JPWO2008102868A1 - Method for producing roll-shaped resin film having transparent conductive film and organic electroluminescence device using the same - Google Patents

Abstract

This invention is providing the method of manufacturing the roll-shaped resin film provided with the transparent conductive film on the barrier film continuously by roll to roll. In the method for producing a roll-shaped resin film having a transparent conductive film of the present invention, a barrier film is formed at least under atmospheric pressure or a pressure environment in the vicinity thereof, and then the vacuum film is formed through a pressure adjusting unit. A transparent conductive film is continuously formed on a resin film substrate by roll-to-roll.

Description

  The present invention relates to a method for producing a roll-shaped resin film in which a transparent conductive film is provided on a barrier film having at least a barrier property.

  Light and flexible resin films are widely used as base materials for devices such as electronic paper and flexible displays. However, since the resin film has a low barrier property against the permeation of moisture and oxygen, there is a problem that an electronic device mounted on the resin film is deteriorated. For this reason, a barrier film is provided on the resin film, and a transparent conductive film that supplies voltage and current to the electronic device is provided on the barrier film to make the electronic device flexible. As the barrier film, an inorganic film such as silicon-based silicon nitride film (SiNx), silicon nitride oxide film (SiOxNx), silicon oxide film (SiOx), metal oxide-based magnesium oxide (MgOx), aluminum oxide (AlOx), etc. A film mainly composed of is used. In the case of a configuration in which the display of the electronic device formed on the resin film is taken out from the barrier film, a barrier film with high transparency is required.

  The conventional barrier film as described above is formed by a thin film forming method such as an electron beam method, a sputtering method, a plasma CVD method, or an ion plating method. According to these thin film forming methods, an inorganic film having a high barrier property can be formed relatively easily even with a compound of a high melting point material in a vacuum environment. However, from the viewpoint of productivity, the barrier film is formed by a roll-to-roll method using a long roll-shaped resin film, and compared with a single wafer method in which film formation processing is performed for each sheet. On the other hand, in the vacuum environment, a large amount of water absorbed by the roll-shaped resin film is vaporized in the chamber under a vacuum environment, so that the deposited barrier film quality is deteriorated.

  As a conventional technique, Japanese Patent Application Laid-Open No. 2006-175633 discloses a technique for forming a barrier film on a resin film under a pressure environment at or near atmospheric pressure as a barrier film forming technique. By forming the barrier film in the vicinity of atmospheric pressure, a vacuum chamber for maintaining a vacuum and a device for performing vacuum evacuation are unnecessary, and the influence of moisture evaporated from the resin film in a vacuum environment can be reduced.

  On the other hand, in recent years, organic EL elements have attracted attention as self-luminous elements. An organic EL device is a device in which a light-emitting layer of a thin organic compound is sandwiched between electrodes on a substrate, and emits light when a current is supplied between the electrodes. Since the light emitting layer is an organic compound, a flexible organic EL element is realized when a resin film is used as the substrate. In addition, the organic EL element is also likely to be deteriorated by oxygen and moisture, and it is desirable to provide a barrier film on the resin film and completely block the moisture and oxygen entering through the resin film from the organic EL element. In addition, since the organic EL element is a self-luminous electronic device, a wiring for supplying current is required, but a wiring in a direction in which light emission is emitted requires a transparent conductive film that reduces light loss. .

  Here, since the film formation of the transparent conductive film is performed on the resin film, it is necessary to form the film at a temperature lower than the temperature at which the film is conventionally formed on the glass substrate. For example, although the conventional film formation temperature on a glass substrate is about 300 ° C., the film formation temperature needs to be 200 ° C. or less in consideration of thermal deformation of the resin film. Furthermore, it is desired to reduce the resistance of the transparent conductive film as much as possible in order to efficiently supply current to the electronic device. Therefore, physical vapor deposition methods (PVD, Physical Vapor Deposition) such as sputtering and ion plating can be formed at a lower temperature than chemical vapor deposition methods (CVD, Chemical Vapor Deposition). It is widely used as a method for forming a transparent conductive film having the above characteristics.

