JPWO2017158920A1 - Method for manufacturing organic electroluminescence element - Google Patents

Abstract

An object of the present invention is a method of manufacturing an organic electroluminescent element for patterning an organic electroluminescent element having a high gas barrier property, which suppresses an increase in cost and a decrease in production efficiency, and is used for patterning through a mask. An object of the present invention is to provide a method for manufacturing an organic electroluminescence element with reduced occurrence of irradiation pattern deviation.
The method for producing an organic electroluminescence device of the present invention comprises a laminate of at least a first gas barrier film and a second gas barrier film as a substrate, and patterning is performed by irradiating light from the gas barrier film side. In addition, after forming the organic electroluminescence element using the first gas barrier film as a substrate, patterning is performed by irradiating light, and then the second gas barrier film is pasted on the first gas barrier film. It is characterized by making it the said laminated body.

Description

  The present invention relates to a method for manufacturing an organic electroluminescent element, and more specifically, when patterning an organic electroluminescent element having a high gas barrier property, suppresses an increase in cost and a decrease in production efficiency, and generates an irradiation pattern shift. The present invention relates to a method for manufacturing a reduced organic electroluminescence element.

  At present, organic electroluminescence elements are attracting attention as thin light emitting devices.

  An organic electroluminescence element (hereinafter also referred to as “organic EL element”) using organic electroluminescence (EL) is a thin-film type capable of emitting light at a low voltage of about several volts to several tens of volts. It is a complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it has been attracting attention in recent years as surface light emitters such as backlights for various displays, display boards such as signboards and emergency lights, and illumination light sources.

  Such an organic EL element has a configuration in which an organic functional layer including at least a light emitting layer is disposed between a pair of electrodes on a substrate, and emitted light generated in the light emitting layer passes through the electrode and is extracted to the outside. .

  Here, in such an organic EL element, the function of the organic functional layer is changed for each predetermined region by irradiating the organic functional layer with light while adjusting the exposure amount for each predetermined region. A method of forming a light emission pattern having a gradation of light emission luminance corresponding to the amount of change has been proposed (see, for example, Patent Document 1). As an apparatus for performing such a pattern forming method, an apparatus for forming a light emitting pattern by irradiating ultraviolet rays onto a predetermined region of an organic functional layer by a UV lamp is known.

  On the other hand, the organic EL element has a gas barrier layer to protect the organic functional layer from various gases such as water vapor and oxygen. However, in order to further improve durability and gas barrier properties, a plurality of gas barrier layers are formed. It is in the direction to do. For example, in Patent Document 2, the second gas barrier layer is formed on the first gas barrier layer by a coating method. Patent Document 3 discloses a method of bonding two gas barrier films with an adhesive.

  When patterning by irradiating ultraviolet rays through a mask to an organic EL device having such a plurality of gas barrier layers and gas barrier films, the thickness is increased by the gas barrier layers and gas barrier films, There is a problem that irradiation pattern shift increases and accurate patterning cannot be performed.

  In particular, when irradiating non-parallel ultraviolet rays, light from an oblique direction tends to enter the inside of the mask, the amount of penetration increases by the thickness of the gas barrier layer, and the irradiation pattern deviation tends to become remarkable. .

  Furthermore, when there are a plurality of gas barrier layers and gas barrier films, it is necessary to increase the ultraviolet irradiance by reducing the light transmittance such as ultraviolet rays because Fresnel reflection occurs at the interface or the layer itself becomes thick. If the power cost is increased, or if the irradiation time is increased without increasing the irradiance, the production tact becomes longer and the production efficiency decreases.

  Patent Document 4 discloses an example in which patterning is performed by irradiating an element after sealing with ultraviolet rays from the substrate side. When the substrate has a low ultraviolet transmittance, the output of ultraviolet rays is increased or the irradiation time is increased. There is a description that patterning is possible if the length is long. However, when the output is increased, there is a problem that the power consumption of the irradiation device increases and the running cost increases, and even if the irradiation time is lengthened, there is a problem that, in addition to the increase in the power cost, the production tact becomes longer and the production efficiency decreases. is there.

  The patent document 4 does not disclose these production problem solving means.

JP 2012-28335 A Japanese Patent Laying-Open No. 2015-147952 JP 2011-110913 A Japanese Patent No. 2793373

  The present invention has been made in view of the above problems and situations, and a solution to the problem is a method of manufacturing an organic electroluminescent element for patterning an organic electroluminescent element having a high gas barrier property, which increases costs and increases production efficiency. It is an object of the present invention to provide a method for manufacturing an organic electroluminescence element that suppresses the decrease in the thickness and reduces the occurrence of irradiation pattern deviation when patterning through a mask.

  In order to solve the above problems, the present inventor forms an organic electroluminescence element using the first gas barrier film as a substrate in the process of examining the cause of the above problem, and then irradiates light to form the organic electroluminescence. The element is patterned, and then the manufacturing method of the organic electroluminescence element in which the second gas barrier film is bonded to the first gas barrier film side suppresses the increase in cost and the decrease in production efficiency, and the irradiation pattern shift It discovered that the manufacturing method of the organic electroluminescent element which reduced generation | occurrence | production was obtained.

  That is, the said subject which concerns on this invention is solved by the following means.

1. A method for producing an organic electroluminescence device comprising at least a laminate of a first gas barrier film and a second gas barrier film as a substrate,
After forming the organic electroluminescence element using the first gas barrier film as a substrate,
Patterning is performed by irradiating light to the organic electroluminescence element from the first gas barrier film side,
The second gas barrier film is bonded to the surface of the first gas barrier film opposite to the surface on which the organic electroluminescence element is formed via an adhesive layer or an adhesive layer, and the laminate. A method for producing an organic electroluminescence element, comprising:

  2. 2. The method for producing an organic electroluminescent element according to item 1, wherein the wavelength of the light is in a range of 360 to 410 nm.

  3. 3. The method of manufacturing an organic electroluminescent element according to claim 1, wherein the light is irradiated as non-parallel light through a mask.

  4). The manufacturing method of the organic electroluminescent element of the 1st term | claim or 2nd item which concentrates the said light, forms a light spot on the said organic electroluminescent element, and performs the said patterning by point drawing.

  5. The thickness of the said 1st gas barrier film exists in the range of 20-500 micrometers, The manufacturing method of the organic electroluminescent element as described in any one of Claim 1 to 4 characterized by the above-mentioned.

  6). 6. The organic electroluminescence device according to any one of items 1 to 5, wherein the first gas barrier film has a light transmittance of 60% or more in a wavelength range of 360 to 410 nm. Manufacturing method.

  7). The refractive index difference between the gas barrier layer of the first gas barrier film and the functional layer in contact with the gas barrier layer is 1.5 or less, and the refractive index difference is 1.5 or less. The manufacturing method of organic electroluminescent element of this.

  8). The organic electroluminescence device according to any one of items 1 to 7, wherein the second gas barrier film, the adhesive layer, or the pressure-sensitive adhesive layer has ultraviolet light shielding properties. Production method.

  An organic electroluminescent element manufacturing method for patterning an organic electroluminescent element having a high gas barrier property by the above-described means of the present invention, wherein cost increase and reduction in production efficiency are suppressed, and patterning is performed through a mask. The manufacturing method of the organic electroluminescent element which reduced generation | occurrence | production of the irradiation pattern shift | offset | difference of this can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is as follows.

  According to the method for producing an organic electroluminescent element of the present invention, after forming an organic electroluminescent element using the first gas barrier film as a substrate, patterning is performed by irradiating light, and then the second gas barrier film is formed. By bonding to the first gas barrier film side, patterning by light irradiation can be performed without going through a plurality of gas barrier films, so the absorption and scattering of light in the gas barrier film is suppressed and the use efficiency of irradiation light is improved. It is possible to provide a method for manufacturing an organic electroluminescence device that is improved and has reduced running costs and improved production efficiency. In addition, by using a plurality of gas barrier films, a patterned organic electroluminescence device having a high gas barrier property can be provided.

  In addition, when patterning an organic electroluminescent element using non-parallel light to increase the irradiance of light, by not stacking a plurality of gas barrier films, the mask and the organic electroluminescent element to be patterned are not laminated. Since the distance from the organic functional layer can be reduced, it is possible to reduce the penetration of light into the mask and suppress the occurrence of irradiation pattern deviation. In addition, since light transmittance and Fresnel reflection between the gas barrier films can be reduced, light utilization efficiency is improved, and running costs and patterning with improved production efficiency are possible. doing.

Schematic diagram showing the occurrence of irradiation pattern deviation Schematic diagram showing the occurrence of irradiation pattern deviation Schematic diagram showing the occurrence of irradiation pattern deviation Schematic configuration diagram of an example of a patterning apparatus used in the present invention Schematic which shows the structure of a light source part, a mask alignment apparatus, and a to-be-patterned object mounting base. Schematic cross-sectional view showing an example of a method for bringing the organic EL element sheet on the pattern forming body mounting table and the mask on the mask alignment apparatus into close contact at a predetermined position Schematic cross-sectional view showing an example of a method for bringing the organic EL element sheet on the pattern forming body mounting table and the mask on the mask alignment apparatus into close contact at a predetermined position Schematic configuration diagram of a pattern forming device by dot drawing Diagram showing silicon distribution curve, oxygen distribution curve, carbon distribution curve and nitrogen distribution curve The figure which expanded the carbon distribution curve shown in FIG. Diagram showing the refractive index profile of the gas barrier layer The figure which shows the structure of the manufacturing apparatus of a gas barrier layer Graph showing interface transmittance characteristics with respect to refractive index difference Δn The schematic diagram of the organic EL element which comprises the 1st and 2nd gas barrier film which concerns on this invention The schematic diagram which shows an example of the layer structure and patterning of the organic EL element which concerns on this invention The schematic diagram which shows an example of the layer structure and patterning of the organic EL element which concerns on this invention

  The method for producing an organic electroluminescent element of the present invention is a method for producing an organic electroluminescent element comprising at least a laminate of a first gas barrier film and a second gas barrier film as a substrate, wherein the first gas After forming the organic electroluminescence element using the barrier film as a substrate, patterning is performed by irradiating the organic electroluminescence element with light from the first gas barrier film side, and then the second gas barrier film is formed. The first gas barrier film is bonded to the surface opposite to the surface on which the organic electroluminescence element is formed via an adhesive layer or a pressure-sensitive adhesive layer to form the laminate. This feature is a technical feature common to or corresponding to the claimed invention.

