JP2016051569A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electroluminescent element which enables the prevention of degradation owing to water vapor at a higher level, and which can be stored or used over a longer period of time.SOLUTION: An organic electroluminescent element comprises: a transparent support substrate 1; a light-emitting element part 2 including a first electrode 201 and a second electrode 203, and a light-emitting layer 202; a sealing material layer 3 disposed on the transparent support substrate so as to seal the light-emitting element part; and a sealing substrate 4. The transparent support substrate is composed of a gas barrier laminate film. The gas barrier laminate film includes a first thin layer 101(a) and a second thin layer 101(b) which have a gas barrier property, a first base layer 100(a) and a second base layer 100(b), and an adhesive layer 102, and has a laminate structure in which the first thin layer, the first base layer, the adhesive layer, the second thin layer, and the second base layer are laminated in this order. One electrode of the light-emitting element part is laminated on the first thin layer of the gas barrier laminate film.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an organic electroluminescence element.

  An organic electroluminescence element deteriorates when oxygen gas, water vapor, or the like enters the element, and a light emission failure portion called a dark spot occurs. Therefore, in the field of organic electroluminescence elements, in order to suppress oxygen gas and water vapor from entering the inside of the element, a substrate having high gas permeation prevention performance such as water vapor is used for the support substrate of the light emitting element portion. Has been proposed.

  As an organic electroluminescence element of a form using such a substrate having gas permeation prevention performance, for example, in JP-A-2005-235743 (Patent Document 1), a first polymer substrate layer, a second polymer substrate layer, Each of the polymer substrate layers is covered with one or more diffusion prevention barriers, and the polymer substrate layers covered with the diffusion prevention barriers are bonded together so that the diffusion prevention barriers face each other inside. An apparatus including a laminated film obtained in combination and an organic electroluminescence element disposed on the laminated film is disclosed. Moreover, in JP2011-073430A (Patent Document 2), a gas barrier film comprising a base material and at least one thin film layer formed on at least one surface of the base material, At least one of the thin film layers contains silicon, oxygen and carbon, and the distance from the surface of the layer in the thickness direction of the layer and the total amount of silicon atoms, oxygen atoms and carbon atoms Distribution curve showing the relationship between the ratio of the amount of silicon atoms to silicon (the atomic ratio of silicon), the ratio of the amount of oxygen atoms (the atomic ratio of oxygen), and the ratio of the amount of carbon atoms (the atomic ratio of carbon), oxygen A gas barrier film in which a distribution curve and a carbon distribution curve satisfy specific conditions is disclosed, and it is disclosed that the film can be used for an organic electroluminescence device. Patent Document 2 discloses that a plurality of gas barrier films as described above may be bonded together by an adhesive layer.

JP 2005-235743 A JP 2011-073430 A

  However, the organic electroluminescence element as described in Patent Document 1 cannot sufficiently suppress the intrusion of water vapor into the element in a normal use environment such as in an air atmosphere, and is stored for a long time. However, when used over a long period of time, the occurrence of defective light emission could not be sufficiently suppressed. On the other hand, the gas barrier film described in Patent Document 2 is capable of exhibiting a sufficiently high water vapor permeation prevention performance. No specific use method for the electroluminescence element is disclosed, and the technique described in Patent Document 2 is not necessarily sufficient in terms of preventing deterioration due to water vapor at a higher level, and is longer. The advent of an organic electroluminescence device that can be stored and used for a long time is desired.

  The present invention has been made in view of the problems of the prior art, can prevent deterioration due to water vapor at a higher level, can sufficiently suppress the occurrence of defective light emission over a long period of time, and for a longer period of time. An object of the present invention is to provide an organic electroluminescence device that can be stored and used for a long time.

  As a result of intensive studies to achieve the above object, the present inventors have made an organic electroluminescence element comprising a transparent support substrate and a light emitting element portion (a pair of electrodes and the electrode disposed on the transparent support substrate). A light emitting element portion having a light emitting layer disposed therebetween), a sealing material layer disposed on the transparent support substrate so as to seal the light emitting element portion, and disposed on the sealing material layer The transparent support substrate is made of a gas barrier laminate film, and the gas barrier laminate film is made up of first and second thin film layers having gas barrier properties, A second base material layer and an adhesive layer are provided, and the laminated structure thereof is the first thin film layer, the first base material layer, the adhesive layer, the second thin film layer, Laminated in order of the second base material layer In addition, by laminating one electrode of the light emitting element portion on the first thin film layer of the gas barrier laminate film, the organic electroluminescence element prevents deterioration due to water vapor at a higher level. As a result, it has become possible to sufficiently suppress the occurrence of defective light emission over a long period of time, and it has been found that it can be stored and used for a sufficiently long period of time, thereby completing the present invention.

That is, the organic electroluminescence element of the present invention comprises a transparent support substrate,
A light-emitting element unit that is disposed on the transparent support substrate and includes a pair of electrodes and a light-emitting layer disposed between the electrodes;
A sealing material layer disposed so as to seal the light emitting element portion on the transparent support substrate;
A sealing substrate disposed on the sealing material layer;
With
The transparent support substrate is made of a gas barrier laminate film,
The gas barrier laminate film includes first and second thin film layers having gas barrier properties, first and second base material layers, and an adhesive layer, and the first thin film layer and the first thin film layer The base material layer, the adhesive layer, the second thin film layer, and the second base material layer are laminated in this order,
One electrode of the light emitting element part is laminated on the first thin film layer of the gas barrier laminate film,
It is characterized by.

  In the organic electroluminescence device of the present invention, the first thin film layer is preferably a thin film layer containing at least one of a metal oxide, a metal nitride, and a metal oxynitride.

  In the organic electroluminescence device of the present invention, the second thin film layer is preferably a thin film layer containing at least one of a metal oxide, a metal nitride, and a metal oxynitride.

Furthermore, in the organic electroluminescence device of the present invention, at least one of the first and second thin film layers contains silicon, oxygen, and carbon, and
The distance from the surface of the layer in the thickness direction of the layer, the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon), the ratio of the amount of oxygen atoms (the ratio of oxygen In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the atomic ratio) and the ratio of the amount of carbon atoms (carbon atomic ratio), the following conditions (i) to (iii):
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more,
A silicon oxide thin film layer satisfying all of the above is preferable.

  In the organic electroluminescence device of the present invention, it is preferable that both the first and second thin film layers are the silicon oxide-based thin film layers.

  Furthermore, in the organic electroluminescence device of the present invention, a third thin film layer having gas barrier properties is laminated on the surface of the second base material layer on which the second thin film layer is not laminated. It is preferable.

  Moreover, in the organic electroluminescent element of the said invention, it is preferable that the said gas-barrier laminated | multilayer film has the moisture absorption performance which absorbs 0.1 mass% or more of water of own weight.

  According to the present invention, there is provided an organic electroluminescence device that can prevent deterioration due to water vapor at a higher level, can sufficiently suppress the occurrence of defective light emission over a long period of time, and can be stored and used for a longer period of time. It becomes possible to do.

It is a schematic longitudinal cross-sectional view which shows typically suitable one Embodiment of the organic electroluminescent element of this invention. It is a schematic diagram which shows one Embodiment of the manufacturing apparatus of a thin film which can be used suitably for manufacturing the layer which consists of a silicon oxide type thin film suitable as a thin film layer concerning this invention. It is a schematic longitudinal cross-sectional view which shows typically other suitable embodiment of the organic electroluminescent element of this invention. It is a schematic top view which shows typically the structure at the time of seeing the organic electroluminescent element obtained in Example 1 from the sealing substrate side.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and duplicate descriptions are omitted.

The organic electroluminescence device of the present invention comprises a transparent support substrate,
A light-emitting element unit that is disposed on the transparent support substrate and includes a pair of electrodes and a light-emitting layer disposed between the electrodes;
A sealing material layer disposed so as to seal the light emitting element portion on the transparent support substrate;
A sealing substrate disposed on the sealing material layer;
With
The transparent support substrate is made of a gas barrier laminate film,
The gas barrier laminate film includes first and second thin film layers having gas barrier properties, first and second base material layers, and an adhesive layer, and the first thin film layer and the first thin film layer The base material layer, the adhesive layer, the second thin film layer, and the second base material layer are laminated in this order,
One electrode of the light emitting element part is laminated on the first thin film layer of the gas barrier laminate film,
It is characterized by.

  FIG. 1 is a schematic longitudinal sectional view schematically showing a preferred embodiment of the organic electroluminescence element of the present invention. The organic electroluminescent element of the embodiment shown in FIG. 1 includes a transparent support substrate 1, a light emitting element portion 2, a sealing material layer 3, and a sealing substrate 4. Hereinafter, these will be described separately. In the following, “organic electroluminescence element” is sometimes abbreviated as “organic EL element”.

[Transparent support substrate 1]
A transparent support substrate 1 shown in FIG. 1 includes a first base material layer 100 (a), a second base material layer 100 (b), a first thin film layer 101 (a) having gas barrier properties, and a gas barrier. A second thin film layer 101 (b) having a property and an adhesive layer 102, and the first thin film layer 101 (a), the first base material layer 100 (a), and the adhesive layer 102, a gas barrier laminated film having a laminated structure in which the second thin film layer 101 (b) and the second base material layer 100 (b) are laminated in this order. By using such a gas barrier laminate film, in the present invention, it is possible to prevent deterioration due to water vapor at a higher level, and to sufficiently suppress the occurrence of defective light emission over a long period of time. The device (OLED) can be stored and used for a longer period of time.

(First and second base material layers)
The gas barrier laminate film (transparent support substrate 1) of the embodiment shown in FIG. 1 includes two base material layers, a first base material layer 100 (a) and a second base material layer 100 (b). . In addition, when the number of such base material layers is only one layer (in the case of a configuration in which either the first base material layer or the second base material layer is not included in the gas barrier laminate film) ), It becomes difficult to suppress the deterioration of the organic EL element at a sufficiently high level, and the deterioration rate becomes faster than the case where the number of the base material layers is two or more, and the storage life is shortened. It tends to end up. For example, in the embodiment shown in FIG. 1, if the second base material layer 100 (b) is not present, the first base material is further dried after a thin film layer having gas barrier properties is formed on the first base material layer. Even after passing through the step, the surface opposite to the surface on which the thin film layer having the gas barrier property of the first base material is laminated is exposed to the outside. There is a tendency for the time required for moisture to penetrate into one substrate and to reach the saturated water content of the first substrate. Therefore, even if the drying process is performed at the time of manufacture, the effect of the drying tends not to be fully utilized. Further, considering the case where the first base material layer 100 (a) is not provided, if the second and third thin film layers are formed on both surfaces of the second base material, the second base material is formed after the thin film layer is formed. Even if the step of drying the layer is carried out, the base material layer is sandwiched between the thin film layers that express the barrier properties, and it becomes difficult to remove the water inside the second base material. There is a tendency that it cannot be obtained sufficiently.

  The base materials forming the base material layer 100 (a) and the base material layer 100 (b) may be the same or different, and form a gas barrier laminate film. A known base material that can be used for the above can be used as appropriate. As such a base material, from a viewpoint of the flexibility of a base material, light transmittance, flatness, and weight reduction of a device, the 1st base material layer 100 (a) and the 2nd base material layer 100 ( It is preferable that at least one layer of b) is made of an organic polymer material, so that higher flexibility (flexibility) is obtained, and workability such as cutting and bending of the base material is improved. It is preferable that both the one base material layer 100 (a) and the second base material layer 100 (b) are made of an organic polymer material.

  From the viewpoint that such an organic polymer material can be used as a colorless and transparent substrate, for example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene (PE ), Polyolefin resins such as polypropylene (PP) and cyclic polyolefin; polyamide resins; polycarbonate resins; polystyrene resins; polyvinyl alcohol resins; saponified ethylene-vinyl acetate copolymers; polyacrylonitrile resins; acetals Resin; Polyimide resin or the like can be suitably used.

  Moreover, as such an organic polymer material, a polymer material made of a polymer containing a hetero atom (oxygen, nitrogen, etc.) other than carbon and hydrogen is preferable. Polymer materials (polyolefins, etc.) consisting of hydrocarbon polymers consisting only of carbon and hydrogen are nonpolar polymers, and since there is almost no polarization in the molecule, it is generally difficult to fully exhibit hydrophilicity. On the other hand, a polymer material made of a polymer containing a heteroatom (oxygen, nitrogen, etc.) is likely to show polarization due to the heteroatom, and is generally sufficiently hydrophilic. Here, the highly hydrophilic polymer material has a high water content under the usage environment (usually at room temperature (about 25 ° C.) and under normal humidity), and the internal moisture is sufficiently removed by drying. Then, hygroscopicity can be efficiently provided. Therefore, when a polymer material composed of a polymer containing a heteroatom other than carbon and hydrogen is used as the base material, it is possible to produce a gas barrier laminated film having a higher efficiency of moisture absorption more efficiently. It becomes possible, and when used as a substrate of an organic EL element, a higher level of water vapor permeation prevention performance can be exhibited. In addition, as a heteroatom in a polymer containing a heteroatom other than carbon and hydrogen, when the base material is used for a gas barrier laminate film, the film can also exhibit high moisture absorption performance. Therefore, an oxygen atom is preferable.

  Furthermore, as such an organic polymer material, a colorless and transparent base material is obtained, and a polymer containing a heteroatom other than hydrogen, which exhibits higher hygroscopic performance when used after drying. From the standpoint that it becomes possible to exhibit high water vapor permeation prevention performance by the transparent support substrate 1, polyester having an ester bond is preferable. Further, among these polyesters, polyesters having a benzene ring (for example, for example, from the viewpoint that the transparency of the base material and the processability to the film become more advanced, and the strength and heat resistance are further improved) It is particularly preferable to use PET (polyethylene terephthalate) or PEN (polyethylene naphthalate).

  Further, the thickness of such a substrate is not particularly limited, but when a thin film layer is directly formed on the surface of the substrate, the thickness is appropriately set according to the type of the thin film layer to be formed. It is preferable to do. For example, the thickness of such a base material is such that when forming a thin film layer on the surface of the base material, the base material can be transported even in a vacuum. It is preferable that the thickness is 5 to 500 μm. In addition, when the thin film layer is formed by using the plasma CVD method, the thickness of the base material is 50 to 50 from the viewpoint that it is possible to adopt a method of forming the thin film layer while discharging through the base material. More preferably, it is 200 micrometers, and it is especially preferable that it is 50-100 micrometers.

  Moreover, the thickness of such a base material is, for example, particularly in the step of bonding by the thickness of the base material even when a gas barrier laminate film is manufactured by bonding members having thin film layers formed on the base material. Since it does not have the property of being affected, it can be used without particular limitation as long as it has a thickness capable of forming a thin film layer regardless of the method for producing the gas barrier laminate film. In other words, the thickness of such a substrate may be any thickness that can form a thin film layer on the surface of the substrate and can sufficiently support the thin film layer. It can be designed as appropriate.

