JP6903872B2 - Manufacturing method of gas barrier film laminate - Google Patents

Description

The present invention relates to a gas barrier film laminate, a method for producing a gas barrier film laminate, and an organic EL device using the gas barrier film laminate.

In the field of gas barrier films, in addition to conventional food packaging applications, product development for electronic components is being actively pursued. As an electronic component application, it is being used not only as a packaging material for products but also as a protective film for devices whose characteristics deteriorate due to moisture, such as solar cells, which are promising as alternative energy to petroleum.

Among the devices that deteriorate due to moisture, the organic EL device, which is attracting attention as a thin display, is extremely sensitive.

In an organic EL device, electrodes are arranged on both sides of a very thin light emitting layer made of an organic substance, and one is used as an anode for injecting holes and the other is used as a cathode for injecting electrons to emit light by passing an electric current through the light emitting layer. ing. One of the electrodes needs to be transparent in order to extract the emitted light. Therefore, in relation to the work function, the anode is generally made of a transparent metal oxide, and the cathode is often a metal electrode.

However, in general, the organic light emitting layer and the electrode material are chemically changed by water and oxygen, and the charge injection may not be performed efficiently. In particular, the emission brightness of the organic EL device decreases due to moisture, and finally a non-emission region called a dark spot is generated.

Various methods have been established for some time to suppress this dark spot. One is that when the organic EL device is manufactured, the step of forming the electrode and the organic light emitting layer in particular is performed in an inert atmosphere such as N2 or a rare gas. Further, in order to protect the organic EL device from moisture in the atmosphere, it is completely sealed with a cap type cover made of metal or glass. Further, the atmosphere sealed between the organic EL device and the sealing cap is set to be an inert gas. That is, it is common that all the steps from film formation to sealing are performed in an inert atmosphere.

In the organic EL device manufactured in this way, it is said that the allowable external water vapor transmittance is 10 ^-3 g / m ² / day or less.

On the other hand, in recent years, due to the diversification of organic EL devices, flexibility is required for themselves, and devices called flexible organic EL devices in which an organic EL element is formed on a resin base film have been developed. .. In order to maintain the flexibility of the flexible organic EL device, it is not possible to use a thick glass material for the base material as in the conventional case, and it is not possible to seal with a metal or a glass material. Therefore, a flexible material having a water vapor permeability equivalent to that of glass or metal, that is, a high gas barrier film is desired.

The high gas barrier film is a resin base film coated with an inorganic thin film layer or an organic thin film layer called a gas barrier film that suppresses the permeation of water vapor. Well-known resin-based films include polyolefin films, acrylic films, polyester films such as Polyethylene trephthate (PET) and Polyehyrene naphlate (PEN), polyamide films, and polyimide films. In order to coat the gas barrier film on these resin base films, when the gas barrier film is an inorganic thin film layer such as _{aluminum (Al), aluminum oxide (Al 2} O ₃ ) or silicon oxide (SiO _{2), vacuum deposition is performed.} Generally, a film is formed by a method, a sputtering method, or a chemical vapor deposition method (CVD), and in the case of an organic thin film, a film is formed by a wet coating method in which a resin is dissolved in a solvent and applied.

By the way, there are several modes of gas permeation in the gas barrier film. One is the interaction between the gas barrier membrane and the permeated gas, that is, a mode based on chemical properties such as affinity and reactivity. Another mode is derived from the morphology and denseness of the gas barrier membrane, and the gas permeates through the grain boundaries of the particles constituting the gas barrier membrane and the pinholes of the gas barrier membrane.

Various developments have been disclosed to suppress gas permeation for modes derived from the morphology of gas barrier membranes.

A typical example is a method of reducing foreign substances and scratches on the resin base film as much as possible in order to eliminate pinhole defects in the gas barrier film. Patent Document 1 discloses a biaxially oriented polyester film and a vapor-deposited gas barrier film using the same, limits the number of protrusions and surface roughness accompanied by depression on the vapor-deposited film-forming surface of the resin-based film, and also limits the resin-based film. It limits the size and number of foreign substances present inside. In Patent Document 2, a resin thin film layer made of an epoxy compound is laminated on a resin base film, and an inorganic oxide is vapor-deposited on the resin thin film layer by a vacuum film forming method to reduce the surface average roughness to 4 nm or less. The body is disclosed.

