JP2018065328A - Water vapor barrier laminate and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a water vapor barrier laminate which has high transparency and in which deterioration of the water barrier property due to storage is suppressed; and an organic electroluminescent element.SOLUTION: Provided is a water vapor barrier laminate comprising a first water barrier layer and a second water vapor barrier layer, where the first water vapor barrier layer contains Si atoms, O atoms and C atoms, an average value of contents of C atoms relative to whole number of atoms of the Si atoms, O atoms, and C atoms, as measured in a depth direction of the layer thickness by X-ray photoelectron spectroscopy, is 15 atom% or less; and an average value of ratio of a total of C=O bonds and C=OO bonds relative to total amount of C-SiO bonds, C-C bonds, C-O bonds, C=O bonds and C=OO bonds, based on wave form analysis in a depth direction of the layer thickness, is 8% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a water vapor barrier laminate and an organic electroluminescence device using the water vapor barrier laminate.

  An organic electroluminescence element using electroluminescence (hereinafter also simply referred to as EL) of an organic material is a thin-film type complete solid-state element capable of emitting light at a low voltage of about several volts to several tens of volts, and has high luminance. It has many excellent features such as high luminous efficiency, thinness and light weight. For this reason, as a backlight for various displays, display boards such as signboards and emergency lights, and surface light emitters such as illumination light sources, in particular, in recent years, a thin, lightweight and flexible water vapor barrier film having a water vapor barrier layer on a resin substrate An organic EL element using the above has attracted attention.

  In order to obtain a higher water vapor barrier performance for the water vapor barrier film used in such an organic EL device, a structure of a water vapor barrier laminate in which two or more water vapor barrier layers are laminated has been studied. In particular, it has a structure in which two or more water vapor barrier layers containing silicon, oxygen and carbon are formed on a base material, and has a structure in which the layers are laminated via an adhesive layer, thereby preventing deterioration of organic EL elements due to water vapor. However, a technique that can be used for a long time is disclosed (for example, see Patent Document 1). However, with this technique, the storage stability of the water vapor barrier laminate is not sufficient. Moreover, in order to improve the utilization to an electronic device, the water-vapor barrier layer with higher transparency is calculated | required.

Japanese Patent Laid-Open No. 2006-51569

  The subject of this invention is providing the water vapor | steam barrier laminated body and organic electroluminescent element which have high transparency and the deterioration of the water vapor | steam barrier property by storage was suppressed.

  The present inventor has conducted intensive research to solve the above-described problems. As a result, it has been found that the above-described problems according to the present invention can be solved by the following means.

A water vapor barrier laminate comprising a first water vapor barrier layer and a second water vapor barrier layer,
The first water vapor barrier layer contains Si atoms, O atoms, and C atoms, and the total number of Si atoms, O atoms, and C atoms is measured in the depth direction of the layer thickness by X-ray photoelectron spectroscopy. The average value of the content of C atoms with respect to is 15 atm% or less, and
C = O bond and C = OO with respect to the total amount of C—SiO bond, C—C bond, C—O bond, C═O bond and C═OO bond based on the waveform analysis of C1s in the depth direction of the layer thickness The average value of the total amount ratio of the bonds is 8% or less, and the water vapor barrier laminate.

The first water vapor barrier layer is obtained by X-ray photoelectron spectroscopy, the distance from the surface of the layer in the depth direction of the layer thickness, C—SiO bond, C—C bond, C—O bond, C═O. In the bond distribution curve of the C—C bond amount relative to the total amount of bonds and C═OO bonds, each has at least one maximum value and one minimum value, and
2. The water vapor barrier laminate according to item 1, wherein the difference between the maximum maximum value and the minimum minimum value of the C—C bond ratio is in the range of 15 to 95%.

  The said 1st water vapor | steam barrier layer and the said 2nd water vapor | steam barrier layer are laminated | stacked through an adhesion layer, The water vapor | steam barrier laminated body of 1st term | claim or 2nd term | claim characterized by the above-mentioned.

  4. The water vapor barrier laminate according to item 3, wherein the adhesive layer contains one of an epoxy resin and an acrylic resin.

  Item 3 or 4, wherein the adhesive layer has a mass change rate of 0.50% or less when heated from a temperature range of 20 ° C to 140 ° C at a heating rate of 5 ° C / min. The water vapor barrier laminate described.

  Any one of Items 3 to 5, wherein the first substrate, the first water vapor barrier layer, the adhesive layer, the second substrate, and the second water vapor barrier layer are provided in this order. The water vapor barrier laminate according to claim 1.

  An organic electroluminescence device comprising the water vapor barrier laminate according to any one of items 1 to 6.

  ADVANTAGE OF THE INVENTION According to this invention, the water vapor | steam barrier laminated body which has high transparency and the deterioration of the water vapor | steam barrier property by storage was suppressed, and an organic electroluminescent element can be provided.

The figure which shows the structure of a water vapor | steam barrier laminated body The figure which shows the structure of an organic EL element The figure which shows the composition of the water vapor barrier property film The figure which shows the structure of the manufacturing apparatus of a water vapor | steam barrier film The graph which shows the C atom distribution curve obtained by measuring the water vapor | steam barrier layer which is an Example The graph which shows the CC bond distribution curve obtained by measuring the water vapor | steam barrier layer which is an Example The graph which shows the C atom distribution curve obtained by measuring the water vapor | steam barrier layer which is a comparative example The graph which shows the CC bond distribution curve obtained by measuring the water vapor | steam barrier layer which is a comparative example

Hereinafter, the present invention, its components, and embodiments of the present invention will be described in detail.
The description will be given in the following order.
1. 1. Water vapor barrier laminate Organic electroluminescence device

<1. Water vapor barrier laminate>
[Configuration of water vapor barrier laminate]
Hereinafter, specific embodiments of the water vapor barrier laminate of the present invention will be described.

The water vapor barrier laminate according to the present invention has a first water vapor barrier layer and a second water vapor barrier layer. Furthermore, the water vapor barrier laminate according to the present invention may have a base material as appropriate, and the first base material / first base material may have a structure in which the first water vapor barrier layer and the second water vapor barrier layer are laminated on the base material. It has two layers of base materials such as 1 water vapor barrier layer / second base material / second water vapor barrier layer and second base material / second water vapor barrier layer / first base material / first water vapor barrier layer. May be.
In order to laminate the first water vapor barrier layer and the second water vapor barrier layer, each water vapor barrier layer may be provided on both surfaces of one base material, or a water vapor barrier layer is produced on each of the different base materials, The structure bonded with an adhesive may be sufficient. In order to obtain a water vapor barrier laminate that can suppress deterioration due to water vapor at a higher level, it is preferable to use a pressure-sensitive adhesive to form a laminate of the first water vapor barrier layer and the second water vapor barrier layer.
From the viewpoint of obtaining higher storage stability and transparency, the water vapor barrier laminate includes the first base material, the first water vapor barrier layer, the adhesive layer, the second base material, and the second water vapor barrier layer. Are preferably provided in this order.
Furthermore, although the water vapor barrier laminate according to the present invention has two water vapor barrier layers, a water vapor barrier layer may be further laminated on the water vapor barrier laminate. By laminating the base material and the water vapor barrier layer via the adhesive layer, it is also possible to form a water vapor barrier laminate having a multilayer structure.
In addition, it is also preferable to provide an antistatic layer in order to prevent foreign matter from adhering due to charging during production and transportation.

FIG. 1 is an example of the configuration of the water vapor barrier laminate. As shown in FIG. 1, the water vapor barrier laminate 10 includes a first water vapor barrier layer 11 and a second water vapor barrier layer 14.
As shown in FIG. 1, the first water vapor barrier layer 11 is formed on the first main surface of the first base 12 and is configured as a first water vapor barrier film 17. The second water vapor barrier layer 14 is formed on the first main surface of the second base material 15 and is configured as a second water vapor barrier film 18. And the 1st water vapor | steam barrier film 17 and the 2nd water vapor | steam barrier film 18 are bonded together by the adhesion layer 13. As shown in FIG.

  The adhesive layer 13 is provided between the second substrate 15 side of the second water vapor barrier film 18 and the first water vapor barrier layer 11 side of the first water vapor barrier film 17.

  An antistatic layer 16 is provided on the first substrate 12 side of the first water vapor barrier film 17. When the water vapor barrier laminate 10 is wound in a roll shape, the water vapor barrier laminate 10 is wound with the side on which the antistatic layer 16 is formed inside the roll.

  Hereinafter, the water vapor barrier laminate of the present invention will be described in detail. In the following description, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 60% RH.

[Water vapor barrier layer]
Each of the first water vapor barrier layer and the second water vapor barrier layer has a water vapor barrier property.
In the present invention, having a water vapor barrier property means a material having low water vapor permeability and oxygen permeability, and the water vapor permeability of the water vapor barrier layer (25 ±) measured in accordance with JIS-K-7129: 2008. 0.5 ° C., relative humidity 90 ± 2% RH) is 0.01 g / (m ² · 24 hours) or less, and oxygen permeability is 10 ⁻³ ml / (m ² · 24 hours · atm) or less. preferable.

  As long as it has the required water vapor barrier property, the first water vapor barrier layer and the second water vapor barrier layer may have the same configuration or different configurations.

At least one of the first water vapor barrier layer and the second water vapor barrier layer contains Si atoms, O atoms, and C atoms.
As a method for obtaining such a water vapor barrier layer, oxygen, carbon dioxide, carbon monoxide, nitrogen dioxide, or the like is reacted with an organosilicon compound having an Si—C skeleton or oxygen. It is possible to react to form a silicon oxide carbide (SiOC) film. Note that a water vapor barrier layer further containing N atoms may be formed by nitriding by supplying a gas such as nitrogen or ammonia during the film formation.