(Thin film layer)
The gas barrier laminate film (transparent support substrate 1) of the embodiment shown in FIG. 1 includes a first thin film layer 101 (a) and a second thin film layer 101 (b). As described above, the gas barrier laminate film of the embodiment shown in FIG. 1 includes two layers of the first thin film layer 101 (a) and the second thin film layer 101 (b) as thin film layers. When the number of such thin film layers is only one (when the gas barrier laminate film is configured so that one of the first thin film layer and the second thin film layer is not included), it is sufficient. In particular, it is difficult to suppress the deterioration of the organic EL at a high level, and the deterioration rate is increased as compared with the case where the number of thin film layers is two or more, and the storage life tends to be shortened. For example, in the embodiment shown in FIG. 1, even when only the first thin film layer 101 (a) is present, even if the gas barrier laminate film is manufactured through the process of drying the first substrate. Since there is no barrier layer on the surface opposite to the surface on which the first thin film layer having gas barrier properties is laminated, from the surface opposite to the surface on which the thin film layers having gas barrier properties are laminated, There is a tendency that the time until moisture enters the first base material and reaches the saturated water content of the base material is significantly shortened. Therefore, even if the drying process is performed at the time of manufacture, the effect of the drying tends not to be fully utilized. In the embodiment shown in FIG. 1, when only the second thin film layer is present, the organic EL is formed directly on the first substrate, and the moisture inside the substrate is reduced. Organic EL tends to deteriorate directly.

Further, both the first thin film layer 101 (a) and the second thin film layer 101 (b) need to be layers (thin film layers) made of a thin film having gas barrier properties. The “gas barrier property” as used herein refers to the following conditions (A) to (C):
[Condition (A)]
“Gas permeability of substrate (unit: mol / m ² · s · P)” and “gas permeability of substrate on which a thin film layer is formed” measured by a method in accordance with JIS K 7126 (issued in 2006) (Unit: mol / m ² · s · P) ”,“ Gas permeability of base material on which thin film layer is formed ”is smaller by 2 digits or more than“ Gas permeability of base material ” Show value (value of 1/100 or less).
[Condition (B)]
“Substrate water vapor permeability (unit: g / m ² · s · P)” measured by a method based on the method described in JIS K 7129 (issued in 2008) and “base on which a thin film layer was formed” Compared to “Water vapor permeability of base material with thin film layer” compared to “Water vapor permeability of base material” in comparison with “Water vapor permeability of material (Unit: g / m ² · s · P)” Indicates a value that is two or more digits smaller (a value less than one hundredth).
[Condition (C)]
“Vapor permeability of substrate (unit: g / m ² · s · P)” measured by a method based on the method described in JP-A-2005-283561 and “substrate on which a thin film layer is formed” Water vapor permeability (unit: g / m ² · s · P) ”, and“ water vapor permeability of the substrate on which the thin film layer is formed ”is more than“ water vapor permeability of the substrate ” Show a value that is two or more digits smaller (a value less than 1/100).
As long as at least one of the above conditions is satisfied. In general, the water vapor permeability of the substrate on which a thin film layer having water vapor barrier properties (gas barrier properties) is formed exhibits a value of 10 ⁻² g / m ² / day or less, so that the above condition (B) And when (C) is examined, it is preferable that the “water vapor permeability of the base material on which the thin film layer is formed” is a value of 10 ⁻² g / m ² / day or less. Further, as the thin film layer having such gas barrier properties, those satisfying the above condition (C) are more preferable.

  Further, the thickness of one thin film layer having such a gas barrier property is preferably in the range of 5 to 3000 nm, more preferably in the range of 10 to 2000 nm, and further preferably in the range of 10 to 1000 nm. A range of 100 to 1000 nm is particularly preferable. If the thickness of the thin film layer is less than the lower limit, the gas barrier properties such as oxygen gas barrier properties and water vapor barrier properties tend to be inferior. On the other hand, if the thickness exceeds the upper limit, the gas barrier properties tend to decrease due to bending.

  The kind of the first and second thin film layers having such gas barrier properties is not particularly limited, and a known thin film having gas barrier properties can be used as appropriate. These thin film layers are respectively metal oxide and metal nitride. It is preferable that it is a thin film layer containing at least one of a metal and a metal oxynitride.

  Further, the first and second thin film layers may be multilayer films in which organic layers / inorganic layers / organic layers, inorganic layers / organic layers / inorganic layers, and the like are laminated on the base material. In this case, the inorganic layer mainly exhibits gas barrier properties. The composition of the inorganic layer is preferably a metal oxide, metal nitride, metal oxynitride, silicon oxide, or silicon oxide carbide described below. The organic layer has the effect of relieving the stress of the base material and the inorganic layer, or smoothing by filling the surface of the base material with irregularities and particles. Furthermore, the organic layer may have a water capturing function. What is the composition of the organic layer? Organic materials used in thermosetting adhesives and photocurable adhesives described below and two-part curable adhesives are preferred. Note that the types of the first thin film layer 101 (a) and the second thin film layer 101 (b) may be the same or different.

  Also, metal oxides, metal nitrides and metal oxynitrides used for such thin film layers are sputter methods, vacuums from the viewpoint of being able to exhibit high water vapor permeation prevention performance with a thinner film, and transparency. It is preferable to form a film by a method such as an evaporation method, an ALD (atomic layer deposition) method, or an ion plating method. From the viewpoint of ease of production and low production cost, sputtering and ALD are more preferred.

In addition, such a thin film layer is made of a thin film containing at least silicon and oxygen from the viewpoints of exhibiting a higher level of water vapor permeation prevention performance, bending resistance, ease of production, and low production cost. More preferably, it is a layer. Further, the layer made of a thin film containing pre-silicon and oxygen is preferably a thin film layer using a plasma chemical vapor deposition method or a thin film forming method in which a precursor is formed on a substrate surface and plasma treatment is performed. Among such thin film layers, it is a layer containing silicon, oxygen and carbon, and
The distance from the surface of the layer in the thickness direction of the layer, the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon), the ratio of the amount of oxygen atoms (the ratio of oxygen In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the atomic ratio) and the ratio of the amount of carbon atoms (carbon atomic ratio), the following conditions (i) to (iii):
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more,
A silicon oxide thin film layer satisfying all of the above is particularly preferable. Hereinafter, a silicon oxide-based thin film layer suitably used for such a thin film layer according to the present invention will be described.

Such a silicon oxide-based thin film layer first has a distance from the surface of the layer in the thickness direction of the layer and a ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (silicon In the silicon distribution curve, the oxygen distribution curve and the carbon distribution curve respectively showing the relationship between the atomic ratio), the oxygen atom ratio (oxygen atomic ratio) and the carbon atom ratio (carbon atomic ratio), i) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more (more preferably 95% or more, particularly preferably 100%) of the thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
It is necessary to satisfy the condition expressed by When the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon do not satisfy the above conditions, the gas barrier properties of the resulting gas barrier laminate film are insufficient.

  In addition, such a silicon oxide-based thin film layer (ii) requires that the carbon distribution curve has at least one extreme value. In such a silicon oxide-based thin film layer, the carbon distribution curve more preferably has at least two extreme values, and particularly preferably has at least three extreme values. When the carbon distribution curve does not have an extreme value, the gas barrier property when the obtained film of the gas barrier laminate film is bent is insufficient. Further, in the case of having at least three extreme values as described above, from the surface of the thin film layer in the film thickness direction of the thin film layer at one extreme value and an extreme value adjacent to the extreme value of the carbon distribution curve. The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less. Here, the “extreme value” means a maximum value or a minimum value of the atomic ratio of the element to the distance from the surface of the thin film layer in the film thickness direction of the silicon oxide-based thin film layer. In the present invention, the maximum value is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the silicon oxide thin film layer is changed, and It means that the value of the atomic ratio of the element at a position where the distance from the surface of the thin film layer in the film thickness direction of the thin film layer is further changed by 20 nm from the point is reduced by 3 at% or more. Furthermore, in the present invention, the minimum value is a point where the value of the atomic ratio of an element changes from a decrease to an increase when the distance from the surface of the silicon oxide thin film layer is changed, and the element of that point It means that the value of the atomic ratio of the element at a position where the distance from the surface of the thin film layer in the film thickness direction of the thin film layer is further changed by 20 nm from the point increases by 3 at% or more.

  In addition, such a silicon oxide-based thin film layer (iii) requires that the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve be 5 at% or more. In such a thin film layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and particularly preferably 7 at% or more. When the absolute value is less than 5 at%, the gas barrier property when the obtained gas barrier laminate film is bent is insufficient.

  In the silicon oxide-based thin film layer, the oxygen distribution curve preferably has at least one extreme value, more preferably at least two extreme values, and at least three extreme values. Particularly preferred. When the oxygen distribution curve does not have an extreme value, the gas barrier property tends to decrease when the resulting gas barrier laminate film is bent. In the case of having at least three extreme values in this way, from the surface of the thin film layer in the thickness direction of the thin film layer at one extreme value and the extreme value adjacent to the extreme value of the oxygen distribution curve. The absolute value of the difference in distance is preferably 200 nm or less, and more preferably 100 nm or less.

  Further, in the silicon oxide-based thin film layer, the absolute value of the difference between the maximum value and the minimum value of the oxygen atomic ratio in the oxygen distribution curve of the layer is preferably 5 at% or more, and 6 at% or more. More preferably, it is more preferably 7 at% or more. If the absolute value is less than the lower limit, the gas barrier property tends to be lowered when the obtained gas barrier laminate film is bent.

  In the silicon oxide-based thin film layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon in the silicon distribution curve of the layer is preferably less than 5 at%, and preferably less than 4 at%. Is more preferable, and it is especially preferable that it is less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier properties of the obtained gas barrier laminate film tend to be lowered.

  In the silicon oxide-based thin film layer, the distance from the surface of the layer in the thickness direction of the layer and the ratio of the total amount of oxygen atoms and carbon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms In the oxygen carbon distribution curve showing the relationship with (atomic ratio of oxygen and carbon), the absolute value of the difference between the maximum value and the minimum value of the total atomic ratio of oxygen and carbon in the oxygen carbon distribution curve is less than 5 at%. Preferably, it is less than 4 at%, more preferably less than 3 at%. When the absolute value exceeds the upper limit, the gas barrier properties of the obtained gas barrier laminate film tend to be lowered.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. It can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample. A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the thin film layer in the film thickness direction of the thin film layer in the film thickness direction. As the distance from the surface of the thin film layer in the film thickness direction of the thin film layer, the distance from the surface of the thin film layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement may be adopted. it can. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

  Further, from the viewpoint of forming the silicon oxide-based thin film layer having a uniform and excellent gas barrier property over the entire film surface, the layer is substantially in the film surface direction (direction parallel to the surface of the thin film layer). Preferably it is uniform. In the present specification, the fact that the silicon oxide thin film layer is substantially uniform in the film surface direction means that the oxygen distribution curve is measured at any two measurement points on the film surface of the thin film layer by XPS depth profile measurement. When the carbon distribution curve and the oxygen carbon distribution curve are created, the number of extreme values of the carbon distribution curve obtained at any two measurement locations is the same, and the carbon atoms in the respective carbon distribution curves The absolute value of the difference between the maximum value and the minimum value of the ratio is the same as each other or within 5 at%.

Further, in the silicon oxide thin film layer, the carbon distribution curve of the layer is preferably substantially continuous. In the present specification, the carbon distribution curve being substantially continuous means that the carbon distribution curve does not include a portion in which the atomic ratio of carbon changes discontinuously. Specifically, the etching rate, the etching time, From the relationship between the distance (x, unit: nm) from the surface of the layer in the film thickness direction of at least one of the thin film layers calculated from the above, and the atomic ratio of carbon (C, unit: at%) The following mathematical formula (F1):
(DC / dx) ≦ 0.5 (F1)
This means that the condition represented by

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the above formula (1 ), The atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer is preferably 25 to 45 at%, and 30 to More preferably, it is 40 at%. The atomic ratio of the content of oxygen atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the silicon oxide-based thin film layer is preferably 33 to 67 at%, and is preferably 45 to 67 at%. It is more preferable. Furthermore, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the silicon oxide-based thin film layer is preferably 3 to 33 at%, and is 3 to 25 at%. It is more preferable.

  Further, in the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the above formula (2 ), The atomic ratio of the content of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms in the layer is preferably 25 to 45 at%, and 30 to More preferably, it is 40 at%. The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the silicon oxide-based thin film layer is preferably 1 to 33 at%, and preferably 10 to 27 at%. It is more preferable. Further, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the silicon oxide-based thin film layer is preferably 33 to 66 at%, and preferably 40 to 57 at%. It is more preferable.

  The silicon oxide thin film layer is preferably a layer formed by plasma enhanced chemical vapor deposition. As a thin film layer formed by such a plasma enhanced chemical vapor deposition method, the base material is placed on a pair of film forming rolls, and plasma is generated by generating a plasma by discharging between the pair of film forming rolls. A layer formed by a phase growth method is more preferable. Further, when discharging between the pair of film forming rolls in this way, it is preferable to reverse the polarities of the pair of film forming rolls alternately. Further, the film forming gas used in such a plasma chemical vapor deposition method preferably contains an organosilicon compound and oxygen, and the content of oxygen in the film forming gas is the organic gas in the film forming gas. It is preferable that the amount is less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the silicon compound. The thin film layer is preferably a layer formed by a continuous film formation process.

  In addition, as the first thin film layer 101 (a) and the second thin film layer 101 (b), it is possible to exhibit a higher level of water vapor permeation prevention performance. It is preferable that all of them are the above-described silicon oxide-based thin film layers.

(Adhesive layer)
The gas barrier laminate film (transparent support substrate 1) of the embodiment shown in FIG. 1 includes an adhesive layer 102.

  Examples of the adhesive that can be used to form the adhesive layer 102 include a thermosetting adhesive, a photocurable adhesive, and a two-component mixed curing from the viewpoint of ease of manufacture and low volatile components. A curable adhesive such as a curable adhesive is preferred.

  Such a thermosetting resin adhesive is not particularly limited, and a known thermosetting resin adhesive can be appropriately used. Examples of such thermosetting resin adhesives include epoxy adhesives and acrylate adhesives. Examples of such an epoxy adhesive include an adhesive containing an epoxy compound selected from a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenoxy resin. Examples of the acrylate adhesive include a monomer as a main component selected from acrylic acid, methacrylic acid, ethyl acrylate, butyl acrylate, 2-hexyl acrylate, acrylamide, acrylonitrile, hydroxyl acrylate, and the like. An adhesive containing a copolymerizable monomer can be used.

  In addition, the photocurable adhesive is not particularly limited, and a known photocurable adhesive can be appropriately used. Examples thereof include a radical adhesive and a cationic adhesive. Examples of such radical adhesives include adhesives containing epoxy acrylate, ester acrylate, ester acrylate, and the like. Examples of the cationic adhesive include an adhesive including an epoxy resin and a vinyl ether resin.

  Further, such an adhesive layer 102 may further contain a moisture adsorbent (so-called desiccant or hygroscopic agent), a bluing agent, an ultraviolet absorber, an antioxidant, and the like. In addition, when the laminated film is used as a substrate for an organic EL for illumination, it may contain a dye or a pigment having the same color as the emission color of the organic EL. It may contain dyes and pigments of different colors. Furthermore, in order to have a light scattering effect and a light extraction effect, inorganic particles having a refractive index different from that of the adhesive layer may be included.

  In addition, as such an adhesive layer 102, when the adhesive contains moisture, the moisture in the adhesive layer is reduced to sufficiently prevent the performance from being deteriorated based on the moisture generated from the adhesive layer. In addition, the gas barrier laminate film can exhibit high moisture absorption performance, and the gas barrier laminate film can also exhibit advanced water vapor permeation prevention performance. It is preferable. Such a moisture adsorbent (drying agent) is not particularly limited, and examples thereof include silica gel, zeolite (molecular sieve), metal oxides such as magnesium oxide, calcium oxide, barium oxide, and strontium oxide, and dry hydroxide. Examples thereof include metal hydroxides such as aluminum. Among such moisture adsorbents (desiccants), calcium oxide and dried aluminum hydroxide are particularly preferable from the viewpoint of sufficiently high light transmittance.

