JP2004237655A - Alternately laminated moistureproof film, its manufacturing method and alternately laminated moistureproof film with transparent electrode plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alternately laminated moistureproof film with high moistureproofness formed on a base of an organic material, its manufacturing method and an alternately laminated moistureproof film with a transparent electrode plate. <P>SOLUTION: This alternately laminated moistureproof film with high moistureproofness comprises a first film of an inorganic material formed on the base of an organic material; a second film of a carbon fluoride series chemical substance formed on the first film; and a third film of an inorganic material formed on the second film. In addition, the alternately laminated moistureproof film is manufactured by sequentially forming the described films on the base of an organic material by vapor deposition or sputtering. Further, the alternately laminated moistureproof film with a transparent electrode plate is obtained by forming the transparent electrode plate on the third film of an inorganic material of the alternately laminated moistureproof film. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an alternately laminated moisture-proof film having a high degree of moisture resistance, a method for producing the same, and an alternately laminated moisture-proof film with a transparent electrode plate.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, as a substrate on which a sealing material, a transparent electrode plate, or the like is formed, there has been a laminated film having moisture resistance.
[0003]
For example, "At least a gas barrier layer (B) made of a polymer molded product (A), silicon oxide, or silicon nitride, or a mixture of silicon oxide and silicon nitride, which can be suitably used as a substrate for a transparent electrode of a liquid crystal display element. , A laminate in which a thin film layer (C) made of a carbide or a transition metal nitride is formed in the order of ABC ”, and as one example (Example 4), silicon is coated on a polycarbonate film (A). Ar: N for target ₂ A silicon nitride film (B) having a thickness of 15 nm was formed by DC sputtering under a pressure of 0.267 Pa in an atmosphere of = 1: 1, and further thickened by DC sputtering under a pressure of 0.267 Pa in an Ar atmosphere. A laminate having a silicon carbide film (C) having a thickness of 10 nm is disclosed. The water vapor permeability of the laminate thus obtained is 0.7 g / m ² / Day, the light transmittance was 78%. (See Patent Document 1)
[0004]
[Patent Document 1]
JP-A-10-58585 (page 8, table 2)
[0005]
[Problems to be solved by the invention]
However, the water vapor permeability is 0.7 g / m ² A value of 78% per day and light transmittance is not a satisfactory level as a substrate for forming a sealing material or a transparent electrode plate thereon. Therefore, a main object of the present invention is to provide an alternately laminated moisture-proof film, a moisture-proof electroluminescent element, and a method for manufacturing the same, which are formed on a substrate made of an organic material and have high moisture-proof properties.
[0006]
[Means for Solving the Problems]
As shown in FIG. 1, for example, as shown in FIG. 1, the alternate laminated moisture-proof film of the invention according to claim 1 includes a first film 1 made of an inorganic material formed on a substrate 11 made of an organic material; A second film 2 made of a fluorocarbon-based chemical substance, and a third film 3 made of an inorganic material formed on the second film 2;
[0007]
With such a configuration, the water vapor hardly passes through the defects at positions close to each other generated in the two layers of the inorganic material films, and high moisture resistance can be obtained. Furthermore, since a film of a fluorocarbon-based chemical substance is sandwiched between two layers of inorganic material films, a higher moisture-proof property can be obtained.
[0008]
According to a second aspect of the present invention, there is provided the alternately laminated moisture-proof film, wherein the inorganic material of the alternately laminated moisture-proof film is at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide The alternately laminated moisture-proof film according to claim 1, wherein Typically, the inorganic material of the first film and the inorganic material of the third film are the same for simplifying the manufacturing process, but may be different.
[0009]
The first inorganic material film and the third inorganic material film are formed of silicon nitride having low water vapor transmission rate, silicon oxide having high transparency, silicon nitride oxide having characteristics of silicon nitride and silicon oxide, or low. By being formed of aluminum oxide having water vapor permeability and transparency, an alternately laminated moisture-proof film having a high degree of moisture resistance and transparency can be obtained.
[0010]
The alternately laminated moisture-proof film according to the invention of claim 3 is, for example, as shown in FIG. 1, a first film 1 of an inorganic material formed on a substrate 11 of an organic material; and a film formed on the first film. A second film 2 of an organic material having water repellency; and a third film 3 of an inorganic material formed on the second film.
[0011]
With such a configuration, the water vapor hardly passes through the defects at positions close to each other generated in the two layers of the inorganic material films, and high moisture resistance can be obtained. Further, since a film of an organic material having water repellency is sandwiched between two layers of an inorganic material, higher moisture resistance can be obtained.
