JP2010013735A - Method for producing resin film, and organic electroluminescence element using the resin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin film whose sealability of moisture is high, and to provide an organic electroluminescence element which has a long service life and high durability using the resin film produced by the method. <P>SOLUTION: The method for producing a resin film is characterized in that at least either side of a resin film is subjected to discharge plasma treatment under the atmospheric pressure or the pressure in the vicinity thereof, so as to form a metal oxide film or a film made of a metal nitride, and the surface of the metal oxide film or the film made of a metal nitride which has been formed is subjected to pressure discharge plasma treatment in the presence of a mixed gas made of an inert gas and a fluorinated hydrocarbon gas under the atmospheric pressure or under the pressure in the vicinity thereof, so as to form a film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a substrate for a display device or an electronic device having a high moisture sealing property, and to a long-life organic electroluminescence display device using the substrate.

  Conventionally, glass is used as a substrate for a display device such as a liquid crystal display device and an organic electroluminescence (EL) display device or as a substrate for an electronic device such as a CCD or a CMOS sensor because of its high thermal stability and transparency. Has been used.

  In recent years, with the widespread use of portable information terminal devices such as mobile phones, in display devices and electro-optical devices provided in these terminal devices, light plastic substrates and resins that are more flexible and harder to break than glass that is easy to break and heavy. Adoption of film is being studied.

  However, since plastic substrates, resin films, etc. are moisture permeable, they are difficult to apply to applications where the performance is degraded due to the presence of moisture, especially in the case of organic electroluminescence display devices. Therefore, there is a problem of sealing moisture.

  In order to solve this problem, in WO0036665, a monomer containing acrylate is vapor-deposited and polymerized, silica is vapor-deposited, and a monomer containing acrylate is vapor-deposited and polymerized to form a sealing layer. We are trying to obtain a highly moisture-sealing film by forming a composite film using silica with low moisture permeability along with acrylic monomers, but we have not disclosed any specific materials or experimental conditions. The results show that there is a problem that the polymer film and the inorganic film are easily peeled off during handling, and that moisture permeation is allowed from the peeled part, there is no peeling of the film, and the moisture permeability is low. Attempts to obtain materials that can be used as substrates for devices or electronic devices are not completely successful.

  Accordingly, an object of the present invention is to provide a method for producing a resin film having a high moisture sealing property, and to provide a long-life and highly durable organic electroluminescence device using the resin film produced by the method. is there.

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

  1. A metal oxide film or a metal nitride film is formed on at least one surface of the resin film by performing discharge plasma treatment under atmospheric pressure or a pressure in the vicinity thereof, and the formed metal oxide film or metal nitride is formed. Production of a resin film characterized in that a film is formed on a film made of a product by performing a discharge plasma treatment on a mixed gas comprising an inert gas and a fluorinated hydrocarbon gas at atmospheric pressure or in the vicinity thereof Method.

2. The fluorinated hydrocarbon gas is at least one gas selected from CH ₃ F gas, C ₂ H ₅ F gas, C ₄ H ₉ F gas, C ₅ H ₁₁ F gas, and C ₆ H ₁₃ F gas. 2. The method for producing a resin film as described in 1 above.

  3. 3. The method for producing a resin film according to 1 or 2, wherein the inert gas in the mixed gas is an inert gas having a pressure of 50% by pressure or more.

  4). 4. The method for producing a resin film according to any one of 1 to 3, wherein the metal oxide film or the metal nitride film is produced using an organosilicon compound as a raw material.

  5. 5. The method for producing a resin film according to any one of 1 to 4, wherein the metal oxide film or the metal nitride film is a silicon oxide film.

  6). The organic electroluminescent element which has a resin film manufactured by the manufacturing method of the resin film of any one of said 1-5.

  It was possible to obtain a substrate having a high moisture sealing property, no peeling of the film, cracking, etc., and a highly useful substrate as a substrate for a display device or an electronic device, and a long-life element using the substrate.

The schematic block diagram of a surface treatment apparatus. The schematic block diagram which shows one example of a plasma discharge processing chamber. The figure which shows an example of a roll electrode. The schematic perspective view of a fixed electrode. The schematic block diagram of the plasma discharge processing chamber which has arrange | positioned the square-shaped fixed electrode around the roll electrode. 1 is a schematic configuration diagram of a plasma film forming apparatus. The schematic block diagram of another plasma film-forming apparatus. Sectional drawing which shows an example of the EL display apparatus of this invention. Sectional drawing which shows another example of the organic electroluminescence display which sealed the organic electroluminescent element.

  The present invention will be described in detail below.

  In the present invention, at least one surface of the base film is subjected to discharge plasma treatment in the presence of a mixed gas comprising an inert gas and a hydrocarbon gas or a fluorinated hydrocarbon gas under atmospheric pressure or a pressure in the vicinity thereof. Thus, it is considered that the moisture resistance of the base film is improved by forming a thin layer in which hydrocarbon or fluorinated hydrocarbon molecules are bonded to the base surface by forming a thin layer on the surface of the base film.

  Unlike the vacuum plasma method, by using a plasma treatment method at or near atmospheric pressure, a dense hydrophobic film is formed on the surface of the base film, and the moisture permeability of the base film can be effectively reduced. Therefore, the board | substrate excellent in the sealing property of water when used as a board | substrate of electronic devices, such as an electronic display, an electro-optical element, a touch panel, a solar cell, is obtained.

  As a base film to be used, it is preferable to use a resin film or a base film having a film containing a metal oxide or nitride on the resin film, which will be described later.

  In the present invention, plasma discharge treatment is performed in an atmosphere in which 50% by pressure or more of an inert gas is argon (Ar) gas at or near atmospheric pressure. Other inert gases include neon (Ne) gas, helium (He) gas, krypton (Kr) gas, and xenon (Xe) gas. Various inert gases are also used at less than 50% by pressure of the inert gas. However, it is preferable to use argon gas as a main component and to set the argon gas to 60 pressure% or more in order to obtain an efficient modification effect on the surface of the base film.

  The treatment effect in plasma discharge treatment is that argon gas has a larger atomic weight than helium gas and is larger as a monoatomic gas, and etching occurs when argon is struck against the surface of a substrate such as a resin film during treatment. Argon gas has an effective effect as a treatment that causes irregularities on the surface and cannot be seen with helium gas. In addition, argon gas is less expensive than other inert gases, and a remarkable reforming effect can be obtained. Other inert gases, such as krypton gas and xenon gas, require high power and high frequency to generate plasma using them, and the surface treatment is too strong, causing damage to the base film. End up.