  Moreover, as such a water | moisture-content adsorption agent (drying agent), a particulate thing is preferable. Such a particulate water adsorbent (drying agent) has an average particle diameter in the range of 0.01 to 10 μm (more preferably 0.01 to 5 μm, and still more preferably 0.1 to 5 μm). preferable. When the average particle size is less than 0.01 μm, the primary particles tend to aggregate easily, and not only the large aggregated particles (secondary particles) tend to be formed, but also the hygroscopicity is too strong, When entering the adhesive layer, the moisture absorption has already ended and the moisture absorption ability tends not to be exhibited. On the other hand, when the average particle diameter exceeds 10 μm, it becomes difficult to form a smooth layer when formed into a film, and sufficient moisture absorption ability tends to be not obtained.

  Furthermore, the content of such a moisture adsorbent (drying agent) is not particularly limited, but it should be 5 to 50% by mass (more preferably 10 to 30% by mass) in the adhesive. Is preferred. If the content of such an absorbent (drying agent) is less than the lower limit, moisture existing in the adhesive tends to be absorbed and the water supply ability tends to decrease. And the light extraction from the organic EL light emitting layer tends to decrease.

  Moreover, in such an adhesive layer 102, it is preferable to contain a bluing agent, for example according to the use of an organic EL element. Such a bluing agent is not particularly limited, and a known bluing agent can be appropriately used. For example, Bayer Macrolex Violet B and Macrolex Blue RR, Sand Corp. Triazole blue RLS and the like can be suitably used. Further, for example, Solvent Violet-3, Solvent Blue-94, Solvent Blue-78, Solvent Blue-95, Solvent Violet-13, and the like by color index classification can be used.

  Further, the thickness of the adhesive layer 102 is not particularly limited, but solid content such as powder (for example, the above-mentioned moisture adsorbent (drying agent), refractive index adjusting particles, etc.) is used for the adhesive. In the case where the particles constituting the powder (powder particles) do not aggregate, it is preferable that the thickness be about the maximum primary particle diameter of the powder particles. Is usually more preferably 1 to 20 μm. On the other hand, when aggregation occurs in the powder particles, the thickness is preferably about the maximum secondary particle diameter of the powder particles. In this case, the thickness is usually 5 to 50 μm. More preferred. In the case where solid content such as powder is not added to the adhesive and the adhesive layer 102 is formed by applying and drying the adhesive, the thickness of the adhesive layer 102 is determined depending on the adhesive strength and workability. From the viewpoint, it is preferably 0.2 to 30 μm, and more preferably 0.5 to 10 μm. In addition, when using a film-like adhesive (adhesive film) to form the adhesive layer 102, from the viewpoint of workability, the thickness of the adhesive layer 102 is preferably 1 to 100 μm, More preferably, it is 5-50 micrometers.

Moreover, when forming such an adhesive bond layer, the adhesive agent processed into the film form (sheet-like thing) can be utilized. In this case, the water vapor transmission rate of the adhesive film is 100 g / m ² / day or less (more preferably 30 g / m ² / day or less) in an environment where the film thickness is 100 μm, 60 ° C., and 90% RH, In addition, the light transmittance is preferably 70% or more (more preferably 80% or more). When such water vapor permeability exceeds the above upper limit, the water intrusion from the portion where the adhesive part at the end of the gas barrier laminate film is exposed, and the time until the saturated water content of the first substrate is reached. Tends to be short, resulting in a short shelf life of the organic EL. Further, if the light transmittance is less than the lower limit, the internal light cannot be emitted sufficiently to the outside, and the light emission efficiency of the organic EL tends to be lowered. Such water vapor transmission rate is, for example, a calcium-light transmission method (when Ca metal absorbs moisture, it changes to calcium oxide, calcium hydroxide, etc., and the light transmission changes), or MOCON water vapor. A value measured by a transmittance measuring device or the like can be adopted. The light transmittance can be measured by, for example, an optical thin film measuring system apparatus manufactured by Film-Tek (USA).

  The adhesive layer has a ratio of the light refractive index of the first base material layer 100 (a) to the light refractive index of the adhesive layer ([the light refractive index of the first base material layer 100 (a). ] / [Adhesive layer photorefractive index]) is preferably a layer of 0.88 to 1.18 (more preferably 1.01 to 1.11). If the ratio of the optical refractive index is less than the lower limit, it is necessary to further increase the refractive index of the adhesive layer. If the refractive index of the adhesive layer is larger than that of the second thin film layer, the outgoing light to the outside decreases. On the other hand, when the upper limit is exceeded, light refraction is increased at the interface between the first base material and the adhesive layer, and the emission of light from the light emitting layer to the outside tends to decrease. Such a light refractive index can be measured by, for example, an optical thin film measuring system apparatus of Film-Tek (USA) or a general-purpose ellipsometer.

(Laminated film structure, etc.)
The gas barrier laminate film (transparent support substrate 1) of the embodiment shown in FIG. 1 includes a thin film layer 101 (a), a base material layer 100 (a), an adhesive layer 102, a thin film layer 101 (b), and a base material layer 100. It has the laminated structure laminated | stacked in order of (b). With such a laminated structure, a light emitting element portion described later can be laminated directly on the surface of the thin film layer, and the penetration of water vapor into the element can be highly suppressed by the thin film layer. In addition, in the laminated | multilayer film laminated | stacked in order of the thin film layer 101 (a), the base material layer 100 (a), the adhesive bond layer 102, the base material layer 100 (b), and the thin film layer 101 (b), the thin film layer 101 (a) Compared with the laminated structure in which the base material layer 100 (a), the adhesive layer 102, the thin film layer 101 (b), and the base material layer 100 (b) are laminated in this order, the thin film layer 101 (a) and the thin film layer 101 The cross-sectional area of the edge part of the base material layer between (b) becomes large ("the base material layer 100 (a), the adhesive layer 102 between the thin film layer 101 (a) and the thin film layer 101 (b)". This is because the base material layer 100 (b) "is included.) Therefore, in the laminated film in which the thin film layer 101 (a), the base material layer 100 (a), the adhesive layer 102, the base material layer 100 (b), and the thin film layer 101 (b) are laminated in this order, Infiltration increases, and the amount of moisture that permeates through the thin film layer 101 (a) increases as the moisture intrusion increases. Therefore, it is difficult to sufficiently suppress the deterioration of the organic EL device at a higher level. It becomes. Further, in the laminated film having this structure, when an organic EL device is manufactured, one of the surfaces exposed to the outside becomes the thin film layer 101 (b), and therefore mechanical perturbation (for example, rubbing or scratching) is caused by the thin film layer. When added to 101 (b), the thin-film layer tends to be damaged and the barrier performance tends to deteriorate, and this tends to make it difficult to sufficiently suppress deterioration of the organic EL device at a higher level. It is in. Therefore, the laminated film in which the thin film layer 101 (a), the base material layer 100 (a), the adhesive layer 102, the base material layer 100 (b), and the thin film layer 101 (b) are laminated in this order is a transparent support of the organic EL element. When used for the substrate 1, sufficient long-term storage performance is not necessarily obtained.

  Such a gas barrier laminate film (transparent support substrate 1) preferably has a total thickness of 50 to 300 μm, and more preferably 100 to 250 μm. When the thickness of such a film is less than the above lower limit, when the gas barrier laminate film is a long substrate, wrinkles and creases tend to occur in the manufacturing process of the organic EL element, and it is difficult to control the film. On the other hand, if the thickness of the gas barrier laminate film exceeds the upper limit, the amount of light absorption by the film increases, and thus light emission from the light emitting layer to the outside tends to decrease. It is in. Further, when the thickness of the gas barrier laminate film becomes thicker than the upper limit, the base material layer is formed from the direction parallel to the surface of the gas barrier laminate film (end side: direction perpendicular to the end face). It is difficult to maintain the dry state of the base material for a sufficiently long period of time, for example, when a dry base material is used at the time of manufacturing the gas barrier laminate film. Tend to be. In the present invention, the gas barrier laminate film (transparent support substrate 1) is basically the surface of the film (surface perpendicular to the thickness direction: one side is centimeters in consideration of the field of application of the organic EL element). The area of the scale is more than the metric size.) The area of the edge of the film (basically, the area of the surface perpendicular to the direction parallel to the film surface: one side of the surface is the same size as the thickness. , Basically a scale of a micrometer size.) Compared with the area, the water vapor intrusion into the gas barrier laminate film from the surface side through the end side surface is overwhelmingly large. Since the amount of water vapor invades is significantly higher than the amount of water vapor that penetrates, it is possible to sufficiently suppress the invasion of water vapor into the light emitting element part of the organic EL element by sufficiently suppressing the invasion of water vapor from the surface side. it canTherefore, in the gas barrier laminate film (transparent support substrate 1), as shown in FIG. 1, a part of the end surface of the base material layer is in contact with the outside air (atmosphere) as it is (exposed state). It may be. In addition, since the light emitting element part 2 is formed on the thin film layer, the permeation of water vapor from the light emitting surface side is sufficiently suppressed by the gas barrier laminate film (transparent support substrate 1).

  Moreover, in this application, it has the laminated structure laminated | stacked in order of said 1st thin film layer, said 1st base material layer, said adhesive layer, said 2nd thin film layer, and said 2nd base material layer. However, when such a laminated structure is employed, depending on the type of the base material, etc., depending on the base material (first base material layer 100 (a) in this embodiment) disposed between the gas barrier thin film layers, It is also possible to exert the moisture absorption performance of the gas barrier laminate film when using the film. Further, when a moisture adsorbent is contained in the adhesive layer 102, the moisture absorbing performance is exhibited thereby, or the base material layer adjacent to the adhesive layer 102 is dried, so that the base material layer has the moisture absorbing performance. It can also be demonstrated. In addition, when it has the laminated structure which does not arrange | position a base material layer between said 1st and 2nd thin film layers, ie, when it becomes the structure by which thin film layers oppose each other, it is on a base material layer. The light emitting element part is directly formed, and the base material (usually, the base material itself does not necessarily have sufficient gas barrier properties, and water vapor tends to enter the base material or transmit gas). As a result, water vapor in the outside air enters the inside of the device, or moisture absorbed by the base material enters the inside of the device, so that sufficient water vapor permeation preventing properties cannot be exhibited. In this case, moisture tends to easily enter from the surface portion where the element or sealing layer on the substrate is not formed, and the layer in contact with the element becomes a layer containing moisture, The infiltration of moisture cannot be controlled sufficiently. In addition, in the case of having a laminated structure in which no base material layer is disposed between the first and second thin film layers, since there is no base material sandwiched between gas barrier films, it is also included in the outside air. Since moisture (water vapor contained in the outside air under normal humidity conditions) easily comes into contact with the base material and enters the base material, it is difficult to impart sufficient moisture absorption performance to the laminated film.

  Moreover, the gas barrier laminate film of the embodiment shown in FIG. 1 includes a first base layer 100 (a) and a first thin film layer 101 (a) formed on one surface of the layer 100 (a). And a second structure comprising a second substrate layer 100 (b) and a second thin film layer 101 (b) formed on one surface of the layer 100 (b). Part, and these structural parts have a configuration in which they are stacked with an adhesive layer 102 interposed therebetween. As described above, the gas barrier laminate film according to the embodiment shown in FIG. 1 has the first structure portion and the second structure portion, thereby preventing moisture from entering from the outside. The shelf life of the organic EL element formed on the upper portion of the first structure can be extended. In addition, the gas barrier laminate film having such a structure is obtained by using a first film member and a second film member as described in a suitable method for producing a gas barrier laminate film described later. It is possible to manufacture efficiently.

  In the gas barrier laminate film of the embodiment shown in FIG. 1, the first base material layer 100 (a) and the second base material layer 100 (b) each have a thin film layer formed only on one surface. The thin film layer is not formed on the other surface. Thus, when it has a structural unit in which the thin film layer is formed only on one side of the base material layer, the first as described in the first and second methods for producing a gas barrier laminate film of the present invention described later. When the film member and the second film member are used, the first film member or the second film member may be one having a thin film layer formed only on one side, and the member can be easily prepared. This improves productivity.

  Moreover, it is preferable that such a gas barrier laminated film has a hygroscopic performance of absorbing water of 0.1% by mass or more of its own weight (mass of the gas barrier laminated film itself). When such moisture absorption performance is less than the lower limit, it tends to be difficult for the gas barrier laminate film to exhibit further advanced moisture permeation prevention performance.

In addition, the moisture absorption performance of such a gas barrier laminate film can be measured as follows. That is, first, a gas barrier laminate film (50 mm square) having a vertical and horizontal length of 50 mm (50 mm square) is prepared for measuring the moisture absorption performance of the gas barrier laminate film. Next, a 50 mm square film is cut into a strip shape every 1 mm to prepare a strip-shaped sample having a length of 50 mm and a width of 1 mm. Next, in a temperature-controlled room, the mass of a strip-like sample (50 pieces) having a size of 50 mm in length and 1 mm in width is accurately weighed to the fourth decimal place. Let the mass at this time be the above-mentioned film's own weight (W1: initial mass before use). Next, the 50 samples are allowed to stand under a constant temperature and humidity atmosphere (25 ° C., humidity 50%, weight absolute humidity 10 g / kg), and the mass of the sample is accurately weighed to 4 decimal places every 24 hours. . Such weighing is performed until the mass of the sample (50 pieces) becomes constant, and the mass when a constant value is obtained is defined as Wn. Based on the values of Wn and W1 thus determined, the following formula:
[Moisture absorption ratio Bn] = {(Wn−W1) / W1} × 100
In this invention, the value calculated | required by calculating is employ | adopted as a hygroscopic performance of a gas barrier laminated film.

  Such hygroscopic performance is basically a performance exhibited based on the hygroscopicity of the base material layer disposed between the first and second thin film layers having gas barrier properties. The base layer is made of a polymer containing a heteroatom other than hydrogen (more preferably a polyester having an ester bond) so that the base layer disposed between the first and second thin film layers can absorb moisture sufficiently. More preferably, a layer made of a base material made of PET, PEN), and a base material sufficiently dried at the time of producing the gas barrier laminate film is disposed between the first and second thin film layers. Thus, it is preferable to produce a gas barrier laminate film. Therefore, as a method for producing such a gas barrier laminate film, since it becomes possible to arrange the substrate layer in a dry state between the first and second thin film layers more reliably, the gas barrier described later is used. It is preferable to employ a suitable method for producing a conductive laminated film.

  In such a gas barrier laminate film (transparent support substrate 1), the ratio of the total thickness of all substrate layers present in the film to the total thickness of the film ({[all substrate The total thickness of the layers] / [total thickness of the gas barrier laminate film]} × 100) is preferably 90% or more, and more preferably 95% or more. If such a ratio is less than the lower limit, the flexibility tends to decrease, or the substrate is deformed by the stress of the thin film layer formed on the substrate, and the productivity tends to decrease.

  Further, the thickness of the entire base material layer existing between the first thin film layer and the second thin film layer with respect to the thickness of the entire base material layer present in the gas barrier laminate film (transparent support substrate 1). Ratio of total value ({[total value of thickness of all substrate layers existing between the first thin film layer and the second thin film layer] / [of all substrate layers present in the gas barrier laminate film] Thickness]} × 100) is preferably 50% or more, and more preferably 90% or more. If the ratio of the thickness of the base material layer between the thin film layers is less than the lower limit, it tends to be difficult to exhibit a sufficiently high hygroscopic performance when the base material is dried and used to exhibit the hygroscopic performance. There is a tendency.