Further, even if there are pinholes in the gas barrier film due to scratches or foreign matter on the resin base film, the development of improving the gas barrier property by lengthening the gas permeation path and delaying the gas permeation is also disclosed. _{In Patent Document 3, a transparent inorganic gas barrier film made of SiO 2} or the like and a polymer film produced by the sol-gel method are alternately laminated on a resin base film, and the pinholes of the gas barrier film are filled with the polymer film to delay gas permeation. The technology is disclosed. In Patent Document 4, an inorganic monoorganic hybrid polymer film composed of polymethoxysiloxane, an organosilicon compound and an aluminum compound is laminated on an inorganic gas barrier film composed of silicon (Si), oxygen (O) and carbon (C) to form a polymer. A gas barrier film having a gas barrier property of the film is disclosed.

In order to increase the density of the inorganic gas barrier film, a film forming method is also being studied. In recent years, in addition to the conventional film forming method described above, many formations of gas barrier films by an atomic layer deposition method (ALD) have been developed.

The ALD method is a method in which a substance adsorbed on the surface is deposited layer by layer at the atomic level by a chemical reaction on the surface. A special film-forming method in which a thin film is grown layer by layer at the atomic level by adsorption on the substrate surface and subsequent chemical reaction by alternately using highly active gas and reactive gas, which are also called precursors or precursors. is there.

The specific film formation method of the ALD method utilizes the so-called self-limiting effect, in which when the substrate surface is covered with a certain gas, no further adsorption of the gas occurs, and only one layer of the precursor is adsorbed. By the way, the unreacted precursor is exhausted. Subsequently, a reactive gas is introduced to oxidize or reduce the precursor to obtain only one thin film having a desired composition, and then the reactive gas is exhausted. Such a process is regarded as one cycle, and this cycle is repeated to grow the thin film. Therefore, in the ALD method, the thin film grows two-dimensionally. Further, the ALD method is characterized in that there are few film forming defects as compared with the conventional film forming method.

In addition, the ALD method has features such as no oblique shadow effect (a phenomenon in which film-forming particles are obliquely incident on the substrate surface to cause film-forming variation) as compared with other film-forming methods. If there is, uniform film formation is possible. With respect to uneven scratches on the resin base film, the conventional film-forming method cannot completely cover the uneven portion with the film-forming particles, whereas the ALD method forms the film so as to follow the unevenness. Therefore, pinhole defects can be significantly reduced.

Patent Document 5 discloses a technique for forming an inorganic gas barrier film on a resin base film by the ALD method, and realizes a light-transmitting barrier film capable of reducing gas transmission by an order of magnitude at a thickness of several tens of nm. doing.

Further, Patent Document 6 discloses a technique relating to a film forming apparatus for forming a gas barrier film on a resin base film by using the ALD method. According to this technique, an ALD film is formed on the surface of the resin base film mounted on the conveyor in a flow in which the resin base film is mounted on the conveyor and moved through the vacuum chamber. Further, a gas barrier film having a high gas barrier property is produced at high speed by winding a resin base film on which an ALD film is laminated on a winding drum.

Japanese Patent No. 5151000 Japanese Patent No. 4014931 Japanese Unexamined Patent Publication No. 2005-288851 Japanese Unexamined Patent Publication No. 2014-141555 Japanese Patent Application Laid-Open No. 2007-516347 Special Table 2007-522344 Gazette

However, since the gas barrier films disclosed in Patent Documents 1 and 2 have a water vapor transmission rate of ^{about 1 g / m 2} / day, there is a problem that the gas barrier properties for use in organic EL devices are not sufficient. Further, the gas barrier films disclosed in Patent Documents 3 and 4 require a total gas barrier film of 100 nm or more, which causes a problem of productivity.