  Among the above gases, helium is preferable as the inert gas other than argon gas, and it is preferable that less than 40% by pressure of the inert gas other than argon gas be helium gas.

  The plasma discharge treatment of the present invention is characterized by using a hydrocarbon or a fluorinated hydrocarbon gas as a reactive gas together with the inert gas in order to make the substrate film surface hydrophobic. The pressure ratio of the reactive gas to the inert gas is preferably 0.01 to 0.30 pressure%, and preferably 0.02 to 0.2 pressure%. In the present invention, atmospheric pressure or near atmospheric pressure refers to a pressure close to atmospheric pressure, and is a pressure of 20 kPa to 110 kPa, preferably a pressure of 93 kPa to 104 kPa.

Examples of the reactive hydrocarbon gas used in the present invention include methane gas, ethane gas, propane gas, butane gas, pentane gas, hexane gas, and cyclohexane. Those having 4 or more carbon atoms can be processed in a gas state by increasing the processing temperature. Examples of the fluorinated hydrocarbon gas include CH ₃ F gas, C ₂ H ₅ F gas, C ₃ H ₇ F gas, C ₄ H ₉ F gas, C ₅ H ₁₁ F gas, and C ₆ H ₁₃ F gas. I can do it. Both are useful, but fluorinated hydrocarbon gas is particularly preferable. A mixture of hydrocarbon gas and fluorinated hydrocarbon gas may also be used.

  Next, a method of plasma discharge treatment of the base film in the present invention with a processing gas in which 50% by pressure or more of an inert gas containing a reactive gas hydrocarbon gas or a fluorinated hydrocarbon gas is used as an argon gas will be described. The treatment method of the present invention substantially conforms to JP-A-2000-72903.

  FIG. 1 is a schematic configuration diagram of a surface treatment apparatus, which shows an example of an apparatus for performing the treatment of the present invention, but is not limited thereto.

  Into the processing chamber 2 which is at atmospheric pressure or a pressure in the vicinity thereof, an inert gas in which 50% by pressure or more of the inert gas is an argon gas, and another reactive gas, an inert gas, or the like are mixed and the processing gas is mixed. By forming and introducing the mixed gas from the inlet and filling the processing chamber 2, the atmosphere between the pair of electrodes 6 and 7 is also made an atmosphere of the processing gas. Between the electrodes, the substrate film 5 being transferred (conveyed) is subjected to plasma discharge treatment. At this time, the surface treatment efficiency is prevented from being lowered by the air accompanying the substrate film 5. In order to prevent this, the surface treatment apparatus 1 includes a treatment chamber 2 for performing a surface treatment, a preliminary chamber 3a adjacent to the treatment chamber 2 on the upstream side of the support 5 in the transport direction, and as necessary. A preliminary chamber 3 b adjacent to the processing chamber 2 is provided downstream of the support 5 in the transport direction. By introducing at least one component of the processing gas into the preliminary chamber 3a or 3b adjacent to the processing chamber from a means such as a gas inlet (not shown), the preliminary chamber 3a is filled with the introduced gas. It is possible to block the air brought in with the support 5 that is conveyed to 2. The gas introduced into the preliminary chamber 3a preferably has the same composition as that of the processing gas, so that plasma discharge processing can be obtained more stably. The gas may be introduced by a method in which the gas flows out from the processing chamber through the gap. Of the spare chambers 3a or 3b, the upstream spare chamber 3a is more effective for the purpose of blocking the accompanying air. Therefore, the downstream spare chamber 3b may be provided as necessary. Partitioning means (such as nip rolls) 9 are provided between the spare chambers 3a and 3b and the outdoor and processing chambers 2, respectively. The substrate film 5 is continuously conveyed through the gap between the pair of electrodes 6 and 7 in the processing chamber 2 by the partitioning means 9 and a conveying means (not shown). The pair of electrodes 6 and 7 are flat electrodes, and conductive members (for example, stainless steel, aluminum, copper, etc.) of electrode members 6A and 7A and a dielectric (for example, a part of the electrode members 6A and 7A) (Rubber, glass, ceramic, etc.) 6B and 7B (the coating may be all or part of it). In FIG. 1, flat electrodes are used like the pair of electrodes 6 and 7, but one or both electrodes may be cylindrical electrodes or one may be a roll electrode. Of the pair of electrodes 6 and 7, one electrode 6 is connected to a high-frequency power source E, and the other electrode 7 is grounded to a ground G so as to cause a discharge between the pair of electrodes 6 and 7. It is configured. In addition, 8 is a guide roll which conveys a base film to the surface treatment apparatus 1 or from the surface treatment apparatus 1.

  In the present invention, prior to introducing the processing gas into the processing chamber 2, it is preferable to use a processing gas in which an inert gas and a reactive gas are mixed in advance, but even if each gas is independently introduced, It is only necessary that the atmosphere between the pair of electrodes 6 and 7 in the processing chamber 2 is a component of the processing gas described above.

  The discharge state of the plasma discharge treatment of the present invention is a discharge state similar to glow discharge that occurs in a vacuum, but the surface treatment of the present invention is performed by blocking the air accompanied by the base film. In short, the discharge state of the plasma discharge process is more suitable at or near atmospheric pressure.

The discharge intensity of the plasma discharge treatment of the present invention is preferably 50 W · min / m ² or more and less than 500 W · min / m ^{2 in order} to perform stable and effective treatment without causing arc discharge. By performing the plasma discharge treatment in this range, it is possible to achieve uniformity of treatment, finish without damage, and to obtain excellent adhesiveness.

  In addition, by performing the plasma discharge treatment of the present invention in a pulsed electric field, the hydrophobic treatment can be more effectively performed, and the plasma discharge treatment in the pulsed electric field is a preferable method. .