  However, although the above-described physical vapor phase methods such as sputtering and ion plating can form a transparent conductive film at a low temperature in a vacuum environment, the film is formed in the vicinity of atmospheric pressure, which is the previous step. The pressure environment differs from the barrier film formation. For this reason, when trying to continuously form a transparent conductive film on the barrier film by roll-to-roll, a barrier film formed near atmospheric pressure, a transparent conductive film formed in vacuum, This was difficult to achieve because the pressures of

  This invention is made | formed in view of the said point, The objective is to provide the method of manufacturing the roll-shaped resin film provided with the transparent conductive film on the barrier film continuously by roll to roll.

  The above-mentioned problem to be solved by the present invention is achieved by the following means.

  1. In the method for producing a roll-shaped resin film having a transparent conductive film, a barrier film is formed at least under atmospheric pressure or a pressure environment in the vicinity thereof, and then the transparent conductive film is formed under a vacuum environment via a pressure adjusting unit. The manufacturing method of the roll-shaped resin film which has a transparent conductive film characterized by forming into a film by roll-to-roll continuously on a resin film base material.

  2. 2. The method for producing a roll-shaped resin film having a transparent conductive film as described in 1 above, wherein the pressure adjusting unit comprises a plurality of buffer chambers.

  3. The barrier film is supplied with a gas containing a thin film forming gas and a discharge gas in a discharge space under an atmospheric pressure or a pressure environment in the vicinity thereof, and the gas is excited by applying a high-frequency electric field to the discharge space, 3. The method for producing a roll-shaped resin film having a transparent conductive film according to 1 or 2, wherein a film is formed on a resin film substrate by exposing the resin film to the excited gas.

  4). 4. The method for producing a roll-shaped resin film having a transparent conductive film according to any one of 1 to 3, wherein the transparent conductive film is formed by an ion plating method.

  5. 4. The method for producing a roll-shaped resin film having a transparent conductive film according to any one of 1 to 3, wherein the transparent conductive film is formed by sputtering.

  6). 6. An organic electroluminescence device provided on a resin film substrate produced by the method for producing a roll-shaped resin film having the transparent conductive film according to any one of 1 to 5 above.

  The present invention provides a method for producing a roll-shaped resin film having a transparent conductive film on a barrier film continuously by roll-to-roll.

It is a block diagram of the manufacturing process of the roll-shaped resin film which has a transparent conductive film. It is a schematic diagram of the manufacturing process of the roll-shaped resin film which has a transparent conductive film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Barrier film formation process 200 Pressure adjustment part 300 Transparent conductive film formation process 400 Roll winding-up apparatus F Resin film

  First, the roll-shaped resin film concerning this invention is demonstrated.

  The roll-shaped resin film according to the present invention is a long product obtained by winding a resin film into a long roll shape, and there is no particular limitation on the thickness of the resin film, but 50 μm to 300 μm is preferable for flexible use. Furthermore, from the ease of conveyance in roll-to-roll, 100 μm to 200 μm is preferable. The resin film is not particularly limited as long as it can hold the barrier film having the above-described barrier properties. However, as a base material for an electronic device, light emission and image information are transmitted through the resin film. It is desirable to be transparent so as to suppress optical loss at the time.

  Specific examples of the resin material of the resin film include a homopolymer such as ethylene, polypropylene, and butene, or a polyolefin (PO) resin such as a copolymer or a copolymer, an amorphous polyolefin resin (APO) such as a cyclic polyolefin, Polyester resins such as polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polyamide (PA) resins such as nylon 6, nylon 12, copolymer nylon, polyvinyl alcohol (PVA) resin, ethylene-vinyl alcohol Polyvinyl alcohol resin such as copolymer (EVOH), polyimide (PI) resin, polyetherimide (PEI) resin, polysulfone (PS) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin , Polycarbo (PC) resin, polyvinyl butyrate (PVB) resin, polyarylate (PAR) resin, ethylene-tetrafluoroethylene copolymer (ETFE), polytrifluoroethylene chloride (PFA), tetrafluoroethylene- Fluorocarbon resins such as perfluoroalkyl vinyl ether copolymer (FEP), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer (EPA), etc. Can be used.