As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the wavelength of the light is preferably in the range of 360 to 410 nm from the viewpoint of efficiently patterning the organic electroluminescence element. When the wavelength of the light source for patterning is light in the range of 400 to 410 nm in addition to the conventionally known ultraviolet light, it is also referred to as a Blu-ray Disc (registered trademark); hereinafter referred to as “BD”. ) Can be used as a light source for a patterning device, so that the patterning device can be manufactured at low cost and organic electroluminescence can be used. Element patterning can be performed at lower cost. Irradiation of the light as non-parallel light through a mask can increase irradiance, thereby reducing running costs and improving production efficiency. From the viewpoint, it is preferable.

  As yet another embodiment, the light is condensed to form a light spot on the organic electroluminescence element, and the patterning can be performed by dot drawing or patterning without using a mask. This can be avoided and is preferable.

  In addition, the thickness of the first gas barrier film being in the range of 20 to 500 μm can increase the light transmittance and improve the patterning efficiency, and the distance between the mask and the organic electroluminescence element. From the viewpoint of suppressing the irradiation pattern deviation.

  Furthermore, when the light transmittance in the wavelength range of 360 to 410 nm of the first gas barrier film is 60% or more, it is possible to reduce the running cost of patterning and improve the production efficiency by increasing the light utilization efficiency. It is possible and preferable.

  In addition, the difference in refractive index between the gas barrier layer of the first gas barrier film and the functional layer in contact therewith is 1.5 or less, which prevents light scattering at the interface of the gas barrier film and enables patterning. It is preferable from the viewpoint of improving efficiency and suppressing the irradiation pattern deviation.

  Furthermore, the second gas barrier film, the adhesive layer or the pressure-sensitive adhesive layer has ultraviolet light shielding properties, and in the element after patterning, the element deterioration and irradiation pattern due to ultraviolet rays contained in external light such as sunlight. From the viewpoint of preventing deterioration, this is a preferred embodiment.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Manufacturing Method of Organic Electroluminescence Element of the Present Invention >>
The method for producing an organic electroluminescent element of the present invention is a method for producing an organic electroluminescent element comprising at least a laminate of a first gas barrier film and a second gas barrier film as a substrate, wherein the first gas After forming the organic electroluminescent element using the barrier film as a substrate, the organic electroluminescent element is patterned by irradiating light through the first gas barrier layer, and then the second gas barrier film Is bonded to the surface of the first gas barrier film opposite to the surface on which the organic electroluminescence element is formed via an adhesive layer or a pressure-sensitive adhesive layer to form the laminate.

  Hereinafter, the organic electroluminescence device according to the present invention will be simply referred to as an “organic EL device”. The “organic functional layer” refers to a layer composed of an organic compound excluding the substrate, electrode and sealing layer from the “organic EL element”.

  Specifically, the organic EL device patterning method according to the present invention includes, for example, a gas barrier layer formed on a film having high ultraviolet transmittance such as a polyethylene terephthalate film (referred to as PET film or PET in this application). The formed first gas barrier film is used as a substrate, and an anode, a hole injecting and transporting layer, a light emitting layer, an electron injecting and transporting layer, a cathode and the like are formed thereon, and then sealed with a sealing material to form an organic EL element ("Substrate" in the present invention refers to the first gas barrier film according to the present invention or a laminate of the first gas barrier film and the second gas barrier film).

  Next, patterning is performed by irradiating a specific portion of the organic functional layer of the organic EL element with light from the first gas barrier film side using a light irradiation device. Subsequently, a patterned organic EL device having a high gas barrier property by laminating the second gas barrier film through the adhesive layer or the pressure-sensitive adhesive layer so as to be laminated on the first gas barrier film side. Is what you get.

  In the patterning, a mask on which a light-shielding film pattern is formed is placed on a first gas barrier film, and light is uniformly irradiated as non-parallel light to the entire mask by a light irradiation device from the first gas barrier film side. A method, a method of condensing light emitted from the light source of the light irradiation device, forming a light spot on the organic EL element without using a mask, and performing patterning by point drawing, etc. are appropriately adopted. Can do.

  In the present application, light irradiated only from the vertical direction with respect to the object to be patterned is referred to as “parallel light”, and is a light ray group having a collimation half angle within ± 2 ° and a declination angle within ± 1 °. “Parallel light” can be obtained by combining an elliptical condensing mirror with an integrator and a collimator lens in a lamp light source. When an LED array is used as a light source, it can be obtained using a fly-eye lens, a compound parabolic concentrator, or the like.

  The term “non-parallel light” as used in the present application refers to a group of light beams including light from a direction other than the light irradiated from the vertical direction on the object to be patterned. In addition to the light irradiated from the vertical direction, the lens For example, light having a collimation half angle set to 45 °, for example, or a mixed light beam including reflected light and scattered light inside the casing described later.

  The “pattern” in the present invention refers to a design (design or pattern in the figure), characters, images, etc. displayed by the organic EL element. “Patterning” refers to providing these pattern display functions.

  The “light emission pattern” refers to light emitted from an organic EL element that emits light with varying light emission intensity (luminance) depending on the position of the light emitting surface, based on a predetermined design (pattern or pattern in the figure), characters, images, etc. A source having a function of displaying a predetermined design (design or pattern in the figure), characters, images, etc. formed (applied) in advance on the organic EL element to emit light.

  As a preferred embodiment of the “light” to be irradiated used in the present invention, it contains at least ultraviolet rays, and may further have a part of visible light. The ultraviolet ray referred to in the present invention refers to an electromagnetic wave having a wavelength longer than that of X-rays and shorter than the shortest wavelength of visible light. Specifically, the wavelength region is in the range of 10 to 400 nm, preferably, As the wavelength of irradiation light to be applied, it is preferable to use ultraviolet irradiation light having a maximum wavelength in the range of 350 to 400 nm, and it is preferable to use ultraviolet light having a maximum wavelength in the range of 360 to 400 nm as irradiation light.

  As another embodiment, it is also preferable to use blue-violet light of 400 to 410 nm, and a blue-violet semiconductor laser used in a conventionally known optical pickup device that emits and receives light for use in a Blu-ray disc is used as a patterning device. Can be used as a light source.

  Therefore, the light wavelength of the light source used in the present invention is preferably in the range of 360 to 410 nm.

  The irradiation light generating means and the irradiation means are not particularly limited as long as they can generate light using a conventionally known irradiation apparatus or the like and irradiate a predetermined region.

  As a light source applicable to the present invention, a high pressure mercury lamp, a low pressure mercury lamp, a hydrogen (deuterium) lamp, a rare gas (xenon, argon, helium, neon, etc.) discharge lamp, a nitrogen laser, an excimer laser (XeCl, XeF, KrF, KrCl, etc.), hydrogen laser, halogen laser, various semiconductor lasers (LD), harmonics of infrared lasers (THG (Third Harmonic Generation) light of YAG laser), various LEDs (light emitting diode), and the like.

<< Outline of Organic Electroluminescence Device According to the Present Invention >>
First, an outline of the configuration of the organic EL element according to the present invention will be described below.

  The organic EL device according to the present invention includes a laminate of the first gas barrier film and the second gas barrier film according to the present invention as a substrate, and an organic functional layer including a first electrode and a light emitting layer thereon, Two electrodes are laminated in this order. Further, an extraction electrode may be provided at the end of the first electrode, and an external power supply may be connected to the first electrode via the extraction electrode.

  The organic EL element is usually configured such that emitted light is extracted from the substrate side or the opposite side, and an example of the organic EL element according to the present invention is a bottom emission type that extracts emitted light from the substrate side. It is preferable. Moreover, as another preferable aspect, when the 2nd electrode mentioned later is a transparent electrode and a sealing member and a sealing layer are transparent, it is also preferable that it is a double-sided light emission type which takes out emitted light from both surfaces.

  The layer structure of the organic EL element is not particularly limited, and may be a conventionally known general layer structure. For example, the first electrode functions as an anode (that is, an anode), and the second electrode functions as a cathode (that is, a cathode). In this case, for example, the organic functional layer can have a structure in which a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer are stacked in order from the first electrode side which is an anode. It is essential to have at least a light-emitting layer formed using an organic material. The hole injection layer and the hole transport layer may be provided as a hole transport injection layer, and the electron transport layer and the electron injection layer may be provided as an electron transport injection layer. Of these organic functional layers, for example, the electron injection layer may be composed of an inorganic material.

  In addition to these layers, the organic functional layer may have a structure in which a hole blocking layer, an electron blocking layer, or the like is laminated at a necessary position as necessary. Further, the light emitting layer may have a structure in which each color light emitting layer for generating light emitted in each wavelength region is laminated, and each of these color light emitting layers is laminated via a non-light emitting intermediate layer. The intermediate layer may function as a hole blocking layer and an electron blocking layer.

  Further, the second electrode as the cathode may also have a laminated structure as necessary. For the purpose of reducing the resistance of the first electrode, an auxiliary electrode may be provided in contact with the first electrode.

  In such a configuration, only a portion where the organic functional layer is sandwiched between the first electrode and the second electrode (a region where the first electrode, the organic functional layer, and the second electrode overlap when viewed from the stacking direction) is the organic EL. It becomes the light emitting region of the element.

  The organic EL element having the above configuration is sealed with a sealing material on a substrate for the purpose of preventing deterioration of an organic functional layer configured using an organic material or the like. However, it is assumed that the terminal portions of the first electrode, the second electrode, or the extraction electrode are exposed from the sealing material in a state where insulation is maintained on the substrate.

  In addition to the above-described layers, the organic EL device according to the present invention is appropriately provided with functional layers such as a hard coat layer, a smooth layer, a base layer, a protective layer, a back coat layer, a light refraction layer, and a light scattering layer. Is also preferable.

  Hereafter, each element which comprises this invention is demonstrated in detail.

[1] Patterning Device A light emitting pattern having a desired gradation of light emission luminance can be formed on the organic EL element by a patterning device described below.

[1.1] Patterning apparatus and method by non-parallel light irradiation [1.1.1] Patterning apparatus by non-parallel light irradiation As an example of the patterning apparatus used in the present invention, an ultraviolet light emitting unit and an ultraviolet light emitting unit emit light. It is preferable to use a patterning apparatus including a casing that reflects and guides the ultraviolet rays that are reflected and a glass mask that is irradiated with the ultraviolet rays below the casing.

  In the case of this patterning apparatus, since ultraviolet rays are reflected in the casing and irradiated as non-parallel light, the irradiance of the ultraviolet rays is increased, and it is possible to reduce running costs such as power charges and heat generation. Although there is an advantage, an irradiation pattern shift tends to occur when patterning through a mask.