  If plasma discharge treatment is performed with the substrate film to be treated preheated, the treatment can be performed in a short time, and the substrate film is greatly damaged, such as yellowing, breaking, cracking, and laceration on the extreme surface. Can be reduced to The preheating temperature is preferably within a range of ± 35% of the glass transition temperature (absolute temperature) of the base film, for example, a resin film, and preferably ± 20%. By using the above method and the surface treatment apparatus, the air accompanying the substrate film being conveyed can be blocked, and the oxygen concentration in the treatment chamber can be extremely reduced. In order to effectively perform the surface treatment of the present invention on the substrate film surface, the oxygen concentration in the treatment chamber is preferably 1000 ppm or less, preferably 750 ppm or less, particularly 600 ppm or less, and more preferably 200 ppm or less. preferable.

  The resin film used as a base material for producing the substrate of the present invention is not particularly limited, and specific examples of the resin include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, and cellulose diacetate. , Cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose nitrates such as cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, Norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfones, Li ether ketone, polyamide, fluorine resin, nylon, polymethyl methacrylate, can be mentioned acrylic or polyarylates and the like.

  Among these, a particularly preferable base film is a polyester film support. Polyester films containing polyester as a main component are generally used as a support for silver halide photographic materials and other materials because they have higher mechanical strength than the above resin films and are excellent in dimensional stability. ing. As long as the polyester constituting the polyester film is within the range not impairing the effects of the present invention, other copolymer components may be copolymerized, and other polyesters or polymers other than polyesters may be mixed. Also good.

  The polyester film useful in the present invention is obtained by biaxially drawing a sheet obtained by melting polyester obtained by esterification and polycondensation of dicarboxylic acid and diol as constituent components.

  As one of the constituent dicarboxylic acids, terephthalic acid and 2,6-naphthalenedicarboxylic acid are used from the viewpoint of transparency, mechanical strength, dimensional stability, and the other constituent diol is the same as above. Of these, ethylene glycol and 1,4-cyclohexanedimethanol are preferred. Polyesters obtained by esterification and polycondensation by appropriately combining these dicarboxylic acids and diols are preferred. Among them, polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate, particularly polyethylene-2,6-naphthalate (hereinafter sometimes referred to as PEN), terephthalic acid and 2,6-naphthalenedicarboxylic acid and ethylene Polyethylene terephthalate / 2,6-naphthalate copolyester composed of glycol, copolyester obtained by transesterifying a mixture of PET and PEN having different molecular weights, copolyester of terephthalic acid, cyclohexanedimethanol and ethylene glycol, 2,6 -Copolyester of naphthalenedicarboxylic acid, cyclohexanedimethanol and ethylene glycol, diol of ethylene glycol and cyclohexanedimethanol, terephthalic acid and 2,6-naphthalenedicarboxylic Preferred mixed polyester of a dicarboxylic acid is. Among these, when 70% by mass or more of an ethylene terephthalate unit and / or an ethylene-2,6-naphthalate unit is contained with respect to all polyesters, a copolymer excellent in transparency, mechanical strength, dimensional stability, etc. A polyester film is preferably obtained.

  In the present invention, the resin film serving as the substrate has a glass transition point of 70 to 200 ° C., a light transmittance at 500 nm of 60% or more, a thickness of 50 μm or more, particularly 60 to 200 μm, and a Young's modulus of 1.5 GPa. The above is preferable.

  In the present invention, the discharge plasma treatment is performed directly on the surface of these resin films (base materials) in the presence of a mixed gas comprising an inert gas and a hydrocarbon gas or a fluorinated hydrocarbon gas under atmospheric pressure or a pressure in the vicinity thereof. By doing so, it is considered that hydrocarbon or fluorinated hydrocarbon molecules are chemically bonded to the surface, but a hydrophobic surface can be formed as compared with an untreated resin film.

  The degree of hydrophobicity on the surface of the resin film subjected to the plasma discharge treatment of the present invention can be determined by measurement based on the contact angle of methylene iodide and the contact angle of water. Measurement of the contact angle with methylene iodide can indicate the magnitude of the nonpolar component on the surface of the support, and the larger the contact angle, the larger the nonpolar component. Moreover, the contact angle by water can show the magnitude | size of the hydrogen bond component of a support surface, and if a contact angle is large, it will show that a hydrogen bond component falls. Incidentally, the polar component can be known by measuring the contact angle with nitromethane. For example, in the case of polyethylene terephthalate, the contact angle of methylene iodide as a nonpolar component is usually less than 20 °, and the contact angle of water as a hydrogen bond component is 60 to 65 °. According to the treatment of the present invention, the contact angles of methylene iodide and water should be larger than those of untreated, preferably the contact angle of methylene iodide is 20 ° or more, more preferably 30 ° or more. . The contact angle of water is preferably 65 ° or more, more preferably 70 ° or more.

  Furthermore, the nonpolar component and the hydrogen bonding component on the surface are expressed by the Young-Fowbes equation shown below.

here,
γd: nonpolar component of support surface energy γh: hydrogen bond component of support surface energy γ1: surface energy of methylene iodide, 51 mN / m (20 ° C.)
γ2: surface energy of water (H ₂ O), 72 mN / m (20 ° C.)
γd2: non-polar component of water surface energy γh2: hydrogen bond component of water surface energy θ1: contact angle between methylene iodide and support surface (measured value)
θ2: Contact angle between water and support surface (measured value)
It is.

  It is preferable to reduce both the non-polar component and the hydrogen bond component of the surface energy of the resin film by 2 mN / m or more by subjecting the surface energy of the support obtained by the above formula to a hydrophobic treatment.

  As another measure of the hydrophobizing treatment effect, it is preferable to reduce the spectral peak of the support surface by TOF-SIMS (flight-type secondary ion mass spectrum) by 20% or more by treatment. As another measure, it is preferable to measure the proportion of surface atoms by ESCA and increase the proportion of carbon atoms by 1% or more by surface treatment.

  As described above, the resin film having a surface that has been made hydrophobic by the plasma discharge treatment method of the present invention can block moisture that permeates through the film due to the hydrophobicity of the surface, so that it can be used for display devices such as organic electroluminescence display devices. This substrate is used as a substrate for an electronic device such as a CCD or CMOS sensor, and an organic electroluminescence display element or an electronic device such as a CCD or CMOS sensor is used together with a substrate with low moisture permeability. Sealing can increase the life and stability of low water resistance elements and devices such as display devices and electronic devices due to moisture and the like.