  Further, the ratio of the thickness of the base material layer existing between the first thin film layer and the second thin film layer to the entire thickness of the gas barrier laminate film (transparent support substrate 1) ({[first The thickness of the base material layer existing between the thin film layer and the second thin film layer] / [the total thickness of the gas barrier laminate film]} × 100) is preferably 50% or more, particularly 90. % Or more is more preferable. When the ratio of the thickness of the base material layer between the thin film layers is less than the lower limit, the mechanical strength of the first film member on which the organic EL element is formed is reduced. There is a tendency that the possibility of being destroyed tends to increase, and it tends to be difficult to exhibit a sufficiently high hygroscopic performance when the substrate is dried and used to exhibit the hygroscopic performance.

  In the gas barrier laminate film (transparent support substrate 1), when used for organic EL device illumination and display, the yellowness YI is preferably a lower value, more preferably 10 or less. More preferably, it is 5 or less. Such yellowness YI can be measured by using a spectrophotometer capable of calculating the tristimulus value XYX as a measuring device and conforming to JIS K 7373: 2006.

  Moreover, in the said gas-barrier laminated | multilayer film (transparent support substrate 1), when using for an organic EL device illumination and a display, a thing with a higher total light transmittance is preferable. From such a viewpoint, the total light transmittance of the gas barrier laminate film is more preferably 80% or more, and further preferably 85% or more. Such total light transmittance can be measured by using a transmission measuring device having an integrating sphere as a measuring device and conforming to JIS K7375: 2008.

  Furthermore, in the said gas-barrier laminated | multilayer film (transparent support substrate 1), when using for the board | substrate of the organic EL element for image displays, a thing with a lower haze is preferable, it is more preferable that it is 10% or less, and 5% More preferably, it is as follows. On the other hand, when it is used for a substrate for an organic EL element for illumination, not only is the haze not noticeable from the application, but the light emission surface of the organic EL emits light unevenly in a state where shading or spots occur. In such a case, the higher the haze, on the contrary, blurs the uneven light emission, and from this point of view, the one having a higher haze can be suitably used. As described above, the gas barrier laminate film (transparent support substrate 1) can be used while appropriately changing its characteristics so as to have a suitable design according to the use of the organic EL element.

  Moreover, as such a gas barrier laminated film (transparent support substrate 1), a sufficiently flexible film (having sufficient flexibility) is preferable. By setting it as such a flexible film, it can utilize more suitably for the use as which a flexibility is requested | required.

  Here, a method that can be suitably used for producing the gas barrier laminate film (transparent support substrate 1) shown in FIG. 1 will be described.

As such a method, for example, a first film member provided with a first thin film layer having a gas barrier property formed on at least one surface of the first base material layer and the first base material layer; ,
A second film member comprising a second thin film layer having gas barrier properties formed on at least one surface of the second base material layer and the second base material layer;
A process of preparing (process (A)),
A step of obtaining a gas barrier laminate film by bonding with an adhesive so that the second thin film layer in the second film member is laminated on the surface of the base material layer of the first film member (step (step ( B))
It is preferable to employ a method including: Hereinafter, these steps (A) and (B) will be described separately.

(Process (A))
Step (A) is a step of preparing the first and second film members. The method for preparing such first and second film members is not particularly limited, and a known method can be appropriately employed. For example, it is possible to produce a film member (first and second film members) comprising a base material layer and a thin film layer by forming a thin film layer having a gas barrier property on at least one surface on the base material. The film member (first and second film members) may be prepared by a film member (laminate) having a commercially available base material layer and a thin film layer having gas barrier properties. ) May be prepared. Moreover, when forming the said thin film layer on a base material, the well-known method in which the film formation of such a thin film layer can be employ | adopted suitably, From a gas-barrier viewpoint, plasma chemical vapor deposition method ( It is preferable to employ plasma CVD). The plasma chemical vapor deposition method may be a Penning discharge plasma type chemical vapor deposition method.

  Further, when generating plasma in the plasma enhanced chemical vapor deposition method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rolls, and a pair of film forming rolls is used, and the pair of film forming films is used. More preferably, the substrate is disposed on each of the rolls, and plasma is generated by discharging between the pair of film forming rolls. In this way, a pair of film forming rolls are used, a base material is disposed on the pair of film forming rolls, and discharge is performed between the pair of film forming rolls. In addition to forming the surface portion of the base material present on the other film, the surface portion of the base material existing on the other film forming roll can be formed at the same time. Since the film rate can be doubled and a film having the same structure can be formed, the extreme value in the carbon distribution curve can be at least doubled, and a layer that efficiently satisfies all the above conditions (i) to (iii) can be obtained. It becomes possible to form.

  Further, as a method for forming the thin film layer, it is preferable to adopt a roll-to-roll method while utilizing a plasma chemical vapor deposition method from the viewpoint of productivity. An apparatus that can be used when producing a gas barrier laminate film by such a plasma chemical vapor deposition method is not particularly limited, and includes at least a pair of film forming rolls and a plasma power source, and It is preferable that the apparatus has a configuration capable of discharging between a pair of film forming rolls. For example, when a manufacturing apparatus as shown in FIG. It is also possible to manufacture in a roll-to-roll manner while using

  Here, referring to FIG. 2, a layer made of the silicon oxide thin film (the silicon oxide thin film layer) is formed on the base material, and at least one of the base material layer and the base material layer is formed. A method that can be suitably used to manufacture a film member including the silicon oxide-based thin film layer formed on the surface will be described. FIG. 2 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for forming the silicon oxide-based thin film layer on a substrate. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  2 includes a feed roll 11, transport rolls 21, 22, 23, 24, film forming rolls 31, 32, a gas supply pipe 41, a plasma generating power supply 51, a film forming roll 31, and 32 includes magnetic field generators 61 and 62 installed inside 32, and a winding roll 71. In such a manufacturing apparatus, at least the film forming rolls 31, 32, the gas supply pipe 41, the plasma generating power source 51, and the magnetic field generating apparatuses 61, 62 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roll has a plasma generation power source so that the pair of film-forming rolls (film-forming roll 31 and film-forming roll 32) can function as a pair of counter electrodes. 51 is connected. Therefore, in such a manufacturing apparatus, it is possible to discharge into the space between the film forming roll 31 and the film forming roll 32 by supplying power from the plasma generating power source 51, thereby forming the film. Plasma can be generated in the space between the roll 31 and the film forming roll 32. In this way, when the film forming roll 31 and the film forming roll 32 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable that the pair of film forming rolls (film forming rolls 31 and 32) are arranged so that their central axes are substantially parallel on the same plane. Thus, by arranging a pair of film forming rolls (film forming rolls 31 and 32), the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled. And according to such a manufacturing apparatus, it is possible to form a thin film layer on the surface of the film 100 by the CVD method, while depositing a film component on the surface of the film 100 on the film forming roll 31, Furthermore, since the film component can be deposited on the surface of the film 100 also on the film forming roll 32, the thin film layer can be efficiently formed on the surface of the film 100.

  Further, inside the film forming roll 31 and the film forming roll 32, magnetic field generators 61 and 62 fixed so as not to rotate even when the film forming roll rotates are provided, respectively.

  Further, as the film forming roll 31 and the film forming roll 32, known rolls can be appropriately used. As such film forming rolls 31 and 32, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameter of the film forming rolls 31 and 32 is preferably in the range of 5 to 100 cm from the viewpoint of discharge conditions, chamber space, and the like.

  Moreover, in such a manufacturing apparatus, the film 100 is arrange | positioned on a pair of film-forming roll (The film-forming roll 31 and the film-forming roll 32) so that the surface of the film 100 may oppose, respectively. By disposing the film 100 in this manner, each of the films 100 existing between the pair of film forming rolls is generated when the plasma is generated by performing discharge between the film forming roll 31 and the film forming roll 32. It becomes possible to form a film on the surface simultaneously. That is, according to such a manufacturing apparatus, the film component can be deposited on the surface of the film 100 on the film forming roll 31 and further the film component can be deposited on the film forming roll 32 by the CVD method. Therefore, the thin film layer can be efficiently formed on the surface of the film 100.

  Further, as the feed roll 11 and the transport rolls 21, 22, 23, and 24 used in such a manufacturing apparatus, known rolls can be appropriately used. Further, the winding roll 71 is not particularly limited as long as it can wind the film 100 on which the thin film layer is formed, and a known roll can be appropriately used.

  Further, as the gas supply pipe 41, a pipe capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used. Furthermore, as the plasma generating power source 51, a known power source for a plasma generating apparatus can be used as appropriate. Such a power source 51 for generating plasma supplies power to the film forming roll 31 and the film forming roll 32 connected to the power source 51 and makes it possible to use them as a counter electrode for discharging. As such a plasma generation power source 51, it is possible to more efficiently carry out plasma CVD, so that the polarity of the pair of film forming rolls can be alternately reversed (AC power source or the like). Is preferably used. In addition, since the plasma generating power source 51 can perform plasma CVD more efficiently, the applied power can be set to 100 W to 10 kW, and the AC frequency can be set to 50 Hz to 500 kHz. More preferably, it is possible. As the magnetic field generators 61 and 62, known magnetic field generators can be used as appropriate. Furthermore, as the film 100, in addition to the base material used in the present invention, a film in which the thin film layer is formed in advance can be used. As described above, by using the film 100 in which the thin film layer is formed in advance, it is possible to increase the thickness of the thin film layer.

  Using the manufacturing apparatus shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roll, and the film transport speed are adjusted as appropriate. By doing so, a layer (thin film layer) composed of the silicon oxide thin film can be formed on the surface of the substrate 100. That is, by using the manufacturing apparatus shown in FIG. 2 to generate a discharge between a pair of film forming rolls (film forming rolls 31 and 32) while supplying a film forming gas (such as a raw material gas) into the vacuum chamber. The film forming gas (raw material gas or the like) is decomposed by plasma, and the thin film layer is formed on the surface of the film 100 on the film forming roll 31 and on the surface of the film 100 on the film forming roll 32 by the plasma CVD method. Is done. In such film formation, the film 100 is conveyed by the delivery roll 11, the film formation roll 31, and the like, respectively, so that the film 100 is formed on the surface of the film 100 by a roll-to-roll continuous film formation process. A silicon oxide-based thin film layer is formed.

  The source gas in the film-forming gas used for forming the silicon oxide-based thin film layer can be appropriately selected and used depending on the material of the thin film layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1.1.3.3-tetramethyldisiloxane are preferable from the viewpoints of properties such as handling of the compound and gas barrier properties of the obtained thin film layer. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used singly or in combination of two or more. For example, when forming an oxynitride, the reaction gas for forming an oxide and a nitride are formed. Can be used in combination with the reaction gas for

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as the film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon, etc .; hydrogen can be used.

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, a thin film that satisfies all the above conditions (i) to (iii) cannot be obtained. In this case, excellent barrier properties and bending resistance cannot be obtained depending on the formed thin film layer. Further, when the film forming gas contains the organosilicon compound and oxygen, the amount is less than the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film forming gas. It is preferable.

Hereinafter, as the film-forming gas, a gas containing hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O :) as a source gas and oxygen (O ₂ ) as a reaction gas is used. Taking a case of producing a silicon-oxygen-based thin film as an example, a suitable ratio of the source gas and the reactive gas in the film forming gas will be described in more detail.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by plasma CVD to form a silicon-oxygen-based material. When producing a thin film, the following reaction formula (1) is given by the film-forming gas:
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
Reaction occurs as described in 1 to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. ) To (iii) cannot be formed. Therefore, when forming the silicon oxide-based thin film layer, the amount of oxygen is stoichiometrically determined with respect to 1 mole of hexamethyldisiloxane so that the reaction of the above formula (1) does not proceed completely. The ratio should be less than 12 moles. Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied compared to the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by CVD, the molar amount (flow rate) of oxygen is the raw material hexamethyldisiloxane. (It may be about 20 times or more of the molar amount (flow rate).) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the thin film layer, and the above conditions (i) to (iii) It is possible to form a thin film layer satisfying all of the above), and to exhibit excellent barrier properties and bending resistance in the obtained gas barrier laminate film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, carbon atoms and hydrogen atoms that have not been oxidized are excessively taken into the thin film layer. In this case, the transparency of the barrier film decreases, and the barrier film cannot be used for a flexible substrate for a device that requires transparency such as an organic EL device or an organic thin film solar cell. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

  Moreover, although the pressure (vacuum degree) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5 Pa-50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming rolls 31 and 32, an electrode drum connected to the plasma generating power source 51 (in this embodiment, the film is installed on the film forming rolls 31 and 32). The electric power to be applied can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but may be in the range of 0.1 to 10 kW. preferable. If the applied power is less than the lower limit, particles tend to be generated. On the other hand, if the applied power exceeds the upper limit, the amount of heat generated during film formation increases, and the temperature of the substrate surface during film formation increases. Therefore, the substrate loses heat and wrinkles occur during film formation. In severe cases, the film melts due to heat, and a large current discharge occurs between the bare film formation rolls. May cause damage.

  The conveyance speed (line speed) of the film 100 can be adjusted as appropriate according to the type of raw material gas, the pressure in the vacuum chamber, etc., but is preferably in the range of 0.25 to 100 m / min. A range of 5 to 20 m / min is more preferable. If the line speed is less than the lower limit, wrinkles due to heat tend to occur in the film. On the other hand, if the upper limit is exceeded, the thickness of the formed thin film layer tends to be thin.

  In this way, by forming a layer (thin film layer) made of a silicon oxide thin film on the film 100, the base material layer and the gas barrier property formed on at least one surface of the base material layer are provided. A film member provided with a thin film layer (a silicon oxide-based thin film layer containing carbon) can be preferably produced. The first and second film members may be the same or different, and both the first and second film members can be formed as described above. It may be a film member. In this case, it becomes possible to produce a gas barrier laminate in which both the first and second thin film layers are silicon oxide-based thin film layers, and a gas barrier laminate having a higher level of water vapor permeation prevention performance. A film can be produced.

(Process (B))
In step (B), the gas barrier laminate film is formed by laminating with an adhesive so that the second thin film layer in the second film member is laminated on the surface of the base material layer of the first film member. It is the process of obtaining.

  Thus, the film after lamination | stacking is bonded by using an adhesive so that the 2nd thin film layer in a 2nd film member may laminate | stack on the surface of the base material layer of said 1st film member. It is possible to have a laminated structure in which the first thin film layer, the first base material layer, the adhesive layer, the second thin film layer, and the second base material layer are laminated in this order. is there.

  Thus, the method of bonding the first and second film members using an adhesive is not particularly limited, and a known method capable of bonding the film member using an adhesive may be appropriately employed. For example, a method in which a sheet made of an adhesive having a low melting point is sandwiched between the first and second film members, the sheet is melted with heat and bonded, and an adhesive is applied to the adhesive surface. A method of bonding the first and second film members can be appropriately used. The temperature conditions that can be employed in these methods are not particularly limited, and optimal conditions may be employed as appropriate according to the types of the first and second film members, the type of adhesive, and the like. . In addition, since such an adhesive can exhibit a higher level of moisture absorption performance, it is preferable to further contain a moisture adsorbent. In addition, the application method and application thickness of the adhesive are not particularly limited, and a known application method (for example, a doctor blade, a wire bar, An optimal method and its conditions may be appropriately selected from among coating methods such as die coater, comma coater, gravure coater, screen printing, and inkjet.