Examples of organosilicon compounds that can be used include hexamethyldisiloxane, 1.1.3.3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, and diethylsilane. , Propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, trimethoxymethyl Examples include silane. Among them, those having a small number of Si—C bonds in one molecule are preferable. For example, cyclic siloxanes such as tetramethylcyclotetrasiloxane (TMCTS) and octamethylcyclotetrasiloxane (OMCTS), triethoxysilane (TRIES), trimethylsilane. Examples include alkoxysilanes such as methoxymethylsilane (TMOMS), tetramethoxysilane (TMOS), and tetraethoxysilane (TEOS). These organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.
From the viewpoint of improving the flex resistance by increasing the ratio of C—C bonds in the water vapor barrier layer and increasing the transparency by decreasing the ratio of C═C bonds and C═OO bonds, The number of Si—C bonds is preferably 2 or less, more preferably 1 or 0, per one Si atom.

The structures of TMCTS, OMCTS, and TMOMS are shown below.

  The water vapor barrier layer may be formed by a vapor deposition method, a plasma enhanced chemical vapor deposition (PECVD) method, a CVD method such as an organic metal (MO) CVD method, or an atomic layer deposition (ALD) method. From the viewpoint of facilitating adjustment of the atomic composition of the water vapor barrier layer, the PECVD method is preferable. Above all, the counter-roller type PECVD method, which generates plasma between two opposing rollers and forms a water vapor barrier layer in parallel on the substrate transported by each roller, continues the atomic composition in the depth direction. This is preferable because it can be changed.

The first water vapor barrier layer contains Si atoms, O atoms, and C atoms, and is measured in the depth direction of the layer thickness by X-ray photoelectron spectroscopy with respect to the total number of atoms of Si atoms, O atoms, and C atoms. C-SiO bond, C-C bond, C-O bond, C = O bond based on C1s waveform analysis in which the average value of C atom content is 15 atm% or less and the depth direction of the layer thickness And the average value of the total amount ratio of C = O bond and C = OO bond to the total amount of C = OO bond is 8% or less.
Such a water vapor barrier layer is a chromophore, and since there are few C = O bonds and C = OO bonds that can cause coloring such as yellowing, high transparency and storage stability can be obtained.
The average value of the C atom content is more preferably 2 atm% or more. Further, the average value of the total amount ratio of the C═O bond and the C═OO bond is more preferably 2% or more.

The first water vapor barrier layer is obtained by X-ray photoelectron spectroscopy, the distance from the surface of the layer in the depth direction of the layer thickness, the C—SiO bond, the C—C bond, the C—O bond, and the C═O bond. In the bond distribution curve of both C—C bonds with respect to the total amount of C═OO bonds, each has at least one maximum value and one minimum value, and the maximum maximum value and the minimum value of the ratio of the C—C bonds. It is preferable that the difference from the minimum value is in the range of 15 to 95%.
In such a water vapor barrier layer, the C—C bond distribution has an inclined structure, so that the function of stress relaxation is enhanced, and therefore, higher storage stability can be maintained.

The inflection point at which the CC bond ratio changes from an increase to a decrease in the bond distribution curve of the CC bond ratio is referred to as a maximum value. In the bond distribution curve of the CC bond ratio, the inflection point at which the CC bond ratio changes from decreasing to increasing is referred to as a minimum value.
In addition, when the bond distribution curve of the CC bond ratio has a plurality of maximum values or a plurality of minimum values, the difference between the maximum maximum value and the minimum minimum value among the plurality is obtained.

  The C atom ratio and the C—C bond distribution curve can be obtained by combining the XPS method and rare gas ion sputtering. The XPS method is a technique for measuring the kinetic energy of photoelectrons emitted from the sample surface irradiated with X-rays and analyzing the composition and chemical bonding state of atoms constituting the sample surface. ESCA (Electron Spectroscopy for Chemical Analysis) It is also called. By analyzing the atomic composition and chemical bonding state of the sample surface exposed by etching the sample by rare gas ion sputtering using the XPS method, it is possible to grasp changes in the atomic composition and chemical bonding state in the depth direction of the sample. .

An example of measurement conditions by XPS method and rare gas ion sputtering is shown.
(Measurement condition)
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 name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval

Specifically, every time the water vapor barrier layer is etched at the above-described etching interval by rare gas ion sputtering, the atomic composition and chemical bonding state are measured by XPS method.
At each position in the depth direction, the ratio of the number of C atoms to the total number of Si atoms, O atoms, and C atoms obtained by measurement is obtained and averaged to obtain the ratio of C atoms in the water vapor barrier layer ( The average value of (C atom content) can be obtained.
An approximate curve of the ratio of C atoms to the distance (depth) from the surface of the water vapor barrier layer in the depth direction can be obtained as a C atom distribution curve representing the ratio of C atoms in the depth direction.

  For carbon atoms, the carbon bonding state is analyzed by waveform analysis of a C1s high-resolution spectrum (narrow scan analysis). Specifically, for carbon (C), based on the waveform analysis of C1s, for example, chemical bonds such as C—SiO bond, C—C bond, C—O bond, C═O bond, and C═OO bond, etc. Separate peaks. Then, the ratio (Q2 / Q1 × 100) of the C—C bond peak area (Q2) to the C1s peak peak area (Q1) is determined as the C—C bond ratio. That is, the ratio of the C—C bond is determined by one or more chemical bonds forming a C1s peak (for example, C—SiO bond, C—C bond, C—O bond, C═O bond, C═OO bond, etc.). It is equal to the ratio of C—C bonds to the total amount of chemical bonds including atoms. Use analysis software such as Eclipse version 2.1 attached to the XPS device ESCA LAB220i-XL for waveform analysis (peak separation, peak area calculation, peak position identification, etc.) necessary for calculating the ratio Can do.

The position of the water vapor barrier layer in the depth direction is, for example, as shown in FIG. 3, the position of the surface Sb opposite to the base 32 of the water vapor barrier layer 31 is 0%, and the surface of the water vapor barrier layer 31 on the base 32 side. Assuming that the position of Sa is 100%, it can be expressed in a ratio of 0 to 100%. That is, the position in the depth direction of the water vapor barrier layer can be expressed by the ratio of the sputtering depth from the surface Sb to the distance from the surface Sb to the surface Sa of the water vapor barrier layer (layer thickness of the water vapor barrier layer).
The layer thickness of the water vapor barrier layer is determined by observing the cross section of the water vapor barrier film with a transmission electron microscope (TEM). Specifically, the cross section of the water vapor barrier film is observed, and the layer thickness of the water vapor barrier layer is measured. The interface between the water vapor barrier layer and the substrate is determined from the contrast difference between the two. The distance is measured at 10 points at different positions on the film surface, and the average value of each measured value is determined as the layer thickness of the water vapor barrier layer.

As a focused ion beam (FIB) apparatus for preparing a TEM and a sample for TEM, the following apparatus can be used.
(TEM)
Apparatus: JEM2000FX (manufactured by JEOL Ltd.)
Accelerating voltage: 200kV
(FIB equipment)
Apparatus: SMI2050 (manufactured by SII)
Processed ion: Ga (30 kV)
Sample thickness: 100-200 nm

FIG. 5 and FIG. 6 show the measurement results by XPS of the water vapor barrier layer as an example prepared by PECVD using tetramethylcyclotetrasiloxane (TMCTS) and oxygen as raw materials.
7 and 8 show the XPS measurement results of a water vapor barrier layer as a comparative example formed by PECVD using hexamethyldisiloxane (HMDSO) and oxygen as raw materials.

  The ratio of C—C bonds in the depth direction of the water vapor barrier layer and the sum of C═O bonds and C═OO bonds are determined by the ratio of the C atoms, H atoms, and O atoms in the molecule of the organosilicon compound. By selecting, it can be adjusted.

Further, not only the selection of the raw material but also the adjustment of film formation conditions such as the supply amount of the source gas, the distance between the electrodes, the type and supply amount of the inert gas, the applied voltage, etc. The ratio of the number of C bonds and the sum of C = O bonds and C = OO bonds can be adjusted.
For example, in the case of forming a water vapor barrier layer by supplying oxygen gas supplied as a raw material gas together with an organosilicon compound by PECVD method, the target ratio can be adjusted by adjusting the supply amount of oxygen gas. .

  In addition, an inert gas such as nitrogen, argon or helium is supplied during film formation, and by adjusting the supply amount of this inert gas, the plasma is stabilized and the oxidation reaction and deposition of oxygen gas and organosilicon compound are performed. Can be adjusted to the desired ratio.

Also, by continuously changing the distance between electrodes that generate plasma, the ratio of C—C bonds in the depth direction and the sum of C═O bonds and C═OO bonds can be adjusted to the desired ratio. Can do.
When forming a film by the counter-roller type PECVD method, if the distance between the electrodes built in each roller is changed, the density of the plasma generated on the surface of the substrate in contact with the roller changes continuously. The composition of can also be changed continuously.

  If the water vapor barrier layer having the above-mentioned C atom distribution curve and C—C bond distribution curve has a refractive index of light having a wavelength of 450 nm within a range of 1.47 to 1.54, sealing of an organic EL element or the like It can be preferably used as a material.

  If the water vapor barrier layer having the C atom distribution curve and the C—C bond distribution curve described above has a hardness measured by the nanoindentation method within the range of 4.4 to 5.7 GPa, the film hardness is high, It can be preferably used for an electronic device as a sealing material excellent in impact resistance.