  In the present invention, instead of the resin film, the moisture permeability of the substrate is further reduced, and when used as a substrate for an organic electroluminescence display device or an electronic device, it is stable and has excellent moisture sealing properties. In order to obtain a substrate, instead of performing the surface treatment on the resin film itself, a composite film having a film containing a metal oxide or nitride having low moisture permeability on the resin film is used as a base film. It is preferable to perform a hydrophobizing treatment by surface treatment using the hydrocarbon or fluorinated hydrocarbon.

  In the present invention, the phrase “containing a metal oxide or nitride” means that the metal oxide or nitride is contained as a main component, that is, it is preferable that 90% or more of the total constituent components are occupied by the metal oxide or nitride.

  As the metal oxide or nitride contained in the film, metal oxide such as silicon oxide, titanium oxide, indium oxide, tin oxide, ITO (indium tin oxide), alumina, metal nitride such as silicon nitride, oxynitride Examples thereof include metal oxynitrides such as silicon and titanium oxynitride.

  The 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. Similar to the surface treatment, a method by plasma treatment at or near atmospheric pressure, that is, using an organometallic compound as a reactive gas, and exposing the substrate film to a reactive gas in a plasma state between opposing electrodes The atmospheric pressure plasma method in which a film is formed on a base film is preferable because a dense film can be formed, the reactive gas is selected, and the physical properties of the film can be controlled by plasma generation conditions.

  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. However, if the ratio of nitrogen is increased, the gas barrier property is enhanced. However, since the light transmittance is decreased, when the substrate requires light transmittance, for example, silicon oxynitride or titanium oxynitride is used. In this case, it is preferable that x and y are values satisfying the following formulas in terms of compositions of SiOxNy and TiOxNy, and used in a region where the light transmittance is not significantly lowered.

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).

  Therefore, by hydrophobizing the surface of these metal oxides or nitrides using the surface treatment method of the present invention. As in the case of application to the resin film, the moisture permeability of a highly transparent metal oxide or nitride film can be further reduced.

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

  In order to form a film containing these metal oxides or nitrides on a base film by an atmospheric pressure plasma method, an inert gas and a metal compound gas, such as an organometallic compound, under atmospheric pressure or a pressure in the vicinity thereof, The base film is treated with a reactive gas containing a metal hydride or the like.

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

  As the organometallic compound, there is no generation of corrosive and noxious gases in order to form the silicon oxide film, and there is little contamination in the process. For example, it is represented by the following general formulas (1) to (5). 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, more preferably at least two of R ₆₁ to R ₆₃ and R ₆₄ from the viewpoint of evaporability. 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.

  Furthermore, in order to adjust the carbon content in the film, hydrogen gas or the like may be mixed into the mixed gas as described above. For these reactive gases, the 18th group atom of the periodic table, specifically, Helium, neon, argon, krypton, xenon, radon, etc., especially helium and argon are preferably used, but an inert gas is mixed and supplied to the plasma discharge generator (plasma generator) as a mixed gas. Film formation is performed. 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.

  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, the carbon will remain in the film, so that hydrogen gas of 2% by volume or less of the mixed gas is mixed and the carbon is skipped.

  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, a metal oxide (for example, silica) or nitride film does not have a sufficient moisture sealing property unless it has a certain thickness. The film thickness is preferably 70 nm to 1500 nm, more preferably 100 nm to 1000 nm. Therefore, if it has a certain thickness, it may be formed on the base film by coating using a so-called sol-gel method, and this is effective in that a thick film can be formed at a time.

  However, it is preferable to form a thick film by the atmospheric pressure plasma method because the film is dense, and in the case of a slightly thick film, it may be produced by a method such as increasing the number of times of plasma treatment, time, etc. preferable.

  Various apparatuses can be used for a plasma film forming apparatus for forming a metal oxide (for example, silica) or nitride film on a base film, and the above-described processing apparatus may be used. An example of a preferable plasma film forming apparatus used for forming a metal oxide (for example, silica) or nitride film on a long base film is shown in FIGS. In the figure, reference numeral F denotes a long film as an example of a substrate for forming a metal oxide (for example, silica) or nitride film.

  These discharge plasma treatments are performed at or near atmospheric pressure. The vicinity of atmospheric pressure represents a pressure of 20 kPa to 110 kPa as described above, and more preferably 93 kPa to 104 kPa.

  FIG. 2 is a schematic configuration diagram showing an example of a plasma discharge processing chamber provided in the plasma film forming apparatus. In the plasma discharge treatment chamber 10 of FIG. 2, the base film F is conveyed while being wound around a roll electrode 25 that rotates in the conveying direction (clockwise in the figure). The plurality of fixed electrodes 26 fixed around the roll electrode 25 are each formed of a cylinder, and are installed facing the roll electrode 25.

  The discharge vessel 11 constituting the plasma discharge treatment chamber 10 is preferably a treatment vessel made of Pyrex (registered trademark) glass, but may be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

  The base film F wound around the roll electrode 25 is pressed by the nip rollers 15, 15, 16, transported to a discharge processing space regulated by the guide roller 24 and secured in the discharge vessel 11, and subjected to discharge plasma processing. Then, it is conveyed to the next process via the guide roller 27. In the present invention, since a film can be formed by discharge treatment under a pressure close to atmospheric pressure instead of a vacuum system, such a continuous process is possible, and high productivity can be increased.

  In addition, the partition plates 14 and 14 are disposed in the vicinity of the nip rollers 15, 15, and 16 to suppress the air accompanying the base film F from entering the discharge vessel 11. The entrained air is preferably suppressed to 1% by volume or less, more preferably 0.1% by volume or less, with respect to the total volume of the gas in the discharge vessel 11. This can be achieved by the nip rollers 15 and 16.

  The mixed gas used for the discharge plasma treatment is introduced into the discharge vessel 11 from the air supply port 12, and the treated gas is exhausted from the exhaust port 13.

  The roll electrode 25 is a ground electrode, and is discharged between a plurality of fixed electrodes 26 that are application electrodes. A reactive gas as described above is introduced between the electrodes to form a plasma state and is wound around the roll electrode 25. A film derived from a reactive gas is formed by exposing the rotated long base film to the reactive gas in the plasma state.

Between the electrodes, it is preferable to supply a certain amount of electric power at a high frequency voltage in order to obtain a high plasma density, increase the film forming speed, and control the carbon content within a predetermined ratio. Specifically, a high frequency voltage of 3 kHz to 13.56 MHz is preferably applied, more preferably 10 kHz or more, further preferably 50 kHz or more, and even more preferably 100 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 a metal base material coated with a dielectric. At least one of the fixed electrode 26 and the roll electrode 25 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.