  Moreover, when bonding the first film member and the second film member in this manner, at least a step of drying the first film member (one film member) in advance is performed. preferable. By adhering the first film member and the second film member so as to satisfy such conditions, sufficient moisture absorption performance (preferably water having a weight of 0.1% by mass or more of its own weight) It is also possible to more efficiently produce a gas barrier laminate film having a hygroscopic performance to absorb).

  A method (drying method) that can be employed as a step of drying such a film member is not particularly limited, and a known method capable of drying such a film member can be appropriately employed. For example, vacuum drying, heat drying, vacuum heat drying, or the like can be appropriately employed. As such a drying method, it is most preferable to employ vacuum heat drying in which vacuum drying and heat drying are combined from the viewpoint of drying speed. Moreover, the conditions (heating conditions, pressure conditions, etc.) in the case of drying by such vacuum drying, heat drying, or vacuum heat drying may be appropriately set to conditions that allow the film member to be dried, and are particularly limited. It is not a thing. In addition, when such a drying method includes a heating step, it becomes possible to dry the film member more efficiently. Therefore, the heating temperature is preferably set to 50 ° C. or higher, and is set to 100 ° C. or higher. Is particularly preferred. In the case where such a drying method is a step of drying while heating (for example, when heat drying or vacuum heat drying is employed), the upper limit of the heating temperature may be appropriately set according to the type of the substrate. Although not particularly limited, it is preferably 200 ° C. or less, more preferably 150 ° C. or less, from the viewpoint of sufficiently preventing deformation of the substrate due to high temperature.

  When such a drying method is a method of drying under vacuum conditions (for example, when vacuum drying or vacuum heat drying is employed), the pressure condition is set to a pressure lower than the atmospheric pressure of 760 mmHg (101325 Pa). The pressure is not particularly limited, but is preferably a pressure lower than 76 mmHg (10132.5 Pa), and more preferably a pressure lower than 7.6 mmHg (1013.25 Pa). In the present specification, “vacuum drying” may be drying performed by reducing the pressure to a pressure lower than the atmospheric pressure of 760 mmHg (101325 Pa).

  Further, when such a drying method is adopted, the drying time of the film member is not particularly limited, and the implementation time (drying time) is appropriately set so that the film member is sufficiently dried according to the employed conditions. For example, when drying is performed using the above-described heating temperature condition and pressure condition (vacuum condition) (when vacuum heating drying is performed), the drying time is set from the viewpoint of obtaining a more fully dried state. Is preferably 3 hours (180 minutes) or longer, more preferably 6 hours (360 minutes) or longer. In addition, what is necessary is just to set such drying time suitably according to the thickness, kind, etc. of a base material.

  Further, when at least the first film member is dried by performing the drying step, the time during which the dried film member is exposed to an atmosphere having a weight absolute humidity of 10 g / kg or more is less than 1 hour. It is preferable that the first and second film members are bonded to each other. As described above, when the drying process is performed, the time during which the film member after drying is exposed to an atmosphere in which the weight absolute humidity becomes 10 g / kg or more is 1 hour (more preferably 30 minutes, still more preferably 20). Minutes, particularly preferably less than 10 minutes). When exposed to an atmosphere in which the absolute humidity is 10 g / kg or more for more than 1 hour, the dried film member (particularly the base material layer in the member) absorbs moisture, and its own weight is 0.1 mass. It tends to be difficult to obtain a gas barrier laminate film having a high moisture absorption performance that absorbs water having a weight of at least%. Therefore, for example, when the film member is taken out from a dry condition under a normal air atmosphere (for example, a condition where the weight absolute humidity is 10 g / kg or more) and the film member is bonded in the air atmosphere, It is preferable to bond the film members within 1 hour (more preferably 30 minutes, more preferably 20 minutes, particularly preferably 10 minutes) after taking out in the atmosphere. Although it differs depending on the type of film member, if the film member is exposed to the outside air (in the atmosphere) with normal humidity for 10 hours or more, the moisture is absorbed from the outside air and the drying effect cannot be obtained. It tends to end up.

  Even when the film member after drying is taken out from the drying condition, when it is stored under a condition where the absolute humidity is less than 10 g / kg (for example, in a desiccator containing a desiccant or the like). In the case of storage), since the dried state of the film member after drying can be sufficiently retained, it can be used as a film member in a dried state even after long-term storage. Thus, when bonding the 1st and 2nd film member using the film member after the drying, the time which exists in the atmosphere where the weight absolute humidity becomes 10 g / kg or more becomes less than 1 hour. In this way, the first and second film members can be bonded together while preventing moisture absorption of the film member after drying (while maintaining the dry state sufficiently).

  In addition, the gas barrier laminate film is more efficiently manufactured while satisfying the condition that the time (total time) of exposure to an atmosphere in which the weight absolute humidity is 10 g / kg or more is less than 1 hour. From a viewpoint, a drying process and a bonding process are performed in a low-humidity environment such as a dry room (an atmosphere in which the weight absolute humidity is less than 5 g / kg) (for example, a vacuum oven and a bonding apparatus are used in a dry room, etc.) It is preferable to install in a low humidity environment and perform a drying step and a bonding step in a low humidity environment. In addition, such a drying process is from a viewpoint of suppressing the influence which the water | moisture content discharge | released from a 2nd film has with respect to the 1st base material, adhesive layer, etc. of a 1st film during bonding. , And may be applied to both the first and second film members.

  In this manner, the second film member and the second film member are laminated so that the second thin film layer in the second film member is laminated on the surface of the base material layer of the first film member. Is pasted at least a step of drying the first film member in advance, and the dried film member is exposed to an atmosphere in which the weight absolute humidity is 10 g / kg or more for 1 hour. It is preferable to employ a method in which the first film member and the second film member are bonded to each other while maintaining the value below the value. Thus, the gas barrier laminated film having a laminated structure in which the first thin film layer, the first base material layer, the adhesive layer, the second thin film layer, and the second base material layer are laminated in this order. The first base material layer can be disposed between the first and second thin film layers in a dry state, and has sufficient moisture absorption performance (preferably a weight of 0.1% by weight or more of its own weight). It is possible to more efficiently form a gas barrier laminate film having a moisture absorption capability of absorbing water. In addition, the gas barrier laminated film obtained using the film member in a dry state in this way tends to have a sufficiently improved heat resistance.

  In addition, when the first film member and the second film member are bonded together, it is preferable to bond them using an adhesive containing the moisture adsorbent. Thus, when bonding together using the adhesive agent containing a water | moisture-content adsorption agent, the adhesive bond layer provided with a water | moisture-content adsorption agent with a base material layer will also exist fundamentally between thin film layers. When the adhesive layer containing the moisture adsorbent is laminated between the thin film layers in this way, the first base material disposed between the first and second thin film layers by the moisture adsorbent in the adhesive layer. It is possible to dry the layer. Therefore, in the gas barrier laminate film thus obtained, the base material layer existing between the thin film layers can be dried after bonding, and the base material layer can exhibit moisture absorption performance. In addition, since the gas barrier laminate film obtained in this manner includes an adhesive layer containing a moisture adsorbent between the thin film layers, the moisture adsorbent itself in the adhesive layer can also exhibit moisture absorption performance. Is also possible. Therefore, sufficient moisture absorption performance (preferably a weight of 0.1% by mass or more of its own weight) is also obtained by bonding the first film member and the second film member using an adhesive containing the moisture adsorbent. It is possible to more efficiently form a gas barrier laminate film having a moisture absorption capability of absorbing water. In this way, when the first film member and the second film member are bonded using the adhesive containing the moisture adsorbent, before the first and second film members are bonded. In addition, it may or may not include at least the step of drying the first film member, but it is possible to develop a higher level of moisture absorption performance, and a gas barrier laminate film (transparent support substrate 1). It is preferable that a drying step is included from the viewpoint that it is possible to develop a further advanced water vapor permeation prevention performance.

  In the step of bonding the first and second film members, it is preferable to bond the first and second film members under a temperature condition of 20 to 150 ° C. If such a temperature exceeds the upper limit, the substrate tends to be damaged such as deformation, whereas if it is less than the lower limit, the adhesiveness between the adhesive and the substrate or the thin film layer decreases, and water vapor from the interface There is a tendency to increase the likelihood of infiltration.

  Thus, the gas-barrier laminated | multilayer film (transparent support substrate 1) which can be utilized suitably for this invention can be obtained by performing a process (A) and a process (B). The step (B) may be performed after the light emitting element portion 2 is formed on the first thin film layer of the first film member, which will be described later, or before the light emitting element portion 2 is formed. The step (B) may be performed, and then the light emitting element portion 2 may be formed. Moreover, after performing the drying process of the base material layer of said 1st film member in a process (B), you may form the light emitting element part 2, or the said drying process after forming the light emitting element part 2 May be performed.

[Light emitting element part 2]
The light emitting element portion 2 includes a pair of electrodes and a light emitting layer disposed between the electrodes. The pair of electrodes (first electrode 201, second electrode 203) constituting the light emitting element portion 2 and the light emitting layer 202 disposed between the electrodes are not particularly limited, and may be a known organic EL element. The used electrodes and light emitting layers can be used as appropriate. For example, the light extraction surface side electrode may be transparent or semi-transparent, and a low molecular and / or high molecular organic light emitting material may be used for the light emitting layer. Hereinafter, the first electrode 201, the light emitting layer 202, and the second electrode 203 will be described separately.

(First electrode 201)
The first electrode 201 is one of an anode and a cathode. In the light emitting element portion 2 of the embodiment shown in FIG. 1, the first electrode 201 is an electrode that exhibits light transmittance so that light emitted from the light emitting layer 202 can be emitted outside the element portion 2 ( A transparent or translucent electrode). In such an embodiment shown in FIG. 1, the first electrode 201 exhibiting light transmittance is used as the anode.

  As the first electrode 201 (anode) exhibiting such light transmittance, thin films such as metal oxides, metal sulfides, and metals can be used, and those having higher electrical conductivity and light transmittance are preferable. Used. Examples of such an electrode made of a thin film of metal oxide, metal sulfide and metal include, for example, indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, and platinum. , Silver, copper and the like. As such a metal oxide, metal sulfide and metal thin film, a thin film made of ITO, IZO or tin oxide is more preferable. A method for producing such a metal oxide, metal sulfide and metal thin film is not particularly limited, and a known method can be appropriately employed. For example, a vacuum deposition method, a sputtering method, an ion plating method can be employed. Method, plating method, etc. can be adopted.

  As the first electrode 201, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used. Moreover, as such a 1st electrode 201, the film-like electrode (A which consists of resin which has a light transmittance, and the wire-shaped conductor which has the electroconductivity arrange | positioned in this resin which has this light transmittance. ). As such a resin having a light transmittance, a resin having a higher light transmittance is preferable. For example, low density or high density polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer is used. Polymer, ethylene-octene copolymer, ethylene-norbornene copolymer, ethylene-dimethano-octahydronaphthalene copolymer, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, etc. Polyolefin resins; Polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Nylon-6, nylon-6,6, metaxylenediamine-adipic acid condensation polymers; Amide resins such as polymethylmethacrylamide Acrylic resins such as polymethyl methacrylate; Styrene-acrylonitrile resins such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, polyacrylonitrile; Hydrophobized cellulose systems such as cellulose triacetate and cellulose diacetate Resin; halogen-containing resin such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoroethylene; hydrogen-bonding resin such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, cellulose derivative; polycarbonate resin, polysulfone resin, Polyethylene sulfone resin, polyether ether ketone resin, polyphenylene oxide resin, polymethylene oxide resin, polyarylate resin, liquid crystal resin, etc. Such as engineering plastic resins. In addition, when the resin constituting the first electrode 201 is manufactured by applying an organic layer on the anode by a coating method or the like, from the viewpoint that the resin is more difficult to dissolve in the coating liquid, A thermosetting resin, a photocurable resin, or a photoresist material is preferably used.

  The wire-like conductor preferably has a small diameter. The diameter of the wire-like conductor is preferably 400 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. Such a wire-like conductor diffracts or scatters the light passing through the first electrode 201, so that the haze value of the first electrode 201 is increased and the light transmittance is reduced, but the wavelength of visible light or visible light is reduced. By using a wire-like conductor having a diameter smaller than the wavelength of light, the haze value with respect to visible light can be kept low, and the light transmittance can be improved. Moreover, since resistance will become high if the diameter of a wire-like conductor is too small, 10 nm or more is preferable. In addition, when using an organic EL element for an illuminating device, since the one where the haze value of the 1st electrode 201 is high to some extent can illuminate a wide range, the 1st electrode 201 with a high haze value may be used suitably. is there. Thus, the optical characteristics of the first electrode 201 can be set as appropriate according to the device in which the organic EL element is used.

  Further, the number of wire-like conductors included in such a film-like electrode (A) may be one or a plurality. Such a wire-like conductor preferably forms a network structure in the electrode (A). That is, in the electrode (A), one or a plurality of wire-like conductors are arranged so as to be intertwined in a complicated manner throughout the resin, and have a network structure (one wire-like conductor is complicated). Or a plurality of wire-like conductors are arranged in contact with each other to form a two-dimensional or three-dimensional network structure). Furthermore, such a wire-like conductor may be, for example, curved or needle-like. The first electrode 201 having a low volume resistivity can be realized by forming a network structure by contacting curved and / or needle-shaped conductors with each other. This network structure may be regular or non-regular. The volume resistivity of the first electrode 201 can be lowered by a wire-like conductor that forms a network structure.

  At least a part of the wire-shaped conductor may be disposed in the vicinity of the surface opposite to the transparent support base 1 on which the first electrode 201 is disposed (in this embodiment, the surface on the light emitting layer 202 side). preferable. By arranging the wire-like conductor in this way, the resistance of the surface portion of the first electrode 201 can be lowered. In addition, as a material of such a wire-like conductor, for example, a low resistance metal such as Ag, Au, Cu, Al, and alloys thereof is preferably used. The wire-like conductor is, for example, N.I. R. Jana, L.M. Gearheartt and C.C. J. et al. Murphy's method (Chm. Commun., 2001, p617-p618), C.I. Ducamp-Sanguesa, R.A. Herrera-Urbina, and M.M. It can be produced by the method by Figlarz et al. (J. Solid State Chem., Vol. 100, 1992, p272 to p280). Moreover, as such an electrode (A), it is good also as a structure similar to the electrode as described in Unexamined-Japanese-Patent No. 2010-192472, and the manufacturing method employs the method as described in Unexamined-Japanese-Patent No. 2010-192472. Can do.

  In addition, the film thickness of the first electrode 201 (anode) is appropriately set in consideration of required characteristics and process simplicity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm. More preferably, it is 50 nm-500 nm.

(Light emitting layer 202)
The light emitting layer 202 may be a layer made of a known material that can be used for the light emitting layer (layer having a function of emitting light) of the organic EL element, and the material is not particularly limited, but is a light emitting layer made of an organic material. Preferably there is. Such a light emitting layer made of an organic material is not particularly limited. For example, an organic material (low molecular compound and high molecular compound) that emits fluorescence or phosphorescence as a light emitting material and a dopant that assists the organic material. A layer to be formed is preferable. In addition, the high molecular compound here has a polystyrene-equivalent number average molecular weight of 10 ³ or more. Although there is no particular reason for defining such an upper limit of the number average molecular weight, the upper limit of the number average molecular weight in terms of polystyrene is usually preferably 10 ⁸ or less.

  Examples of such luminescent materials (organic substances that emit fluorescence or phosphorescence) include dye-based materials, metal complex-based materials, and polymer-based materials. Examples of such dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, Examples include thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, and pyrazoline dimers.