The layer thickness of the water vapor barrier layer is preferably in the range of 50 to 500 nm, and preferably in the range of 50 to 300 nm.
If the layer thickness is 50 nm or more, sufficient water vapor barrier properties can be obtained, and if the layer thickness is 500 nm or less, the permeability is good because it is thin.

(Characteristics of water vapor barrier film)
When the water vapor barrier film has high transparency, it is preferable because the utility as a sealing material for electronic devices is increased.
Specifically, the light absorption rate (%) at a wavelength of 450 nm is preferably 0.8% or less, more preferably 0.5% or less, and still more preferably 0.3% or less.

(Water vapor barrier film production equipment)
The water vapor barrier film can be produced by a conventionally known general production apparatus. Examples of the manufacturing apparatus include a plasma CVD roll coater W53 series manufactured by Kobelco, a plasma CVD apparatus PD series manufactured by Samco, and the like. As a preferable manufacturing apparatus, a manufacturing apparatus 60 capable of manufacturing the water vapor barrier film is used. As shown in FIG.
As shown in FIG. 4, the water vapor barrier film manufacturing apparatus 60 conveys the substrate 32 by a plurality of rollers 41 to 48 in the vacuum chamber 40, and applies a voltage between a pair of rollers 43 and 46 facing each other. Apply and supply source gas. Thereby, the manufacturing apparatus 60 produces the plasma reaction of source gas, forms a water vapor | steam barrier layer on a base material, and manufactures a water vapor | steam barrier property film.

As shown in FIG. 4, the vacuum chamber 40 is provided with an exhaust port 50, and a vacuum pump 51 is provided at the end of the exhaust port 50.
Moreover, as shown in FIG. 4, the roller 41 unwinds the base material 32, and the roller 48 winds up the water vapor | steam barrier film 30 obtained by formation of a water vapor | steam barrier layer.
The rollers 42 to 47 convey the substrate 32 until it is unwound by the roller 41 and taken up by the roller 48.

The pair of rollers 43 and 46 are disposed so as to face each other, and a gas supply unit 52 that supplies a source gas between the rollers 43 and 46 is provided adjacent to the rollers 43 and 46.
The pair of rollers 43 and 46 are each connected to a power source 49 and incorporate a magnetic field generator 53. By supplying the source gas from the gas supply unit 52 and applying a voltage between the rollers 43 and 46 by the power source 49, plasma is generated in the discharge space between the rollers 43 and 46, and the plasma reaction of the source gas proceeds. Thus, a water vapor barrier layer is formed on the substrate 32 conveyed by the rollers 43 and 46, respectively. At this time, since a racetrack-like magnetic field is formed around the rollers 43 and 46 by the magnetic field generator 53, plasma is generated along the magnetic field lines of the magnetic field. Electrons are confined in the film formation space by the electric and magnetic fields in the discharge space, and high-density plasma is generated, so that the film formation efficiency is improved.

  The gas supply unit 52 illustrated in FIG. 4 is provided on the center line of the roller 43 and the roller 46, but may be offset from the center line toward either the roller 43 or 46. Thereby, the supply amount of the source gas to the rollers 43 and 46 can be made different, and the atomic composition of the film formed on the roller 43 and the film formed on the roller 46 can be made different.

By changing the film formation conditions such as the supply amount of the source gas during film formation, films having different atomic compositions are formed, and the atomic composition in the depth direction changes continuously.
Specifically, when the base material 32 reaches the point A of the roller 43 and the point B of the roller 46, the ratio of C atoms in the depth direction in the water vapor barrier layer 31 changes from increase to decrease, and the ratio of O atoms. Changes from decreasing to increasing.
In contrast, when the base material 32 reaches the C1 and C2 points of the roller 43 and the C3 and C4 points of the roller 46, the ratio of C atoms in the depth direction in the water vapor barrier layer 31 changes from decreasing to increasing. , The ratio of O atoms changes from increasing to decreasing.
Thus, the existence of an extreme value that shifts from decrease to increase or from increase to decrease indicates that the abundance ratio of C atoms and O atoms in the water vapor barrier layer 31 is not uniform, and the compactness is partially low in C atoms. The presence of the low portion of the water vapor barrier layer 31 provides a flexible structure and improves the bending resistance.

  The rollers 43 and 46 are preferably arranged so that the rotation axes thereof are parallel to each other on the same plane, and the surfaces on which the water vapor barrier layer of the base material 32 to be conveyed face each other. With such a configuration, after the water vapor barrier layer is formed on the substrate by the roller 43 upstream in the transport direction, the water vapor barrier layer can be further laminated by the roller 46 downstream in the transport direction, thereby improving the film formation efficiency. be able to.

The rollers 43 and 46 preferably have the same diameter from the viewpoint of increasing the film formation efficiency.
The diameter of each of the rollers 43 and 46 is preferably in the range of 100 to 1000 mm, and in the range of 100 to 700 mm, from the viewpoint of optimization of discharge conditions, space reduction in the vacuum chamber 40, and the like. More preferably.
When the diameter φ is 100 mm or more, a sufficiently large discharge space can be formed, and a reduction in productivity can be prevented. In addition, a sufficient layer thickness can be obtained by short-time discharge, and the residual stress can be suppressed by suppressing the amount of heat applied to the substrate during discharge. If the diameter φ is 1000 mm or less, the uniformity of the discharge space can be maintained, which is practical in device design.

  The gas supply unit 52 supplies the raw material gas for the water vapor barrier layer to the discharge space formed between the pair of rollers 43 and 46. For example, when forming a water vapor barrier layer containing oxidized silicon carbide by oxidizing an organosilicon compound, the gas supply unit 52 supplies a gas of an organosilicon compound and a gas such as oxygen or ozone as a source gas. In the case of nitriding, a source gas such as nitrogen or ammonia may be supplied.

  The gas supply unit 52 can use a carrier gas to supply the source gas as necessary, and can also supply a plasma generation gas to promote the generation of plasma. Examples of the carrier gas include rare gases such as helium, argon, neon, xenon, and krypton, nitrogen gas, and examples of the plasma generating gas include hydrogen.

As the power source 49, a known power source for generating plasma can be used. However, an AC power source capable of alternately reversing the polarities of the rollers 43 and 46 can improve the film formation efficiency, and is preferable.
The amount of power supplied by the power supply 49 can be in the range of 0.1 to 10.0 kW. If it is 0.1 kW or more, the generation of foreign matters called particles can be suppressed. Moreover, if it is 10.0 kW or less, the calorie | heat amount to generate | occur | produce can be suppressed and generation | occurrence | production of the wrinkle of the base material 32 by a temperature rise can be suppressed. Moreover, when setting it as alternating current power supply, it is preferable that the frequency of alternating current exists in the range of 50 Hz-500 kHz.

The pressure in the vacuum chamber 40, that is, the degree of vacuum, can be adjusted by the vacuum pump 51 according to the type of the raw material gas, but is preferably in the range of 0.5 to 100.0 Pa.
Moreover, although the conveyance speed (line speed) of the base material 32 can be determined according to the kind of source gas, a vacuum degree, etc., it is preferable that it exists in the range of 0.25-100.00 m / min, More preferably, it is in the range of 0.5 to 20.0 m / min. If it is in this range, generation | occurrence | production of the wrinkle of the base material 32 can be suppressed and the water vapor | steam barrier layer of sufficient thickness can be formed.

[Base material]
The first base material and the second base material are preferably used as supports for the first water vapor barrier layer and the second water vapor barrier layer. By providing the first water vapor barrier layer and the second water vapor barrier layer on the first base material and the second base material which are supports, the workability in the manufacturing process of the water vapor barrier laminate is improved. For example, the film formability of the first water vapor barrier layer and the second water vapor barrier layer and the workability at the time of bonding with the adhesive layer are improved.
The 1st base material and the 2nd base material may be formed from the same material, and may be formed from a different material.

  Specifically, as the first base material and the second base material, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamide Imide resin, polyether imide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin solvent, fluorene ring Examples include base materials containing thermoplastic resins such as modified polycarbonate resins, alicyclic modified polycarbonate resins, fluorene ring modified polyester resins, and acryloyl compounds. The first base material and the second base material can be used alone or in combination of two or more.

  The first base material and the second base material are preferably made of a material having heat resistance. Specifically, a material having a linear expansion coefficient in the range of 15 to 100 ppm / K and a glass transition temperature (Tg) in the range of 100 to 300 ° C. is used. The Tg and linear expansion coefficient of the first base material and the second base material can be adjusted by an additive or the like.

  When producing an organic EL element using a water vapor | steam barrier laminated body, it is preferable that a water vapor | steam barrier laminated body is exposed to the process of 150 degrees C or less. In this case, if the linear expansion coefficient of the base material in the water vapor barrier laminate is 100 ppm / K or less, the substrate dimensions are stabilized in the thermal process, and the barrier performance is deteriorated with thermal expansion and contraction. prevent. Moreover, if the linear expansion coefficient of a 1st base material and a 2nd base material is 15 ppm / K or more, flexibility and a softness | flexibility will be hold | maintained and it will suppress that a water vapor | steam barrier laminated body breaks like glass.