  In addition to the resins listed above, a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, a resin composition comprising a mercapto compound having an acrylate compound and a thiol group, epoxy acrylate, urethane acrylate It is also possible to use a photocurable resin such as a resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer, and a mixture thereof. Furthermore, it is also possible to use what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, as a transparent resin film.

  These materials can be used alone or in combination as appropriate. Above all, ZEONEX and ZEONOR (manufactured by Nippon Zeon Co., Ltd.), amorphous cyclopolyolefin resin film ARTON (manufactured by JSR Corporation), polycarbonate film Pure Ace (manufactured by Teijin Limited), polyethylene naphthalate film Teonex Commercially available products such as Teijin DuPont Films Co., Ltd. and Konica Katak KC4UX, KC8UX (Konica Minolta Opto Co., Ltd.), which are cellulose triacetate films, can be preferably used.

  Further, in the roll-shaped resin film according to the present invention, before forming the barrier film, in order to improve adhesion, corona treatment, flame treatment, plasma treatment, glow discharge treatment, ultraviolet treatment, roughening treatment, In order to sufficiently remove surface treatment such as chemical treatment or moisture or gas contained in the resin film, dehydration or degassing treatment may be performed by heat treatment, film conveyance under a vacuum environment, or the like.

Furthermore, an anchor coat agent layer may be formed on the surface of the resin film according to the present invention for the purpose of improving the adhesion with the barrier film. Examples of the anchor coating agent used in this anchor coating agent layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Can be used alone or in combination. Conventionally known additives can be added to these anchor coating agents. The anchor coating agent is applied onto the transparent resin film by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and the solvent, diluent, etc. are removed by drying to remove the anchor coating. can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state).

  Next, film formation of the barrier film of the roll-shaped resin film of the present invention will be described.

  In the present invention, the barrier film is formed by applying an electric field to the space in the vicinity of the resin film under atmospheric pressure or in a pressure environment near atmospheric pressure to generate a plasma space in which a gas in a plasma state exists, and volatilizing / subliming. This is due to the atmospheric pressure plasma CVD method in which a thin film such as a barrier film is formed by introducing the raw material into the plasma space and then spraying it on the resin film after a decomposition reaction has occurred. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the gas temperature is kept low, the electron temperature is high, so this high-temperature electron or low-temperature ion -Since it is in contact with an excited state gas such as a radical, the raw material of the barrier film can be decomposed even at a low temperature. Therefore, the temperature of the resin film on which the barrier film is deposited can be lowered, and the film can be sufficiently formed on the resin film.

  Here, the atmospheric pressure in atmospheric pressure plasma CVD or under a pressure environment near atmospheric pressure refers to the pressure range of the discharge space region where the discharge gas is excited, and the excited discharge gas and the gas forming the thin film are in contact with each other. And the pressure range of the region where the thin film is formed, and the pressure range is 20 kPa to 200 kPa.

  The gas used in atmospheric pressure plasma CVD is a thin film forming gas composed of a raw material gas for forming a barrier film and a decomposition gas for decomposing the raw material gas to obtain a thin film forming compound. It consists of a discharge gas or the like.

It is preferable that the source gas is 0.01 to 10% by volume, the decomposition gas is 0.01 to 10% by volume, and the discharge gas is 99.9 to 90% by volume with respect to the total gas. The output condition when plasma discharge treatment is preferably 1.0~50W / cm ^2, preferably further a 1.2~20W / cm ^2. The gas supply speed to the plasma generator can be appropriately selected depending on the size of the apparatus.

  The barrier film in the present invention is a thin film obtained by atmospheric pressure plasma CVD, and the composition and the like are not particularly limited as long as it has at least an inorganic film that reduces permeation of oxygen and water vapor. The configuration of the barrier film may be a single layer of an inorganic film, a stacked layer of an inorganic film and an organic film, a gradient layer that gradually changes the configuration of the inorganic film and the organic film, and the like. By laminating the inorganic film with the organic film, the deterioration of the barrier property due to film cracking is reduced. In the case of lamination with an organic film, the uppermost layer is an inorganic film from the viewpoint of barrier properties.