  Examples of the metal complex-based material include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazolyl zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, etc. And metal complexes having a rare earth metal such as Tb, Eu, or Dy and having a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, or the like as a ligand.

  Further, the polymer material includes polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinyl carbazole derivatives, the above chromophores and metal complex light emitting materials. And the like.

  Among such luminescent materials, materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like. it can. Of these, polymer materials such as polyvinyl carbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferred.

  Examples of the light-emitting material that emits green light include quinacridone derivatives, coumarin derivatives, polymers thereof, polyparaphenylene vinylene derivatives, and polyfluorene derivatives. Of these, polymer materials such as polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferred.

  Examples of the light-emitting material that emits red light include a coumarin derivative, a thiophene ring compound, and a polymer thereof, a polyparaphenylene vinylene derivative, a polythiophene derivative, and a polyfluorene derivative. Among these, polymer materials such as polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.

  In addition, the manufacturing method in particular of such a luminescent material is not restrict | limited, A well-known method can be employ | adopted suitably, For example, you may employ | adopt the method as described in Unexamined-Japanese-Patent No. 2012-144722.

  In the light emitting layer 202, it is preferable to add a dopant for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. In addition, it is preferable that the thickness of such a light emitting layer is about 20-2000 mm normally.

  The formation method of such a light emitting layer 202 is not specifically limited, A well-known method can be employ | adopted suitably. Among such formation methods of the light emitting layer 202, it is preferable to form by the coating method. The coating method is preferable in that the manufacturing process can be simplified and the productivity is excellent. Examples of such coating methods include casting methods, spin coating methods, bar coating methods, blade coating methods, roll coating methods, gravure printing, screen printing, and ink jet methods. In the case of forming a light emitting layer using the coating method, first, a composition in a solution state containing a light emitter and a solvent is prepared as a coating solution, and this coating solution is formed into a desired layer or electrode by the predetermined coating method described above. A light emitting layer having a desired film thickness can be formed by applying it on the substrate and drying it.

(Second electrode 203)
The second electrode 203 is an electrode having a polarity opposite to that of the first electrode 201, and is disposed to face the first electrode 201. In the embodiment shown in FIG. 1, the second electrode is a cathode.

  The material of the second electrode 203 (cathode) is not particularly limited, and a known material can be used as appropriate. The work function is small, the electron injection into the light emitting layer is easy, and the electric conductivity is low. It is preferable to use high materials. Further, as in the embodiment shown in FIG. 1, in the organic EL element configured to extract light from the anode side, light emitted from the light emitting layer is reflected to the anode side by the cathode, and light is extracted more efficiently. From the viewpoint, the material of the second electrode 203 (cathode) is preferably a material having a high visible light reflectance.

  Examples of the material of the second electrode 203 (cathode) include alkali metals, alkaline earth metals, transition metals, and Group 13 metals of the periodic table. More specifically, as the material of the second electrode 203 (cathode), lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, Metals such as cerium, samarium, europium, terbium, ytterbium, two or more alloys of the metals, one or more of the metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, An alloy with one or more of tungsten and tin, graphite, or a graphite intercalation compound can be suitably used. Examples of such alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, calcium-aluminum alloys, and the like. Can be mentioned.

  Further, as the second electrode 203 (cathode), a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used. Specifically, examples of the conductive metal oxide include indium oxide, zinc oxide, tin oxide, ITO, and IZO, and examples of the conductive organic substance include polyaniline or a derivative thereof, polythiophene or a derivative thereof, and the like. In addition, the 2nd electrode 203 (cathode) may be comprised by the laminated body which laminated | stacked two or more layers. A so-called electron injection layer may be used as the cathode.

  The film thickness of the second electrode 203 (cathode) can be appropriately designed in consideration of required characteristics and process simplicity, and is not particularly limited, but is preferably 10 nm to 10 μm, preferably Is 20 nm to 1 μm, more preferably 50 nm to 500 nm. Examples of a method for producing the second electrode 203 (cathode) include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.

  In the embodiment shown in FIG. 1, the second electrode 203 (cathode) is electrically connected to a connection portion (extraction electrode 203 (a)) that can be electrically connected to the outside. . Here, in the embodiment shown in FIG. 1, the extraction electrode 203 (a) is formed of the same material as the first electrode 201. Such an extraction electrode 203 (a) can be appropriately manufactured and designed by a known method. For example, when the first electrode 201 is formed, the portion of the extraction electrode 203 (a) is also patterned. It can be easily manufactured, for example, by forming a film.

(Relationship between transparent support substrate 1 and light-emitting element portion 2)
The light-emitting element portion 2 including the pair of electrodes as described above and the light-emitting layer disposed between the electrodes is disposed on the surface of the gas barrier laminate film (transparent support substrate 1). One electrode (first electrode 201) of the part 2 is laminated on the first thin film layer 101 (a) of the gas barrier laminate film (transparent support substrate 1). Thus, by arranging one electrode (first electrode 201) on the thin film layer having gas barrier properties in the gas barrier laminated film (transparent support substrate 1), water vapor is transmitted from the transparent support substrate 1 side to the light emitting element portion. Intrusion can be prevented at a higher level. In addition, when one electrode (first electrode 201) of the light-emitting element part 2 is directly arranged on the surface of the base material layer, water enters the light-emitting element part 2 due to moisture contained in the base material. It becomes difficult to sufficiently suppress deterioration. That is, when one electrode (first electrode 201) of the light emitting element portion 2 is directly disposed on the surface of the base material layer, a region where the base material layer directly contacts outside air is generated in addition to the end portion (base). The surface of the material layer where the light emitting element part or the sealing material layer is not formed can be in contact with the outside air.) The entire surface of the base material layer easily contains water vapor (easily in the base material layer) This is because water vapor enters.) Since moisture in the base material layer easily enters the light emitting element portion formed on the surface of the base material layer, deterioration of the light emitting element portion is not necessarily sufficiently suppressed. I can't do that.

[Sealing material layer 3]
The sealing material layer 3 is a layer disposed on the transparent support substrate 1 so as to seal the light emitting element portion 2, and is a known sealing material (for example, an adhesive sheet having a sufficiently low water vapor permeability). Etc.) can be used as appropriate. That is, such a sealing material layer 3 is a layer that covers the periphery of the light emitting element portion 2 on the transparent support substrate 1 and seals the light emitting element so that it does not come into contact with outside air. In such sealing, in order to function as a light emitting element, a connection portion for electrically connecting a pair of electrodes to the outside [for example, a connection wiring or a so-called extraction electrode portion (implementation shown in FIG. 1 In the embodiment, the portion indicated by 203 (a) connected to the second electrode 203 and the portion that can come into contact with the outside air of the first electrode 201 (a portion of the first electrode drawn out) correspond. .)] Is removed and sealed.

  The sealing material for forming such a sealing material layer 3 may be appropriately formed using any conventionally known suitable material in consideration of adhesiveness, heat resistance, barrier properties against moisture, oxygen, and the like. For example, in addition to an epoxy resin, a silicone resin, an acrylic resin, a methacrylic resin, etc., the same materials as those described as the adhesive that can be used to form the adhesive layer are appropriately used. be able to. In addition, in order to form such a sealing material layer 3, you may utilize a sheet-like sealing material. Such a sheet-like sealing material can be formed by appropriately forming by a known method.

  Moreover, the thickness of such a sealing material layer 3 should just have the thickness which can be covered so that it can seal the light emitting element part 2, and although it does not restrict | limit in particular, It is preferably 120 μm, more preferably 5 to 60 μm, more preferably 10 to 60 μm, and particularly preferably 10 to 40 μm. When the thickness of the sealing material layer (thickness between the transparent support substrate 1 and the sealing substrate 4) is less than the lower limit, when pressure is applied to the sealing substrate from the outside, the light emitting element portion is pushed and The possibility of short-circuiting between one electrode and the second electrode increases, and the mechanical strength tends to decrease. On the other hand, if the upper limit is exceeded, the amount of moisture intrusion from the end of the sealing material Tends to increase and it becomes difficult to sufficiently suppress the deterioration of the organic EL.

[Sealing substrate 4]
The sealing substrate 4 is a substrate disposed on the sealing material layer 3, and water vapor enters the inside of the light emitting element portion 2 from the surface on the side opposite to the surface in contact with the transparent substrate of the sealing material layer 3. It is used from the viewpoint of more efficiently suppressing the intrusion of oxygen and oxygen, and from the viewpoint of improving heat dissipation. In addition, since the sealing material layer 3 is disposed so as to cover the light emitting element part 2, in the embodiment shown in FIG. 1, the light emitting element part 2 is interposed between the light emitting element part 2 and the sealing substrate 4. And the sealing material layer 3 will exist. As described above, in the embodiment shown in FIG. 1, the sealing material 4 is sealed so that the light emitting element portion 2 and the sealing material layer 3 are interposed between the transparent support substrate 1 and the sealing substrate 4. Arranged on layer 3.

  As such a sealing substrate 4, a material made of a known material can be used as appropriate. For example, a plate or foil of a metal such as copper or aluminum or an alloy containing the metal, glass, or a barrier layer is laminated. What consists of a plastic substrate etc. can be utilized suitably. Further, the sealing substrate 4 may be a rigid substrate or a flexible substrate.

  Moreover, as a material of such a sealing substrate, it is preferable to consist of metal materials in any one of copper, a copper alloy, aluminum, and an aluminum alloy from a viewpoint of heat dissipation and the ease of a process. Suitable examples of the sealing substrate made of such a metal material include aluminum foil (aluminum foil) and copper foil (copper foil).

  Further, among such sealing substrates 4, the copper foil produced by the electrolytic method has fewer pinholes, and the viewpoint that water vapor, oxygen, etc. tend to be more effective in preventing intrusion. Therefore, it is more preferably made of a copper foil produced by an electrolytic method. That is, by using the copper foil (copper foil) manufactured by such an electrolytic method for the sealing substrate 4, the organic EL element can be more efficiently sealed. It is possible to more sufficiently suppress the organic EL element from entering and deteriorating. In addition, it does not restrict | limit especially as such an electrolysis method, The well-known electrolysis method which can manufacture copper foil is employable suitably.

  The thickness of the sealing substrate 4 is not particularly limited, but is preferably 5 to 100 μm, and more preferably 8 to 50 μm. When the thickness of the sealing substrate 4 is less than the lower limit, it becomes difficult to sufficiently suppress the generation of pinholes during the manufacturing of the sealing substrate 4, and moisture penetrates from the pinholes to deteriorate the organic EL element. On the other hand, when the upper limit is exceeded, the flexibility of the sealing substrate 4 decreases, and as a result, the curvature radius when the organic EL element is bent is decreased. This increases and the flexibility of the organic EL element tends to decrease.

  Further, the distance between the sealing substrate 4 and the light emitting element portion 2 in the thickness direction (direction perpendicular to the sealing substrate 4) (the sealing material layer 3 between the light emitting element portion 2 and the sealing substrate 4). The thickness of the second electrode 203 is preferably 5 to 120 μm as the distance between the surface of the second electrode 203 in contact with the sealing agent layer 3 and the surface of the sealing substrate 4 in contact with the sealing agent layer 3. More preferably, it is ˜60 μm. When the distance between the sealing substrate 4 and the light emitting element portion 2 (thickness of the sealing material layer 3 between the light emitting element portion 2 and the sealing substrate 4) is less than the lower limit, the second electrode is bent. The contact between 203 and the sealing substrate 4 cannot necessarily be sufficiently suppressed, and it tends to be difficult to sufficiently suppress the occurrence of a short circuit, and the light emitting quality tends to be lowered. In addition, when the second electrode 203 is pressed and pressed by the unevenness on the surface of the sealing substrate 4 when bent, the first electrode 201 tends to short-circuit. On the other hand, when the upper limit is exceeded, the surface of the sealing layer 3 in contact with the outside air increases, and the lateral direction of the sealing material layer (direction perpendicular to the thickness direction: parallel to the surface of the transparent resin substrate 1). The amount of water vapor entering from (direction) increases, and it tends to be difficult to suppress a decrease in storage life of the organic EL element at a higher level.

  Such a sealing substrate 4 has a surface roughness of the surface of the sealing substrate 4 on the side of the sealing material layer 3 on the basis of the arithmetic average roughness Ra of JIS B 0601-1994. It is preferable to use the surface of the other surface so as to be smaller than the surface roughness (outside surface roughness). When the arithmetic average roughness of the surface of the sealing substrate 4 on the side of the sealing material layer 3 is larger than the arithmetic average roughness Ra of the other surface of the sealing substrate, the organic EL element is bent. In this case, the unevenness on the surface of the sealing substrate 4 (the unevenness present due to the roughness of the surface) tends to cause a short circuit, for example, because the light-emitting element portion is damaged. In addition, it is considered that the surface roughness of the sealing substrate 4 is smoothed. However, if such a smoothing treatment (for example, polishing or surface treatment) is performed, the cost increases, and the organic EL Not only is the economic efficiency of the device lowered and mass production becomes difficult, but if the surface is made too smooth, the adhesiveness with the sealing material layer 3 is lowered and easily peeled off, and the organic EL device can be removed over a long period of time. Tend to be difficult to use. Further, when the surface of the sealing substrate 4 becomes smooth, the emissivity tends to decrease and heat dissipation tends to be difficult.

Moreover, in this invention, the arithmetic mean roughness of the surface by the side of the sealing material layer 3 of the sealing substrate 4 and the thickness of the sealing material layer 3 are following formula (I):
0.002 <(Ra / t) <0.2 (I)
[In formula (I), Ra represents the arithmetic mean roughness of JIS B 0601-1994 on the surface of the sealing substrate on the sealing material layer side, and t represents the thickness of the sealing material layer. ]
It is necessary to satisfy the conditions shown in. When the ratio (Ra / t) between the arithmetic average roughness Ra and the thickness t of the sealing material layer 3 is 0.002 or less, the surface of the sealing substrate 4 on the sealing material layer 3 side becomes too smooth. In addition, the adhesiveness with the sealing material layer 3 is lowered, and it becomes easy to peel off, and moisture enters from the interface between the sealing material layer 3 side surface of the sealing substrate 4 and the sealing material layer 3, and the organic EL element It tends to speed up the deterioration. Moreover, since the thickness of the sealing material layer 3 tends to increase, moisture tends to enter from the portion exposed to the outside of the end portion of the sealing material layer 3 to accelerate the deterioration of the organic EL element. On the other hand, when the thickness is 0.2 or more, the unevenness of the surface of the sealing substrate 4 on the sealing material layer 3 side becomes large and the thickness of the sealing material layer 3 is relatively reduced. Not only can the short substrate be sufficiently prevented from coming into contact with the stop substrate 4 but also the light emitting quality tends to be lowered, and the pressure on the second electrode 203 is caused by the irregularities on the surface of the sealing substrate 4 when bent. The first electrode 201 tends to be short-circuited by being pressed. In addition, since a higher effect is obtained from the same viewpoint, the ratio (Ra) of the arithmetic average roughness Ra of the surface of the sealing substrate 4 on the sealing material layer 3 side and the thickness t of the sealing material layer 3 (Ra / T) is preferably in the range of 0.003 to 0.03, and more preferably in the range of 0.005 to 0.01. In addition, the thickness t of the sealing material layer 3 here refers to the thickness from the surface of the transparent support substrate 1 and has the same value as the distance between the transparent support substrate 1 and the sealing substrate 4.