  1A to 1C are schematic diagrams showing the occurrence of irradiation pattern deviation.

  FIG. 1A is a schematic diagram illustrating a patterning method of a comparative example.

After forming the organic EL element 3 and the sealing material 4 using the laminate of the first gas barrier film 1 and the second gas barrier film 2 as a substrate, a mask 5 is disposed on the second gas barrier film 2. It is a schematic diagram when irradiating ultraviolet rays (UV). The mask 5 is composed of a glass substrate and a light shielding film 7. In this case, since the ultraviolet light is the non-parallel light 6, light sneak inside the light shielding film 7 of the mask 5 occurs, and only the sneaking amount δ _{1 with} respect to the width of the light shielding film 7 of the intended mask. The pattern is shifted. That is, the light emission pattern of the organic EL element becomes narrower by 2δ ₁ than the intended mask width. This pattern shift is referred to as “irradiation pattern shift” in the present application.

  FIG. 1B is a schematic view showing a patterning method according to the present invention.

After forming the organic EL element 3 and the sealing material 4 using the first gas barrier film 1 as a substrate, a mask 5 is placed on the first gas barrier film 1 and irradiated with ultraviolet rays (UV). In this case, since the ultraviolet rays include the non-parallel light 6, similarly, although light sneaks inside the light-shielding film 7 of the mask 5, the ultraviolet rays are transmitted only through the first gas barrier film 1. Since the distance between the mask and the organic EL element is close, the intrusion of light into the inside of the light shielding film 7 of the mask 5 is the amount of infiltration δ ₂ (δ ₂ <δ) with respect to the width of the light shielding film 7 of the intended mask. ₁ ), and the irradiation pattern deviation can be made smaller than in the case of FIG. 1A. In addition, since Fresnel reflection does not occur at the interface between the gas barrier films 1 and 2, there is no reduction in the amount of ultraviolet irradiation, and there is a cost merit that can reduce irradiance. Can be further improved.

  The irradiation pattern shift will be further described.

  When irradiating with non-parallel light through a mask, as shown in FIG. 1C, oblique rays (non-parallel light) whose incident angle with respect to the light-shielding film of the mask is not 0 ° enter under the light-shielding film of the mask. In this case, the illuminance does not become zero in the vicinity of the light shielding film edge, and the irradiance distribution has an inclination as shown in FIG. 1C. This amount of dive δ is t × tan (θ). Here, θ is a collimation half angle which is the maximum incident angle, t is an air-converted length from the light shielding film to the organic layer, the thickness of the base material of the first gas barrier film of the organic EL element is ts, and the refractive index is n. In this case, t = ts / n. The thickness of the gas barrier layer constituting the first gas barrier film is very thin compared to the thickness of the base material, and the amount of penetration is substantially determined by the base material thickness.

Due to the irradiance distribution in the vicinity of the edge portion of the light shielding film, the luminance distribution also has an inclination in the edge of the light emission pattern of the irradiated organic EL element. Since the inclination width determines the resolution of the light emission pattern, the resolution can be increased as the base material thickness of the gas barrier film is thinner and the collimation half angle is smaller. However, if the collimation half angle is reduced, the irradiance cannot be increased. In order to shorten the irradiation time by utilizing the illuminance failure characteristic of the organic EL element, an irradiance of 1 W / cm ² is preferable at least. As a result of designing the collimation half angle as small as possible with this irradiance, the collimation half angle is 23. It was found that it can be reduced to °°. In this collimation half angle, when the substrate of the first gas barrier film is PET and the thickness is reduced to 20 μm (n = 1.7), δ = 5 μm, and a considerable resolution can be secured. On the other hand, when the tact time is prioritized and an increase in the collimation half angle is allowed, for example, when θ = 45 ° that can secure 4 W / cm ² and the substrate thickness is 500 μm, δ = 294 μm, and a half pitch of 0.3 mm is solved. It becomes the image limit. If the resolution is about half pitch 0.3 mm, most patterns appealing to the visual feeling (characters, simple shape patterns, etc.) can be reproduced, so that the gradient width of the edge luminance distribution is in the range of 10 to 300 μm. desirable. Accordingly, the substrate thickness of the first gas barrier film is desirably in the range of 20 to 500 μm as will be described later. Furthermore, when θ = 45 ° and the substrate thickness is 130 μm, δ = 76 μm, and a half pitch of 0.1 mm can be sufficiently resolved. Therefore, it can be said that the base material thickness of the first gas barrier film is more preferably in the range of 20 to 130 μm.

  FIG. 2 is a schematic configuration diagram of an example of a patterning apparatus used in the present invention. The patterning apparatus 10 includes a light source unit 20 including an ultraviolet light emitting unit 11, a housing 12, and an air flow generation unit 15, and a pattern forming body mounting table 19. The ultraviolet light emitting unit arranges a light source 11b (for example, a UV-LED having a wavelength of 365 nm or 385 nm) that irradiates ultraviolet light in a two-dimensional (planar) form on the light source substrate 11a, and divergent light emitted from the light source is emitted by the lens array 11c. The light beam is shaped into a light beam having a predetermined spread angle, and the organic EL element 16 is irradiated with ultraviolet rays through the glass mask 13. The heat of the light source generated during irradiation escapes to the heat radiating plate 21 and prevents the light emission efficiency of the light source from decreasing. More preferably, a cooling pipe is provided inside the radiator plate, the cooling water is circulated, and the light source is cooled with water. The light emitted from the lens array is confined in the casing 12 whose inner surface is a reflection surface to prevent the light amount from decreasing, and is irradiated onto the glass mask with a uniform light amount. In order to secure the amount of light in the periphery of the irradiation area, the distance 17 between the lower end of the housing and the glass mask should be as narrow as possible, and is preferably about 5 mm. If it is this space | interval, a layered air flow can be sprayed uniformly on a glass mask. The light source is turned on and off by a controller (not shown), and the irradiation output and the irradiation time during lighting are controlled to perform intermittent irradiation. Although a lens array is used for divergence angle shaping, a condensing mirror such as a compound parabolic concentrator may be used.

  The organic EL element 16 is placed on the pattern forming body placing table with the first gas barrier film surface as an upper surface, and the glass mask is adjusted to a predetermined position and placed on the first gas barrier film. The organic EL element and the first gas barrier film are preferably adsorbed and fixed. When PET or PEN (polyethylene naphthalate) is used as the base material of the first gas barrier film, it may be easily deformed by heat, but by adsorbing the entire surface, it is fixed to the pattern forming object mounting table with good flatness. It is possible to prevent an irradiation pattern shift during patterning.

As described above, the pattern forming body mounting table 19 desirably cools the first gas barrier film and the organic EL element by the water cooling method. A water-cooled tube is provided inside the pattern forming body mounting table, and cools the heat generated in the glass mask and the organic EL element by the ultraviolet irradiation. Cold water is introduced through a water-cooled pipe (introduction) 19a, and the water that has absorbed heat by the pattern forming body mounting table is discharged from the water-cooled pipe (discharge) 19b, and the discharged water is discharged from a chiller unit (not installed). The cooling water having a reduced water temperature is supplied again to the pattern forming body mounting table. Cooling water circulates through the chiller unit and the cooling stand. The cooling function is always operated while the device is in operation. The water temperature introduced into the pattern forming body mounting table is preferably 30 ° C. or less as long as the organic EL element and the mask are not condensed. 10-20 degreeC is more preferable. The material of the pattern forming body mounting table is preferably a metal having high thermal conductivity. For example, aluminum is preferable.
The air flow generation unit 15 is provided with a slit-shaped spray unit, and air is blown out in a line shape to cool the glass mask surface as an air flow 14.

  According to the present invention, since patterning with high dimensional accuracy is possible, productivity can also be improved by producing a plurality of organic EL elements having the same pattern by one ultraviolet irradiation.

  When the plurality of organic EL elements are formed in a sheet shape, it is preferable that alignment marks are formed at the four corners. This alignment mark is used for alignment of a film formation mask when forming an electrode or an organic layer in the manufacture of an organic EL element.

  A predetermined pattern is formed on the glass mask at a position corresponding to each organic EL element, and an alignment mark corresponding to the alignment mark position on the organic EL element sheet is formed. Ultraviolet rays are shielded by a light shielding film of a glass mask. Therefore, the organic EL element is irradiated with ultraviolet rays in the light emitting area other than the light shielding film and does not emit light, and only the light shielding film pattern emits light as the element.

  3A to 3C are schematic views illustrating the configuration and positions of the light source unit, the mask alignment apparatus, and the pattern forming body mounting table. Note that the same reference numerals as those in FIG. 2 are the same as those in FIG.

  The pattern forming body mounting table 19 is movable, and the organic EL element sheet is installed and collected at a retracted position away from the light source unit 20. A mask alignment device 25 is preferably disposed next to the light source unit 20, and the glass mask 13 is placed on a mask holding table 22, which is used to adjust X, Y, Z, and θ in the XY plane. Is possible. The mask alignment apparatus includes an elevating unit 23 and a support base 24, and can freely control the height of the mask. The pattern forming object mounting table 19 raises the elevating unit 23 of the mask alignment apparatus. The mask and the organic EL element can be brought into close contact with each other by being introduced into the generated gap and descending the elevating part 23.

  The patterning apparatus used in the present invention has a narrow gap in order to ensure high irradiance, and it is difficult to replace the glass mask at the irradiation position where the pattern forming body mounting table is located directly under the light source unit. There are cases. Therefore, it is preferable to arrange a mask alignment apparatus next to the light source unit so that glass mask replacement and mask alignment are possible.

  Next, each component of the patterning apparatus will be described.

<Ultraviolet light emitting part>
A light source that emits ultraviolet light is attached to the ultraviolet light emitting unit. The light source is not particularly limited as long as it is a light source that emits a desired amount of ultraviolet light. For example, an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, a UV light laser, etc. Ultraviolet light in the wavelength region can be used.

  Further, as the light source, it is also preferable to use a UV-LED having a light wavelength in the range of 365 to 385 nm capable of high-power and high-speed irradiation extinction control.

In order to shorten the tact time by utilizing the reciprocity failure characteristic of the organic EL element, the irradiance is preferably 1 W / cm ² or more. In order to significantly shorten the tact time, 4 W / cm ² or more is more preferable. Further, the irradiance and the collimation half angle are in a trade-off relationship, and in order to ensure a high irradiance of 4 W / cm ² , it is preferable that the collimation half angle is 45 ° and non-parallel light. In addition, the ultraviolet irradiation time is preferably within a range of 1 to 150 seconds in order to suppress a decrease in adhesion between the glass mask and the first gas barrier film due to heat generation.