  The shortest distance between the solid dielectric and the electrode when a solid dielectric is placed on one of the electrodes 25 and 26, and the distance between the solid dielectrics when a solid dielectric is placed on both of the electrodes are either case. From the viewpoint of performing uniform discharge, 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, when the substrate is placed between the electrodes or transported between the electrodes and exposed to plasma, not only is the roll electrode specification that allows the substrate to be transported in contact with one of the electrodes, but also the dielectric surface is polished. By finishing and making the surface roughness Rmax (JIS B 0601) of the electrode 10 μm or less, the thickness of the dielectric and the gap between the electrodes can be kept constant, and the discharge state can be stabilized. 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.

  FIG. 3A and FIG. 3B are diagrams showing an example of the roll electrode 25, and show the roll electrodes 25c and 25C.

  As shown in FIG. 3A, the roll electrode 25c, which is an earth electrode, is formed by applying a ceramic-coated dielectric 25b that has been subjected to sealing treatment with an inorganic material after thermal spraying ceramics on a conductive base material 25a such as metal. It is composed of a coated combination. A ceramic coating treated dielectric is coated with 1 mm, and the roll diameter is made to be 200φ after coating, and grounded to earth. 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 25B which provided the inorganic material by lining to 25 A of conductive base materials, such as a metal, like the roll electrode 25C shown in FIG.3 (b). 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 materials 25a and 25A such as metal include metals such as silver, platinum, stainless steel, aluminum, and iron. Stainless steel is preferable from the viewpoint of processing.

  In this embodiment, the base material of the roll electrode is a stainless steel jacket roll base material having a cooling means with cooling water (not shown).

  Further, the roll electrodes 25c and 25C (same for the roll electrode 25) are configured to be rotationally driven around the shaft portions 25d and 25D by a drive mechanism (not shown).

  FIG. 4A shows a schematic perspective view of the fixed electrode 26. Further, the fixed electrode is not limited to a cylindrical shape, but may be a prismatic type like the fixed electrode 36 of FIG. Compared to the cylindrical electrode 26, the prismatic electrode has an effect of extending the discharge range, and is therefore preferably used according to the properties of the film to be formed.

  Any of the fixed electrodes 26 and 36 has the same structure as the roll electrode 25c and the roll electrode 25C described above. That is, the surroundings of the hollow stainless steel pipes 26a and 36a are covered with the dielectrics 26b and 36b in the same manner as the roll electrodes 25 (25c and 25C), and cooling with cooling water can be performed during discharge. The dielectrics 26b and 36b may be either ceramic-coated dielectrics or lining dielectrics.

  The fixed electrodes are manufactured so as to have 12φ or 15φ after coating with the dielectric, and the number of the electrodes is set, for example, 14 along the circumference of the roll electrode.

  FIG. 5 shows a schematic configuration diagram of the plasma discharge processing chamber 30 in which the square fixed electrode 36 of FIG. 4B is disposed around the roll electrode 25. In FIG. 5, the same members as those in FIG.

  FIG. 6 shows a schematic configuration diagram of a plasma film forming apparatus 50 in which the plasma discharge processing chamber 30 of FIG. 5 is provided. In FIG. 6, in addition to the plasma discharge treatment chamber 30, a gas generator 51, a power source 41, an electrode cooling unit 55, and the like are arranged as an apparatus configuration. The electrode cooling unit 55 includes a tank 57 containing a coolant and a pump 56. As the coolant, an insulating material such as distilled water or oil is used.

  The gap between the electrodes in the plasma discharge processing chamber 30 of FIG. 6 is set to about 1 mm, for example.

  The roll electrode 25 and the fixed electrode 36 are disposed at predetermined positions in the plasma discharge treatment chamber 30, the flow rate of the mixed gas generated by the gas generator 51 is controlled, and the mixture gas is supplied from the air supply port 12. It is filled with a mixed gas used for plasma processing, and unnecessary portions are exhausted from an exhaust port.

  Next, a voltage is applied to the fixed electrode 36 by the power source 41, and the roll electrode 25 is grounded to the ground to generate discharge plasma. Here, the base material is supplied from the roll-shaped original winding base material FF through the rolls 54, 54, 54, and the electrodes in the plasma discharge treatment chamber 30 are brought into one-side contact with the roll electrode 25 through the guide roll 24. It is conveyed in the state. At this time, the surface of the substrate F is subjected to a discharge treatment by the discharge plasma, and then conveyed to the next step via the guide roll 27. Here, the surface of the base film F that is not in contact with the roll electrode 25 is discharged.

  Moreover, in order to suppress the bad influence by the high temperature at the time of discharge, the temperature of a base material is normal temperature (15 to 25 degreeC)-less than 200 degreeC, More preferably, electrode cooling is performed so that it may be suppressed within normal temperature to 100 degreeC. Cool by unit 55.

  FIG. 7 is a schematic configuration diagram of another plasma film forming apparatus that can be used in the film forming method of the present invention, such that the film cannot be placed between electrodes, for example, a film on a thick substrate. In the case of forming the thin film, a reactive gas that has been in a plasma state is sprayed onto the substrate to form a thin film.

  In the plasma film-forming apparatus 60 of FIG. 7, 35a is a dielectric, 35b is a metal base material, and 65 is a power supply. A mixed gas composed of an inert gas and a reactive gas is introduced from above into a slit-like discharge space in which a metal base material 35b is coated with a dielectric 35a, and a high frequency voltage is applied by a power source 65 to plasma the reactive gas. Then, a film is formed on the surface of the substrate 61 by injecting the reactive gas in the plasma state onto the substrate 61.

  The power source of the plasma film forming apparatus used for forming the film of the present invention, such as the power source 41 of FIG. 6 and the power source 65 of FIG. 7, is not particularly limited, but is an impulse high frequency power source (100 kHz used in continuous mode) manufactured by HEIDEN Laboratory. Pearl industrial high frequency power supply (200 kHz), Pearl industrial high frequency power supply (800 kHz), JEOL high frequency power supply (13.56 MHz), Pearl Industrial high frequency power supply (150 MHz), and the like can be used.