  Here, the inorganic film is a metal atom (Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn in the film. , Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Nd , Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.) is a film having an atomic concentration exceeding 20% and a carbon content of 5% or less. The metal atom concentration is measured by an XPS surface analyzer. The optimum thickness of the barrier film varies depending on the type and configuration of the material used and is appropriately selected, but is preferably in the range of 1 to 1000 nm. When the thickness of the barrier film is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain a high barrier property against gas such as moisture. When it is thicker than the range, it becomes difficult to maintain flexibility in the resin film. Further, the barrier film is preferably transparent with little optical loss in a configuration that transmits optical information of the electronic device.

  The organic film is a thin film having the same composition as that of the inorganic film obtained by atmospheric pressure plasma CVD, and the carbon content in the film exceeds 5% as the atomic number concentration.

  As a raw material of the inorganic film for atmospheric pressure plasma CVD, an organic metal compound, a halogen metal compound, a metal hydrogen compound, and the like, and an organic metal compound with a low risk of explosion are particularly preferable due to handling problems. For example, tetraethylsilane, tetramethylsilane, tetraisopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanedi (2,4-pentanedionate ), Organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane, and silicon halide compounds such as tetrahydrogen silane and hexahydrogen disilane, such as tetrachlorosilane, methyltrichlorosilane, and diethyldichlorosilane. And the like. Further, two or more of these can be mixed and used at the same time.

  The raw material of the inorganic film may be in a gas, liquid, or solid state at normal temperature and pressure. The method of vaporizing the raw material as the raw material gas can be directly introduced into the discharge space when the raw material is a gas, but in the case of a liquid or solid, it is vaporized by means such as heating, bubbling, decompression, ultrasonic irradiation, etc. . 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.

  In addition, as a decomposition gas for decomposing these source gases to obtain a barrier film, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas, oxidation Examples thereof include nitrogen gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas. Various metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.

  A discharge gas that tends to be in a plasma state is mainly mixed with these raw material gas and decomposition gas, and the gas is sent to the plasma discharge generator. As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used.

  A barrier film is formed by mixing the above-described gases and supplying the mixture as a mixed gas to an atmospheric pressure plasma CVD apparatus.

  In addition, the barrier film in the present invention may have a configuration in which an organic film having a stress relaxation effect is laminated on the barrier film, or a plurality of layers may be laminated. The organic film to be laminated with the inorganic film is not particularly limited as long as the carbon content in the film exceeds 5%. However, when an organic polymer is used, the organic compound as a raw material component may be a known organic compound. Among them, an organic compound having at least one unsaturated bond or a cyclic structure in the molecule can be preferably used, and in particular, a monomer of a (meth) acrylic compound, an epoxy compound, or an oxetane compound. Or an oligomer is preferable. Of course, an organic film having a carbon content exceeding 5% in the inorganic film may be used.

  In the barrier film having the laminated structure, the total thickness is in the range of 0.05 μm to 5 μm.

  When an inorganic film having a carbon content of 5% or less in atomic concentration and an organic film in which the carbon content in the inorganic film exceeds 5% in the atomic concentration are laminated, a barrier film formation described later is performed. In the process, a plurality of atmospheric pressure plasma CVD apparatuses may be continuously provided and an inorganic film and an organic film may be continuously formed (not shown). For example, by adjusting the film formation conditions of the atmospheric pressure plasma CVD method in the first barrier film forming process and the second barrier film forming process, the number of carbon atoms is 5% from the organic metal compound as the raw material. What is necessary is just to comprise so that the following inorganic films and organic films exceeding 5% of carbon atoms can be continuously formed.

  Further, for the purpose of planarizing the surface of the barrier film, a planarizing film may be provided on the barrier film by coating or the like. The material for the planarizing film is not particularly limited, but an organic material or an organic silicon oxide compound is desirable from the viewpoint of surface planarity. Alternatively, various metal alkoxide materials are preferable from the viewpoint of plasma resistance when forming the transparent conductive film in the next step. As a method for applying the flattening film, it is applied by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating or sol-gel method, and then formed by predetermined heat drying.