<Glass mask>
A glass mask has a role which changes the light quantity irradiated to an organic EL element. A glass mask having a negative pattern on a glass substrate can be manufactured using a known mask material that can change the amount of transmitted ultraviolet light. By irradiating the organic EL element with ultraviolet rays, an organic EL element having a light emission pattern can be produced. For example, it can be produced by applying a black and white photosensitive material on a glass plate, baking it, and developing it.

  As a glass substrate, it does not specifically limit as a raw material, For example, the well-known glass raw material used for optics and a board | substrate can be used. Specifically, glass ceramics such as aluminosilicate glass, soda lime glass, soda aluminosilicate glass, aluminoborosilicate glass, borosilicate glass, quartz glass, chain silicate glass, crystallized glass, phosphate glass or lanthanum glass Etc.

Of these, those having a low coefficient of thermal expansion are preferred. Specifically, it is preferable that the linear expansion coefficient of the substrate is 3 × 10 ⁻⁶ / ° C. or less. Examples of such glass include heat-resistant glass such as quartz glass, glass ceramic, and borosilicate glass (for example, Tempax Float (registered trademark) manufactured by Schott). By using such a base material, the amount of thermal deformation can be further suppressed. The thickness of the glass mask is not particularly limited, but a glass mask having a thickness of 3 to 10 mm can be used.

<Case for reflecting light guide>
A casing (reflector) that reflects and guides light has a function of preventing a decrease in the amount of ultraviolet light emitted from the ultraviolet light emitting unit and irradiating the glass mask with a uniform amount of light. Therefore, it is preferable that the inner surface is covered with a reflective material. Since the reflective material is resistant to heat and durable, a metal material can be used. For example, aluminum is preferably used because it is lightweight.

  If the housing has an ultraviolet light emitting part attached to the upper part and a gap with a glass mask at the lower end, the height and bottom area are not particularly limited, and the organic EL element that irradiates ultraviolet light is not limited. It can be set according to the size. The bottom surface is preferably larger than the pattern to be produced.

  The height of the housing can be adjusted as appropriate based on the amount of ultraviolet light, unevenness in the amount of irradiation light, and the like. For example, it can be about 0.5 to 5 m.

<Air flow generator>
The air flow generation unit 15 is blown toward the center of the glass mask 13 in parallel with the glass mask 13 through the gap 17 between the glass mask 13 and the housing 12 at a position facing the upper surface of the glass mask 13. Has been placed.

  The air flow generation unit 15 is disposed on the upper surface of the glass mask 13 and sprayed in parallel with the glass mask 13, so that the air flow 14 to be sprayed travels uniformly on the glass mask 13 and merges at the center of the glass mask 13. Spraying in parallel means spraying at an angle of ± 2 degrees or less with respect to the plane of the glass mask 13. If the glass mask plane is blown upward at more than 2 degrees, the glass mask is not sufficiently cooled. Moreover, when it sprays downward over 2 degree | times with respect to a glass mask plane, since the disorder | damage | failure will arise in the air sprayed on the glass mask and cooling of a glass mask will arise, it is unpreferable.

  The air blown onto the glass mask merges at the center of the glass mask 13. By joining at the center, the glass mask 13 and the housing 12 can be cooled uniformly. For this reason, the airflow generation part 15 is arrange | positioned in parallel with the position which the glass mask 13 upper surface opposes. Moreover, it is preferable that the side surface of the casing to be sprayed is also parallel.

  The distance 18 between the housing 12 and the airflow generator 15 is not particularly limited as long as air is efficiently blown onto the mask, but is preferably within a range of 10 to 200 mm. More preferably, it exists in the range of 50-100 mm. Moreover, it is preferable that the length of the airflow generation part is equal to or larger than the width of the casing on the side to be sprayed.

  The air blown from the air flow generator 15 is blown into the housing 12 through the gap 17 between the glass mask 13 and the housing 12. The gap 17 functions as an air inlet / outlet for the inside of the casing, but also affects the air blown through the casing 12 efficiently. It is preferable to be within a range of 2 to 20 mm. Preferably it exists in the range of 3-10 mm. If the gap is within 20 mm, the air is efficiently circulated in the housing 2 and the heat generated in the housing 12 can be cooled. If the clearance is 2 mm or more, the airflow for cooling is sufficient. Can get to.

  In addition, the pair of air flow generation units 15 is preferably disposed at positions symmetrical with respect to the casing 15 and the central portion of the glass mask 13.

<Blowing part>
In order to efficiently cool the entire light irradiation range of the glass mask without unevenness, it is preferable that the airflow generation part is provided with a slit-like or nozzle-like spraying part. It is more preferable to have a slit-shaped spraying part.

  The airflow generation part provided with the slit-like spraying part can spray the laminar airflow 14. For example, air blown out at a high speed from a thin slit having a gap of about 50 to 100 μm can entrain a large amount of surrounding air and spray layered air. By blowing such layered air, the glass mask and the housing can be efficiently cooled.

  Instead of the slit-shaped spraying part, a nozzle provided with a nozzle-shaped spraying part can also be used. In that case, the number of nozzles should be large, and the number of nozzles is preferably one at intervals of 5 to 20 mm. The size of the nozzle diameter can be adjusted as appropriate.

  A commercially available product can be used as the slit-shaped spraying part used for the spraying part. For example, a layered airflow generator 750 type manufactured by Sanwa Enterprise, a blower knife air nozzle manufactured by Spraying System Japan, or the like can be used.

  The amount of air blown from the pair of blowing parts is preferably the same. The air volume can be 1000 to 4000 L / min. The air flow generation unit is preferably connected to an air compressor. According to the irradiation light quantity of an ultraviolet-ray, it can adjust to a desired air volume and a wind speed suitably. A known air compressor can be used.

  Moreover, it is preferable that the air to be blown is temperature-adjusted. If necessary, the cooling efficiency can be increased by using air whose temperature is adjusted to about 5 to 15 degrees, for example.

  Using the above patterning apparatus, patterning is performed in the following steps.

  4A and 4B are schematic cross-sectional views showing an example of a method for bringing the organic EL element sheet on the pattern-formed object mounting table and the mask on the mask alignment apparatus into close contact at a predetermined position. 4A is a front view and FIG. 4B is a side view.

(S1)
In a state where the pattern forming body mounting table 19 is in the retracted position, the laminate 16 (hereinafter also referred to as a sheet) of the first gas barrier film and the organic EL element is mounted on the pattern forming body mounting table, and is placed at the corner of the sheet. The corners of the arranged element outline and the reference line provided on the pattern forming body mounting table are matched. The reference line may be a marking line or may be drawn with paint or the like. By this step, the alignment mark 29 of the sheet can be reliably put in the photographing range of the camera at the time of mask alignment, and re-positioning of the sheet can be prevented. The sheet installation and positioning may be performed manually, but it is desirable to perform it automatically from the viewpoint of reducing the number of man-hours. The positioning of the sheet is not limited to the outer shape of the organic EL element, but an alignment mark for manufacturing the electrode part or the organic EL element itself, a cut position indicating mark for cutting the element into individual pieces, a discard pattern, or the like may be used. Thus, by diverting the pattern formed on the sheet for manufacturing the organic EL element, it is not necessary to form a mark dedicated to the patterning process, and an increase in the number of manufacturing steps can be suppressed.

  After the sheet is positioned, the sheet is sucked from the suction hole E provided in the pattern forming body mounting table 19, and the sheet is sucked and fixed.

  It is preferable to press the entire sheet with a roller or the like in order to conform the entire sheet to the surface of the light irradiation table having flatness.

(S2)
A glass mask is placed on the mask holding table 22 of the mask alignment apparatus 25 by its own weight, and the holding table is raised so that the pattern forming object mounting table on which the sheet is mounted can move directly below the mask 13. ing. After the pattern forming body mounting table moves to a predetermined position directly below the glass mask, the support table is lowered to the point where the sheet and the glass mask are in close contact with each other.

  Subsequently, the camera 26 moves onto the glass mask, and recognizes the sheet of the alignment unit 27 and the alignment marks (28 and 29) on the glass mask. The glass mask is adjusted by X, Y, and θ together with the support so that the center of the alignment mark of the glass mask comes to the center of the alignment mark of the opposite sheet. The alignment mark may be used using only two diagonal positions.

  After completion of the alignment, the support table is further lowered and separated from the glass mask, and the glass mask is placed on the pattern forming body placing table 19 by its own weight and is in close contact with the sheet. Since the light shielding film of the glass mask is directed to the sheet side, the heat of the light shielding film that generates heat by absorbing ultraviolet rays can be released to the pattern forming body mounting table through the sheet. Further, curling of the sheet is suppressed, and the floating portion is eliminated, thereby enabling accurate patterning.

  Subsequently, the pattern forming body mounting table on which the sheet and the glass mask are mounted moves to the irradiation position directly below the light source unit. During this time, the sheet and the glass mask are cooled by the cooling function of the pattern forming body mounting table.

(S3)
Layered air is blown from the air flow generator 15 onto the glass mask surface. A flow meter is installed between the air flow generator and the air supply source, and constantly monitors the air flow rate. An anemometer may be installed in front of a part of the air outlet that is outside the irradiation area in the longitudinal direction of the air flow generation unit to monitor the wind speed.

(S4)
When the air flow rate reaches a predetermined flow rate value, the sheet is irradiated with ultraviolet rays through a glass mask under predetermined irradiation conditions. Light irradiation can be performed, for example, by intermittently irradiating at an irradiance of 4 W / cm ² and performing 40 cycles of irradiation for 15 seconds and extinguishing 15 seconds for 10 minutes.

(S5)
After the light irradiation, the air flow 14 is stopped.

  The pattern forming body mounting table on which the sheet and the glass mask are mounted is retracted to the mask alignment position.

  The mask support is raised, the glass mask is placed on the support, and further raised to release the glass mask from the sheet.

  The pattern forming body mounting table on which the sheet is placed moves to the retracted position, the suction is stopped, and the sheet is collected.

  The mask alignment apparatus and the light irradiation table may be integrated and moved as a whole. In this case, the entire position of the apparatus can be saved by setting the alignment position and the retracted position at the same position. In this case, sheet placement / collection, mask alignment, and glass mask replacement are performed at the retracted position.

