds the two resin substrates together It is formed of a sealing material for shielding the display element from the outside air, and the cut surfaces of the two resin substrates are cut so as to form a taper, and at least the cut surfaces of the two resin substrates are subjected to metal oxidation. At least one layer containing an oxide or nitride is formed. The organic electroluminescence display device characterized by comprising. The organic electro according to claim 1, wherein at least one layer containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Luminescence display device. An organic electroluminescence display element, two opposing resin substrates respectively superimposed on the upper and lower surfaces of the organic electroluminescence display element, and an outer periphery of the organic electroluminescence display element between the opposing resin substrates In a sealed container that is provided to surround and seals the organic electroluminescence display element from the outside air that bonds the opposing resin substrates together, the cut surfaces of the two resin substrates are tapered. The organic electroluminescence display element is characterized in that at least one layer containing a metal oxide or nitride is formed on at least a cut surface of the two resin substrates. Stop method. 4. The organic electroluminescence display element according to claim 3, wherein at least one layer containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Sealing method. At least one film containing the metal oxide or nitride and having a film thickness of 100 nm or more is formed by an atmospheric pressure plasma method using a reactive gas containing an organosilicon compound. The sealing method of the organic electroluminescent display element of Claim 3 or 4. By exposing at least the resin substrate cut surface to a plasma flow generated by bringing a reactive gas containing an organosilicon compound into a plasma state by discharge between opposing electrodes under atmospheric pressure or pressure near atmospheric pressure 6. The organic electroluminescence display element sealing method according to claim 5, wherein at least one film containing metal oxide or nitride is formed on at least a cut surface of the resin substrate. 7. The organic electroluminescence display according to claim 6, wherein at least one layer containing a metal oxide or nitride is formed on all of the resin substrate surface, the cut surface, and the outer peripheral surface of the sealing material of the sealed container. Device sealing method. The film containing the metal oxide or nitride has a film thickness of 100 nm or more, further contains a metal oxide or nitride on the outermost surface of the film, and the film thickness does not exceed 70 nm. The method of sealing an organic electroluminescence display element according to claim 6, wherein a film having a carbon content of 0.2% or less is formed. The method for sealing an organic electroluminescence display element according to any one of claims 5 to 8, wherein a high frequency voltage exceeding 100 kHz and a power of 1 W / cm ² or more are supplied and discharged.

Images