[0012]
The alternate layered moisture-proof film according to the invention of claim 4, wherein the inorganic material of the first film or the third film is at least one selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide. The alternately laminated moisture-proof film according to claim 3. Typically, the inorganic material of the first film and the inorganic material of the third film are the same for simplifying the manufacturing process, but may be different.
[0013]
As described above, the first inorganic material film and the third inorganic material film are made of silicon nitride having a low water vapor transmission rate, silicon oxide having a high degree of transparency, and nitride having characteristics of silicon nitride and silicon oxide. By being formed of silicon oxide or aluminum oxide having low water vapor permeability and transparency, an alternately laminated moisture-proof film having a high degree of moisture resistance and transparency can be obtained.
[0014]
The alternate laminated moisture-proof film according to the invention of claim 5, wherein the substrate of the organic material is a translucent resin film; the alternate laminated moisture-proof film has a water vapor permeability of 0.05 g / m2. ² / Day or less; the alternately laminated moisture-proof film according to any one of claims 1 to 4.
[0015]
Since the substrate made of an organic material is a light-transmitting resin film, transparency as an alternately laminated moisture-proof film is obtained. The water vapor permeability of the alternately laminated moisture-proof film is 0.05 g / m2. ² / Day or less, it has a satisfactory level of moisture resistance as an alternately laminated moisture-proof film for forming a sealing material or a transparent electrode plate thereon.
[0016]
In the method for manufacturing an alternately laminated moisture-proof film according to the invention according to claim 6, for example, as shown in FIG. 1, an inorganic material is deposited on a substrate 11 made of an organic material by vapor deposition or sputtering to form a first film 1 of an inorganic material. Forming a second film 2 by depositing a fluorocarbon-based chemical substance on the first film 1 by vapor deposition or sputtering; and forming an inorganic material on the second film 2 Forming a third film 3 by depositing by vapor deposition or sputtering; a method for producing an alternately laminated moisture-proof film.
[0017]
The first and third films of the inorganic material and the second film of the fluorocarbon-based chemical substance are formed by any one of vapor deposition and sputtering. The forming method may be different for each of the first, second, and third films. Since the first, second and third films are formed by vapor deposition or sputtering, the production method of the present invention is suitable for industrial production.
[0018]
The method for manufacturing an alternately laminated moisture-proof film according to the invention according to claim 7 is, for example, as shown in FIG. 1, selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide or aluminum oxide on a substrate 11 made of an organic material. Depositing one or more materials by vapor deposition or sputtering to form a first film 1; and depositing a fluorocarbon-based chemical substance on the first film 1 by vapor deposition or sputtering to form a second film. Forming a film 2; and depositing at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide on the second film 2 by vapor deposition or sputtering. A step of forming the film 3.
[0019]
In the method of manufacturing an alternately laminated moisture-proof film according to the invention of claim 8, as shown in FIG. 1, for example, a step of forming a first film 1 by depositing an inorganic material on a substrate 11 of an organic material by vapor deposition or sputtering. Depositing an organic material having water repellency on the first film by vapor deposition or sputtering to form a second film 2; depositing an inorganic material on the second film by vapor deposition or sputtering. And forming a third film 3 by the method.
[0020]
The first and third films of the inorganic material and the second film of the organic material having water repellency are formed by any of vapor deposition and sputtering. The forming method may be different for each of the first, second, and third films. Since the first, second and third films are formed by vapor deposition or sputtering, the production method of the present invention is suitable for industrial production.
[0021]
The method for manufacturing an alternately laminated moisture-proof film according to the ninth aspect of the present invention is selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide or aluminum oxide on a substrate 11 made of an organic material, for example, as shown in FIG. Depositing one or more materials by vapor deposition or sputtering to form a first film 1; and depositing a water-repellent organic material on the first film 1 by vapor deposition or sputtering to form a second film. Forming a film 2; and depositing at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide or aluminum oxide on the second film 2 by vapor deposition or sputtering. A step of forming the film 3.
[0022]
According to a tenth aspect of the present invention, in the method of manufacturing the alternately laminated moisture-proof film, in the step of forming the second film 2, polytetrafluoroethylene is used as a raw material of the film. Note that the film material is a sputtering target or a film material for vapor deposition.
[0023]
With such a configuration, since polytetrafluoroethylene is used as a raw material for the film, a film of a fluorocarbon-based chemical substance having high water repellency can be formed.