Further, the gas barrier film disclosed in Patent Document 5 and the gas barrier film produced by the manufacturing method disclosed in Patent Document 6 are ^{about 1 × 10 -3} g / m ² / day due to the thin film OLED gas barrier film that follows the unevenness of the base material. Although the gas barrier performance was remarkably improved, there was a problem that it was not sufficient to completely suppress the dark spots of the organic EL device.

In order to suppress dark spots in the organic EL device, it is necessary to suppress surface irregularities as much as possible in addition to the high gas barrier performance of the gas barrier film. This is because the members such as the organic light emitting layer and the electrodes constituting the organic EL device have a thickness of several tens of nm, and defects are easily formed in the organic EL device member due to the unevenness existing on the surface of the organic EL device base material. .. The resin base film used for the gas barrier film originally has surface scratches, and the protrusions of the surface scratches have a height of several hundred nm or more. Until now, defects in the gas barrier film made of a resin base film containing protrusions and the organic EL device member using this laminate as a base have been unavoidable.

The present invention has been made in view of such circumstances, the gas barrier film has a simple structure of a single layer, and the water vapor permeability under the conditions of 40 ° C. and 90% RH is 5 × 10 ^-4 g / m. ^{It is an object of the present invention to provide a gas barrier film laminate having 2} / day or less and less surface unevenness, a method for producing a gas barrier film laminate, and an organic EL device using the gas barrier film laminate.

The gas barrier film laminate according to the present invention has one layer of inorganic gas barrier film laminated on the resin base film and at least one layer of passivation film laminated on the inorganic gas barrier film, and the surface maximum height of the passivation film surface is high and low. The difference is 100 nm or less, and the water vapor permeability under the conditions of 40 ° C. and 90% RH is 5 × 10 ^-4 g / m ² / day or less.

Further, in the gas barrier film laminate according to the present invention, the pore radius of the inorganic gas barrier film is preferably 0.15 nm or less.

Further, in the gas barrier film laminate according to the present invention, the film thickness of the inorganic gas barrier film is preferably 10 nm or more and 100 nm or less.

Further, in the gas barrier film laminate according to the present invention, it is preferable that the inorganic gas barrier film is a metal oxide, a metal nitride, or a metal carbide.

Further, in the gas barrier film laminate according to the present invention, the metals are aluminum (Al), silicon (Si), titanium (Ti), zinc (Zn), zirconium (Zr), niobium (Nb), tin (Sn), and hafnium. (Hf), tantalum (Ta), cerium (Ce), or a mixture thereof is preferable.

Further, in the gas barrier film laminate according to the present invention, it is preferable that the passivation film is silicon oxide (SiO ₂ ), silicon nitride (SiN), or silicon oxynitride (SiON).

Further, in the gas barrier film laminate according to the present invention, it is preferable that the water vapor permeability of the resin base film under the conditions of 40 ° C. and 90% RH is 5 g / m ² / day or less.

Further, in the gas barrier film laminate according to the present invention, it is preferable that the resin base film is any one of polyester-based resin, acrylic-based resin, and polyimide-based resin.

Further, in the gas barrier film laminate according to the present invention, the thickness of the resin base film is preferably 50 μm or more.

In the method for producing a gas barrier film laminate according to the present invention, a layer of an inorganic gas barrier film is laminated on a resin base film by the ALD method, and at least one more passivation film made of a silicon compound is laminated on the inorganic gas barrier film. The resist layer is laminated so as to cover the entire surface, and the surface of the gas barrier film laminate on which the resist layer is laminated is completely dry-etched back to remove the resist layer and a part of the passivation film, and the surface of the gas barrier film laminate is removed. The maximum height difference on the surface of the film is 100 nm or less.

Alternatively, in the gas barrier film laminate according to the present invention, one layer of an inorganic gas barrier film is laminated on a resin base film by the ALD method, and at least one passivation film made of a silicon compound is laminated on the inorganic gas barrier film to form a passivation film. A part of the passivation film is removed by laminating a resist layer having a thickness thinner than the maximum height difference of the passivation layer on the surface and wet-etching back the entire surface of the gas barrier film laminate on which the resist layer is laminated to remove a part of the passivation film. It may be manufactured by setting the maximum surface height difference of the surface of the film laminate to 100 nm or less.