  Using such a plasma film forming apparatus, a film containing a metal oxide or nitride according to the present invention can be formed by an atmospheric pressure plasma method.

  One of the preferred substrates according to the present invention is that at least one surface on a resin film such as a polyethylene terephthalate film as a base film is an inert gas and a hydrocarbon gas or a fluorinated carbonization under atmospheric pressure or a pressure in the vicinity thereof. Although it is the board | substrate which hydrophobized by performing the discharge plasma process in presence of the mixed gas which consists of hydrogen gas, as a more preferable board | substrate, the film | membrane containing a metal oxide or nitride is sequentially from the resin film side. A substrate having at least one layer of a film having a thickness of 70 nm or more, preferably 1500 nm or less, wherein the film containing the metal oxide or nitride has been subjected to a hydrophobic treatment by the discharge plasma treatment. By having a film containing the metal oxide or nitride having a thickness of 70 nm or more, preferably 1500 nm or less, water permeability is further kept low, and water is sealed by making the surface hydrophobic. A good substrate with improved stopping properties.

  Since the substrate according to the present invention can seal moisture such as moisture in the resin film and permeate through the resin while maintaining the flexibility characteristic of the resin film as the base material, for example, An organic electroluminescence (EL) element itself can be formed on these substrates, and can also be formed as a flexible display device by sealing with a flexible material such as a film, preferably the same substrate, Moisture-sensitive organic electroluminescent elements can avoid the problem that their characteristics gradually deteriorate due to moisture contained in conventional sealing materials and substrates, etc., by keeping the sealed internal space at low humidity. The lifetime of the organic electroluminescence display element can be greatly increased.

  Further, as a preferred embodiment, a substrate in which a resin film having a metal oxide (for example, silica) film having a film thickness of 70 nm or more is used as a base film, and the surface of the metal oxide film is hydrophobized by the surface treatment method according to the present invention. The effect is even greater when using.

  In addition, a substrate in which one surface of a resin base material having a metal oxide film such as silica on both sides is hydrophobized by the surface treatment method according to the present invention is hydrophobized on one surface, and the substrate is co-operated with the metal oxide layer. On the other hand, a metal oxide film (eg, a silica film) on the opposite side of the resin base material is more preferable as a substrate because it acts as a hard coat layer and hardly scratches the surface.

  Next, the organic electroluminescence display element will be described.

  In the present invention, the organic electroluminescence (EL) 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 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 structure. 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 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.

  In addition, a dopant (guest material) may be used in combination with the light emitting layer, and an arbitrary one can be selected from known materials used as a dopant for an EL 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.

  Further, a buffer layer (electrode interface layer) may exist between the anode and the light emitting layer or the hole injection layer and between the cathode 4 and the light emitting layer or the 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 described in JP-A-9-45479, 9-260062, and 8-288069. Specific examples thereof include a phthalocyanine buffer layer represented by copper phthalocyanine, and 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 element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode substances include metals such as Au, and 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, or when the pattern accuracy is not so high (100 μm). 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 layer, 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 An aluminum / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, and the like are preferable. 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 element is transparent or translucent, the light emission efficiency is improved, which is convenient.

  Below, the suitable example which seals the organic EL element which consists of an anode / hole injection layer / light emitting layer / electron injection layer / cathode concerning this invention using the said board | substrate of this invention is demonstrated.

  FIG. 8 is a cross-sectional view showing an example of an EL display device of the present invention in which an organic EL element is sealed using a substrate according to the present invention. In this example, the EL element has a structure sealed with two transparent substrates 100 according to the present invention. The substrate 100 has a hydrophobic surface layer 102 formed on one surface of a plastic sheet substrate 101 made of a resin such as polyester, polyacrylate, polycarbonate, polysulfone, or polyetherketone by atmospheric pressure plasma discharge treatment. A substrate according to the invention.

A plurality of anodes (anodes) 103 are provided in parallel to each other on a hydrophobic surface layer 102 on the substrate 100. The anode 103 is formed by forming a thin film made of a desired electrode material, for example, an anode material, 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 10 nm to 200 nm. As an anode in an organic EL element, a metal, an alloy, an electrically conductive compound and a mixture thereof having a high work function (4 eV or more), such as a metal such as Au, CuI, indium tin oxide (ITO), indium zinc oxide A conductive transparent material such as (IZO), SnO ₂ , or ZnO is used.

  Next, the organic EL layer 104 is formed thereon. That is, although not shown here, a 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) 105 selected from the aforementioned materials is formed on the organic EL layer 104 by forming a thin film by a method such as vapor deposition or sputtering. As described above, in order to transmit light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the light emission efficiency is improved, which is convenient.

As described above, the organic EL layer 104 can be prepared by spin coating, casting, vapor deposition, etc., but it is easy to obtain a uniform film and it is difficult to generate pinholes. 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 element can be obtained.

  The organic EL device is preferably produced from the hole injection layer to the cathode consistently by a single vacuum, but the order of production is reversed, the cathode, the electron injection layer, the light emitting layer, and the hole injection. It is also possible to produce the layer and the anode in this order. In the case of applying a DC voltage to the organic EL device 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 layer 104 including the cathode 105. Inorganic protective layer, for example, is made from those dispersed SiO ₂ in CeO _2. The inorganic protective film 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) 105, the inorganic protective film can be formed continuously in a 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 organic EL layer 104 including the cathode 105, polyester, polyacrylate, polycarbonate, polysulfone, polyether having a hydrophobic surface layer 102 formed on one surface by atmospheric pressure plasma discharge treatment as an opposing substrate. Another plastic sheet base material 101 made of a resin such as ketone, that is, the substrate 100 of the present invention is overlaid (in this case, the surface treatment layer faces the outside) to seal the element.

Sealing is performed by bonding the two substrates to each other via a substantially frame-shaped sealing material 106 provided by a coating method, a transfer method, or the like on the periphery of the surfaces of the two substrates 100 facing each other. The sealing material 106 is made of a thermosetting epoxy resin, an ultraviolet curable epoxy resin, or a room temperature curable epoxy resin in which a reaction is initiated by pressurizing and encapsulating a reaction initiator. In this case, an air escape opening or the like is provided at a predetermined location of the sealing material 106 (not shown) to complete the sealing. The air escape opening is one of the above curable epoxy resins in a reduced pressure atmosphere (preferably 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.