  More preferable specific examples of the thermoplastic resin that can be used as the first base material and the second base material include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), alicyclic polyolefin (for example, ZEONOR (registered trademark) 1600: 160 ° C., manufactured by Nippon Zeon Co., Ltd.), polyarylate (PAr: 210 ° C.), polyethersulfone (PES: 220 ° C.), polysulfone (PSF: 190 ° C.), cycloolefin copolymer (COC: compound described in JP 2001-150584 A: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C., manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP 2000-227 A 03 compound: 225 ° C., alicyclic modified polycarbonate (IP-PC: JP 2000-227603 compound: 205 ° C.), acryloyl compound (JP 2002-80616 Compound: 300 ° C. or higher), etc. (in parentheses indicate Tg).

  The first base material and the second base material may be unstretched films or stretched films. The first base material and the second base material can be manufactured by a conventionally known general method. About the manufacturing method of these base materials, the matter described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

  The surface of the first base material and the second base material may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and is necessary. Depending on the above, the above processes may be combined.

  The first substrate and the second substrate may be a single layer or a laminated structure of two or more layers. The thickness of the first base material and the second base material (in the case of a laminated structure of two or more layers, the total thickness) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

(Hard coat layer)
The first base material and the second base material may have a hard coat layer on the surface (one side or both sides). Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a material containing a monomer having an ethylenically unsaturated double bond is preferably used. This material is cured by irradiating active energy rays such as ultraviolet rays and electron beams to form a layer containing a cured product of the active energy ray curable resin, that is, a hard coat layer. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. Moreover, you may use the commercially available 1st base material and 2nd base material in which the hard-coat layer is formed previously.

[Adhesive layer]
In the water vapor barrier laminate, an adhesive layer is preferably provided in order to laminate the first water vapor barrier layer and the second water vapor barrier layer.

(Outline of adhesive layer)
In a water vapor barrier laminate using a conventional adhesive layer, the generation of bubbles in the adhesive layer under vacuum or high temperature is a problem in a process for producing an electronic device such as an organic EL element. This foaming in the adhesive layer is considered to be caused by the generation of gas from the adhesive used in the adhesive layer. In particular, in a water vapor barrier laminate having a structure sandwiched between water vapor barrier films, gas generated from the pressure-sensitive adhesive is contained in the pressure-sensitive adhesive layer by the laminated water vapor barrier layer. For this reason, the generated gas is not released to the outside of the water vapor barrier laminate, and bubbles remain in the water vapor barrier laminate. If air bubbles remain in the water vapor barrier laminate, the adhesive strength of the water vapor barrier film in the adhesive layer decreases, which causes peeling. Further, when the water vapor barrier laminate is applied to the organic EL element, whitening of the water vapor barrier laminate and a decrease in light extraction efficiency are caused by bubbles.

  It has been found that such a problem is related to the mass change rate when the temperature of the pressure-sensitive adhesive layer is increased and foaming in the pressure-sensitive adhesive layer. That is, since the mass decreases due to the generation of gas from the adhesive layer due to the temperature rise, by defining the mass change rate when the temperature of the adhesive layer rises, in the process of manufacturing an electronic device such as an organic EL element It was found that foaming was suppressed. Specifically, when the mass change rate of the adhesive layer when heated from a temperature range of 20 ° C. to 140 ° C. at a rate of temperature increase of 5 ° C./min is 0.50% or less, an electronic device such as an organic EL element is It has been found that bubbles generated in the manufacturing process can be suppressed within a range that does not affect the characteristics of the visual equipment.

When the temperature rising rate is 5 ° C./min in the temperature rise of the adhesive layer, it is possible to prevent nonuniform alteration from occurring due to a rapid temperature change. This non-uniform alteration affects the measurement of mass change rate as an error, and the measurement accuracy decreases, but it can be suppressed.
Specifically, the mass change rate of the adhesive layer can be determined under the following conditions.

(Mass change rate of adhesive layer; thermogravimetry (TG) analysis)
Measuring instrument: TG / DTA6200 manufactured by Hitachi High-Tech Science Sample: About 6 mg is scraped and placed in an aluminum open container for measurement. Use the same aluminum container as a reference.
Temperature rising condition: Temperature rising from 30 ° C. to 150 ° C. at 5 ° C./min Atmospheric gas: Measured while flowing 200 mL / min nitrogen

Further, when the water vapor barrier layer containing silicon, oxygen and carbon and the adhesive layer are bonded, bubbles are likely to be generated due to the interaction between the organic component of the water vapor barrier layer and the adhesive component of the adhesive layer. It is also considered. The intermolecular interaction at the interface of the adhesive layer is classified into van der Waals force, hydrogen bond, and chemical bond, and generally the bond strength and affinity increase in this order. In particular, when a portion contributing to a chemical bond such as C═O or C═OO bond is present at the interface of the adhesive layer, strong affinity and binding force are easily formed at the interface of the adhesive layer. Therefore, there are few portions that contribute to chemical bonds such as C═O and C═OO bonds at the interface of the adhesive layer, and by reducing the affinity at the interface of the adhesive layer, bubbles are introduced into the interface of the adhesive layer. It is thought that it can suppress taking in.
That is, in order to achieve both maintenance of adhesiveness and suppression of bubbles, a configuration in which the first water vapor barrier layer is provided in contact with the adhesive layer is preferable.

(Adhesive)
As the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer, it is preferable to use a pressure-sensitive pressure-sensitive adhesive. If it is a pressure sensitive adhesive, when forming an adhesive layer, the requirements for heat, organic solvent, etc. are not required, and the first water vapor barrier film and the second water vapor barrier film are bonded together simply by applying pressure. Can do. Pressure sensitive adhesives are broadly classified according to the type of material, and examples include pressure sensitive adhesives including epoxy resins, acrylic resins, rubber resins, urethane resins, vinyl ether resins, and silicon resins. it can. As the form of the pressure-sensitive adhesive, for example, a solvent type, an emulsion type, and a hot melt type can be used. Since it has more excellent cohesive force and elasticity, can maintain stable adhesiveness for a long time, and is more excellent in transparency, it preferably contains an epoxy resin or an acrylic resin.
Specific examples of the acrylic resin include, for example, SK Dyne 2147 manufactured by Soken Chemical Co., Ltd., PD-S1 manufactured by Panac, ZB7011W manufactured by DIC, and the like.
As a specific example of the epoxy resin, for example, ThreeBond 1655 manufactured by Three Bond Co., Ltd. may be mentioned.

  In addition to the above resins contained in the pressure-sensitive adhesive, various additives can be used from the viewpoint of improving the physical properties of the pressure-sensitive adhesive layer. For example, natural resins such as rosin, modified rosin, rosin and modified rosin derivatives, polyterpene resins, terpene modified products, aliphatic hydrocarbon resins, cyclopentadiene resins, aromatic petroleum resins, phenolic resins, alkyl- A tackifier such as phenol-acetylene resin, coumarone-indene resin, vinyltoluene-α-methylstyrene copolymer, anti-aging agent, stabilizer, softener and the like can be used as necessary. . Two or more of these may be used as necessary. Moreover, in order to improve light resistance, organic ultraviolet absorbers, such as a benzophenone series and a benzotriazole series, can also be added to an adhesive.

[Antistatic layer]
The water vapor barrier laminate may have an antistatic layer. By having an antistatic layer, antistatic performance can be imparted. For this reason, when the water vapor barrier laminate is wound into a roll shape by the roll-to-roll method, and when the water vapor barrier laminate is unwound from the roll and conveyed, charging of the water vapor barrier laminate can be suppressed.

  By using a base material having an antistatic layer, a water vapor barrier laminate excellent in transmittance, resistance, reliability, and cost can be formed. Furthermore, by using this water vapor barrier laminate, an electronic device excellent in efficiency, voltage, reliability, and cost can be configured.

Further, the other configuration described above may be provided between the first base material and the antistatic layer. Even in this case, the antistatic layer is preferably provided in the outermost layer of the water vapor barrier laminate.
The water vapor barrier laminate has an antistatic layer on the second main surface side of the first substrate. The antistatic layer is composed of an antistatic agent and a binder resin for holding the antistatic agent.

  The antistatic layer preferably contains an organic antistatic agent as an antistatic agent. The organic antistatic agent contained in the antistatic layer preferably contains one or more selected from conjugated polymers and ionic polymers. In addition, the antistatic layer may be configured to include other conductive polymers and antistatic agents.

The antistatic layer preferably does not contain metal oxide particles that are easily desorbed during lamination as an antistatic agent. For this reason, the content of the metal oxide particles with respect to the total mass of the antistatic layer is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably a configuration not containing metal oxide particles. Examples of the metal oxide particles that are preferably not contained in the antistatic layer include, for example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , MgO, BaO, MoO ₂ , V ₂ O _5, etc. These composite oxides can be mentioned. However, SiO ₂ is excluded from the definition of metal oxide particles that are preferably not contained in the antistatic layer.

(Organic antistatic agent)
The organic antistatic agent is basically composed of an organic material having antistatic ability. When the antistatic layer is formed, the organic antistatic agent has a sheet resistance value of 1 × 10 ¹¹ Ω / sq. Hereinafter, preferably 1 × 10 ¹⁰ Ω / sq. Hereinafter, more preferably 1 × 10 ⁹ Ω / sq. A material that can be:

  Examples of the organic antistatic agent include conventionally known surfactant-type antistatic agents, silicon-based antistatic agents, organic boric acid-based antistatic agents, polymer-based antistatic agents, and antistatic polymer materials. In particular, it is preferable to use an ion conductive material or the like as the organic antistatic agent from the viewpoint of antistatic of the antistatic layer. The ion conductive material is a material containing ions exhibiting electrical conductivity. Examples of the ion conductive substance include conjugated polymers and ionic polymers.