  Next, the transparent conductive film will be described below.

  The transparent conductive film used in the present invention is a transparent metal oxide film having a total light transmittance of 50% or more, such as indium tin oxide (ITO), indium zinc oxide (IZO), and aluminum zinc oxide (AZO). It is a thin film used for an electrode of an electronic device. The method for forming the transparent conductive film is preferably a method called physical vapor deposition from the viewpoint of low-temperature film formation. Physical vapor deposition is a sputtering method in which a high-energy atom excited in a plasma space is struck against a metal or oxide target in a vacuum environment, and the target atom is repelled to form a film on a resin film. An ion plating method is desirable in which a target is disposed as an anode, a plasma beam is supplied thereto, the raw material is evaporated, a part of the evaporated particles are used as ions or excited particles, and activated evaporated particles are formed on a resin film.

(Preferred embodiment of the present invention)
Next, an embodiment of the present invention will be described with reference to the drawings. First, the specific manufacturing process of the roll-shaped resin film by roll-to-roll is demonstrated below. FIG. 1 is a block diagram of a manufacturing process of a roll-shaped resin film having a transparent conductive film.

  The method for producing a roll-shaped resin film includes a barrier film forming process 100, a pressure adjusting unit 200, a transparent conductive film forming process 300, and the like. The resin film unwound from the roll is formed in a barrier film forming environment near atmospheric pressure. After the barrier film is formed in the film process 100, the pressure adjustment unit 200 changes from near atmospheric pressure to a vacuum pressure environment, and the transparent conductive film is continuously formed in the transparent conductive film formation process 300 in the vacuum environment. And wound into a roll. Therefore, the pressure difference between the barrier film forming process 100 performed in an environment near atmospheric pressure and the transparent conductive film forming process 300 performed in a vacuum environment are eliminated through the pressure adjusting unit 200. Continuous film formation is possible, and production efficiency is greatly improved. In FIG. 1, before the barrier film is formed, for example, various surface treatments such as corona treatment and heat treatment for dehydration are added to improve adhesion.

  In addition, the roll-to-roll in the present invention refers to a flexible long resin film wound in a roll shape, and a barrier film is formed on the resin film while being intermittently or continuously conveyed. Thereafter, a transparent conductive film is continuously formed through a pressure adjusting unit, and is wound around a roll again. Compared to the single-wafer method that transports individually separated resin films for each film formation process, the single-wafer method requires the provision of a substrate carry-in section and a carry-out section in each process, and a device for each process. Although the scale tends to increase, in the roll-to-roll method, the resin film flows intermittently or continuously between the film formation processes, so the processes can be connected to each other, reducing the work involved in transporting the substrate and downsizing the equipment. It becomes possible.

  Next, details of a specific manufacturing process of the present invention will be described below.

  FIG. 2 is a schematic view of a production process of a roll-shaped resin film having the transparent conductive film of the present invention.

  The resin film F wound in a roll shape is fed out to the surface treatment 10, and here, an ultraviolet irradiation treatment is performed in order to improve the adhesion with the barrier film. Thereafter, the resin film F is absorbed by the buffer zone 20 in the transport speed difference from the subsequent process, and sent to the barrier film forming process 100. The buffer zone 20 is also provided in front of the pressure adjusting unit 200 to absorb the difference in transport speed between the barrier film forming process 100 and the transparent conductive film forming process 300.

  The barrier film forming step 100 is a step of forming a barrier film by atmospheric pressure plasma CVD in an environment near atmospheric pressure. The first electrode 111 has a high frequency from the AC power source 121 and the second electrode 112 has a high frequency. An electric field is applied, and a plasma discharge space is formed between the opposing electrodes of the first electrode 111 and the second electrode 112. The mixed gas G of the thin film forming gas and the discharge gas is introduced into the plasma discharge space, and the generated gas G ｀ in the plasma state is blown out from the lower side between the counter electrodes, and the resin film F conveyed from the previous step is discharged. The film formation surface is exposed to this to form a barrier film on the resin film.