  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 106 is formed by a transfer method, it is preferably a film.

About the board | substrate 100 used as an opposing board | substrate, you may form with glass, resin, a ceramic, a metal, a metal compound, or these composites etc., and the thickness is 1 micrometer in the test based on JISZ-0208. Although the water vapor transmission rate may be selected from a base material having a water vapor transmission rate of 1 g / m ² · 1 atm · 24 hr (25 ° C.) or less, the substrate of the present invention having the surface treatment layer is preferably low in water vapor transmission rate, and Flexible and preferable.

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

  In the organic EL element configured as described above, since the two substrates are bonded to each other via the frame-shaped sealing material 106, the anode 103 provided on the substrate 100 by the substrate 100 and the sealing material 106, The organic EL element composed of the organic EL layer 104, the cathode (cathode) 105 and the like can be sealed while maintaining a low humidity inside, and at the same time, moisture permeation through the substrate is suppressed, and the moisture resistance of the organic EL display device This can be further improved and the generation and growth of dark spots can be suppressed.

  FIG. 9 shows an organic EL device in which an organic EL element is sealed using a substrate in which one surface of a resin base material having a metal oxide film (for example, a silica film) is hydrophobized by the surface treatment method according to the present invention. It is sectional drawing which shows another example of a display apparatus. In FIG. 9, reference numeral 107 denotes a metal oxide layer formed by plasma treatment, and reference numeral 102 denotes a hydrophobic surface layer made of hydrocarbons formed on the surface of the metal oxide film. By subjecting the surface of the silica layer to plasma treatment using the hydrocarbon or fluorinated hydrocarbon of the present invention as a reactive gas, a highly transparent substrate with excellent water sealing properties can be obtained.

  In addition, the said structure by the base material of this invention and the said organic EL element is one aspect of this invention, and the structure containing the organic EL element structure and the board | substrate of this invention is not restricted to these.

  The present invention is specifically described in the following examples, but is not limited thereto.

Example 1
[Sample preparation]
<Base film surface treatment>
Under the following conditions, using the apparatus shown in FIG. 1, purging into the processing chamber for 10 minutes after starting the gas introduction, starting the processing by transporting the base film, and processing from 2 minutes after the transport is stabilized For the support, the following surface properties were measured. In addition, the processed base material film was wound up in roll shape with the winder.

<Conditions for implementation>
Processing chamber: Capacity 0.2m ³ , width 420mm
Base film: PET (polyethylene terephthalate) film having a width of 400 mm and a thickness of 100 μm Processing gas: The inert gas to be introduced is 100% argon gas, and the ratio of the inert gas to the reactive gas is represented by argon gas: reactive gas. = 100: 10, and methane gas, propane gas, and methyl fluoride gas are used as reactive gases.
Frequency: 10kHz
Gap between electrodes: 5mm
Substrate film conveyance speed: 150 m / min Processing time: 0.5 seconds Output: 22 kW / m ²
As for the oxygen concentration, a commercially available oxygen concentration measuring device (manufactured by Toray Industries, Inc .: LC800) was used and purged for 10 minutes after gas introduction under the above processing conditions. As a result of later measurement, it was 100 ppm. Those using methane gas, propane gas, and methyl fluoride gas as the reactive gas are respectively substrate sample Nos. 1, 2 and 3, and the untreated base film is substrate sample No. It was set to 4.

<Measurement and evaluation of properties of substrate film surface>
<Measurement of contact angle>
As a contact angle measurement solution, a reagent-grade methylene iodide and pure water was used. In a clean room conditioned at 23 ° C and 55% RH, a drop of shrunk was placed on the surface of the base film, and a contact angle measuring instrument (FIBLO) The contact angle after 3 seconds from dropping was measured.

<< Spectrum measurement by TOF-SIMS >>
Using a TOF-SIMS measuring device (PHI Corporation: TRIFT II) capable of measuring functional groups and molecular weight distribution on the surface of the base film, the base film after treatment was treated for 1 hour (23 ° C., 55% Stored within RH).

<< Measurement of carbon atom ratio by ESCA >>
Within 1 hour (stored at 23 ° C., 55% RH) after processing the substrate film using an ESCA measuring apparatus (manufactured by VG: ESCALAB 200-R) that can measure the surface elemental composition of the substrate film. It was measured.

  Table 1 shows the results of evaluation of treatment conditions, measured values of contact angles, fluctuations in spectral peaks by TOF-SIMS, and fluctuations in the proportion of carbon atoms by ESCA.

  From Table 1, the substrate sample No. 1 in which the base film was subjected to a hydrophobic treatment to form a hydrophobic film was obtained. A contact angle of 1 to 3 indicates sample No. 4 is larger than that of the untreated PET film, and the fluctuation of the spectrum peak due to TOF-SIMS and the fluctuation of the proportion of carbon atoms due to ESCA are also large, indicating that a substrate having a hydrophobic surface is obtained. .

  Next, these substrate samples No. 1 to 3 and comparative untreated PET film (Sample No. 4) were used to prepare organic EL display devices OLED-1 to OLED-1 as shown below.

Production of Organic EL Display Device OLED-1 An organic EL display device was produced with the configuration shown in FIG.

First, as the transparent substrate 100 in FIG. 1 and a sintered body made of a mixture of indium oxide and zinc oxide (In atomic ratio In / (In + Zn) = 0.80) as a sputtering target on the surface having the outermost hydrophobic film, An IZO (Indium Zinc Oxide) film, which is a transparent conductive film, was formed by DC magnetron sputtering. 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 this IZO film to form an anode 103, the transparent support base 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 104 in FIG. 8 has an α-NPD layer (film thickness of 25 nm), and the ratio of the CBP and Ir (ppy) deposition rate is 100 by vacuum deposition through a square perforated mask on this transparent conductive film. : 6 co-deposited layer (film thickness 35 nm), BC layer (film thickness 10 nm), Alq ₃ layer (film thickness 40 nm), and lithium fluoride layer (film thickness 0.5 nm) were sequentially laminated (details in FIG. 8) Not shown). Furthermore, a cathode (cathode) 105 made of aluminum having a thickness of 100 nm was formed through a mask on which another pattern was formed.

  In the thus obtained laminate, the same substrate sample No. 1 is stacked and sealed using a photo-curing adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) as a sealing material 106 so that a transparent electrode and a part of the aluminum cathode can be taken out as terminals around the organic EL display. A device OLED-1 was obtained.