Further, in the method for producing a gas barrier film laminate according to the present invention, the passivation film may be formed by a CVD method.

Further, the organic EL device according to the present invention is characterized in that at least one of the base material and the sealing material is the above-mentioned gas barrier film laminate.

According to the present invention, it is possible to provide a gas barrier film having ^{a water vapor transmittance of 5 × 10 -4} g / m ² / day or less under the conditions of 40 ° C. and 90% RH and having less surface unevenness. Further, by using the gas barrier film, it becomes possible to provide an organic EL device having few dark spots.

It is sectional drawing which shows the structure of the gas barrier film laminated body which concerns on embodiment of this invention. It is a figure which shows the 1st manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is the cross-sectional view of the gas barrier film laminated body after the passivation film film formation. It is a figure which shows the 1st manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is sectional drawing of the gas barrier film laminated body after resist coating. It is a figure which shows the 1st manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is the cross-sectional view of the gas barrier film laminated body after dry etching of a resist and a passage film. It is a figure which shows the 2nd manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is the cross-sectional view of the gas barrier film laminated body after the passivation film film formation. It is a figure which shows the 2nd manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is sectional drawing of the gas barrier film laminated body after resist coating. It is a figure which shows the 2nd manufacturing method of the gas barrier film laminated body which concerns on embodiment of this invention, and is the cross-sectional view of the gas barrier film laminated body after wet etching. It is sectional drawing of the organic EL apparatus which concerns on embodiment of this invention.

<Embodiment of Gas Barrier Film Laminated Body>
FIG. 1 is a cross-sectional view showing an example of a gas barrier film laminate 1 according to an embodiment of the present invention.

As shown in FIG. 1, the gas barrier film laminate 1 has a structure in which an inorganic gas barrier film 3 and a passivation film 4 are laminated on a resin base film 2.

Here, the material of the resin base film 2 can be selected from polyester resin, acrylic resin, and polyimide resin, but polyester resin such as PET or PEN having low water vapor permeability and oxygen permeability is preferable. Further, a PEN film is more preferable from the viewpoint of heat resistance. Further, since the gas permeability of the resin base film 2 itself depends on the thickness of the film, the thickness is set to 50 μm or more in order to obtain a higher gas permeability, and the water vapor permeability is 5 g / m ² / day or less. ..

The inorganic gas barrier film 3 is a transparent ceramic thin film such as a metal oxide, a metal nitride, or a metal carbide formed by the ALD method. Generally, when the barrier membrane is a resin material, the free volume becomes high due to the interaction between the polymers and the gas easily permeates, but the ceramic film has a low free volume, so that the gas does not easily permeate. Further, the inorganic gas barrier film 3 formed by the ALD method is denser than the film formed by other film forming methods because it grows two-dimensionally as described above, and its average pore radius is smaller than the molecular radius of water vapor. It will be 0.15 nm or less. Moreover, since the inorganic gas barrier film 3 formed by the ALD method is formed so as to follow the fine irregularities of the resin base film, there are extremely few defects. Examples of the metal include Al, Si, Ti, Zn, zr, Nb, Sn, Hf, Ta, and Ce, and the composition thereof is selected depending on the intended use of the gas barrier film laminate 1. For example, when used as a base material for a bottom emission type organic EL device, SiO ₂ and Al ₂ O ₃ are suitable because insulation is required in addition to high light transmittance.

When the inorganic gas barrier film 3 on the resin base film 2 has a film thickness of 10 nm or more, its water vapor permeability is 5 × ^10-4 g / m ² / day or less, and therefore, from the viewpoint of gas barrier performance, it is 10 nm or more. A film thickness is sufficient, but as the film thickness increases, the inorganic gas barrier film 3 is liable to crack due to bending, and cracks, that is, linear film defects occur. Therefore, the inorganic gas barrier film 3 is set to 100 nm or less.

The passivation film 4 is a SiO ₂ or SiN or SiON film having high transparency and chemical durability. Further, the film thickness of the passivation film 4 needs to be equal to or larger than the protrusion height of the resin base film, and is 300 nm or more, preferably 500 nm or more. The passivation film 4 may be in contact with the inorganic gas barrier film 3, but a buffer layer (not shown) such as a resin coat film may be provided between the passivation film 4 and the inorganic gas barrier film 3.