  The AC power supply 121 and the AC power supply 122 apply an electric field to the same plasma discharge space at mutually different frequencies, so that a discharge capable of forming a thin film is generated and a dense barrier film can be formed.

  The resin film F on which the barrier film is formed is then sent to the pressure adjusting unit 200.

  The pressure adjusting unit 200 includes a plurality of buffer chambers 210a, 210b, 210c, and 210d. Each buffer chamber is partitioned by a partition wall having an orifice-shaped seal roll 220 at an opening through which the transported resin film passes. The pressure can be adjusted independently by the exhaust of each exhaust pump (not shown). The seal roll 220 has a gap that allows the film-forming surface of the resin fill F to pass through without contact, and the resin film F passes through the gap of the seal roll 220 and is at atmospheric pressure on the inlet side of the buffer chamber 210a. The buffer chambers 210 a, 210 b, 210 c, and 210 d are adjusted from the vicinity so that the pressure is reduced in order, and the pressure is adjusted to reach the pressure of the vacuum environment at the outlet of the buffer chamber 210 d and sent to the transparent conductive film forming process 300 of the next process. .

  The transparent conductive film forming step 300 is a step of forming a transparent conductive film by ion plating in a vacuum environment. The transparent conductive film is filled with the plasma beam P from the pressure gradient plasma gun 310 and the raw material of the transparent conductive film. The raw material container 320 made of carbon is directly irradiated. The pressure gradient type plasma gun 310 is a pressure gradient type holo-cathode plasma gun, and thermal electrons are emitted from the composite cathode 311 by the introduction of a discharge gas, and a plasma beam P is generated. The inside of the pressure gradient plasma gun 310 is always kept at a higher pressure than the outside, and has a structure that prevents the composite cathode 310 exposed to a high temperature from being deteriorated by introduction of a reaction gas.

  The coil 330 controls the plasma width of the plasma beam P of the pressure gradient plasma gun 310, and the coil 340 controls the convergence position of the plasma beam P. The raw material of the transparent conductive film in the raw material container 320 is evaporated by the irradiation of the plasma beam P, and the evaporated raw material is ionized in the plasma atmosphere. The ionized raw material I is accelerated by the difference between the plasma potential in the plasma atmosphere and the floating potential of the resin film F, reaches the resin film F with large energy, and is formed on the barrier film. That is, the ion plating method is a desirable film formation method for a resin film because the deposited raw material is ionized and has a large energy, so that a dense transparent conductive film with low resistance can be formed.

  The resin film F on which the transparent conductive film is formed is then sent to the roll winding device 400. The roll winding device 400 winds up the resin film F in a roll shape under the same vacuum environment as in the previous step.

  In addition, the roll-shaped resin film F in which the transparent conductive film is formed on the barrier film is subjected to the cutting process after the organic EL element is formed on the transparent conductive film by the offline organic EL forming process 500 and is predetermined. The organic EL device is formed. Therefore, the roll-shaped resin film of the present invention achieves a flexible organic EL device having high barrier properties, low power consumption, and high production efficiency.

  As described above, according to the production method of the present invention, the roll-shaped resin film is formed by continuously forming a barrier film and a transparent conductive film on the barrier film by a roll-to-roll method, and winding up again in a roll shape.

  Hereinafter, preferred embodiments will be described.

  A barrier film (70 nm) made of silicon oxide and an ITO film with a thickness of 100 nm were formed on a polyethylene terephthalate film with a thickness of 200 nm according to the method for producing a roll-shaped resin film having a transparent conductive film described above.

In addition, the barrier film forming step
(Gas condition)
Discharge gas: Nitrogen gas 94.99 volume%
Thin film forming gas: tetraethoxysilane 0.01% by volume
Additive gas: Oxygen gas 5.0% by volume
(Electrode condition)
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10 W / cm ² (the voltage Vp at this time was 7 kV)
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10 W / cm ² (the voltage Vp at this time was ² kV)
Electrode temperature 90 ° C
In addition, the film formation in the transparent conductive film forming step was performed as follows.