(Conjugated polymer)
Examples of the conjugated polymer include π electron conductive polymer composites of polymers having the following (1) to (8) in the side chain via a connecting group.
(1) Aliphatic conjugated system: a carbon-carbon conjugated system, such as polyacetylene, which is continuously long alternately. For example, polyacetylene, poly (1,6-heptadiene), etc. (2) Aromatic conjugated system: poly (3) Heterocyclic conjugated systems such as polypyrrole, polythiophene, etc. (3) Heterocyclic conjugated systems such as polypyrrole and polythiophene. Polymers in which a conjugated system is developed by combining cyclic compounds, such as polypyrrole and its derivatives, polyfuran and its derivatives, polythiophene and its derivatives, polyisothionaphthene and its derivatives, polyselenophene and its derivatives, etc. (4) Heteroatom-containing conjugated system: Aliphatic or aromatic conjugated systems such as polyaniline bonded with heteroatoms Polymers such as polyaniline and derivatives thereof, poly (paraphenylene sulfide) and derivatives thereof, poly (paraphenylene oxide) and derivatives thereof, poly (paraphenylene selenide) and derivatives thereof, and poly (vinylene sulfide) in aliphatic systems ), Poly (vinylene oxide), poly (vinylene selenide), etc. (5) Mixed conjugated system: a conjugated polymer having a structure in which structural units of the conjugated system such as poly (phenylene vinylene) are alternately bonded, for example, Poly (paraphenylene vinylene) and its derivatives, poly (pyrrole vinylene) and its derivatives, poly (thiophene vinylene) and its derivatives, poly (furanylene) and its derivatives, poly (2,2'-thienylpyrrole) and its derivatives Etc. (6) Double chain conjugated system: Conjugated system with multiple conjugated chains in the molecule, aromatic A polymer having a structure close to a group conjugated system, such as polyperiphthalene, etc.
(7) Metal phthalocyanine series: Metal phthalocyanines or polymers in which these molecules are bonded with hetero atoms or conjugated systems, for example, metal phthalocyanine, etc. (8) Conductive complex: Grafting the above conjugated polymer chain onto a saturated polymer A composite obtained by polymerizing the conjugated polymer in a copolymerized polymer and a saturated polymer, for example, polythiophene (including derivatives), polypyrrole (including derivatives) of (3), and (4) Polyaniline (including derivatives), etc., poly (paraphenylene vinylene) (including derivatives thereof), poly (thiophene vinylene) (including derivatives thereof), etc. of (5) above

(Ionic polymer)
Examples of the ionic polymer include the following (1) to (3).
(1) Anionic polymer compounds such as those described in JP-B-49-23828, JP-B-49-23827, JP-B-47-28937, etc. (2) JP-B 55-734, JP-A 50-54672, JP-B-59-14735, JP-B-57-18175, JP-B-57-18176, JP-B-57-56059, etc. Ionene-type polymer possessed (3) JP-B 53-13223, JP-B 57-15376, JP-B 53-45231, JP-B 55-145578, JP-B 55-65950, JP-B 55-67746 See in Japanese Patent Publication Nos. 57-11342, 57-19735, 58-56858, JP 61-27853, 62-9346, etc. So that a cationic pendant polymer having a cationic dissociative group in the side chain

(Other antistatic agents)
Examples of other antistatic agents constituting the antistatic layer include antistatic hard coating agents described in JP-A-2006-265271, JP-A-2007-70456, JP-A-2009-62406, and the like. Can be used. In addition, for example, an antistatic agent available from Aika Kogyo Co., Ltd., which is available as a commercial product, can be appropriately selected and used.

(Binder resin)
Examples of the binder resin for holding the antistatic agent in the antistatic layer include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, or cellulose nitrate, polyvinyl acetate, polystyrene, Polyesters such as polycarbonate, polybutylene terephthalate, or copolybutylene / tere / isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate , Polyethyl methacrylate, polypropylyl methacrylate, polybutyl methacrylate DOO, acrylic resins such as polymethyl acrylate, and copolymer of acrylic resin and other resins. In particular, a cellulose derivative and an acrylic resin are preferable, and an acrylic resin is most preferably used.

  The binder resin used for the antistatic layer is preferably a thermoplastic resin having a weight average molecular weight of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. The glass transition temperature can be determined by the method described in JIS K7121. The binder resin used here is 60% by mass or more, more preferably 80% by mass or more of the total resin mass constituting the antistatic layer, and an active ray curable resin or a thermosetting resin is applied as necessary. You can also.

[Anchor coat layer]
The water vapor barrier laminate can include an anchor coat layer between the base material and the water vapor barrier layer from the viewpoint of improving the adhesion between the base material and the water vapor barrier layer.
The anchor coat layer is applied with a coating solution containing, for example, polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, alkyl titanate, It can be formed by drying.

[Smoothing layer]
The water vapor barrier laminate can also include a smoothing layer as a lower layer of the water vapor barrier layer. By the smoothing layer, the water vapor barrier layer can be formed on a flat surface, and a water vapor barrier layer having a high water vapor barrier property can be obtained by preventing the occurrence of pinholes due to unevenness.
The smoothing layer can be formed, for example, by applying a coating solution containing a photosensitive resin and performing a curing process. Examples of the photosensitive resin include a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, poly Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as ether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved.

<2. Organic electroluminescence device>
Next, an organic electroluminescence element (organic EL element) using the above-described water vapor barrier laminate will be described. The organic EL element of this embodiment uses the above-described water vapor barrier laminate. On the water vapor barrier laminate, a transparent electrode, a light emitting unit having one or more light emitting layers containing an organic light emitting material, and a counter electrode are provided.
For this reason, in the following description of the organic EL element, detailed description of the same configuration as the above-described water vapor barrier laminate is omitted.

[Configuration of organic EL element]
The organic EL element preferably includes a transparent electrode and a counter electrode on the water vapor barrier layer forming surface of the water vapor barrier laminate, and a light emitting unit is provided between the electrodes. An example of the configuration of the embodiment of the present invention is shown in FIG.

The layer structure of the organic EL element is not particularly limited, and may be a general layer structure. For example, when the transparent electrode 23 functions as an anode (anode) and the counter electrode 21 functions as a cathode (cathode) as in the organic EL element 20 shown in FIG. 2, the light emitting units 22 are arranged in order from the transparent electrode 23 side. The hole injection layer 22e / hole transport layer 22d / light emitting layer 22c / electron transport layer 22b / electron injection layer 22a may be stacked. The organic EL element may include a plurality of the light emitting units according to a desired light emission color.
A known organic EL material can be appropriately selected and used for the organic EL element.

[Sealing member]
The organic EL element may be sealed with a sealing member (not shown) for the purpose of preventing deterioration of a light emitting unit configured using an organic material or the like. The sealing member is a plate-like (film-like) member that covers the upper surface of the organic EL element, and is fixed to the water vapor barrier laminate side by an adhesive portion. The sealing member may be a sealing film. Such a sealing member is provided in a state in which the electrode terminal portion of the organic EL element is exposed and at least the light emitting unit is covered. Moreover, the structure which provides an electrode in a sealing member and makes the electrode terminal part of an organic EL element and the electrode of a sealing member electrically connect may be sufficient.

  Moreover, in order to mechanically protect the organic EL element, a protective member (not shown) such as a protective film or a protective plate may be provided. The protective member is disposed at a position where the organic EL element and the sealing member are sandwiched between the water vapor barrier laminate. In particular, when the sealing member is a sealing film, mechanical protection for the organic EL element is not sufficient, and thus it is preferable to provide such a protective member.

[Light extraction structure]
The organic EL element may have a light extraction layer (not shown). The light extraction layer may be a conventionally known nano-concave structure or a configuration (optical scattering layer) in which materials having different refractive indexes are mixed. In addition, in the organic EL element having the light extraction layer, a smoothing layer may be provided on the light extraction layer in order to flatten the unevenness on the surface of the light extraction layer.

In the case where the light extraction layer has a configuration in which materials having different refractive indexes are mixed (optical scattering layer), the light extraction layer is composed of a binder which is a layer medium and light scattering particles contained in the layer medium, as will be described later. Preferably, it is configured. In this configuration, light scattering by the mixture can be generated by utilizing the refractive index difference between the layer medium and light scattering particles having a higher refractive index than the layer medium.
Moreover, the nano uneven structure can preferably be adapted to the structure described in JP-A-2006-269163.

[Method of manufacturing organic EL element]
Next, an example of a method for manufacturing an organic EL element will be described.
First, a water vapor barrier laminate is produced by the manufacturing method described above. Then, a transparent electrode is formed on the surface of the water vapor barrier layer of the water vapor barrier laminate by an appropriate film forming method such as vapor deposition or sputtering. Then, on the transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are formed in this order to form a light emitting unit. As a method for forming these layers, conventionally known conditions can be appropriately selected.

  After the light emitting unit is formed, a counter electrode is formed thereon by an appropriate film forming method such as vapor deposition or sputtering. At this time, the counter electrode is patterned in a shape in which the terminal portion is drawn from the upper side of the light emitting unit to the periphery of the water vapor barrier laminate while maintaining the insulating state with respect to the transparent electrode by the light emitting unit. Thereby, an organic EL element is manufactured. Further, after that, a sealing member that covers at least the light emitting unit is provided in a state where the terminal portions of the extraction electrode and the counter electrode in the organic EL element are exposed.