[1.2] Patterning apparatus and method by point drawing Since the patterning by the point drawing used in the present invention is based on spot light, “irradiation pattern deviation” when using the non-parallel light and the glass mask is used. Although generation | occurrence | production can be avoided, the light transmittance of gas barrier film itself becomes a rate-limiting factor of patterning efficiency from a viewpoint of irradiance. Therefore, also in this case, the excellent effect of the present invention can be exhibited by forming an organic EL element using only the first gas barrier film as the first substrate and then patterning.

  FIG. 5 is a schematic configuration diagram of the patterning apparatus 100 by point drawing used in the present invention. The patterning apparatus 100 is a point drawing apparatus that forms a plurality of minute dot marks on the organic EL element 1 to form a light emission pattern.

  The patterning apparatus 100 includes a light source 101 (for example, a semiconductor laser having a wavelength of 405 nm), a collimator lens 103 that converts light emitted from the light source 101 into parallel light, and light that has been collimated by the collimator lens 103 with a predetermined spot diameter. The condenser lens 104, the beam splitter 105 that reflects part of the light emitted from the collimator lens 103, the light detector 106 that detects the intensity of the light reflected by the beam splitter 105, and the light emitted from the condenser lens 104. The reflecting mirror 107 that reflects the emitted light toward the organic EL element 1, the adjustment unit 108 that adjusts the inclination of the reflecting mirror 107, the organic EL element 3, and the stack of the first gas barrier film 1 are moved in the horizontal direction. The moving part 109 and the control part 110 etc. which control each member are provided. The collimator lens 103, the condenser lens 104, the beam splitter 105, the photodetector 106, the reflection mirror 107, the adjustment unit 108, the moving unit 109, and the control unit 110 constitute a light irradiation unit 102.

  The light source 101 is fixed to a metal holder (not shown), and the holder is further fixed to a metal casing (not shown). Thereby, the heat dissipation of the light source 101 is ensured. Further, grease having high thermal conductivity may be applied to the contact surface between the holder and the housing, and the heat dissipation of the light source 101 can be further enhanced.

As the collimator lens 103 and the condensing lens 104, aspherical lenses are used, and antireflection films for controlling the transmittance of incident light are provided on the surfaces thereof. As a material for the antireflection film used for the collimator lens 103 and the condenser lens 104, for example, MgF ₂ is used.

  The reflection mirror 107 and the adjustment unit 108 are configured as, for example, a uniaxially driven galvanometer mirror, and can scan a light spot formed on the organic EL element 1 in the Y direction. The moving unit 109 is configured to be able to move the organic EL element 1 in the X direction. Thereby, the light spot can be moved in the X direction and the Y direction on the organic EL element 1. Here, the X direction is the horizontal direction and refers to the left and right direction in FIGS. 1A to 1C, and the Y direction is the horizontal direction and refers to the direction perpendicular to the paper surface in FIG.

  Note that the reflection mirror 107 and the adjustment unit 108 do not have to be configured as a uniaxially driven galvanometer mirror. For example, the reflecting mirror 107 and the adjusting unit 108 may be configured by combining two uniaxially driven galvanomirrors. A galvanometer mirror and a polygon mirror may be combined. In this case, the light spot can be moved in the X direction and the Y direction on the organic EL element 1 only by the reflection mirror 107 and the adjustment unit 108, and the configuration of the moving unit 109 is not necessary. Cost can be reduced.

  Further, the adjustment unit 108 may not be provided. In this case, the moving unit 109 may move the stacked body of the organic EL element triplet and the first gas barrier film 1 in the X direction and the Y direction. It is configured to be able to.

  The light irradiation unit 102 collects the light emitted from the light source 101 and forms a light spot on the organic EL element 3 through the first gas barrier film 1 of the laminate. By adjusting the spot diameter with the numerical apertures of the collimator lens 103 and the condenser lens 104, the accuracy of the light emission pattern to be formed and the time required for pattern formation can be adjusted.

  According to such a patterning apparatus 100, first, the control unit 110 uses the light emission luminance for each coordinate of the image from image data input from an external device (not shown) (for example, a PC, various servers, a printer, a scanner, or the like). Is generated.

  Next, the control unit 110 sets the irradiation power [W] and the irradiation time [s] necessary for forming a dot mark having a desired relative light emission luminance.

  For example, the patterning apparatus 100 forms a dot mark having a desired light emission luminance by changing the irradiation power [mW] of light applied to the organic EL element 3 while keeping the light irradiation time constant for each dot mark. Is configured to do. Therefore, the control unit 110 sets the light irradiation time for each relative light emission luminance to 1 ms, for example, and calculates the light irradiation power [mW] necessary for forming the dot mark of each relative light emission luminance. The control unit 110 calculates a current [mA] to be applied to the light source 101 from the irradiation power [mW] of light corresponding to each relative light emission luminance.

  Subsequently, the control unit 110 adjusts the tilt of the reflection mirror 107 and the horizontal position of the organic EL element 3 at predetermined time intervals by the adjustment unit 108 and the moving unit 109, respectively. While scanning the spot position in the X and Y directions, a pulse signal indicating the value of the LD current is output to the light source 101 for each coordinate based on the generated emission luminance data. The light source 101 emits light based on the input pulse signal, thereby forming a plurality of dot marks on the organic EL element 3 and forming a desired light emission pattern. Note that, when the light irradiation is performed, the control unit 110 detects the intensity of the reflected light from the beam splitter 105 by the light detector 106 and monitors the detected data. As a result, when an error occurs in the intensity of light emitted from the light source 101 due to changes in temperature / humidity environment or the like, the control unit 110 corrects the LD current I applied to the light source 101 to correct the desired light. The intensity is emitted accurately.

  Further, in the patterning apparatus 100 described above, the light irradiation time is fixed and the light irradiation power is changed to form a dot mark having a desired relative light emission luminance. However, the light irradiation power is constant and the irradiation time is constant. It is good also as what changes. In this case, it is not necessary to detect the intensity of light over a wide range, and it is not necessary to use a sensor having a wide dynamic range and a good S / N ratio for the photodetector 106, thereby reducing the cost of the patterning apparatus 100. be able to.

  Furthermore, in the patterning apparatus 100 described above, the light irradiation time is fixed and the light irradiation power is changed to form a dot mark having a desired relative light emission luminance. However, both the light irradiation power and the irradiation time are used. It may be changed.

[2] Gas barrier film The first gas barrier film and the second gas barrier film according to the present invention are not particularly limited, and a gas barrier film having a known gas barrier layer can be used. The first gas barrier film and the second gas barrier film may be the same gas barrier film or different gas barrier films. In the case of different gas barrier films, the type and thickness of the substrate used, the configuration of the gas barrier layer, the material and thickness, and the like can be adjusted as appropriate.

  In addition, the second gas barrier film or the adhesive layer or the pressure-sensitive adhesive layer according to the present invention has an ultraviolet light shielding property due to ultraviolet rays contained in external light such as sunlight with respect to the organic EL element after patterning. This is preferable from the viewpoint of preventing element deterioration and pattern deterioration.

The “gas barrier property” referred to in the present invention is preferably an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, JIS K 7129. -The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to 1992 is 1 × 10 ⁻² g / m ² · 24 h or less. .

[2.1] Substrate As a substrate applied to the first gas barrier film and the second gas barrier film according to the present invention, a flexible material capable of giving flexibility to the organic EL element. If it is a base material, it will not specifically limit. An example of the flexible base material is a transparent resin film.

  Moreover, it is preferable that a base material consists of a raw material which has heat resistance. Specifically, a substrate 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 base material satisfies the requirements for use as a laminated film for electronic parts and displays.

  The Tg and the linear expansion coefficient of the substrate can be adjusted with an additive or the like. More preferable specific examples of the thermoplastic resin that can be used as the substrate include, for example, polyethylene terephthalate (PET: 70 ° C.), polyethylene naphthalate (PEN: 120 ° C.), polycarbonate (PC: 140 ° C.), and 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-A No. 2001-150584: 162 ° C.), polyimide (for example, Neoprim (registered trademark): 260 ° C. manufactured by Mitsubishi Gas Chemical Co., Ltd.), fluorene ring-modified polycarbonate (BCF-PC: JP In 2000-227603 Listed compound: 225 ° C.), alicyclic modified polycarbonate (IP-PC: compound described in JP 2000-227603 A: 205 ° C.), acryloyl compound (compound described in JP 2002-80616 A: 300 ° C.) And the like) (Tg is shown in parentheses).

  Among these resin films, films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and alicyclic polyolefin are preferably used in terms of cost and availability.

  The thickness of the substrate is preferably about 20 to 500 μm, more preferably 20 to 130 μm, from the viewpoint of reducing light transmittance and irradiation pattern deviation as described above.

  Moreover, it is preferable that a base material has a light transmittance. Since the base material has light transmittance, not only the running cost in patterning can be reduced, but also an organic EL element having light transmittance can be formed. In particular, the light transmittance in the wavelength range of 360 to 410 nm of the first gas barrier film according to the present invention is preferably 60% or more.

It was confirmed by the following model experiment that the light transmittance is preferably 60% or more. That is, a gas barrier film having a gas barrier layer having a thickness of 1.0 μm and a 130 μm-thick PET base material having an ultraviolet transmittance measured at a wavelength of 385 nm of 64% is modeled, and this gas barrier is produced. An organic EL element was formed using the film as a substrate. Next, as a result of patterning the organic EL element by irradiating ultraviolet rays having a wavelength of 385 nm and 4 W / cm ² , the organic EL element having a luminance ratio of 200 could be patterned in a short time of an integrated light irradiation time of 10 minutes. , Derived.

Luminance ratio = (luminance of light emitting part not exposed to ultraviolet rays) / (luminance of non-light emitting part irradiated with ultraviolet rays)
Accordingly, the light transmittance in the wavelength range of 360 to 410 nm of the base material used for the first gas barrier film and the gas barrier film itself is preferably 60% or more, and more preferably 70% or more. The light transmittance can be measured, for example, using a spectrophotometer (such as U-3300 manufactured by Hitachi High-Technologies Corporation) in an environment of 25 ° C. and 55% RH.

[2.2] Gas barrier layer The gas barrier layer may be formed on the surface of the film substrate as an inorganic film, an organic film, or a hybrid film of both, and is measured by a method according to JIS K 7129-1992. It is preferable that the gas barrier layer has a water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) of 1 × 10 ⁻² g / m ² · 24 h or less. Furthermore, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / m ^2. -It is preferable that it is a high gas barrier layer of 24 hours or less.

  The material for forming the gas barrier layer may be any material as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. .