[0024]
An alternately laminated moisture-proof film with a transparent electrode plate according to the invention according to claim 11 is, for example, as shown in FIG. 4, the alternately laminated moisture-proof film 100 according to any one of claims 1 to 5; A transparent electrode plate 13 fixed to the laminated moisture-proof film; an alternate laminated moisture-proof film with a transparent electrode plate.
[0025]
According to this structure, since the transparent electrode plate and the alternately laminated moisture-proof film according to any one of claims 1 to 5 are provided, it is suitable as a material for an electroluminescence element.
[0026]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, with reference to the cross-sectional view of FIG. 1, an alternately laminated moisture-proof film according to a first embodiment of the present invention will be described.
[0027]
The alternately laminated moisture-proof film 100 according to the present invention is generally formed on a substrate 11 made of an organic material that cannot be said to have high moisture-proof properties.
[0028]
The substrate 11 made of an organic material on which the alternately laminated moisture-proof film according to the present invention is formed is required to have transparency and heat resistance to withstand vapor deposition or sputtering. As long as it has such characteristics, an arbitrary resin is used as the substrate material resin. For example, polyarylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polysulfone, polyamide, cellulose triacetate, acrylic resin, methacrylic resin, polyester, polyimide, polychlorotrifluoroethylene, ethylene tetrafluoroethylene In addition to polymers, vinylidene fluoride, polyetheretherketone, and combinations of these resins, cyclic olefin (co) polymers having good surface flatness are also suitably used.
[0029]
A first film 1 of an inorganic material is formed on a substrate 11 made of such an organic material. The first film 1 of inorganic material is formed by exciting the inorganic material to decompose it into fragments, and condensing the excited fragments on a substrate of organic material. A supply gas such as argon or nitrogen which has been made into plasma is made to collide with a film material, and minute fragments (also called sputtered particles) are decomposed and fly out of the film material. These sputtered particles are mainly neutral particles, and some of them are turned into plasma.
[0030]
Specifically, silicon oxide (SiO ₂ ) Or silicon nitride (Si ₃ N ₄ The first film 1 of silicon oxide or silicon nitride may be formed by sputtering in an inert gas atmosphere using a material mainly containing) as a raw material of the film, or a very small amount of oxygen gas in argon gas. The first film 1 of silicon oxide, silicon nitride, or silicon oxynitride may be formed by reactive sputtering in an atmosphere containing nitrogen gas or a slight amount of nitrogen gas in argon gas. Alternatively, silicon oxide or silicon oxide can be obtained by reactive sputtering using silicon (Si) alone as a raw material of a film in an atmosphere containing a small amount of oxygen gas in argon gas or in an atmosphere containing a small amount of nitrogen gas in argon gas. The first film 1 of silicon nitride may be formed. Alternatively, the first film 1 of aluminum oxide may be formed by sputtering in an argon gas atmosphere using aluminum oxide as a raw material of the film. Alternatively, the first film 1 of aluminum oxide may be formed by reactive sputtering in an atmosphere containing a trace amount of oxygen gas in argon gas using the raw material of the film of aluminum alone. Further, the first film 1 of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide may be formed by depositing silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide. When there is a deficiency in the type of film to be generated, oxygen gas, nitrogen gas, or the like is actively supplied for reactive sputtering described later.
[0031]
An example of a sputtering apparatus used in the embodiment of the present invention will be described with reference to a schematic sectional view of FIG. As shown in the figure, the sputtering is carried out by introducing an inert gas (mainly argon gas) as a supply gas 36 into a vacuum chamber 41 evacuated by a vacuum pump 42 while interposing the electrodes placed in the vacuum chamber 41. And a glow discharge obtained by applying a voltage from a DC high-voltage power supply 43 to the power supply. The target 31 which is a raw material of the film is placed on the cathode 44, and the substrate 33 made of an organic material is placed on the anode 45 provided opposite to the cathode 44. Therefore, when the inert gas 34, which has been turned into plasma by applying a high DC voltage, collides with the target 31, the target 31 is decomposed into molecular or atomic-level fragments 35, and is flipped off onto the organic material substrate 33. To form a film 32. The material of the film 32 corresponds to the target 31, but is not always exactly the same as the target, as can be seen from an example using polytetrafluoroethylene described later. Furthermore, when sputtering is performed while supplying a reactive gas (for example, a mixed gas of argon and nitrogen or a mixed gas of argon and oxygen) as the supply gas 36, the fragments and the reactive gas (the above example) Then, a nitrogen gas or an oxygen gas) reacts to form a film 32 of the synthesized component.