  By the above, an organic EL element can be produced on the water vapor barrier laminate. In the production of such an organic EL element, it is preferable to produce from the transparent electrode to the counter electrode consistently by one evacuation, but it may be taken out from the vacuum atmosphere in the middle and subjected to different film forming methods. . At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

Example 1
[Production of water vapor barrier film]
(Formation of water vapor barrier layer)
As a base material, Cosmo Shine (registered trademark) A4300 (manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm and both surfaces subjected to easy adhesion processing was prepared.
On one surface of this substrate, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 (manufactured by JSR Corporation) was applied with a wire bar so that the layer thickness after drying was 3 μm. The coating film was dried at 80 ° C. for 3 minutes and then cured under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere to form an anchor coat layer. Subsequently, the same treatment was performed on the opposite surface of the substrate to form anchor coat layers on both surfaces of the substrate.

  The substrate after humidity conditioning was set in the manufacturing apparatus 60 shown in FIG. 4, and a water vapor barrier layer having a layer thickness of 140 nm was formed on both surfaces of the anchor coat layer by the manufacturing apparatus 60 under the following film forming conditions. A water vapor barrier film was obtained.

(Deposition conditions)
Source gas 1: Tetramethylcyclotetrasiloxane (TMCTS)
Supply amount of raw material gas 1: 100 sccm (Standard Cubic Centimeter per Minute)
Source gas 2: oxygen Supply amount of source gas 2: 300 sccm
Degree of vacuum: 1.5Pa
Power supplied by power supply for plasma generation: 1.4kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 12 m / min

[Production of Water Vapor Barrier Film of Samples 102 to 107]
(Formation of water vapor barrier layer)
In the production of the water vapor barrier film of the sample 101 described above, the types and supply amounts of the source gases 1 and 2 are as shown in Table 1 below so that the C atom ratio in the water vapor barrier layer changes in the depth direction. Except for the change, the water vapor barrier films of Samples 102 to 106 were produced in the same manner as the water vapor barrier film of Sample 101. Moreover, the water vapor | steam barrier film of the sample 107 which formed the water vapor | steam barrier layer only in the single side | surface was also produced.

[C atom distribution curve and CC bond distribution curve]
In the produced water vapor barrier films 101 to 107, the C atom distribution curve and the C—C bond distribution curve of one of the water vapor barrier layers (first water vapor barrier layer) were determined as follows.
In each of the water vapor barrier films 101 to 107, one surface of the water vapor barrier layer is etched from the surface opposite to the base material to the surface of the base material by rare gas ion sputtering, and the atomic composition and chemical bonding state of the exposed surface are changed. Measured by XPS method.
The measurement conditions are as follows.
(Measurement condition)
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 name “VG Theta Probe” manufactured by Thermo Fisher Scientific
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and size: 800 × 400 μm oval

Each time etching was performed by rare gas ion sputtering, the atomic composition and chemical bonding state at the position in the depth direction were measured by the XPS method.
And the average value of content (atm%) of C atom with respect to the total number of atoms of Si atom, O atom, and C atom measured in the position of each layer thickness direction was calculated | required. The results are shown in Table 1.

  For the C atom, based on the waveform analysis of C1s, the peaks of constituent bonds of C—SiO bond, C—C bond, C—O bond, C═O bond and C═OO bond are separated, and C1s The ratio (Q2 / Q1 × 100) of the peak area (Q2) of the CC bond to the peak area (Q1) of the peak was determined as the ratio of the CC bond. Similarly, the ratio of the sum of the peak area of the C═O bond and the peak area of the C═OO bond to the peak area of the C1s peak is obtained and averaged to obtain a C—SiO bond, a C—C bond, and a C—O bond. The average value of the ratio of the total amount of C═O bond and C═OO bond to the total amount of C═O bond and C═OO bond (100%) was obtained.

The obtained C—C bond ratio was plotted against the distance in the depth direction etched from the surface of the water vapor barrier layer on the side opposite to the base material to create a depth profile. In this depth profile, an approximate curve of the plotted ratio was obtained as a CC bond distribution curve.
In the obtained CC bond distribution curve, the presence or absence of one or more local maximum values and local minimum values was confirmed, and the difference between the maximum local maximum value and the minimum local minimum value was determined. The results are shown in Table 1.

The depth profile shown in FIGS. 5 and 6 was obtained by analyzing the water vapor barrier film 101.
Further, the depth profile shown in FIGS. 7 and 8 was obtained by analyzing the water vapor barrier film 106.

<Evaluation method>
[Preservation: Ca method evaluation of water vapor barrier film]
The Ca method evaluation sample (type evaluated by permeation concentration) prepared as described below was stored in an 85 ° C., 85% RH environment, and the corrosion rate of Ca was observed at regular intervals. 1 hour, 5 hours, 10 hours, 20 hours, and thereafter, observation and transmission density measurement (average of 4 points) every 20 hours, and when the measured transmission density is less than 50% of the initial transmission density value Was used as an index of water vapor barrier properties.
5: 400 hours or more 4: 300 hours or more and less than 400 hours 3: 200 hours or more and less than 300 hours 2: 100 hours or more and less than 200 hours 1: 1: 100 hours or less

(Ca method evaluation sample)
After the surface of the water vapor barrier layer was UV washed on the water vapor barrier film produced in Samples 101 to 107, a thermosetting sheet-like adhesive (epoxy resin) as a sealing resin layer was formed on the surface of the water vapor barrier layer. Bonding was performed at 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  Next, one side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. And Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm. Furthermore, the Ca vapor-deposited glass plate was moved into the glove box, and was placed so that the sealing resin layer surface of the water vapor barrier film and the Ca vapor-deposited surface of the glass plate were in contact with each other, and adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down and cured for 30 minutes to produce a Ca method evaluation cell.

[Transparency evaluation]
The absorption rate (%) of light having a wavelength of 450 nm of the water vapor barrier films of Samples 101 to 107 was measured. From this absorption rate, the transparency was ranked according to the following evaluation criteria. The smaller the numerical value of the absorptance, the higher the transparency.
5: Absorption rate is 0.2 or less 4: Absorption rate is greater than 0.2 and 0.5 or less 3: Absorption rate is greater than 0.5 and 0.8 or less 2: Absorptivity is greater than 0.8 and 1.5 or less 1: Absorptivity is greater than 1.5 and 5.0 or less

In Table 1 below, the evaluation results are shown.
In Table 1 below, TRIE, TEOS, TMOMS, TMCTS, and HMDSO are abbreviations for triethoxysilane, tetraethoxysilane, trimethoxymethylsilane, tetramethylcyclotetrasiloxane, and hexamethyldisiloxane, respectively.

  As shown in Table 1, the water vapor barrier layers of the samples 101 to 104, which are examples of the present invention, are superior in storage stability compared to the samples 105 to 107, which are comparative examples. It can be seen that deterioration due to water vapor can be suppressed and transparency is excellent, so that the utility to electronic devices can be enhanced.

  From Table 1, in the water vapor barrier layer, the average value of the content of C atoms with respect to the total number of Si atoms, O atoms, and C atoms measured in the depth direction of the layer thickness by X-ray photoelectron spectroscopy is 15 atm. % With respect to the total amount of C—SiO bond, C—C bond, C—O bond, C═O bond and C═OO bond based on the waveform analysis of C1s in the depth direction of the layer thickness. Samples 101 to 104, in which the average value of the total amount ratio of O bonds and C = OO bonds is 8% or less, have superior storage stability and transparency results as compared to Samples 105 and 106 that are not. Yes. From these results, it is shown that deterioration due to water vapor can be suppressed because it is excellent in storability, and that utilization in electronic devices is enhanced because it is excellent in transparency.

  Further, from Table 1, in the water vapor barrier layer, the distance from the surface of the layer in the depth direction of the layer thickness obtained by X-ray photoelectron spectroscopy, the C—SiO bond, the C—C bond, the C—O bond, In the bond distribution curve of the C—C bond amount relative to the total amount of C═O bond and C═OO bond, the difference between the maximum maximum value and the minimum minimum value of the ratio of the C—C bond is 15% or more. Sample 101 and sample 104, which are 95% or less, have superior storage stability results compared to sample 102 and sample 103 that are not. From these results, it is shown that deterioration due to water vapor can be further suppressed because of better storage stability.

  Further, from Table 1, the sample 101 having two water vapor barrier layers is superior in storage stability to the sample 107 having only one water vapor barrier layer. From this, it is shown that by having two water vapor barrier layers, it is more excellent in storage stability, so that deterioration due to water vapor can be further suppressed.

  In addition, from Table 1, the sample 101 using tetramethylcyclotetrasiloxane (TMCTS) for the water vapor barrier layer is more storable than the samples 102, 103, and 104 using other organosilicon compounds for the water vapor barrier layer. And the transparency results are excellent. This shows that it is more preferable to use tetramethylcyclotetrasiloxane (TMCTS) for the water vapor barrier layer.

Example 2
[Production of water vapor barrier film]
(Formation of water vapor barrier layer)
As a base material, Cosmo Shine (registered trademark) A4300 (manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm and both surfaces subjected to easy adhesion processing was prepared.
On one surface of this substrate, a UV curable organic / inorganic hybrid hard coat material OPSTAR (registered trademark) Z7501 (manufactured by JSR Corporation) was applied with a wire bar so that the layer thickness after drying was 3 μm. The coating film was dried at 80 ° C. for 3 minutes and then cured under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere to form an anchor coat layer.

  The substrate after humidity adjustment is set in the manufacturing apparatus 60 shown in FIG. 4, and a water vapor barrier layer having a layer thickness of 140 nm is formed on the anchor coat layer under the following film forming conditions by the manufacturing apparatus 60. 1 A water vapor barrier film was obtained.