  The gas barrier layer is not particularly limited. For example, in the case of an inorganic gas barrier layer such as silicon oxide, silicon dioxide, or silicon nitride, an inorganic material is sputtered (for example, magnetron cathode sputtering, flat plate magnetron sputtering, bipolar AC Flat-plate magnetron sputtering, 2-pole AC rotating magnetron sputtering, etc.), vapor deposition methods (for example, resistance heating vapor deposition, electron beam vapor deposition, ion beam vapor deposition, plasma assisted vapor deposition, etc.), thermal CVD methods, catalytic chemical vapor deposition (Cat-CVD) ), Capacitively coupled plasma CVD (CCP-CVD), photo CVD, plasma CVD (PE-CVD), epitaxial growth, atomic layer growth, chemical vapor deposition such as reactive sputtering, etc. preferable.

  Furthermore, after applying a coating liquid containing an inorganic precursor such as polysilazane and tetraethyl orthosilicate (TEOS) on a support, a modification treatment is performed by irradiation with vacuum ultraviolet light, etc., and an inorganic gas barrier layer is formed. The inorganic gas barrier layer can also be formed by a metal filming technique such as metal plating on a resin substrate or bonding a metal foil and a resin substrate.

  The inorganic gas barrier layer may include an organic layer containing an organic polymer. That is, the inorganic gas barrier layer may be a laminate of an inorganic layer containing an inorganic material and an organic layer.

  The organic layer is formed by, for example, applying an organic monomer or oligomer to a resin substrate to form a layer, followed by polymerization and using, for example, an electron beam device, a UV light source, a discharge device, or other suitable device. It can form by bridge | crosslinking as needed. For example, it can also be formed by depositing an organic monomer or organic oligomer capable of flash evaporation and radiation cross-linking and then forming a polymer from the organic monomer or organic oligomer. The coating efficiency can be improved by cooling the resin substrate.

  Examples of the method for applying the organic monomer or organic oligomer include roll coating (for example, gravure roll coating) and spray coating (for example, electrostatic spray coating). Moreover, as an example of the laminated body of an inorganic layer and an organic layer, the laminated body of the international publication 2012/003198, international publication 2011/013341, etc. are mentioned, for example.

  In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The layer thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 300 nm. The layer thickness of the organic layer is preferably in the range of 100 nm to 100 μm, more preferably in the range of 1 to 50 μm.

  Hereinafter, the preferable gas barrier layer is demonstrated in detail about the gas barrier film which concerns on this invention.

[2.2.1] Polysilazane modified layer The polysilazane modified layer is preferably formed by applying and drying a coating liquid containing polysilazane to form a coating film, and then modifying the coating film by irradiation with active energy rays. Formed.

  In the polysilazane modified layer, a region in which the modification of polysilazane has progressed further is formed on the surface, and a region with a small amount of modification or an unmodified region is formed below this region. In the present invention, the polysilazane modified layer includes the region with a small amount of modification and the unmodified region.

Polysilazane is a polymer having a silicon-nitrogen bond, and a ceramic precursor such as SiO ₂ , Si ₃ N ₄ having a bond such as Si—N, Si—H, or N—H, or an intermediate solid solution SiO _x N _y thereof. Body inorganic polymer.

  Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . In this case, R ₁ , R ₂ and R ₃ may be the same or different.

  Here, as an alkyl group, a C1-C8 linear, branched or cyclic alkyl group is mentioned. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

  Moreover, as an aryl group, a C6-C30 aryl group is mentioned. Specifically, non-condensed hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group and pentarenyl group, indenyl group, naphthyl group, azulenyl group, heptaenyl group, biphenylenyl group, fluorenyl group, acenaphthylenyl group, preadenenyl group, Examples include condensed polycyclic hydrocarbon groups such as acenaphthenyl group, phenalenyl group, phenanthryl group, anthryl group, fluoranthenyl group, acephenanthrenyl group, aceantrirenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, etc. It is done.

  Examples of the (trialkoxysilyl) alkyl group include an alkyl group having 1 to 8 carbon atoms having a silyl group substituted with an alkoxy group having 1 to 8 carbon atoms. Specific examples include 3- (triethoxysilyl) propyl group and 3- (trimethoxysilyl) propyl group.

The substituent optionally present in R _{1 to} R ₃ is not particularly limited. For example, an alkyl group, a halogen atom, a hydroxy group (—OH), a mercapto group (—SH), a cyano group (—CN), There are a sulfo group (—SO ₃ H), a carboxy group (—COOH), a nitro group (—NO ₂ ), and the like. In addition, the substituent which exists depending on the case does not become the same as R < ₁ > -R < ₃ > to substitute. For example, when R _{1 to} R ₃ are alkyl groups, they are not further substituted with an alkyl group. Of these, R ₁ , R ₂ and R ₃ are preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a vinyl group, 3 -(Triethoxysilyl) propyl group or 3- (trimethoxysilylpropyl) group.

  Moreover, in the said general formula (I), n is an integer, and it is preferable to determine so that the polysilazane which has a structure represented by general formula (I) may have a number average molecular weight of 150-150,000 g / mol.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  The polysilazane preferably has a structure represented by the following general formula (II).

In the general formula (II), R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R ₁ ′, R ₂ ′, R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ may be the same or different. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group has the same definition as in the general formula (I), and thus the description thereof is omitted.

  In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred. Note that n ′ and p may be the same or different.

Of the polysilazanes of the above general formula (II), R ₁ ′, R ₃ ′ and R ₆ ′ each represent a hydrogen atom, and R ₂ ′, R ₄ ′ and R ₅ ′ each represent a methyl group, R ₁ ′, R ₃ ′ and R ₆ ′ each represent a hydrogen atom, R ₂ ′ and R ₄ ′ each represent a methyl group, and R ₅ ′ represents a vinyl group, or R ₁ ′, R ₃ ′ and R ₄ A compound in which 'and R ₆ ' each represents a hydrogen atom and R ₂ 'and R ₅ ' each represents a methyl group is preferred.

The polysilazane preferably has a structure represented by the following general formula (III).

In the general formula (III), R ₁ ″, R ₂ ″, R ₃ ″, R ₄ ″, R ₅ ″, R ₆ ″, R
₇ ″, R ₈ ″ and R ₉ ″ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. In this case, R ₁ ″, R ₂ ″, R ₃ ″, R ₄ ″, R ₅ ″, R ₆ ″, R ₇ ″, R ₈ ″ and R ₉ ″ may be the same or different. Good. The substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group has the same definition as in the general formula (I), and thus the description thereof is omitted.

  In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. Preferably, it is defined. N ″, p ″, and q may be the same or different.

Of the polysilazanes of the general formula (III), R ₁ ″, R ₃ ″ and R ₆ ″ each represent a hydrogen atom, and R ₂ ″, R ₄ ″, R ₅ ″ and R ₈ ″ each represent a methyl group. , R ₉ ″ represents a (triethoxysilyl) propyl group, and R ₇ ″ represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has an alkyl group such as a methyl group, whereby adhesion to an adjacent layer is improved. Furthermore, toughness can be imparted to the ceramic film made of hard and brittle polysilazane. For this reason, there is an advantage that generation of cracks can be suppressed even when the (average) thickness is increased. For this reason, perhydropolysilazane and organopolysilazane may be selected as appropriate according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. The molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a coating liquid for forming a polysilazane modified layer. As a commercial item of polysilazane solution, AZ Electronic Materials Co., Ltd. Aquamica (registered trademark) NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110 NP140, SP140 and the like.

  Other examples of the polysilazane that can be used are not particularly limited. For example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827), or a glycidol obtained by reacting glycidol. Addition polysilazane (JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting metal carboxylate (special Kaihei 6-299118), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (JP-A-6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles ( Of No. 7-196986 JP) or the like, and a polysilazane ceramic at low temperatures.

  When polysilazane is used, the content of polysilazane in the polysilazane modified layer before the modification treatment can be 100% by mass when the total mass of the polysilazane modified layer is 100% by mass. Moreover, when the polysilazane modified layer contains other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more and 95% by mass or less. More preferably, it is 70 to 95 mass% especially preferably.

  The formation method by the coating method of the polysilazane modified layer is not particularly limited, and a known method can be applied, but a polysilazane modified layer forming coating solution containing polysilazane and, if necessary, a catalyst in an organic solvent is known wet. A method of applying a modification treatment after applying and removing the solvent by evaporation is preferable.

(Coating liquid for forming polysilazane modified layer)
The solvent for preparing the coating liquid for forming a polysilazane modified layer is not particularly limited as long as it can dissolve polysilazane. An organic solvent that does not contain water and reactive groups (for example, a hydroxy group or an amine group) that easily react with polysilazane and is inert to polysilazane is preferable. In particular, an aprotic organic solvent is more preferable.

  Specifically, as the solvent, aprotic solvents, for example, hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, turben, etc. Solvents, halogen hydrocarbon solvents such as methylene chloride and trichloroethane, esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran, and alicyclic Ethers such as ether (for example, tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes)) and the like can be mentioned.

  These solvents are selected according to purposes such as the solubility of the silicon compound and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the coating liquid for forming a polysilazane modified layer is not particularly limited, and varies depending on the thickness of the layer and the pot life of the coating liquid, but is preferably in the range of 1 to 80% by mass, more preferably 5 to 50. It is in the range of 10% by mass, particularly preferably in the range of 10-40% by mass.

  The coating liquid for forming a polysilazane modified layer preferably contains a catalyst in order to promote the modification. Examples of applicable catalysts include N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ′, N′-tetramethyl- 1,3-diaminopropane, amine compounds such as N, N, N ′, N′-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, Pd compounds such as propionic acid Pd, Rh acetyl Metal catalysts such as Rh compounds such as acetonate, N-heterocyclic compounds, pyridine compounds such as pyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, DBU (1,8- Diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3 0] -5-nonene), acetic acid, propionic acid, butyric acid, valeric acid, maleic acid, organic acids such as stearic acid, hydrochloric acid, nitric acid, and sulfuric acid, and inorganic acids such as hydrogen peroxide. Among these, it is preferable to use an amine compound. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on polysilazane. By setting the addition amount of the catalyst within this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  Additives listed below can be used in the polysilazane modified layer forming coating solution as required. For example, cellulose ethers, cellulose esters (eg, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc.), natural resins (eg, rubber, rosin resin, etc.), synthetic resins (eg, polymerized resin, etc.), condensation Resins (eg aminoplasts, in particular urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyesters or modified polyesters, epoxides, polyisocyanates or blocked polyisocyanates or polysiloxanes, etc.).

(Method of applying a coating liquid for forming a polysilazane modified layer)
As a method of applying the polysilazane modified layer forming coating solution, a conventionally known appropriate wet coating method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method.