[0032]
Here, silicon nitride of the formed film has a non-stoichiometric composition, _x N _y Expressed by Similarly, the silicon oxide of the formed film is SiO 2 _z The silicon nitride oxide of the formed film is Si _x N _y O _z Expressed by Note that among silicon oxides, silicon monoxide (SiO) is brownish, but silicon dioxide (SiO 2) ₂ ), The transparency is high. _z Where z is about 1.7.
[0033]
Returning to FIG. 1, the first embodiment of the present invention will be further described. On the substrate on which the first film 1 has been formed as described above, a second film 2 of a fluorocarbon-based chemical substance is formed. For example, in an inert gas atmosphere, polytetrafluoroethylene (PTFE), which is a fluorocarbon-based chemical substance, is decomposed into fragments, and the excited fragments are condensed on a substrate made of an organic material. As a result, a fluorocarbon-based chemical substance, for example, fluorocarbon (CF) is formed on the substrate on which the first film 1 is formed. _x 2) is formed. In this case, nitrogen gas or oxygen gas may be contained as impurities. When there is an insufficient atom in the type of film to be generated, oxygen gas, nitrogen gas, or the like is actively supplied for reactive sputtering.
[0034]
The second film 2 of the fluorocarbon-based chemical substance formed as described above has a sufficient water repellency because the contact angle according to JIS R 3257 is 80 ° or more, preferably 90 ° or more. It is suitable as the second film. In the examples of the present invention, the contact angle was measured using an automatic contact angle meter “CA-V type” manufactured by Kyowa Interface Science.
[0035]
The second film of the water-repellent organic material is a film of a water-repellent organic material having a contact angle of 80 ° or more, preferably 90 ° or more, more preferably 100 ° or more according to JIS R3257. Is fine.
[0036]
A third film 3 of an inorganic material is formed on the first and second films 1 and 2 formed on the substrate of such an organic material. The third film 3 made of an inorganic material is formed in the same manner as the method of forming the first film 1 made of the inorganic material.
[0037]
Although the case where the film is formed by sputtering has been described above, the film may be formed by vapor deposition. In vapor deposition, fragments as vapor generated by heating a raw material of a film in a vacuum condense on a substrate of an organic material to form a film.
[0038]
When the first and third films of an inorganic material and the second film of a fluorocarbon-based chemical substance are formed by sputtering, the excited fragments are minute. It does not impair the smoothness of the substrate. In addition, since the excited fragments are minute, the water vapor permeability generally decreases.
[0039]
On the other hand, when the first and third films of the inorganic material and the second film of the fluorocarbon-based chemical substance are formed by vapor deposition, the rate of condensation of the excited fragments on the substrate becomes 100% in the case of forming by sputtering. More than double, high productivity.
[0040]
As described above, when the third films 1, 2, and 3 are formed by sputtering from the first film, the smoothness of the alternately laminated moisture-proof film is governed by the smoothness of the substrate 11 made of an organic material. Therefore, when smoothness is required for the alternately laminated moisture-proof film, a photopolymer is applied to the surface of the substrate 11 of the organic material by a method such as spin coating before forming the first film 1, and ultraviolet light is applied. Curing is performed to eliminate unevenness. Then, the smoothness of the organic material substrate 11 is increased, and as a result, the smoothness of the alternately laminated moisture-proof film is increased.
[0041]
In addition, the first film 1 and the third film 3 made of an inorganic material are preferably set to have a thickness of 10 nm or more from the viewpoint of moisture resistance. However, if the thickness is too large, cracks easily occur in the films, and the film is transparent. Therefore, the thickness is preferably in the range of 10 to 300 nm. More preferably, the thickness is in the range of 10 to 240 nm. The second film 2 made of a fluorocarbon-based chemical substance preferably has a thickness of 10 to 300 nm from the viewpoint of water repellency and film strength. More preferably, the thickness is in the range of 10 to 240 nm.