(Deposition conditions)
Source gas 1: Tetramethylcyclotetrasiloxane (TMCTS)
Supply amount of raw material gas 1: 100 sccm (Standard Cubic Centimeter per Minute)
Source gas 2: oxygen Supply amount of source gas 2: 300 sccm
Degree of vacuum: 1.5Pa
Power supplied by power supply for plasma generation: 1.4kW
Frequency of power source for plasma generation: 70 kHz
Film transport speed: 12 m / min

  Also in the second water vapor barrier film, the raw material gas 1 of the water vapor barrier layer is hexamethyldisiloxane (HMDSO), and the supply amount thereof and the supply amount of oxygen of the raw material gas 2 are as shown in Table 2, It produced by the method similar to the above-mentioned 1st water vapor | steam barrier film.

[Preparation of water vapor barrier laminate; bonding]
SK dyne 2147 (acrylic resin adhesive) manufactured by Soken Chemical Co., Ltd. was applied to the surface of the first water vapor barrier film formed above with a thickness of 25 μm to form an adhesive layer. And the base material surface of the 2nd water vapor | steam barrier film was bonded together to the said adhesion layer. Thereafter, a laminate composed of the first water vapor barrier film, the adhesive layer, and the second water vapor barrier film is bonded under the conditions of a conveyance speed of 3 m / min, a tension of the laminate of 110 N / m, and a nip pressure of 25 kPa. A water vapor barrier laminate of sample 201 was produced.

[Production of organic EL element]
(Production of the first electrode)
Next, ITO (indium tin oxide) having a thickness of 150 nm was formed by sputtering on the surface of the water vapor barrier laminate on which the water vapor barrier layer was formed, and patterned by photolithography to form a first electrode.

[Production of organic EL element]
(Production of light emitting unit)
Next, the water vapor barrier laminate on which the first electrode was formed was overlapped with a mask having an opening with a width of 30 mm × 30 mm in the center and fixed to a substrate holder of a commercially available vacuum deposition apparatus. Moreover, each material which comprises a light emission unit was filled in each heating boat in a vacuum evaporation system in the optimal quantity for formation of each layer. In addition, the heating boat used what was produced with the resistance heating material made from tungsten.

Next, the inside of the vapor deposition chamber of the vacuum vapor deposition apparatus was depressurized to a vacuum degree of 4 × 10 ⁻⁴ Pa, and each layer was formed as follows by sequentially energizing and heating the heating boat containing each material.
First, as a hole transport injection material, a heating boat containing α-NPD represented by the following structural formula is energized and heated, and hole transport injection serving as both a hole injection layer and a hole transport layer made of α-NPD A layer was formed on the first electrode. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 140 nm.

Next, the heating boat containing the host material H4 represented by the following structural formula and the heating boat containing the phosphorescent compound Ir-4 represented by the following structural formula were respectively energized independently, and the host material H4 and phosphorous A light emitting layer composed of the photoluminescent compound Ir-4 was formed on the hole transport injection layer. At this time, the energization of the heating boat was adjusted so that the deposition rate was host material H4: phosphorescent compound Ir-4 = 100: 6. The layer thickness was 30 nm.
Next, a heating boat containing BAlq represented by the following structural formula as a hole blocking material was energized and heated to form a hole blocking layer made of BAlq on the light emitting layer. At this time, the deposition rate was 0.1 to 0.2 nm / second, and the layer thickness was 10 nm.

Thereafter, a heating boat containing the following compound 10 and a heating boat containing potassium fluoride are energized independently to form an electron transport layer composed of the compound 10 and potassium fluoride on the hole blocking layer. did. At this time, the energization of the heating boat was adjusted so that the deposition rate was compound 10: potassium fluoride = 75: 25. The layer thickness was 30 nm.
Next, a heating boat containing potassium fluoride as an electron injection material was energized and heated to form an electron injection layer made of potassium fluoride on the electron transport layer. At this time, the deposition rate was 0.01 to 0.02 nm / second, and the layer thickness was 1 nm.

[Production of organic EL element]
(Preparation of second electrode to sealing)
The water vapor barrier laminate formed up to the light emitting unit was transferred to a second vacuum tank equipped with a tungsten resistance heating boat containing aluminum (Al) while maintaining a vacuum state. And it overlapped and fixed with the mask with the opening part of width 20mm * 20mm arrange | positioned so that it may orthogonally cross with the 1st electrode. Next, a reflective second electrode made of Al having a thickness of 100 nm was formed as a cathode at a film formation rate of 0.3 to 0.5 nm / second in the processing chamber.

  Next, a thermosetting liquid adhesive (epoxy resin) having a thickness of 25 μm was formed as a sealing resin layer on one surface of a sealing member having the same configuration as the water vapor barrier film. And the sealing member which provided this sealing resin layer was piled up on the sample in which even the 2nd electrode was formed. At this time, the sealing resin layer forming surface of the sealing member is continuously overlapped with the water vapor barrier film side of the organic EL element so that the end portions of the extraction portions of the first electrode and the second electrode come out. It was.

  Next, the sample to which the sealing member was bonded was placed in a decompression device, and pressed at 90 ° C. under a decompression condition of 0.1 MPa and held for 5 minutes. Subsequently, the sample was returned to the atmospheric pressure environment and further heated at 90 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a moisture content of 1 ppm or less, in accordance with JIS B 9920, with a measured cleanliness of class 100, a dew point temperature of −80 ° C. or less, and an oxygen concentration of 0.8 ppm or less. At atmospheric pressure.

  The organic EL element of sample 201 was produced by the above method. In addition, in the manufacturing process of an organic EL element, the description regarding formation of the extraction part from a 1st electrode and a 2nd electrode was abbreviate | omitted.

[Preparation of Sample 202]
Except for the water vapor barrier layer of the second water vapor barrier film, the raw material gas 1 is tetramethylcyclotetrasiloxane (TMCTS), and the supply amount thereof and the oxygen supply amount of the raw material gas 2 are as shown in Table 2. A water vapor barrier laminate of Sample 202 and an organic EL element were produced in the same manner as Sample 201 described above.

[Preparation of Sample 203]
The water vapor barrier layer of the second water vapor barrier film is such that the raw material gas 1 is tetramethylcyclotetrasiloxane (TMCTS) and the supply amount thereof and the oxygen supply amount of the raw material gas 2 are as shown in Table 2; Was formed with PD-S1 (acrylic resin pressure-sensitive adhesive) manufactured by Panac Co., and a water vapor barrier laminate of Sample 203 and an organic EL device were produced in the same manner as Sample 201 described above.

[Preparation of Sample 204]
In the water vapor barrier layer of the second water vapor barrier film, the raw material gas 1 is tetramethylcyclotetrasiloxane (TMCTS), the supply amount thereof and the oxygen supply amount of the raw material gas 2 are as shown in Table 2, and 1 A method similar to the above-described sample 201 except that the water vapor barrier layer of the water vapor barrier film is made of tetraethoxysilane (TEOS) as the raw material gas 1 and the oxygen supply amount of the raw material gas 1 is as shown in Table 2. Thus, a water vapor barrier laminate of sample 204 and an organic EL element were produced.

[Preparation of Sample 205]
In the water vapor barrier layer of the second water vapor barrier film, the raw material gas 1 is tetramethylcyclotetrasiloxane (TMCTS), the supply amount thereof and the oxygen supply amount of the raw material gas 2 are as shown in Table 2, and 1 A water vapor barrier layer of a water vapor barrier film is the same as the sample 201 described above except that the raw material gas 1 is trimethoxymethylsilane (TMOMS) and the oxygen supply amount of the raw material gas 1 is as shown in Table 2. A water vapor barrier laminate of sample 205 and an organic EL element were produced by the method.

[Preparation of Sample 206]
A water vapor barrier laminate of Sample 206 and an organic EL device were produced in the same manner as Sample 201 described above except that the adhesive layer was formed of ZB7011W (acrylic resin adhesive) manufactured by DIC.

[Preparation of Sample 207]
For the water vapor barrier layer of the first water vapor barrier film, the raw material gas 1 is triethoxysilane (TRIES), the oxygen supply amount of the raw material gas 2 is as shown in Table 2, and the adhesive layer is manufactured by DIC. A water vapor barrier laminate of Sample 207 and an organic EL element were produced in the same manner as Sample 201 described above except that it was formed of ZB7011W.

[Preparation of Sample 208]
The water vapor barrier layer of the first water vapor barrier film is such that the raw material gas 1 is hexamethyldisiloxane (HMDSO), the supply amount thereof and the oxygen supply amount of the raw material gas 2 are as shown in Table 2, and further the adhesive layer Was formed with ZB7011W manufactured by DIC, and a water vapor barrier laminate of Sample 208 and an organic EL element were produced in the same manner as Sample 201 described above.

[C atom distribution curve and CC bond distribution curve]
In the produced samples 201 to 208, the C atom distribution curve and the C—C bond distribution curve of the first water vapor barrier layer were determined in the same manner as in Example 1. The results are shown in Table 2.

<Evaluation method>
The following evaluation was performed with respect to the water vapor | steam barrier laminated body of the produced samples 201-208, and the organic EL element.