  The coating thickness can be appropriately set according to the purpose. For example, the coating thickness per polysilazane modified layer is preferably about 10 nm to 10 μm after drying, more preferably 15 nm to 1 μm, and even more preferably 20 to 500 nm. . If the thickness is 10 nm or more, sufficient gas barrier properties can be obtained, and if it is 10 μm or less, stable coating properties can be obtained at the time of layer formation, and high light transmittance can be realized.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable polysilazane modified layer can be formed. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used, the drying temperature is preferably set to 150 ° C. or less in consideration of deformation of the substrate due to heat. The temperature is set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set to 30 minutes or less. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  The coating film obtained by applying the coating liquid for forming the polysilazane modified layer may include a step of removing moisture before or during the modification treatment. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies with temperature, the relationship between temperature and humidity shows a preferred form by defining the dew point temperature.

  A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. (temperature 25 ° C./humidity 10%) or lower, and the maintained time is the thickness of the polysilazane modified layer. It is preferable to set as appropriate. Under the condition where the thickness of the polysilazane modified layer is 1.0 μm or less, it is preferable that the dew point temperature is −5 ° C. or less and the maintaining time is 1 minute or more.

  The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. From the viewpoint of promoting the dehydration reaction of the polysilazane modified layer converted to silanol by removing water before or during the modification treatment.

(Modification treatment of polysilazane coating film formed by coating method)
The modification treatment of the polysilazane coating film formed by the coating method refers to a conversion reaction of polysilazane to silicon oxide or silicon oxynitride. Specifically, this is a treatment for modifying the polysilazane coating film into an inorganic layer capable of exhibiting gas barrier properties.

  The conversion reaction of polysilazane to silicon oxide or silicon oxynitride can be applied by appropriately selecting a known method. As the modification treatment, from the viewpoint of adapting to the resin base material, a plasma treatment capable of a conversion reaction at a lower temperature or a conversion reaction by ultraviolet irradiation treatment is preferable.

(Plasma treatment)
As the plasma treatment that can be used as the modification treatment, a known method can be used, and an atmospheric pressure plasma treatment or the like can be preferably used.

  The atmospheric pressure plasma CVD method for performing plasma CVD processing near atmospheric pressure does not need to be reduced in pressure and has higher productivity than the plasma CVD method under vacuum. In addition, since the plasma density is high, the deposition rate is high. Furthermore, compared with the conditions of normal CVD, under a high pressure condition of atmospheric pressure, the mean free path of gas is very short, so that a very homogeneous film can be obtained.

  In the case of atmospheric pressure plasma treatment, as the discharge gas, nitrogen gas or a gas containing Group 18 atoms in the long-period periodic table, specifically helium, neon, argon, krypton, xenon, radon, or the like is used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of its low cost.

(UV irradiation treatment)
As a method for the modification treatment, treatment by ultraviolet irradiation is preferable. Since ozone and active oxygen atoms generated by ultraviolet rays (synonymous with ultraviolet rays) have high oxidation ability, it is possible to form silicon oxide films and silicon oxynitride films having high density and insulating properties at low temperatures. Is possible.

By this ultraviolet irradiation, adjacent layers are heated, and O ₂ and H ₂ O contributing to ceramicization (silica conversion), an ultraviolet absorber, and polysilazane itself are excited and activated. For this reason, polysilazane is excited and the ceramicization of polysilazane is promoted. Also. The resulting polysilazane modified layer becomes denser. The ultraviolet irradiation may be performed at any time after the formation of the coating film.

  In the ultraviolet irradiation treatment, any commonly used ultraviolet ray generator can be used.

  The ultraviolet rays are generally electromagnetic waves having a wavelength of 10 to 400 nm, but in the present invention, ultraviolet rays of 210 to 375 nm are used in the case of ultraviolet irradiation treatment other than the vacuum ultraviolet ray (10 to 200 nm) treatment described later. It is preferable.

  In the irradiation with ultraviolet rays, it is preferable to set the irradiation intensity and the irradiation time within a range in which the adjacent layer carrying the polysilazane modified layer to be irradiated is not damaged.

In the case where a resin film is used as a substrate as in the present invention, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to It is preferable to set the distance between the substrate and the ultraviolet irradiation lamp so as to be 200 mW / cm ² and to perform irradiation for 0.1 second to 10 minutes.

  In general, when the substrate temperature during ultraviolet irradiation treatment is 150 ° C. or more, in the case of a resin film or the like, the properties of the substrate are impaired, for example, the substrate is deformed or its strength is deteriorated. Become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Accordingly, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and it can be appropriately set by those skilled in the art depending on the type of substrate. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air | atmosphere.

  Examples of such ultraviolet ray generating means include metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, and excimer lamps (single wavelengths of 172 nm, 222 nm, and 308 nm, for example, USHIO INC. Manufactured by M.D. Com Co., Ltd.), UV light laser, and the like, but are not particularly limited. In addition, when irradiating the polysilazane modified layer with the generated ultraviolet light, from the viewpoint of achieving improved efficiency and uniform irradiation, the ultraviolet light from the source is reflected by the reflector and then applied to the polysilazane modified layer. Is preferred.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, a laminate having a polysilazane modified layer on the surface can be processed in an ultraviolet baking furnace equipped with the above-described ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used.

  Moreover, when the laminated body which has a polysilazane modified layer on the surface is a long film form, it ceramicizes by irradiating an ultraviolet-ray continuously in the drying zone provided with the said ultraviolet-ray generation source, conveying this. be able to. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate used and the polysilazane modified layer.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
In the polysilazane modified layer, the most preferable modification treatment method is treatment by vacuum ultraviolet irradiation (excimer irradiation treatment). The treatment by vacuum ultraviolet irradiation uses light energy having a wavelength of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound. By using light energy of this wavelength, the oxidation reaction by active oxygen or ozone can proceed while the atomic bond is directly cut by the action of only a photon called a photon process. For this reason, the silicon oxide film can be formed at a relatively low temperature (about 200 ° C. or less). In addition, when performing an excimer irradiation process, it is preferable to use heat processing together as mentioned above, and the detail of the heat processing conditions in that case is as above-mentioned.

  The radiation source may be any light source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator having a maximum emission at about 172 nm (eg, Xe excimer lamp), and a low-pressure mercury vapor having an emission line at about 185 nm. Lamps, and medium and high pressure mercury vapor lamps with wavelength components of 230 nm or less, and excimer lamps with maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the target object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is necessary for the reaction at the time of ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process is likely to decrease. It is preferable to carry out in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20000 ppm by volume, more preferably 50 to 10,000 ppm by volume. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, preferably the intensity of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is a ^{1mW / cm 2 ~10W / cm 2} , more preferably 30~200mW / cm ^2, 50 More preferably, it is ˜160 mW / cm ² . By being 1 mW / cm ² or more, the reforming efficiency can be maintained, and by being 10 W / cm ² or less, vacuum ultraviolet rays are irradiated without causing ablation of the coating film or damaging the substrate. can do.

It irradiation energy amount of the VUV in the coated surface (irradiation amount) is preferably from 10 to 10000 mJ / cm ^2, more preferably 100~8000mJ / cm ^2, a 200~6000mJ / cm ² Is more preferable. When it is 10 mJ / cm ² or more, a sufficiently modified layer can be obtained, and when it is 10000 mJ / cm ² or less, cracking due to over-reformation and thermal deformation of the substrate are suppressed. Can do.

Further, the vacuum ultraviolet light used for the modification may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ .

Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), a carbon-containing gas may be used alone, but rare gas or H ₂ is used as a main gas. It is also preferable to add a small amount of carbon-containing gas. Examples of plasma generation methods include capacitively coupled plasma.

  The film composition constituting the polysilazane modified layer can be measured by measuring the atomic composition ratio using an XPS surface analyzer. It is also possible to cut the polysilazane modified layer and measure the atomic composition ratio of the cut surface with an XPS surface analyzer.

Moreover, the film density which comprises a polysilazane modified layer can be set appropriately according to the objective. For example, it is preferably in the range of 1.5 to 2.6 g / cm ³ . By being in this range, it is possible to improve the denseness of the film and gas barrier properties, and to suppress oxidative deterioration of the film due to humidity.

  The polysilazane modified layer may be a single layer or a laminated structure of two or more layers.

[2.2.2] Gas barrier layer containing silicon, carbon and oxygen The gas barrier layer preferably used in the present invention contains silicon (Si), carbon (C) and oxygen (O), and is contained in the gas barrier layer. The element ratio of silicon, carbon, and oxygen has, for example, a continuous composition change from the surface toward the thickness direction. Furthermore, the composition distribution of the silicon, carbon, and oxygen has an extreme value in a continuous composition change in the thickness direction of the gas barrier layer. That is, the gas barrier layer has a laminated structure including a plurality of layers having different silicon, carbon, and oxygen content rates.

The gas barrier layer having such a composition has a water vapor permeability (25 ± 0.5 ° C., relative humidity 90 ± 2% RH) measured by a method according to JIS K 7129-1992, 1 × 10 ⁻² g. / M ² · 24h or less is preferable. Further, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and the water vapor permeability is 1 × 10 ⁻⁵ g / m ² · 24 h or less. It is preferable that

  The thickness of the gas barrier layer is preferably 1000 nm or less, more preferably in the range of 50 to 500 nm, and more preferably in the range of 100 to 300 nm from the viewpoints of flex resistance and gas barrier properties. Further preferred.

  The method for forming the gas barrier layer is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used. In particular, the plasma CVD method described in JP2012-96531A can be preferably used.

(Gas barrier layer: composition)
The gas barrier layer is characterized by a distribution curve of each element showing the relationship between the distance from the surface of the gas barrier layer in the layer thickness direction and the ratio of atomic weight of silicon, oxygen and carbon (atomic ratio) contained. doing.

  The atomic ratio of silicon, oxygen, and carbon is represented by the ratio [(Si, O, C) / (Si + O + C)] of silicon, oxygen, or carbon to the total amount of each element of silicon, oxygen, and carbon.

  The silicon distribution curve, oxygen distribution curve and carbon distribution curve indicate the atomic ratio of silicon, oxygen or carbon at a distance from the surface of the gas barrier layer.

The gas barrier layer preferably contains nitrogen in addition to silicon, oxygen and carbon. This is because the refractive index of the gas barrier layer can be controlled by containing nitrogen. For example, the refractive index of SiO ₂ is 1.5, whereas the refractive index of SiN is about 1.8 to 2.0. For this reason, it becomes possible to make the value of a refractive index into 1.6-1.8, for example by containing nitrogen in a gas barrier layer and forming SiON (silicon oxynitride) in a gas barrier layer. . Thus, it is possible to control the refractive index of the gas barrier layer by adjusting the nitrogen content.