<Embodiment of Method for Manufacturing Gas Barrier Film Laminated Body>
An embodiment of a method for producing the gas barrier film laminate 1 will be described. The gas barrier film laminate 1 according to the present embodiment can be manufactured by any of the first manufacturing method and the second manufacturing method described below.

(First manufacturing method)
FIGS. 2 to 4 are views showing a first manufacturing method of the gas barrier film laminate according to the embodiment of the present invention.

First, the resin base film 2 is prepared. Generally, the resin base film 2 heats and pressurizes the raw material resin, and stretches the resin coming out of the die slit in two axes in the flow direction (MD) and the width direction (TD) to form a film. The produced base resin film is divided (slit) into a desired width, and each is wound into a roll.

The resin base film 2 produced in this way has a protrusion of 300 nm or more on the surface due to contact with a transport roller of a manufacturing apparatus or a slitter, or foreign matter being caught in the film roll during winding. Deformation often occurs. Further, since environmental suspended matter and chips at the time of slitting are attached to the surface of the resin base film 2, the resin base film 2 may be washed before forming the inorganic gas barrier film 3. The cleaning means of the resin base film 2 is selected from a film contact type rubber roller cleaning method, an ultrasonic dry air cleaning method in which air to which ultrasonic waves are applied is blown at a high pressure, a wet cleaning method using water and chemicals, and the like. ..

Next, as shown in FIG. 2, the inorganic gas barrier layer 3 is formed on the resin base film 2 by the ALD method. The resin base film 2 is allowed to stand in the film forming chamber of the ALD film forming apparatus, and the inside of the chamber is evacuated. Next, when the inorganic gas barrier film 3 is Al ₂ O ₃ , an organoaluminum compound (trimethylaluminum: TMA) precursor containing Al is introduced into the chamber. As a result, when the TMA is adsorbed on the resin base film 2 and the excess precursor is purged for a certain period of time, the TMA for one molecular layer is adsorbed on the surface of the base resin film 2.

Subsequently, water (H ₂ O), ozone (O ₃ ), plasmatized oxygen (O ₂ ), or the like is introduced into the chamber as a reactive gas to oxidize the TMA, and then the excess reactive gas is purged. ..

This series of steps is regarded as one cycle, and the cycle is repeated until the desired thickness is reached, so that the inorganic gas barrier film 3 is formed on the resin base film 2. At this time, in the protrusions of the resin base film 2, the inorganic barrier membrane 3 is formed following the protrusions.

Next, as shown in FIG. 2, a _{passivation film 4 made of SiO 2} or SiN or SiON is formed on the inorganic gas barrier film 3 by the CVD method. The resin base film 2 on which the inorganic gas barrier film 3 is formed is allowed to stand on the lower electrode in the film forming chamber of the CVD film forming apparatus, and the inside of the chamber is evacuated. Next, when the inorganic gas barrier film 3 is SiO ₂ , the organic silicon compound precursor containing Si, the O ₂ gas, and the diluted gas are introduced into the chamber, and when a high frequency is applied to the upper electrode and the lower electrode, O is formed between the counter electrodes. ₂ Plasma is formed. The organic silicon compound is oxidized to _{SiO 2} by this O _{2 plasma.} The passivation film 4 is formed on the inorganic gas barrier film 3 by forming a film until it reaches a desired thickness. At this time, since the film thickness of the passivation film 4 needs to be thicker than the height of the protrusions on the resin base film 2, it is preferably 300 nm or more, and more preferably 500 nm or more. However, as shown in FIG. 2, on the surface of the passivation film 4, there are still protrusions having a maximum height difference of about 250 nm.

Next, as shown in FIG. 3, a resist film 5 is applied onto the passivation film 4 so as to cover the entire surface of the passivation film 4. The resist film 5 is selected in the dry etching described later, in which the reaction selectivity in the dry etching gas is equal to that of the passivation film 4 which is the object to be etched. At this time, as shown in FIG. 3, since the resist film 5 is a liquid coating film, the difference in surface height is almost alleviated and becomes 100 nm or less. The film thickness of the resist film 5 is preferably 500 nm or more.