[0042]
In general, a film made of an inorganic material has a drawback that a high degree of moisture resistance cannot be easily obtained because water vapor passes through a defect generated in the process of forming the film. Therefore, the alternately laminated moisture-proof film has two layers of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide. The probability that defects in the two layers of inorganic material films occur at positions close to each other is extremely low in probability. Further, in the alternately laminated moisture-proof film, a film of a fluorocarbon chemical substance is sandwiched between two layers of inorganic material films. Then, due to the water repellency of the fluorocarbon-based chemical film, water vapor that has passed through defects in the first layer of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide film is turned into silicon nitride of the second layer. , Silicon oxide, silicon oxynitride, or aluminum oxide film, and the number of defects that pass through both layers is extremely small. For the above reasons, it is understood that the alternately laminated moisture-proof film has a high moisture-proof property. Here, the water repellency means a water repellency having a contact angle of 80 ° or more, preferably 90 ° or more, and more preferably 100 ° or more.
[0043]
Next, an alternately laminated moisture-proof film with a transparent electrode plate according to a second embodiment of the present invention will be described.
[0044]
First, an electroluminescence device (hereinafter, abbreviated as an EL device) will be described with reference to the cross-sectional view of FIG. The EL element has a structure in which a light emitting layer 12 is sandwiched between a transparent electrode plate 13 and a back electrode plate 14. EL elements are roughly classified into organic EL elements and inorganic EL elements depending on the material of the light-emitting layer. In the organic EL device, a low molecular material such as an aluminum complex or anthracene, or a high molecular material such as a derivative of polyparaphenylenevinylene or a derivative of polyacetylene is used for a phosphor material of the light emitting layer 12. On the other hand, as the inorganic EL element, one obtained by adding copper as an activator to zinc sulfide or the like is used.
[0045]
Lead wires 16 connected to a DC or AC power supply are attached to the transparent electrode plate 13 and the back electrode plate 14 so that a voltage can be applied to the light emitting layer 12. Note that, in detail, a hole transport layer is formed between the transparent electrode plate and the light emitting layer in the case of the organic EL element, and an insulator layer is formed in the case of the inorganic EL element. 3, 4, 5, and 6, the hole transport layer and the insulator layer are omitted.
[0046]
The EL element is covered (sealed) with a moisture proof material to prevent wiring corrosion including the transparent electrode plate. In particular, the phosphor constituting the light emitting layer of the organic EL element is required to have a high moisture proof property because the light emission luminance thereof becomes extremely low when moisture is absorbed. Further, the moisture-proof material on the transparent electrode plate side is required to have transparency in addition to moisture-proof properties. Therefore, the alternately laminated moisture-proof film having a high degree of moisture-proofness and transparency is suitable for use in moisture-proofing the transparent electrode plate side. In addition, it may be used on the back electrode plate side where moisture resistance is required and transparency is not required.
[0047]
Therefore, as shown in the sectional view of FIG. 4, the transparent electrode plate 13 is fixed to the alternately laminated moisture-proof film 100. That is, zinc oxide, tin oxide, indium oxide, zinc-doped indium oxide, tin-doped indium oxide, or the like is formed on the third film of the inorganic material of the alternately laminated moisture-proof film 100 by sputtering, vapor deposition, ion plating, or the like. Sticks. When an organic EL element is manufactured using such a transparent electrode plate, a moisture-proof material is provided on the transparent electrode plate side in advance, so that the EL element can be quickly and easily covered with the moisture-proof material.
[0048]
Next, as shown in, for example, a cross-sectional view of FIG. 5, an example of an application of the alternately laminated moisture-proof film described in the above embodiment will be described. In this example, a moisture-proof EL element including the alternately laminated moisture-proof films 100a and 100b and the EL elements 12, 13, and 14 wrapped with the alternately laminated moisture-proof film will be described. The EL element is typically an organic EL element that requires particularly high moisture resistance.
[0049]
With this configuration, the EL element is wrapped with the alternately laminated moisture-proof film, so that the EL element can be protected from moisture, and a highly durable moisture-proof EL element can be obtained.
[0050]
More specifically, with reference to the cross-sectional view of FIG. 5, a moisture-proof EL device in which the organic EL devices 12, 13, and 14 are wrapped by the alternately laminated moisture-proof film 100 will be described. In FIG. 5, the lead wires are omitted.
[0051]
As described above, the organic EL element has a structure covered with a moisture-proof material, and at least the moisture-proof material on the transparent electrode plate 13 side is required to have transparency.
[0052]
Therefore, as shown in FIG. 5A, the moisture-proof EL element in which the organic EL elements 12, 13, and 14 are wrapped with the alternately laminated moisture-proof films 100a and 100b has a high moisture-proof property. In addition, the light emission luminance of the organic light emitting layer due to moisture absorption is hardly reduced. Further, corrosion of wiring including the transparent electrode plate is prevented. Further, since the alternately laminated moisture-proof film 100 has transparency, it is suitable for coating the organic EL elements 12, 13, and 14.