  The arithmetic average roughness Ra of the surface of the sealing substrate 4 on the sealing material layer 3 side is preferably 0.1 to 1.0 μm, and more preferably 0.2 to 0.5 μm. If the arithmetic mean roughness Ra of the surface is less than the lower limit, not only the adhesion to the sealant layer 3 is lowered, but also the heat radiation tends to be lowered. On the other hand, if the upper limit is exceeded, the organic EL When the element is bent, not only the peak of the convex portion of the surface breaks through the sealing material layer and the element is easily short-circuited, but also the sealing substrate 4 and the second electrode 203 come into contact with each other and short-circuit. In addition, in the case of an element configured such that the sealing substrate 4 can be seen through the transparent support substrate 1, it tends to be low in appearance due to light reflection. When the arithmetic average roughness Ra is less than or equal to the above upper limit, the surface of the sealing substrate 4 visible from the transparent support substrate 1 in the case of an element having a configuration in which the sealing substrate 4 can be seen through the transparent support substrate 1 The surface roughness becomes a relatively small surface, and the design property tends to be further improved. When measuring the arithmetic average roughness (arithmetic average roughness defined by JIS B 0601 (1994)), for example, a contact type step surface roughness measuring device may be used as a measuring device. Good.

  The arithmetic average roughness Ra of the outer surface of the sealing substrate 4 (the surface opposite to the surface on the sealing material layer 3 side) is preferably 0.25 to 3.8 μm, 0.5 More preferably, it is -2.5 micrometers. When the arithmetic average roughness Ra of the outer surface is less than the lower limit, the surface area of the outer surface is decreased, the amount of heat released from the light emitting element portion is decreased, and the organic EL element is heated to deteriorate. In addition, when a heat dissipation layer or a heat transfer layer is provided on the surface of the outer surface, the adhesion at the interface between the heat dissipation layer or the heat dissipation layer and the outer surface is lowered and easily peeled off. As a result, the element tends to break down. On the other hand, when the upper limit is exceeded, a special roughening step is applied to the outer surface, and the productivity tends to decrease.

  The ten-point average roughness Rz of JIS B 0601-1994 on the surface of the sealing substrate 4 on the side of the sealing material layer 3 is preferably 0.4 to 4.0 μm, and 0.8 to 2.0 μm. It is more preferable that When the ten-point average roughness Rz is less than the lower limit, the adhesiveness to the sealing material layer 3 tends to be lowered. On the other hand, when the upper limit is exceeded, the surface of the organic EL element is bent when bent. The peak of the convex portion tends to break through the sealing material layer and easily cause a short circuit in the organic EL element, and the sealing substrate 4 and the second electrode 203 tend to come into contact with each other to easily cause a short circuit.

  The ten-point average roughness Rz of JIS B 0601-1994 on the outer surface of the sealing substrate 4 (the surface opposite to the surface on the sealing material layer 3 side) is 0.5 to 10 μm. preferable. When the ten-point average roughness Rz is less than the lower limit, the surface area of the surface decreases, the amount of heat released from the light-emitting element portion decreases, the organic EL element tends to become high temperature, and deterioration tends to be accelerated. In addition, when a heat dissipation layer or a heat transfer layer is provided on the surface of the outer surface, the adhesion at the interface between the heat dissipation layer or the heat dissipation layer and the surface is reduced and the device is likely to be peeled off. It tends to be easier.

  In addition, it does not restrict | limit especially as a method of laminating | stacking such a sealing material layer 3 and the sealing substrate 4, A well-known method can be employ | adopted suitably, for example, it covers so that the light emitting element part 2 on the transparent support substrate 1 may be covered. A sealing material made of an adhesive material is applied, a sealing substrate 4 is laminated thereon, and then the sealing material is fixed, so that the sealing material layer 3 and the sealing substrate 4 are transparent supporting substrates. A method of laminating on 1 may be adopted. In addition, a layer made of a sealing material is formed in advance on the sealing substrate 4, and the layer made of the sealing material is formed on the sealing substrate 4 in which the layer made of the sealing material is a light emitting element portion. A method may be employed in which the sealing material layer 3 and the sealing substrate 4 are stacked on the transparent support substrate 1 while being pressed so as to cover the periphery of the transparent support substrate 1.

  As mentioned above, about suitable embodiment of the organic electroluminescent element of this invention, dividing into the transparent support substrate 1, the light emitting element part 2, the sealing material layer 3, and the sealing substrate 4, referring FIG. As described above, the organic electroluminescence element of the present invention is not limited to the above embodiment.

  For example, in the embodiment shown in FIG. 1, the gas barrier laminate film is a thin film layer 101 (a), a base material layer 100 (a), an adhesive layer 102, a thin film layer 101 (b), and a base material layer 100 (b). In the present invention, the gas barrier laminate film includes the first and second thin film layers having gas barrier properties, and the first and second base material layers. And an adhesive layer, and the first thin film layer, the first base material layer, the adhesive layer, the second thin film layer, and the second base material layer are stacked in this order. The structure is not particularly limited as long as it has a structure. For example, on the surface of the base material layer and / or the thin film layer, if necessary, a primer coat layer, a heat-sealable resin layer, etc. May be further provided. In addition, expressions such as “first” and “second” in the present specification are used for convenience in describing two or more identical or corresponding elements (for example, a base material layer, a thin film layer, a film member, etc.). There is no special meaning to the numbers or the order of explanation (no dominance by numbers), and these elements may be the same or different.

  Furthermore, in the embodiment shown in FIG. 1, the gas barrier laminate film has only two layers of the first substrate layer and the second substrate layer as the substrate layer. In, as long as it is provided with the first base material layer and the second base material layer, the number of base material layers is not particularly limited, according to the use etc., the design is appropriately changed, for example, It is good also as what has 1 or more base material layers (for example, 3rd base material layer etc.) in addition.

  Further, in the organic electroluminescence device of the present invention, since higher gas barrier properties can be obtained, the surface of the gas barrier film on the side where the second thin film layer of the second base material layer is not laminated is provided. In addition, a third thin film layer having gas barrier properties is preferably laminated. Such a third thin film layer is more preferably the above-described silicon oxide-based thin film layer, and such a structure is used as the above-described second film member on both surfaces of the base material. This can be easily achieved by using a laminate in which a silicon oxide-based thin film layer is formed by the method (laminate laminated in the order of thin film layer / base material / thin film layer), whereby an embodiment as shown in FIG. The organic electroluminescence device can be efficiently produced.

  In the embodiment shown in FIG. 1, the light emitting element portion 2 includes a pair of electrodes (first electrode 201, second electrode 203) and a light emitting layer 202 disposed between the electrodes. In the organic electroluminescence element of the present invention, the light emitting element portion 2 may appropriately include other layers as long as the object and effect of the present invention are not impaired. Hereinafter, such other layers will be described.

  As a layer other than the pair of electrodes (first electrode 201, second electrode 203) and the light emitting layer 202 that can be used in such an organic EL element, known layers used in the organic EL element Can be used as appropriate, and examples thereof include a layer provided between the cathode and the light emission, and a layer provided between the anode and the light emission layer. Examples of the layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer. When only one layer is provided between the cathode and the light emitting layer, this layer is an electron injection layer. When two or more layers are provided between the cathode and the light emitting layer, the layer in contact with the cathode is referred to as an electron injection layer, and the other layers are referred to as electron transport layers.

  Such an electron injection layer is a layer having a function of improving electron injection efficiency from the cathode, and the electron transport layer is a layer having a function of improving electron injection from the electron injection layer or the electron transport layer closer to the cathode. It is. In the case where the electron injection layer or the electron transport layer has a function of blocking hole transport, these layers may be referred to as a hole blocking layer. Having such a function of blocking hole transport makes it possible, for example, to produce an element that allows only hole current to flow, and confirm the blocking effect by reducing the current value.

  Examples of the layer provided between the anode and the light emitting layer include a so-called hole injection layer, hole transport layer, electron blocking layer and the like. Here, when only one layer is provided between the anode and the light emitting layer, such a layer is a hole injection layer. When two or more layers are provided between the anode and the light emitting layer, the layer in contact with the anode is a hole. It is called an injection layer, and the other layers are called a hole transport layer or the like. Such a hole injection layer is a layer having a function of improving the hole injection efficiency from the cathode, and the hole transport layer is a hole injection from the hole injection layer or the hole transport layer closer to the anode. It is a layer having a function of improving In addition, when the hole injection layer or the hole transport layer has a function of blocking electron transport, these layers may be referred to as an electron block layer. Note that having the function of blocking electron transport makes it possible, for example, to produce an element that allows only electron current to flow, and confirm the blocking effect by reducing the current value.

In addition, the structure of the light-emitting element portion including such other layers includes a structure in which an electron transport layer is provided between the cathode and the light-emitting layer, and a structure in which a hole transport layer is provided between the anode and the light-emitting layer. And a structure in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer. As such a structure, the following structures a) to d) can be specifically exemplified.
a) Anode / light emitting layer / cathode (Embodiment shown in FIG. 1)
b) Anode / hole transport layer / light-emitting layer / cathode c) Anode / light-emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light-emitting layer / electron transport layer / cathode (where / represents each layer) (Indicates that they are stacked adjacently. The same shall apply hereinafter.)
Here, the hole transport layer is a layer having a function of transporting holes, and the electron transport layer is a layer having a function of transporting electrons. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently. Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  Furthermore, in order to improve the adhesion with the electrode or the improvement of charge injection from the electrode, the charge injection layer or the insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be increased. In order to improve or prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. In this manner, the order and number of layers stacked on the light emitting element portion, and the thickness of each layer can be appropriately designed and used in consideration of light emission efficiency and element lifetime.

  The light emitting element portion (organic EL element portion) provided with such a charge injection layer (electron injection layer, hole injection layer) has a structure in which a charge injection layer is provided adjacent to the cathode, and is adjacent to the anode. And a structure having a charge injection layer.

Examples of the structure of the light emitting element part (organic EL element part) include the following structures e) to p).
e) Anode / charge injection layer / light emitting layer / cathode f) Anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole Transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / charge injection layer / cathode j) anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode k) anode / charge Injection layer / light emitting layer / charge transport layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode n) anode / Charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) anode / charge injection layer / hole transport Layer / light emitting layer / electron transport layer / charge injection layer / cathode When the light emitting layer and other layers (for example, a charge transport layer described later) are laminated In this case, it is desirable to form the hole transport layer on the anode before providing the light emitting layer, or to form the electron transport layer after providing the light emitting layer. Moreover, the material of these other layers is not particularly limited, and a known material can be appropriately used. A manufacturing method thereof is not particularly limited, and a known method can be appropriately used. For example, as a hole transporting material for forming a hole transport layer, which is a layer provided between an anode and a light emitting layer or between a hole injection layer and a light emitting layer, triphenylamines, bis , Heterocyclic compounds typified by pyrazoline derivatives and porphyrin derivatives, and polymer systems such as polycarbonates, styrene derivatives, polyvinyl carbazole, polysilanes and the like having the above monomers in the side chain. Moreover, as a film thickness of such a hole transport layer, about 1 nm-1 micrometer are preferable.

  In addition, as a material for forming the hole injection layer (a layer that can be provided between the anode and the hole transport layer or between the anode and the light emitting layer) in the charge injection layer, a phenylamine system, Examples include starburst amine-based, phthalocyanine-based, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, and polythiophene derivatives.

  Furthermore, as a material for forming an electron transport layer, which can be provided between the light emitting layer and the cathode or between the light emitting layer and the electron injection layer, for example, oxadiazoles, aluminum quinolinol complexes, etc. In general, a substance that forms a stable radical anion and has a high ionization potential can be mentioned. Specific examples include 1,3,4-oxadiazole derivatives, 1,2,4-triazole derivatives, imidazole derivatives, and the like. The thickness of the electron transport layer is preferably about 1 nm to 1 μm.

  Moreover, as an electron injection layer (it is a layer provided between an electron carrying layer and a cathode or between a light emitting layer and a cathode) among the said charge injection layers, according to the kind of light emitting layer, for example. , An electron injection layer having a single layer structure of Ca layer, or a metal of group IA and IIA of the periodic table excluding Ca and having a work function of 1.5 to 3.0 eV and an oxide of the metal In addition, an electron injection layer having a laminated structure of a layer formed of any one or two or more of halides and carbonates and a Ca layer can be provided. Examples of metals of Group IA of the periodic table having a work function of 1.5 to 3.0 eV or oxides, halides, and carbonates thereof include lithium, lithium fluoride, sodium oxide, lithium oxide, lithium carbonate, and the like. Can be mentioned. Examples of metals of Group IIA of the periodic table excluding Ca having a work function of 1.5 to 3.0 eV or oxides, halides and carbonates thereof include strontium, magnesium oxide, magnesium fluoride, fluorine Strontium fluoride, barium fluoride, strontium oxide, magnesium carbonate and the like. The electron injection layer is formed by vapor deposition, sputtering, printing, or the like. The thickness of the electron injection layer is preferably about 1 nm to 1 μm.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Preparation Example 1: Preparation of film member (A))
The film member (A) was manufactured using the manufacturing apparatus shown in FIG. That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films, Inc., trade name “Teonex Q65FA”) is used as a base material (film 100). -It was attached to And while applying a magnetic field between the film-forming roll 31 and the film-forming roll 32 and supplying electric power to the film-forming roll 31 and the film-forming roll 32, respectively, In this discharge region, a film-forming gas (mixed gas of hexamethyldisiloxane (HMDSO) as a source gas and oxygen gas (which also functions as a discharge gas) as a reactive gas) is generated in such a discharge region. A thin film formed by a plasma chemical vapor deposition method (plasma CVD method: PECVD) under the following conditions and formed of a base material on which a thin film layer having a thickness of 1.2 μm is formed (thin film layer / The film member (A) which is a laminated body laminated in the order of the base material layer was obtained.

<Film formation conditions>
Supply amount of raw material gas: 50 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas: 500 sccm
Degree of vacuum in the vacuum chamber: 1Pa
Applied power from the power source for plasma generation: 0.8 kW
Frequency of power source for plasma generation: 70 kHz
Film conveyance speed: 0.5 m / min.

In addition, XPS depth profile measurement was performed on the thin film layer of such a film member (A) under the following conditions to obtain a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve.
Etching ion species: Argon (Ar ⁺ )
Etching rate (SiO ₂ thermal oxide equivalent value): 0.05 nm / sec
Etching interval (SiO ₂ equivalent value): 10 nm
X-ray photoelectron spectrometer: Model “VG Theta Probe”, manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval.

The carbon distribution curve of the thin film layer thus obtained has a plurality of distinct extreme values, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is 5 at% or more, and The atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are represented by the formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
It was confirmed that the conditions indicated in were satisfied.

Moreover, the gas barrier property of such a film member was measured by the method based on the calcium corrosion method (method described in Unexamined-Japanese-Patent No. 2005-283561). That is, after drying treatment, metal calcium is vapor-deposited on the film member, sealed with metal aluminum from above, fixed to glass, and sealed with resin. The temperature is 40 ° C. and the humidity is 90% RH. The water vapor permeability was calculated by examining the increase of the corrosion point with time in the image analysis. In calculating the water vapor transmission rate, the corrosion point is photographed with a microscope, the image is taken into a personal computer, the image of the corrosion point is binarized, and the corrosion area is calculated and obtained. The water vapor permeability was calculated. As a result, the water vapor permeability of the film member (base material having a thin film layer formed on the surface) was 1 × 10 ⁻⁵ g / m ² / day. In addition, when the gas barrier property was measured by a method based on the above calcium corrosion method (the method described in Japanese Patent Application Laid-Open No. 2005-283561) using a sample consisting of only the base material (PEN film), the base material The gas barrier property was 1.3 g / m ² / day. From these results, it was confirmed that the “water vapor permeability of the base material on which the thin film layer was formed” showed a value two or more digits smaller than the “water vapor permeability of the base material”. The thin film layer was confirmed to have gas barrier properties.