Subsequently, the resin base film on which the resist film 5 is formed is etched by a dry etching method. Since the passivation film 4 and the resist film 5 have the same reaction selectivity with respect to the etching gas, they are uniformly etched from the surface depending on the etching time. That is, when all the resist film 5 is etched, the protrusions of the passivation film 4 are etched together with the resist film 5, and as a result, the passivation film 4 becomes a flat film having a maximum height difference of 100 nm or less as shown in FIG. Become.

In this way, the gas barrier film laminate 1 is manufactured.

(Second manufacturing method)
FIGS. 5 to 7 are views showing a second manufacturing method of the gas barrier film laminate according to the embodiment of the present invention.

First, as shown in FIG. 5, the inorganic gas barrier film 3 and the passivation film 4 are laminated on the resin base film 2. The inorganic gas barrier film 3 and the passivation film 4 can be formed by the method described in the first manufacturing method.

Next, as shown in FIG. 6, the resist film 5 is applied onto the passivation film 4 by a spin coating method or the like. The film thickness of the resist film 5 is made thinner than the maximum height difference on the surface of the passivation film 4. When the maximum height difference of the passivation film 4 is 100 nm or less, the film thickness of the resist film 5 is preferably 100 nm or less. At this time, as shown in FIG. 6, since the resist film 5 is a liquid coating film, the resist is not applied to the protrusions of the passivation film 4, and the passivation film 4 on the protrusions is exposed from the resist film 5.

Subsequently, the surface of the passivation film 4 on which the resist film 5 is formed is wet-etched with dilute hydrofluoric acid or phosphoric acid. At this time, only the portion where the resist film 5 does not cover the passivation film 4, that is, the protrusion of the passivation film 4 is etched, and as shown in FIG. 7, the passivation film 4 is a flat film having a maximum height difference of 100 nm or less. Become. After that, the gas barrier film laminate 1 can be obtained by peeling off the resist film 5.

<Embodiment of Organic EL Device>
FIG. 8 is a cross-sectional view showing an example of the organic EL device 6 according to the present invention.

In the organic EL device 6, the anode 7, the hole injection layer 8, the hole transport layer 9, the light emitting layer 10, the electron transport layer 11, and the cathode 12 are laminated in this order on the passivation film 4 of the gas barrier film laminate 1. Further, the cap sealing material 13 is attached to the upper part with the resin adhesive material 14 so as to cover all the layers.

Next, a specific example of the gas barrier film laminate realized based on the above embodiment will be described.

<Example 1>
First, a water vapor barrier film laminate was prepared. At this time, a PET film having a thickness of 100 μm and a maximum height difference of about 400 nm showing a water vapor transmittance of 4.7 g / m ^{2 / day was used as the base material.} The PET film cut out in the form of a sheet was fixed to a jig of a nozzle-type ultrasonic cleaner with the surface facing up, and 950 kHz ultrasonic applied pure water was discharged for cleaning. Immediately after that, dry air was blown onto the surface of the PET film with an air knife device under the conditions of 0.5 MPa and a flow velocity of 50 m / s to dry the PET film, and then the washed PET film was allowed to stand in a clean oven for 24 hours at 80 ° C. It was dried.

Next, an ALD-Al ₂ O ₃ film was formed on the dried PET film. A PET film was placed on a substrate stage in the ALD film forming apparatus chamber, the substrate stage was held at 90 ° C., the chamber was sealed, and then exhausted with a vacuum pump. Next, the precursor TMA was introduced into the chamber together with the carrier gas N2 for 60 msec, adsorbed on the surface of the PET film, and then exhausted for 10 sec while flowing N2 to purge the surplus TMA.

_{Subsequently, H 2} O, which is a reaction gas, was introduced into the chamber together with the carrier gas N ₂ for 60 msec, and TMA and H ₂ O were reacted to form Al ₂ O ₃ . Then, _{while flowing N 2} , the excess H ₂ O was purged by exhausting for 10 seconds. A series of operations from these TMA introduced until surplus _{H 2} O purge to as one cycle, was deposited 138 cycles repeat _Al 2 _{O 3. The film thickness of Al 2} O ₃ formed at this time was 24.0 nm.