[0053]
Note that the third film of the inorganic material of the alternately laminated moisture-proof film 100a on the transparent electrode plate 13 side and the third film of the inorganic material of the alternately laminated moisture-proof film 100b on the back electrode plate 14 are bonded to each other. Then, the adhesive 22 is applied. Both layers are adhered by the adhesive 22, and the transparent electrode plate 13 and the back electrode plate 14 are insulated. Further, since the length from the end face of the adhesive in contact with the outside air to the inner end face sealed by the alternately laminated moisture-proof film is sufficiently longer than the thickness of the adhesive, water vapor does not pass therethrough, Adhesion of the alternately laminated moisture-proof films does not impair moisture-proof properties.
[0054]
Further, as shown in FIG. 5B, the transparent electrode plate 13 side of the EL element may be covered with the alternately laminated moisture-proof film 100a, and the back electrode plate 14 side of the EL element may be covered with another moisture-proof film 21. The other moisture-proof film 21 used on the non-light-emitting surface side may be a quartz glass substrate or a film having no transparency such as an aluminum film.
[0055]
Further, as shown in, for example, a cross-sectional view of FIG. 6, an example of the use of the alternately laminated moisture-proof film described in the above embodiment will be described. In this example, the EL element 12, 13, 14, 16 is formed by fixing the transparent electrode plate 13 to the alternately laminated moisture-proof film 100 and using the transparent electrode plate 13 fixed to the alternately laminated moisture-proof film 100. A method for manufacturing a moisture-proof EL element comprising the steps of:
[0056]
When manufactured in this manner, a moisture-proof EL element having an alternately laminated moisture-proof film having a high degree of moisture-proof properties is manufactured.
[0057]
More specifically, with reference to the cross-sectional view of FIG. 6, a process of manufacturing an organic electroluminescence from the transparent electrode plate 13 fixed to the alternately laminated moisture-proof film 100 will be described.
[0058]
As described above, the alternately laminated moisture-proof film 100 with the transparent electrode plate 13 is manufactured. On the transparent electrode plate 13, an amine compound, which is a hole transporting material, such as diphenylnaphthyldiamine or triphenylmethane, is attached by vapor deposition to form a hole transporting layer (not shown). Next, the organic light emitting layer 12 is formed on the hole transport layer. For the organic light emitting layer 12, a low molecular material such as an aluminum complex or anthracene, or a high molecular material such as a polyparaphenylene vinylene derivative or a polyacetylene derivative is used. One of these materials is deposited on the hole transport layer by vapor deposition to form the organic light emitting layer 12. In the case of a polymer material, it may be formed by a printing technique such as an inkjet method. On the organic light emitting layer 12, a metal electrode such as calcium, magnesium-silver alloy, or magnesium-lithium alloy is deposited to form the back electrode plate. When a low molecular material is used for the organic light emitting layer, the back electrode plate 14 may be formed by evaporating aluminum.
[0059]
In the organic EL elements 12, 13, and 14 having the alternately laminated moisture-proof film 100 manufactured as described above on the transparent electrode plate 13 side, the back electrode plate 14 side is sealed with a metal or non-metal oxide moisture-proof film 21. By stopping, the moisture-proof EL element is manufactured. Alternatively, in addition to or in addition to this, a moisture-proof EL element may be manufactured by forming a layer of a cured product of an epoxy resin or an acrylic ultraviolet curing resin.
[0060]
The method of manufacturing the organic EL element has been described above, but the inorganic EL element may be manufactured using a transparent electrode plate fixed to the alternately laminated moisture-proof film. In the inorganic EL element, a barium titanate powder is placed in cyanoethylpolyvinyl alcohol, N, N′-dimethylformamide is added and uniformly mixed on a transparent electrode plate by screen printing or the like, and the insulating layer is formed. Form. On top of that, phosphor powder obtained by adding copper as an activator to zinc sulfide is placed in cyanoethyl polyvinyl alcohol in the same manner as the insulator layer, and N, N'-dimethylformamide is added and uniformly mixed, and screen-printed. To form an inorganic light emitting layer. A back electrode plate is formed thereon as described above, and sealed with a moisture-proof film to manufacture a moisture-proof EL element. When the inorganic EL element is sealed, an adhesive may be used in the same manner as for sealing the organic EL element, and if necessary, a hot-melt material, a layer of an adhesive resin or an inorganic material may be used. A layer of a conductive ceramic or alloy may be provided on the inner surface of the moisture-proof film to perform heat fusion or heat melting while suppressing the influence of heat on the light emitting layer.