[Preservation: Ca method evaluation of water vapor barrier laminate]
The prepared Ca method evaluation samples (types evaluated by permeation concentration) were stored in an 85 ° C., 85% RH environment, and the corrosion rate of Ca was observed at regular intervals. 1 hour, 5 hours, 10 hours, 20 hours, and thereafter, observation and transmission density measurement (average of 4 points) every 20 hours, and when the measured transmission density is less than 50% of the initial transmission density value Was used as an index of water vapor barrier properties.
5: 400 hours or more 4: 300 hours or more and less than 400 hours 3: 200 hours or more and less than 300 hours 2: 100 hours or more and less than 200 hours 1: 1: 100 hours or less

(Ca method evaluation sample)
The surface of the water vapor barrier layer exposed on one surface of the water vapor barrier laminate is UV washed with respect to the water vapor barrier laminate produced in each of the samples 201 to 208, and then a thermosetting type sealing resin layer on the water vapor barrier layer surface. A sheet adhesive (epoxy resin) was pasted at a thickness of 20 μm. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  Next, one side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned. And Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from an EILS technology. The thickness of Ca was 80 nm. Furthermore, the Ca vapor-deposited glass plate was moved into the glove box, and was placed so that the sealing resin layer surface of the water vapor barrier film and the Ca vapor-deposited surface of the glass plate were in contact with each other, and adhered by vacuum lamination. At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down and cured for 30 minutes to produce a Ca method evaluation cell.

[Measurement of mass change rate]
With respect to the pressure-sensitive adhesive used for preparing the water vapor barrier laminates of Samples 201 to 208, the mass change rate during heating was measured under the following measurement conditions.

(Mass change rate of adhesive layer; thermogravimetry (TG) analysis)
Measuring instrument: TG / DTA6200 manufactured by Hitachi High-Tech Science Sample: About 6 mg is scraped and placed in an aluminum open container for measurement. Use the same aluminum container as a reference.
Temperature rising condition: Temperature rising from 30 ° C. to 150 ° C. at 5 ° C./min Atmospheric gas: Measured while flowing 200 mL / min of nitrogen

[Bubble evaluation]
The light emitting surfaces of the organic EL elements of Samples 201 to 208 that were stored in an environment of 85 ° C. and 85% RH for 500 hours were observed, and 0.5 mm or more bubbles per 100 cm ² were counted. The generation of bubbles in the adhesive layer was evaluated according to the following criteria.
5: Less than 2 4: 2 or more and less than 10 3: 11 or more and less than 20 2: 21 or more and less than 50 1: 50 or more

[Bending preservation test]
The organic EL elements of the samples 201 to 208 are stored for 500 hours in an environment of 85 ° C. and 85% RH in a state where the organic EL element forming surface is wound around a plastic roller having a curvature of 6 mmφ. did. Thereafter, a current of 1 mA / cm ² was applied to each organic EL element removed from the roller to emit light. Next, a part of the light emitting portion of the organic EL element was enlarged and photographed with a 100 × optical microscope (Mortex Corp. MS-804, lens MP-ZE25-200). Next, the captured image was cut out in a 2 mm square, and the presence or absence of dark spots was observed for each image. From the observation results, the ratio of the dark spot generation area to the light emission area was determined, and the dark spot resistance was evaluated according to the following criteria.

5: Generation of dark spots is not recognized at all 4: Dark spot generation area is 0.1% or more and less than 1.0% 3: Dark spot generation area is 1.0% or more; Less than 0% 2: Dark spot generation area is 3.0% or more and less than 6.0% 1: Dark spot generation area is 6.0% or more

Table 3 shows the evaluation results of the storage stability, air bubbles, folding storage stability, and mass change rate of the adhesive layer of the samples 201 to 208 described above.
In Table 2 below, TRIE, TEOS, TMOMS, TMCTS, and HMDSO are abbreviations for triethoxysilane, tetraethoxysilane, trimethoxymethylsilane, tetramethylcyclotetrasiloxane, and hexamethyldisiloxane, respectively.

  As shown in Table 2 and Table 3, the water vapor barrier laminates of samples 201 to 207 which are examples of the present invention are superior in storage stability compared to the water vapor barrier laminate of sample 208 which is a comparative example. It can be seen that deterioration due to water vapor during storage and use can be suppressed, generation of bubbles can be suppressed, and the generation rate of dark spots can be suppressed by excellent folding storage stability.

  From Tables 2 and 3, the content of C atoms relative to the total number of Si atoms, O atoms, and C atoms in the first water vapor barrier layer measured in the depth direction of the layer thickness by X-ray photoelectron spectroscopy. Of the C—SiO bond, C—C bond, C—O bond, C═O bond and C═OO bond based on the waveform analysis of C1s in the depth direction of the layer thickness. The average value of the total amount ratio of the C═O bond and the C═OO bond relative to the total amount is 8% or less, and the sample 201 to the sample 207 have better storage stability and folding storage property than the sample 208 which does not. The results are excellent. From this, it is shown that deterioration due to water vapor can be suppressed because of excellent storage stability, and that the occurrence rate of dark spots can be suppressed because of excellent storage stability.

  Further, from Table 2 and Table 3, the first water vapor barrier layer is obtained by X-ray photoelectron spectroscopy, the distance from the surface of the layer in the depth direction of the layer thickness, the C—SiO bond, the C—C bond, In the bond distribution curve of the C—C bond amount relative to the total amount of C—O bond, C═O bond, and C═OO bond, the maximum maximum value and the minimum minimum value of the ratio of the C—C bond The sample 202 in which the difference is in the range of 15 to 95% is superior in the storage stability and the folding storage stability as compared with the sample 204 which is not. From these results, it is shown that deterioration due to water vapor can be further suppressed because of superior storage stability, and that the occurrence rate of dark spots can be further suppressed because of excellent folding storage stability.

Moreover, from Table 2 and Table 3, the organic EL element of the samples 201-205 using the adhesive whose mass change rate is 0.50% or less used the adhesive whose mass change rate exceeded 0.50%. Compared to Samples 206 and 207, good results were obtained in the number of bubbles generated and folding storage stability. Thus, it is shown that the smaller the mass change rate of the pressure-sensitive adhesive of the water vapor barrier laminate, the smaller the generation of bubbles and the better the storability of folding, so that the dark spot generation rate can be further suppressed.
Furthermore, it was confirmed that the same effect was obtained even when the adhesive of Sample 202 was replaced with ThreeBond 1655 manufactured by ThreeBond, which is an epoxy resin adhesive.

  Also, from Table 2 and Table 3, the sample 202 using tetramethylcyclotetrasiloxane (TMCTS) for both the first water vapor barrier layer and the second water vapor barrier layer is more storable and generates bubbles. Good results have been obtained in terms of number and folding storage. Accordingly, it is more preferable to use tetramethylcyclotetrasiloxane (TMCTS) for both the first water vapor barrier layer and the second water vapor barrier layer. The light absorption rate of the water vapor barrier laminate in sample 202 was 0.3%.

  The present invention is not limited to the configuration described in the above-described embodiment, and various modifications and changes can be made without departing from the configuration of the present invention.

DESCRIPTION OF SYMBOLS 10 Water vapor | steam barrier laminated body 11 1st water vapor | steam barrier layer 12 1st base material 13 Adhesive layer 14 2nd water vapor | steam barrier layer 15 2nd base material 16 Antistatic layer 17 1st water vapor | steam barrier film 18 2nd water vapor | steam barrier film 20 Organic EL element 21 Counter electrode 22 Light emitting unit 22a Electron injection layer 22b Electron transport layer 22c Light emission layer 22d Hole transport layer 22e Hole injection layer 23 Transparent electrode 30 Water vapor barrier film 31 Water vapor barrier layer 32 Base material Sa Water vapor on the base material side Surface of the barrier layer Sb Surface of the water vapor barrier layer opposite to the substrate 40 Vacuum chamber 41, 42, 43, 44, 45, 46, 47, 48 Roller 49 Power supply 50 Exhaust port 51 Vacuum pump 52 Gas supply unit 53 Magnetic field generation Equipment 60 Production equipment

Claims (7)

A water vapor barrier laminate comprising a first water vapor barrier layer and a second water vapor barrier layer,
The first water vapor barrier layer contains Si atoms, O atoms, and C atoms, and the total number of Si atoms, O atoms, and C atoms is measured in the depth direction of the layer thickness by X-ray photoelectron spectroscopy. The average value of the content of C atoms with respect to is 15 atm% or less, and
C = O bond and C = OO with respect to the total amount of C—SiO bond, C—C bond, C—O bond, C═O bond and C═OO bond based on the waveform analysis of C1s in the depth direction of the layer thickness The average value of the total amount ratio of the bonds is 8% or less, and the water vapor barrier laminate. The first water vapor barrier layer is obtained by X-ray photoelectron spectroscopy, the distance from the surface of the layer in the depth direction of the layer thickness, C—SiO bond, C—C bond, C—O bond, C═O. In the bond distribution curve of the C—C bond amount relative to the total amount of bonds and C═OO bonds, each has at least one maximum value and one minimum value, and
2. The water vapor barrier laminate according to claim 1, wherein a difference between a maximum maximum value and a minimum minimum value of the C—C bond ratio is in a range of 15 to 95%.   The water vapor barrier laminate according to claim 1 or 2, wherein the first water vapor barrier layer and the second water vapor barrier layer are laminated via an adhesive layer.   The water vapor barrier laminate according to claim 3, wherein the adhesive layer contains one of an epoxy resin and an acrylic resin.   The mass change rate of the pressure-sensitive adhesive layer when heated from a temperature range of 20 ° C to 140 ° C at a heating rate of 5 ° C / min is 0.50% or less. The water vapor barrier laminate described.   The first base material, the first water vapor barrier layer, the adhesive layer, the second base material, and the second water vapor barrier layer are provided in this order. The water vapor barrier laminate according to claim 1.   An organic electroluminescence device comprising the water vapor barrier laminate according to any one of claims 1 to 6.

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