Subsequently, CVD-SiO ₂ was formed on the ALD-Al ₂ O _{3 film. A PET film on which ALD-Al 2} O ₃ was formed was placed on a lower electrode mounted in a chamber of a plasma (PE) CVD film forming apparatus, sealed, and then exhausted by a vacuum pump. Hexamethyldisiloxane (HMDSO) was used as a raw material, and O ₂ and argon (Ar) gas were used as reaction gases. _{The film was formed by forming a CVD-SiO 2} film having a film thickness of about 800 nm under the conditions of a total pressure of 5.0 Pa, a substrate temperature of 80 ° C., a discharge power frequency of 13.56 MHz, and a power of 100 W to prepare a laminate. At this time, the maximum height difference on the surface of _{the CVD-SiO 2 film was 318 nm.}

Subsequently, a resist was applied onto the CVD-SiO _{2 film. As the resist, one having a selectivity of 1 with the SiO 2} film was selected for dry etching, and the resist was applied by a spin coating method at a rotation speed of 3000 rpm. At this time, the resist film thickness was about 500 nm.

Subsequently, the surface of the laminate coated with the resist was entirely etched by a dry etching method using a reactive ion etching apparatus. The laminate coated with the resist was placed on the electrode stage, sealed, and then exhausted by a pump. _{A mixed gas of C 4} F ₈ / CO / Ar was used as the etching gas, ^{and the treatment was performed at a power density of 3.0 W / cm 2} , a total pressure of 5.0 Pa, and a substrate temperature of 30 ° C. First, about 500 nm, which corresponds to the resist film thickness, was etched, and then the CVD-SiO ₂ film was etched by about 200 nm under the same etching conditions. At this time, the maximum height difference of the surface of _{the exposed CVD-SiO 2 film was 78 nm.}

The water vapor permeability of the produced water vapor barrier film laminate was confirmed by the calcium (Ca) corrosion method. Ca was deposited at 100 nm on the passivation film of the water vapor barrier film laminate by a vacuum vapor deposition method, and then Al was deposited on Ca at 1 μm. The film formation area was 1 cm square for Ca and 2 cm square for Al so as to cover Ca. A water vapor barrier film laminate in which Ca and Al were laminated was attached to a glass plate using a resin adhesive to prepare a structure for measuring water vapor transmittance.

The water vapor barrier film laminate according to Example 1 was held at 40 ° C. and 90% temperature and humidity for a predetermined time, and the water vapor transmittance was calculated while measuring the corrosion area ratio of the entire surface of Ca over time. As a result, 6.4 × 10 ^{It was -5} g / m ² / day.

Next, an organic EL element was formed on the produced water vapor barrier film laminate. After forming a take-out electrode on the water vapor barrier film, the anode, the hole injection layer, the hole transport layer, and the light emitting layer were sequentially applied by a spin coating method. Next, the electron injection layer and the cathode were formed by vacuum deposition, and the cap sealing layer was attached with a resin adhesive in a nitrogen atmosphere.

When the organic EL element according to Example 1 was stored for 168 hours in a moist heat environment of 40 ° C./90% and a lighting test was performed, four dark spots of 100 to 800 μm were confirmed per ^{1 cm 2.}

<Example 2>
_{An ALD-Al 2} O ₃ film and a CVD-SiO ₂ film were formed on the PET film by the same material and manufacturing method as in Example 1. The film thicknesses of the _{Al 2} O ₃ film and the SiO _{2 film, and the maximum height difference on the surface of the SiO 2} film are the same as in Example 1.

Subsequently, a resist was applied onto the CVD-SiO2 film. The resist was applied by a spin coating method at a rotation speed of 4000 rpm. At this time, the resist film thickness was 108 nm.