When sealing the organic EL element, the above-mentioned heat fusion or heat melting can be applied. However, since the light emitting layer of the organic EL element is particularly susceptible to heat, the light emitting layer is formed so as not to be affected by the heat of the heat fusion or the heat melting.
[0061]
【Example】
Hereinafter, the alternately laminated moisture-proof film of the present invention will be described more specifically with reference to Examples and Comparative Examples.
[0062]
First, a method for measuring physical properties will be described. The water vapor permeability was measured under the conditions of 40 ° C. and 100% RH using “PERMATRAN 3/31” manufactured by Modern Control Co., USA in accordance with JIS K 7129B. The parallel light transmittance is calculated from the total light transmittance (JIS K 7361-1) and the haze (JIS K 7136) as parallel light transmittance = total light transmittance × (1− (haze / 100)). The value was measured by "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd.
[0063]
In Example 1, a cyclic olefin resin film (manufactured by Zeon Corporation, trade name “Zeonor Film ZF16”: 188 μm in thickness, surface arithmetic mean) was obtained using a magnetron sputtering apparatus (“SPR-403” manufactured by Tokki Corporation). A substrate having a roughness Ra of 0.82 nm (hereinafter abbreviated as “COC”) and having a diameter of 100 mm ₃ N ₄ And argon (Ar) 7cm ³ / Min and nitrogen (N ₂ ) 5cm ³ The reactive sputtering was performed for 30 minutes while setting the gas pressure in the apparatus at 0.8 Pa and the substrate temperature at 100 ° C. while flowing a mixed gas at a flow rate of / min. Subsequently, sputtering was performed for 30 minutes using PTFE having a diameter of 100 mm as a target without supplying a gas and under the same conditions as above. Subsequently, the reactive sputtering was performed for 30 minutes under the same conditions as the reactive sputtering performed earlier.
[0064]
The water vapor permeability of the alternately laminated moisture-proof film formed as described above was measured by the method described above. ² / Day or less, the parallel light transmittance was 88%. In addition, 0.02 g / m of water vapor permeability ² / Day is the lower limit of the measurement accuracy of "PERMATRAN 3/31".
[0065]
FIG. 7 summarizes the results measured by the above method for examples in which various alternately laminated moisture-proof films were formed by changing the conditions for forming (depositing) each film.
[0066]
FIG. 8 shows the results of measurements by the above method for a comparative example in which one layer of various inorganic materials was formed on an organic substrate.
[0067]
In the examples or comparative examples in FIG. 7 or FIG. 8, PET described in the type of the substrate is a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Corporation, trade name “Diafoil T600E50”, thickness 50 μm, Ra). = 12.8 nm). In addition, “type of film” and “raw material of film” are represented by composition components, and in the case of non-stoichiometry, the number of atoms is indicated by x, y, and z.
[0068]
The embodiment or the comparative example of FIGS. 7 and 8 will be supplementarily described below.
[0069]
In each of the alternately laminated moisture-proof films according to the examples of the present invention, the water vapor permeability is 0.02 g / m2. ² / Day or less, showing high moisture resistance. In addition, the parallel light transmittance is 82% or more, indicating good transparency.
[0070]
On the other hand, when one layer of the inorganic material film shown in the comparative example was formed on the organic substrate, the water vapor permeability of the comparative example 1 was 0.06 g / m 2. ² / Day is the highest value.
[0071]
In Comparative Example 4, a polyethylene terephthalate (PET) film was used as the substrate, and the substrate had low surface smoothness. On the other hand, in Comparative Example 1, the same film was formed on a substrate using COC having a high surface smoothness as the substrate. The water vapor permeability was 0.06 g / m in Comparative Example 1. ² / Day, 0.51 g / m in Comparative Example 4 ² / Day.
[0072]
On the other hand, in Example 5 and Example 1, similarly, the same alternately laminated moisture-proof film was formed on the substrate using a PET film and COC. .02g / m ² / Day or less.
[0073]
As can be seen from these results, the alternately laminated moisture-proof film according to the present invention has good moisture-proof properties regardless of the surface roughness of the substrate.
[0074]
In Example 6, the fourth film made of a fluorocarbon-based chemical substance and the fifth film made of an inorganic material were further formed on the third film made of an inorganic material. It has a high degree of transparency, and the transparency shows good results with a parallel light transmittance of 83%.