  In the same manner, the substrate sample No. 1 is the substrate sample no. 2, 3 and comparative substrate sample No. Organic EL display devices OLED-2, 3 and 4 were produced in place of 4 (untreated PET film). Table 2 shows the results of the following evaluation on the light emitting layers of the organic EL display devices OLED-1 to OLED-1 produced.

<Evaluation item 1>
Immediately after encapsulation, a 50x magnified photograph was taken. After storage at 80 ° C. for 300 hours, 50 times magnified photograph was taken and the area increase rate of the observed dark spots was evaluated.

  The dark spot area increase rate was evaluated according to the following criteria.

◎; Less than 5% ○; 5% or more and less than 10% △; 10% or more and less than 15% ×; 15% or more and less than 50% XX; 50% or more << Evaluation Item 2 >>
Immediately after encapsulation, a 50x magnified photograph was taken. A bending test for bending the 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 rate of increase in the dark spot area in the same manner.

  From these results, the organic EL display devices OLED-1, 2, and 3 manufactured using the substrate of the present invention have a dark spot area increase rate higher than that of the display device OLED-4 manufactured using the comparative substrate. It is clear that it is small. It can also be seen that the sealing performance is less affected when bending stress is applied.

  In this embodiment, materials that adsorb moisture or react with moisture (for example, barium oxide) are not encapsulated in the device, but this does not preclude encapsulating these materials in the device.

Example 2
Each substrate shown below was produced. A plasma discharge treatment chamber 30 shown in FIG. 5 was used for the plasma discharge treatment, and a high frequency power supply JRF-10000 manufactured by JEOL Ltd. was used as a power supply for plasma generation. Moreover, when using reactive gas, the gas of the following compositions 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
A frequency of 13.56 MHz and power of 20 W / cm ² are supplied, and a silicon oxide film is sequentially formed on both sides of a polyethylene terephthalate film having a thickness of 100 μm to a thickness of 200 nm. A polyethylene terephthalate film having

<Base film surface treatment>
Under the following conditions, the apparatus shown in FIG. 1 was used, purged into the treatment chamber for 10 minutes after starting the gas introduction, and 100 μm PET (polyethylene terephthalate) having silicon oxide films on both sides produced as described above as the base film. The film was conveyed and processed under the same conditions as in Example 1 below. The treated film was wound into a roll with a winder. In addition, after 2 minutes passed from the time of stable conveyance, the substrate after the treatment was stabilized was used for the following tests.

<Conditions for implementation>
Processing chamber: Capacity 0.2m ³ , width 420mm
Base film: 400 mm width, 100 μm PET (polyethylene terephthalate) film having silicon oxide films on both sides produced as described above Processing gas: Inactive gas and reactive gas with an inert gas introduced as 100 pressure% argon gas The ratios of argon gas: reactive gas = 100: 10 were used, and substrates 5, 6 and 7 were obtained using methane gas, propane gas, and methyl fluoride gas as reactive gas types. An untreated base film was used as a comparative substrate 8.
Frequency: 10kHz
Gap between electrodes: 5mm
Substrate film conveyance speed: 150 m / min Processing time: 0.5 seconds Output: 22 kW / m ²
In the same manner as described above, for the oxygen concentration, a commercially available oxygen concentration measuring device (manufactured by Toray Industries, Inc .: LC800) was used, and purged for 10 minutes after gas introduction under the above processing conditions. As a result of measuring after 2 minutes, it was 100 ppm.

  In the production of the organic EL display device OLED-1 of Example 1, organic EL display devices OLED-5 to 8-8 were produced in the same manner except that the substrates 5 to 8 were used instead of the substrate 1 (FIG. 9). .

  Table 3 shows the results of evaluating the light emitting portions of these organic EL display devices OLED-5 to 8 according to the evaluation items 1 and 2.

  From these results, the organic EL display devices OLED-5, 6 and 7 manufactured using the substrate of the present invention have a dark spot area increase rate higher than that of the display device OLED-8 manufactured using the comparative substrate. It is clear that it is small. Furthermore, it can be seen that the sealing performance is less affected when bending stress is applied.

DESCRIPTION OF SYMBOLS 1 Surface treatment apparatus 2 Processing chamber 3a, 3b Preliminary chamber 5, F Base film 6, 7 Electrode 9 Partition means E High frequency power supply G Earth 10, 30 Plasma discharge processing chamber 12 Air supply port 13 Exhaust port 15, 16 Nip roller 24, 27 Guide roller 25, 25c, 25C Roll electrode 26, 26c, 26C, 36, 36c, 36C Electrode 25a, 25A, 26a, 36a Conductive base material such as metal 25b, 26b, 36b Ceramic coated dielectric 25B Lining dielectric Body 35a Dielectric 35b Metal base material 41, 65 Power source 51 Gas generator 55 Electrode cooling unit 60 Plasma film forming device 61 Base material FF Original winding base material 100 Substrate 102 Hydrophobic surface layer 103 Anode 104 Organic EL layer 105 Cathode 106 Sealing material

Claims (6)

  A metal oxide film or a metal nitride film is formed on at least one surface of the resin film by performing discharge plasma treatment under atmospheric pressure or a pressure in the vicinity thereof, and the formed metal oxide film or metal nitride is formed. Production of a resin film characterized in that a film is formed on a film made of a product by performing a discharge plasma treatment on a mixed gas comprising an inert gas and a fluorinated hydrocarbon gas at atmospheric pressure or in the vicinity thereof Method. The fluorinated hydrocarbon gas is at least one gas selected from CH ₃ F gas, C ₂ H ₅ F gas, C ₄ H ₉ F gas, C ₅ H ₁₁ F gas, and C ₆ H ₁₃ F gas. The method for producing a resin film according to claim 1.   The method for producing a resin film according to claim 1 or 2, wherein the inert gas in the mixed gas is an inert gas of 50 pressure% or more.   The method for producing a resin film according to claim 1, wherein the metal oxide film or the metal nitride film is produced using an organosilicon compound as a raw material.   The method for producing a resin film according to claim 1, wherein the metal oxide film or the metal nitride film is a silicon oxide film.   The organic electroluminescent element which has a resin film manufactured by the manufacturing method of the resin film of any one of Claims 1-5.

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