(Preparation Example 2: Preparation of film member (B))
The film member (B) was manufactured using the manufacturing apparatus shown in FIG. That is, first, a film member (A) was obtained in the same manner as in Preparation Example 1. Next, using the obtained film member (A) as a base material (film 100), the film member (A) is mounted on the delivery roll 11, and on the surface of the film member (A) on which the thin film layer is not formed, A laminate (thin film layer) comprising a base material in which a thin film layer is newly formed by adopting the same conditions as the film forming conditions employed in Preparation Example 1 and a thin film layer having a thickness of 1.2 μm is formed on both surfaces. A film member (B) which is a laminate laminated in the order of / base material layer / thin film layer) was obtained.

As is clear from the fact that the thin film layers are formed under the same conditions as in Preparation Example 1, both thin film layers on both sides of the film member (B) have the same gas barrier properties as in Preparation Example 1. It is clear that it has. Further, when the carbon distribution curves of these layers were measured, each carbon distribution curve had a plurality of distinct extreme values, and the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon. Is 5 at% or more, and the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are represented by the formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
The conditions indicated in were met.

(Example 1)
First, a film member (A) prepared in the same manner as in Preparation Example 1 and a film member (B) prepared in the same manner as in Preparation Example 2 were prepared. Both of these film members were heated at 100 ° C. in a vacuum oven. It dried for 360 minutes on temperature conditions. Thereafter, the two film members are taken out from the vacuum oven into the atmosphere (temperature: 25 ° C., relative humidity: 50%, weight absolute humidity: 10 g / kg (dry air)), and bisphenol A type epoxy resin is used as an adhesive. The base material side surface of the film member (A) and the thin film of the film member (B) using a two-pack type epoxy adhesive that cures at room temperature (25 ° C.) by mixing the main agent and the curing agent made of modified polyamide The gas barrier laminate film was obtained by bonding with a silicon rubber roll bonding apparatus having a rubber hardness of 60 so that the layers face each other. Here, the time required to take out the two film members from the vacuum oven and start the process of bonding them was 10 minutes, and the time required for bonding was 15 minutes. Thus, it took a total of 25 minutes to take out the two film members after the drying step from the vacuum oven to form the gas barrier laminated film. The laminated structure of the gas barrier laminate film thus obtained is in the order of “first thin film layer / first base material layer / adhesive layer / second thin film layer / second base material layer / third thin film layer”. It became the laminated structure. In addition, the laminated structure portion of “first thin film layer / first base material layer” in the gas barrier laminate film is a structure derived from the film member (A), and “second thin film layer / second base material layer / first The laminated structure portion of “three thin film layers” is a structure derived from the film member (B). The gas barrier laminate film thus obtained was measured for the moisture absorption performance of the gas barrier laminate film as described above (the ratio Bn of the amount of moisture absorption described above). It was confirmed that the water can be absorbed and retained.

  Next, an ITO film having a thickness of 150 nm is patterned on the first thin film layer (thin film layer derived from the film member (A)) in the gas barrier laminate film by a sputtering method using a metal shadow mask. Filmed. In this pattern formation, the ITO film is formed in a pattern so that two regions are formed on the surface of the gas barrier laminate film, and one region is used as an extraction electrode for the cathode, The region was used as an anode (ITO electrode).

Next, cleaning and surface modification of the surface on which the UV-O ₃ device (manufactured by Technovision) is formed with respect to the surface on which the ITO film (ITO electrode) of the gas barrier laminate film is formed. Went.

  Next, a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (trade name “AI4083” manufactured by Heraeus) is applied on the surface of the gas barrier laminate film on which the ITO film is formed. The filtrate obtained by filtering with a 0.2 micron diameter filter was formed into a film by spin coating, dried in air at a temperature of 130 ° C. for 30 minutes on a hot plate, and 65 nm thick on the ITO film. A hole injection layer having a thickness was formed.

  Next, a xylene solution in which a light emitting material (polymer compound 1) was dissolved in xylene as an organic solvent was prepared. Such a light emitting material (polymer compound 1) was prepared by a method similar to the method for preparing the composition 1 described in Example 1 of JP2012-144722A. The concentration of the polymer compound 1 in such a xylene solution was 1.2% by mass.

  Next, the xylene solution is applied by spin coating on the surface on which the hole injection layer of the gas barrier laminate film on which the ITO film and the hole injection layer have been formed is formed in an air atmosphere by spin coating. A coating film for the light emitting layer having a thickness of 80 nm is formed, and then dried by holding for 10 minutes at a temperature of 130 ° C. in a nitrogen gas atmosphere in which the oxygen concentration and water concentration are each controlled to 10 ppm or less by volume. Thus, a light emitting layer was laminated on the hole injection layer. Next, the hole injection layer and the light emitting layer formed on the contact portion with the external electrode (the portion of the extraction electrode for the anode and the cathode) are removed so that the contact with the external electrode becomes possible. Then, the gas barrier laminated film on which the ITO film, the hole injection layer, and the light emitting layer are formed is transferred to the vapor deposition chamber, and the position of the light emitting layer is adjusted (aligned) with the cathode mask. In order to form the cathode so that the cathode is electrically connected to the portion of the cathode extraction electrode while the cathode is stacked on the surface, the cathode was deposited while rotating the mask and the substrate. The cathode thus formed is first heated to vaporize sodium fluoride (NaF) at a deposition rate of about 0.5 mm / sec until the thickness is about 4 nm, and then aluminum (Al) is deposited at a rate of about 4 mm. It was set as the structure laminated | stacked by vapor-depositing until it became thickness of about 100 nm at / sec.

  Next, when an electrolytic copper foil having a thickness of 35 μm is laminated on the cathode and viewed from the cathode side, the entire light emitting layer can be covered, and the contact portion with the external electrode (for anode and When the electrolytic copper foil (sealing substrate 4) is viewed from the upper side as shown in FIG. 4 (see FIG. 4), a part of the cathode extraction electrode portion) protrudes to the outside. One of contact portions (parts for the anode and cathode take-out electrodes) formed on the gas barrier laminate film and having a larger area than the cathode so that the cathode cannot be seen. A part was cut out using a roller cutter into a shape having such a size that the portion appeared to protrude outside the foil, and a sealing substrate was prepared. In addition, the sealing board | substrate which consists of a copper foil prepared in this way was a thing of length 40mm, width 40mm, and thickness 35micrometer.

  Then, the sealing substrate (the copper foil) was heated in a nitrogen atmosphere at a temperature of 130 ° C. for 15 minutes to remove water adsorbed on the surface (which was subjected to a drying treatment). Next, using a two-pack type epoxy adhesive that cures at room temperature (25 ° C.) by mixing a main agent composed of a bisphenol A type epoxy resin and a curing agent composed of a modified polyamide as a sealing material, an ITO film / hole injection layer Apply a sealing material to cover the light emitting element part consisting of the laminated structure consisting of / light emitting layer / cathode, and paste the sealing substrate on the sealing material layer so that the sealing substrate and the cathode face each other In addition, sealing was performed. That is, the sealing material (adhesive) is applied so as to cover the laminated structure portion composed of ITO film / hole injection layer / light emitting layer / cathode (however, each electrode is electrically connected to the outside). Except for a part of the connection part (extraction electrode part) for enabling the above-mentioned), sealing on the surface of the gas barrier laminate film after forming the cathode so as to prevent bubbles from entering in nitrogen A light emitting element portion (a laminated structure portion of ITO film / hole injection layer / light emitting layer / cathode: excluding a part of the extraction electrode) is sealed by bonding a sealing substrate on the material layer. Thus, an organic EL element was manufactured. Such an organic EL element is flexible and has a structure in which a hole injection layer is further laminated on the light emitting element portion 2 of the organic EL element of the embodiment shown in FIG. Although the configuration of the light emitting element portion is different from that of the light emitting element portion 2 shown in FIG. Here, the thickness of the sealing material layer was 10 μm. The sealing substrate had an arithmetic average roughness Ra on one surface of 0.25 μm and an arithmetic average roughness Ra on the other surface of 2.4 μm. In this example, the surface of the sealing substrate on the side in contact with the sealing material layer was a surface having a surface Ra of 0.25 μm.

  FIG. 4 shows a schematic diagram when such an organic EL element is viewed from the sealing substrate side. Further, as shown in FIG. 4, when the organic EL element obtained in Example 1 is viewed from the sealing substrate 4 side, the transparent support substrate 1 and a portion drawn out of the anode 201 (connection to the outside) Part (extraction electrode), the connection part (extraction electrode) 203 (a) between the cathode and the outside, and the sealing substrate 4 can be confirmed. As described above, in the present example, when sealing using the sealing material and the sealing substrate, the light emitting element portion (ITO film) was made while keeping a part of the extraction electrode of each electrode connectable to the outside. (See FIG. 3 and FIG. 4: the embodiment shown in FIG. 1 and FIG. 3 is also confirmed from the sealing substrate side). Basically, the shape is the same as in FIG. In the light emitting element portion, the size of the light emitting area (area of the light emitting portion) was 10 mm in length and 10 mm in width.

(Comparative Example 1)
Gas barrier laminate film used in Example 1 (structure laminated in the order of “first thin film layer / first base material layer / adhesive layer / second thin film layer / second base material layer / third thin film layer”) Instead of, a structure in which “first base material layer / first thin film layer / adhesive layer / second thin film layer / second base material layer / third thin film layer” obtained in the following order is laminated Except for using a gas barrier laminate film for comparison, and laminating an ITO film, a hole injection layer, a light emitting layer and a cathode on the surface of the first base material layer of the gas barrier laminate film for comparison. A method similar to that employed in Example 1 was employed to produce an organic EL device for comparison.

<Method for preparing gas barrier laminate film for comparison>
When obtaining the gas barrier laminate film, instead of bonding the surface of the film member (A) on the base material side and the thin film layer of the film member (B) facing each other, the film member (A) on the thin film layer side Except that the surface and the surface of the thin film layer of the film member (B) were bonded to each other, the same method as that used when obtaining the gas barrier laminate film in Example 1 was adopted and compared. Gas barrier laminated film for film (film having a structure laminated in the order of "first base layer / first thin layer / adhesive layer / second thin layer / second base layer / third thin layer") Manufactured.

[Evaluation of characteristics of organic EL elements obtained in Example 1 and Comparative Example 1]
The organic EL devices obtained in Example 1 and Comparative Example 1 were stored under accelerated test conditions of 60 ° C. and relative humidity 90%, respectively. Each organic EL element was allowed to emit light until 500 hours passed after the start of storage, and the initial light emission state before the start of storage was compared with the respective light emission state for 500 hours after the start of storage. The organic EL elements obtained in Example 1 and Comparative Example 1 are basically the same except for the configuration of the gas barrier laminate film, and the area of the light emitting area in the initial state (the area of the light emitting layer) is the same. It was a size.

  As a result of such a measurement, in the organic EL element obtained in Example 1, there is almost a region where the luminance decreases by 90% or more even when 500 hours have elapsed or compared with the initial light emission state. The area of the area where the luminance is reduced by 90% or more was less than 5% of the light emitting area (the area of the light emitting layer), and thus sufficiently high weather resistance (performance to prevent deterioration due to water vapor) It was confirmed that the light emission quality can be sufficiently maintained. On the other hand, in the organic EL element obtained in Comparative Example 1, after 500 hours have elapsed since the start of storage, the area of the region where the luminance is reduced by 90% or more compared to the initial light emitting state is the light emitting area (light emitting The area of the layer) was 30% or more, and the light emission quality was lowered. From these results, it was confirmed that the organic EL device of the present invention (Example 1) has a sufficiently high resistance to water vapor and can sufficiently suppress the occurrence of defective light emission over a long period of time. It was done. From these results, it is clear that the organic EL element (Example 1) of the present invention can be stored and used for a longer period of time.

  As described above, according to the present invention, deterioration due to water vapor can be prevented at a higher level, generation of defective light emission can be sufficiently suppressed over a long period of time, and storage and use over a long period of time are possible. An organic electroluminescence device can be provided.

  Therefore, the organic electroluminescence element of the present invention is a highly reliable element that can prevent deterioration due to water vapor at a higher level and can sufficiently suppress the occurrence of defective light emission over a long period of time. It can be suitably used for illumination devices, planar light sources, display devices, and the like.

  DESCRIPTION OF SYMBOLS 1 ... Transparent support substrate, 2 ... Light emitting element part, 3 ... Sealing material layer, 4 ... Sealing substrate, 11 ... Sending roll, 21, 22, 23, 24 ... Conveyance roll, 31, 32 ... Film-forming roll, 41 DESCRIPTION OF SYMBOLS ... Gas supply pipe | tube, 51 ... Power supply for plasma generation, 61, 62 ... Magnetic field generator, 71 ... Winding roll, 100 ... Base material (film), 100 (a) ... First base material layer, 100 (b ) ... second substrate layer, 101 (a) ... first thin film layer having gas barrier property, 101 (b) ... second thin film layer having gas barrier property, 102 ... adhesive layer, 201 ... first Electrode, 202... Light emitting layer, 203... Second electrode, 203 (a).

Claims (7)

A transparent support substrate;
A light-emitting element unit that is disposed on the transparent support substrate and includes a pair of electrodes and a light-emitting layer disposed between the electrodes;
A sealing material layer disposed so as to seal the light emitting element portion on the transparent support substrate;
A sealing substrate disposed on the sealing material layer;
With
The transparent support substrate is made of a gas barrier laminate film,
The gas barrier laminate film includes first and second thin film layers having gas barrier properties, first and second base material layers, and an adhesive layer, and the first thin film layer and the first thin film layer The base material layer, the adhesive layer, the second thin film layer, and the second base material layer are laminated in this order,
One electrode of the light emitting element part is laminated on the first thin film layer of the gas barrier laminate film,
An organic electroluminescence device characterized by the above.   The organic electroluminescence device according to claim 1, wherein the first thin film layer is a thin film layer containing at least one of a metal oxide, a metal nitride, and a metal oxynitride.   The organic electroluminescence device according to claim 1 or 2, wherein the second thin film layer is a thin film layer containing at least one of a metal oxide, a metal nitride, and a metal oxynitride. At least one of the first and second thin film layers contains silicon, oxygen and carbon, and
The distance from the surface of the layer in the thickness direction of the layer, the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms and carbon atoms (atom ratio of silicon), the ratio of the amount of oxygen atoms (the ratio of oxygen In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve showing the relationship between the atomic ratio) and the ratio of the amount of carbon atoms (carbon atomic ratio), the following conditions (i) to (iii):
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the film thickness of the layer, the following formula (1):
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (1)
Satisfying the condition represented by
(Ii) the carbon distribution curve has at least one extreme value;
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more,
A silicon oxide thin film layer that satisfies all
The organic electroluminescent element according to any one of claims 1 to 3, wherein   The organic electroluminescence device according to claim 4, wherein both of the first and second thin film layers are the silicon oxide-based thin film layers.   6. The third thin film layer having gas barrier properties is laminated on the surface of the second base material layer on which the second thin film layer is not laminated. The organic electroluminescent element as described in any one of them.   The organic electroluminescent element according to claim 1, wherein the gas barrier laminate film has a moisture absorption performance of absorbing water of 0.1 mass% or more of its own weight.