The inside of the chamber is evacuated to about 10 ⁻⁵ to 10 ⁻⁶ Torr, the evaporation material made of the raw material In / Sn oxide of the transparent conductive film is used in the raw material container 320, and the pressure gradient plasma gun 310 outputs The supply voltage was adjusted to 100 A, Ar gas was supplied from the plasma gun 310 into the chamber at a flow rate of about 50 sccm, and the chamber was adjusted to a pressure of about 10 ⁻³ to 10 ⁻⁴ Torr. Also, O2 gas, which is a reactive gas, was adjusted and supplied so that the oxygen partial pressure became a maximum of 1 × 10 ⁻⁴ Torr or less during film formation.

The substrate temperature was 150 ° C. in the film formation state. Under this condition, the pressure gradient type plasma gun 310 is operated to focus the plasma beam P on the evaporation material of the raw material container 320, and the evaporated evaporation material reacts with the O ₂ gas, and on the substrate F in the film formation region. An ITO film was formed. The formed ITO film had a resistivity of 1.5 × 10 ⁻⁴ Ω · cm or less.

An organic EL device can be obtained by forming, for example, each of the following organic EL layers on the roll-shaped resin film having a barrier film and a transparent conductive film (ITO film) thus obtained. That is, an organic EL element material α-NPD is used as a hole transport layer to form a vapor deposition layer having a thickness of 500 mm, Alq ₃ is vapor deposited to a thickness of 600 mm, and a light emitting layer is further formed from aluminum (cathode). ) Is deposited to a film thickness of 2000 mm.

  The structure of each layer of the organic EL is not limited to the above, and various types such as those composed of anode / light emitting layer / electron transport layer / cathode, and those composed of anode / hole transport layer / light emitting layer / electron transport layer / cathode, etc. The known configuration may be used. The light emitting layer is not limited to the above, and there is a phosphorescent light emitting type containing a host compound and a phosphorescent dopant compound in addition to the fluorescent light emitting type.

  As described above, the resin film having the transparent conductive film of the present invention is used as a substrate, and each organic layer and cathode constituting the organic EL are separately formed on the transparent conductive film by the organic EL formation process 500, and the cutting process is performed. The organic EL panel is formed by cutting into a predetermined size.

  Further, when a gas barrier film such as a vapor deposition film of silica, alumina or the like is used, and this is adhered to a substrate to seal the element, an organic EL panel having high resistance to gas such as moisture and oxygen can be obtained.

Claims (6)

In the method for producing a roll-shaped resin film having a transparent conductive film, a barrier film is formed at least under atmospheric pressure or a pressure environment in the vicinity thereof, and then the transparent conductive film is formed under a vacuum environment via a pressure adjusting unit. The manufacturing method of the roll-shaped resin film which has a transparent conductive film characterized by forming into a film by roll-to-roll continuously on a resin film base material. The method for producing a roll-shaped resin film having a transparent conductive film according to claim 1, wherein the pressure adjusting unit comprises a plurality of buffer chambers. The barrier film is supplied with a gas containing a thin film forming gas and a discharge gas in a discharge space under an atmospheric pressure or a pressure environment in the vicinity thereof, and the gas is excited by applying a high-frequency electric field to the discharge space, 3. The production of a roll-shaped resin film having a transparent conductive film according to claim 1 or 2, wherein a film is formed on a resin film substrate by exposing the resin film to the excited gas. Method. The method for producing a roll-shaped resin film having a transparent conductive film according to any one of claims 1 to 3, wherein the transparent conductive film is formed by an ion plating method. The said transparent conductive film is formed into a film by a sputtering method, The manufacturing method of the roll-shaped resin film which has a transparent conductive film of any one of the Claims 1-3 characterized by the above-mentioned. An organic electro, which is provided on a resin film substrate produced by the method for producing a roll-shaped resin film having a transparent conductive film according to any one of claims 1 to 5. Luminescence element.