[0075]
【The invention's effect】
As described above, the alternately laminated moisture-proof film comprises a first film of an inorganic material formed on a substrate of an organic material; and a second film of a fluorocarbon-based chemical formed on the first film. And; a third film of an inorganic material formed on the second film, so that the film has a high degree of moisture resistance. Therefore, according to the present invention, it is possible to provide an alternately laminated moisture-proof film having a high moisture-proof property.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a first embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view showing a sputtering method.
FIG. 3 is a cross-sectional view illustrating an EL element.
FIG. 4 is a cross-sectional view illustrating a second embodiment of the present invention.
FIG. 5 is a cross-sectional view illustrating a moisture-proof EL element in which an organic EL element is wrapped by alternately laminated moisture-proof films.
FIG. 6 is a cross-sectional view illustrating a process of manufacturing an organic electroluminescence element from a transparent electrode plate fixed to the alternately laminated moisture-proof film.
FIG. 7 is a table illustrating an example of the present invention.
FIG. 8 is a table illustrating a comparative example of the present invention.
[Explanation of symbols]
1 First film of silicon nitride, silicon oxide, silicon nitride oxide or aluminum oxide
2 Second film of fluorocarbon-based chemical substance
3. Third film of silicon nitride, silicon oxide, silicon nitride oxide or aluminum oxide
11 Substrate of organic material
12 Organic light emitting layer
13 Transparent electrode plate
14 Back electrode plate
16 Lead wire
21 Other moisture-proof films
22 Adhesive
31 Raw materials for membrane
32 Film formed
33 substrate
34 Inert Gas Plasma
35 Membrane raw material fragments
36 Supply gas for sputtering
41 vacuum chamber
42 vacuum pump
43 DC high voltage power supply
44 Cathode
45 anode
100 On a substrate of an organic material, a first film of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide, a second film of carbon fluoride oxide, and a first film of silicon nitride, silicon oxide, silicon nitride oxide, or aluminum oxide. Laminated moisture-proof film comprising:
100a Alternating moisture-proof film on transparent electrode plate side of EL element
100b Alternating moisture-proof film on back electrode plate side of EL element

Claims (11)

A first film of an inorganic material formed on a substrate of an organic material;
A second film of a fluorocarbon-based chemical formed on the first film;
A third film of an inorganic material formed on the second film;
Alternating moisture-proof film. The inorganic material of the first film or the third film is at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide;
The alternately laminated moisture-proof film according to claim 1. A first film of an inorganic material formed on a substrate of an organic material;
A second film of a water-repellent organic material formed on the first film;
A third film of an inorganic material formed on the second film;
Alternating moisture-proof film. The inorganic material of the first film or the third film is at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide;
The alternately laminated moisture-proof film according to claim 3. The organic material substrate is a translucent resin film;
The water vapor transmission rate of the alternately laminated moisture-proof membrane is 0.05 g / m ² / day or less;
The alternate laminated moisture-proof film according to any one of claims 1 to 4. Forming a first film by depositing an inorganic material on a substrate of an organic material by evaporation or sputtering;
Depositing a fluorocarbon-based chemical substance on the first film by vapor deposition or sputtering to form a second film;
Forming a third film by depositing an inorganic material on the second film by vapor deposition or sputtering;
Manufacturing method of alternately laminated moisture-proof film. The inorganic material of the first film or the third film is at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide;
A method for producing the alternately laminated moisture-proof film according to claim 6. Forming a first film by depositing an inorganic material on a substrate of an organic material by evaporation or sputtering;
Depositing an organic material having water repellency on the first film by vapor deposition or sputtering to form a second film;
Forming a third film by depositing an inorganic material on the second film by vapor deposition or sputtering;
Manufacturing method of alternately laminated moisture-proof film. The inorganic material of the first film or the third film is at least one material selected from the group consisting of silicon nitride, silicon oxide, silicon nitride oxide, and aluminum oxide;
A method for producing the alternately laminated moisture-proof film according to claim 8. In the step of forming the second film, polytetrafluoroethylene is used as a raw material of the film;
The method for producing an alternately laminated moisture-proof film according to any one of claims 6 to 9. An alternately laminated moisture-proof film according to any one of claims 1 to 5, and
A transparent electrode plate fixed to the alternately laminated moisture-proof film;
Alternating moisture-proof film with transparent electrode plate.

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