Subsequently, the laminate coated with the resist was entirely etched with dilute hydrofluoric acid. The laminate was fixedly placed on a fluororesin plate and then rotated at 500 rpm, and 5% hydrofluoric acid was sprayed on the resist surface of the laminate with a spray nozzle for 30 seconds. Then, pure water was sprinkled from the rinse nozzle, the dilute hydrofluoric acid was thoroughly washed, and then spin-dried at 3000 rpm.

Subsequently, the resist on the laminate completely etched with dilute hydrofluoric acid was removed by an oxygen ashing treatment. At this time, the maximum height difference of the surface of the exposed CVD-SiO2 film was 92 nm.

The water vapor transmittance of the water vapor barrier film laminate according to Example 2 was 8.2 × ^10-5 g / m ² / day as measured by the above-mentioned calcium (Ca) corrosion method.

Next, an organic EL element was formed on the water vapor barrier film laminate according to Example 2 by the method described above. When the produced organic EL device was stored for 168 hours in a moist heat environment of 40 ° C./90% and a lighting test was performed, 12 dark spots of 100 to 800 μm were confirmed per ^{1 cm 2.}

<Comparative example 1>
_{An ALD-Al 2} O ₃ film is formed on the PET film by the same material and manufacturing method as in Example 1, a CVD-SiO _{2 film is formed on the ALD-Al 2} O ₃ at 600 nm, and the film is dried after the film formation. A steam barrier film was prepared without etching back. When the water vapor transmittance was measured by the Ca method after preparation, it was 3.8 × 10 ^-4 g / m ² / day. After that, an organic EL device was produced under the same conditions as in Example 1, stored for 168 hours in a moist heat environment of 40 ° C./90%, and then a lighting test was performed. As a result, there were 81 ^{dark spots of 100 to 800 μm per 1 cm 2.} ..

As described above, according to the present invention 40 ° C., a high gas barrier film and a dark spot less organic EL device the water vapor transmission rate is not more than ^{5 × 10- 4 g / m 2} / day at 90% RH conditions It was confirmed that it could be provided.

Although the embodiment of the laminate according to the present invention has been described in detail with reference to the drawings, the specific configuration of the present invention is not limited to the contents of the above-described embodiment and does not deviate from the gist of the present invention. Even if there are changes in the design of the range, they are included in the present invention.

The present invention can be used for a gas barrier film, and particularly preferably for a gas barrier film used as a base material for an organic EL device.

1 Gas barrier film laminate 2 Resin base film 3 Inorganic gas barrier film 4 Passion film 5 Resist film 6 Organic EL device 7 Anode 8 Hole injection layer 9 Hole transport layer 10 Light emitting layer 11 Electron transport layer 12 Cathode 13 Cap encapsulant 14 Resin adhesive

Claims (2)

A single layer of inorganic gas barrier film is laminated on the resin base film by the ALD method.
At least one layer of a silicon oxide (SiO ₂ ), silicon nitride (SiN), or silicon nitride (SiON) film is laminated on the inorganic gas barrier film by a CVD method.
A resist layer is laminated so as to cover the entire surface of the silicon oxide, silicon nitride, or silicon nitride film.
By dry etching back the entire surface of the gas barrier film laminate on which the resist layer is laminated, the resist layer and a part of the silicon oxide or silicon nitride or silicon nitride film are removed, and the surface of the gas barrier film laminate is removed. A method for producing a gas barrier film laminate, wherein the maximum surface height difference is 100 nm or less. A single layer of inorganic gas barrier film is laminated on the resin base film by the ALD method.
At least one layer of a silicon oxide (SiO ₂ ), silicon nitride (SiN), or silicon nitride (SiON) film is laminated on the inorganic gas barrier film by a CVD method.
A resist layer having a thickness thinner than the maximum height difference of the silicon oxide, silicon nitride, or silicon nitride film is laminated on the surface of the silicon oxide, silicon nitride, or silicon nitride film.
A part of the silicon oxide, silicon nitride, or silicon nitride film is removed by wet-etching back the entire surface of the gas barrier film laminate on which the resist layer is laminated, and then the resist layer is removed to remove the gas barrier film. A method for producing a gas barrier film laminate, wherein the maximum surface height difference on the surface of the laminate is 100 nm or less.

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