  When nitrogen is contained in the gas barrier layer, the distribution curve of each element (silicon, oxygen, carbon and nitrogen) constituting the gas barrier layer is such that the atomic ratio of silicon, oxygen, carbon or nitrogen is silicon, oxygen, carbon and It is represented by the ratio [(Si, O, C, N) / (Si + O + C + N)] of silicon, oxygen, carbon or nitrogen with respect to the total amount of each element of nitrogen.

  The silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve indicate the atomic ratio of silicon, the atomic ratio of oxygen, the atomic ratio of carbon, and the atomic ratio of nitrogen at a distance from the surface of the gas barrier layer.

(Relationship between element distribution curve and refractive index distribution)
The refractive index distribution of the gas barrier layer can be controlled by the amount of carbon and the amount of oxygen in the thickness direction of the gas barrier layer.

  FIG. 6 shows an example of a distribution curve of elements constituting the gas barrier layer according to the present invention, an example of a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve of the gas barrier layer. Further, FIG. 7 shows an enlarged view of the range of the atomic ratio of the carbon distribution curve from 0 to 40 at% from the silicon distribution curve, oxygen distribution curve, carbon distribution curve and nitrogen distribution curve shown in FIG.

  6 and 7, the horizontal axis indicates the distance [nm] from the surface of the gas barrier layer in the layer thickness direction. The vertical axis indicates the atomic ratio [at%] of silicon, oxygen, carbon, or nitrogen with respect to the total amount of each element of silicon, oxygen, and carbon.

  As shown in FIG. 6, the atomic ratio of silicon, oxygen, carbon, and nitrogen changes depending on the distance from the surface of the gas barrier layer. In particular, for oxygen and carbon, the atomic ratio varies greatly depending on the distance from the surface of the gas barrier layer, and each distribution curve has a plurality of extreme values. In addition, the oxygen distribution curve and the carbon distribution curve are in a correlation, and the oxygen atomic ratio decreases at a distance where the carbon atomic ratio is large, and the oxygen atomic ratio increases at a distance where the carbon atomic ratio is small.

  FIG. 8 shows a refractive index distribution curve of the gas barrier layer. In FIG. 8, the horizontal axis represents the distance [nm] from the surface of the gas barrier layer in the layer thickness direction. The vertical axis represents the refractive index of the gas barrier layer.

  The refractive index of the gas barrier layer shown in FIG. 8 is a measured value of the distance from the surface of the gas barrier layer in the layer thickness direction and the refractive index of the gas barrier layer to visible light at this distance. The refractive index distribution of the gas barrier layer can be measured by a known method, for example, using a spectroscopic ellipsometer (ELC-300 manufactured by JASCO Corporation).

  As shown in FIGS. 7 and 8, there is a correlation between the atomic ratio of carbon and the refractive index of the gas barrier layer. Specifically, in the gas barrier layer, the refractive index of the gas barrier layer also increases at the position where the atomic ratio of carbon increases.

  Thus, the refractive index of the gas barrier layer changes according to the atomic ratio of carbon. That is, in the gas barrier layer, the refractive index distribution curve of the gas barrier layer can be controlled by adjusting the distribution of the atomic ratio of carbon in the layer thickness direction.

  In addition, since the atomic ratio of carbon and the atomic ratio of oxygen are correlated as described above, the refractive index distribution curve of the gas barrier layer can be controlled by controlling the atomic ratio of oxygen and the distribution curve. Can do.

  By providing a gas barrier layer having an extreme value in the refractive index distribution, for example, reflection and interference occurring at the interface of the base material of the organic EL element can be suppressed. For this reason, the light which permeate | transmits an organic EL element can come out, without receiving the influence of total reflection or interference by the effect | action of a gas barrier layer. Therefore, the light quantity is not reduced, and the patterning efficiency of the organic EL element and the light extraction efficiency can be improved.

  In addition, when a metal transparent conductive layer made of silver or the like is used as the first electrode, light that passes through the organic EL element is reflected or interfered with at the first electrode, and a large viewing angle dependency problem is likely to occur. . This is thought to be due to the aggregation of the metal in the metal transparent conductive layer or the reflection of a specific wavelength region at the metal transparent conductive layer or its interface to interfere with the emission spectrum, and the emission spectrum changes to show viewing angle dependence. ing.

  Therefore, the viewing angle dependency can be suppressed by adjusting the refractive index distribution of the gas barrier layer so as not to interfere with a specific wavelength of the emitted light. The refractive index distribution of the gas barrier layer can be controlled by the atomic ratio of carbon. For this reason, arbitrary optical characteristics can be imparted to the gas barrier layer by controlling the carbon distribution curve.

  In the organic EL device according to the present invention, the gas barrier layer has one or more extreme values in the refractive index distribution curve, whereby the emission spectrum can be controlled to adjust the color gamut. For this reason, it is possible to disperse the interference conditions of the organic EL element and to prevent interference at a specific wavelength. Therefore, the light distribution property of the light transmitted through the organic EL element can be controlled by the gas barrier layer, and the viewing angle dependency of the emission spectrum can be eliminated, and the uniform light distribution property of the organic EL element can be realized.

(Conditions for each element's distribution curve)
In the gas barrier layer, the atomic ratio of silicon, oxygen and carbon or the distribution curve of each element preferably satisfies the following conditions (i) to (iii).
(I) In a region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the thickness of the gas barrier layer, the following formula (1):
(Atomic ratio of oxygen)> (Atomic ratio of silicon)> (Atomic ratio of carbon) (1)
The condition represented by is satisfied.

Alternatively, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the thickness of the gas barrier layer, the following formula (2):
(Atomic ratio of carbon)> (Atomic ratio of silicon)> (Atomic ratio of oxygen) (2)
The condition represented by is satisfied.
(Ii) The carbon distribution curve has at least one local maximum and local minimum.
(Iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

  The organic EL device according to the present invention preferably includes a gas barrier layer that satisfies at least one of the above conditions (i) to (iii). In particular, it is more preferable to provide a gas barrier layer that satisfies all of the above conditions (i) to (iii).

  Further, two or more gas barrier layers satisfying all the above conditions (i) to (iii) may be provided. When two or more gas barrier layers are provided, the materials of the plurality of thin film layers may be the same or different.

As described above, the refractive index of the gas barrier layer can be controlled by the atomic ratio of silicon, carbon, and oxygen contained in the gas barrier layer. Therefore, the above conditions (i) to (iii)
Thus, the refractive index of the gas barrier layer can be adjusted to a preferred range.

(Carbon distribution curve)
The gas barrier layer preferably has a carbon distribution curve having at least one extreme value. In such a gas barrier layer, the carbon distribution curve more preferably has at least two extreme values, and particularly preferably has at least three extreme values. Furthermore, it is preferable that the carbon distribution curve has at least one maximum value and one minimum value.

  When the carbon distribution curve has extreme values, the light distribution of the obtained gas barrier layer can be improved. For this reason, the angle dependency of the light of the organic EL element obtained through the first electrode can be eliminated.

  When the gas barrier layer has three or more extreme values, one extreme value of the carbon distribution curve and another extreme value adjacent to the extreme value are the layers from the surface of the gas barrier layer. The difference in the distance in the thickness direction is preferably 200 nm or less, and more preferably 100 nm or less from the viewpoint of improving light distribution and relieving stress in the gas barrier layer.

(Extreme value)
In the gas barrier layer, the extreme value of the distribution curve is the maximum or minimum value of the atomic ratio of the element to the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer, or the refractive index distribution corresponding to that value. It is a measured value of the curve.

  In the gas barrier layer, the maximum value of the distribution curve of each element is a point where the value of the atomic ratio of the element changes from increasing to decreasing when the distance from the surface of the gas barrier layer is changed. In addition, from this point, the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer is further changed by 20 nm is reduced by 3 at% or more.

  On the other hand, in the gas barrier layer, the minimum value of the distribution curve of each element is that the value of the atomic ratio of the element changes from decrease to increase when the distance from the surface of the gas barrier layer is changed. In addition, from this point, the value of the atomic ratio of the element at a position where the distance from the surface of the gas barrier layer is further changed by 20 nm is increased by 3 at% or more.

  In the carbon distribution curve of the gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is preferably 5 at% or more. In such a gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and further preferably 7 at% or more. By setting the difference between the maximum value and the minimum value of the atomic ratio of carbon within the above range, the refractive index difference in the refractive index distribution curve of the obtained gas barrier layer is increased, and the light distribution can be further improved.

  There is a correlation between the amount of carbon distribution and the refractive index, and when the absolute value of the maximum value and the minimum value of the preferable carbon atom is 7 at% or more, the absolute value of the difference between the maximum value and the minimum value of the obtained refractive index is It is known to be 0.2 or more.

(Oxygen distribution curve)
The gas barrier layer preferably has an oxygen distribution curve having at least one extreme value. In particular, the gas barrier layer preferably has an oxygen distribution curve having at least two extreme values, and more preferably has at least three extreme values. Furthermore, it is preferable that the oxygen distribution curve has at least one maximum value and one minimum value because higher light distribution can be obtained from the refractive index distribution curve of the obtained gas barrier layer.
(Silicon distribution curve)
In the silicon distribution curve, the gas barrier layer preferably has an absolute value of a difference between the maximum value and the minimum value of the atomic ratio of silicon being less than 5 at%. In such a gas barrier layer, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of silicon is more preferably less than 4 at%, and further preferably less than 3 at%. When the difference between the maximum value and the minimum value of the atomic ratio of silicon is less than the above range, higher light distribution can be obtained from the refractive index distribution curve of the obtained gas barrier layer.

(XPS depth profile)
The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, the oxygen carbon distribution curve and the nitrogen distribution curve described above are used in combination with X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon. By doing so, it can be created by so-called XPS depth profile measurement in which surface composition analysis is sequentially performed while exposing the inside of the sample.

  A distribution curve obtained by XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio (unit: at%) of each element and the horizontal axis as the etching time (sputtering time).

  In the element distribution curve with the horizontal axis as the etching time, the etching time generally correlates with the distance from the surface in the layer thickness direction of the gas barrier layer. For this reason, when measuring the XPS depth profile, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time is adopted as the “distance from the surface of the gas barrier layer in the layer thickness direction”. be able to.

For XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and an etching rate (etching rate) is set to 0.05 nm / sec (SiO ₂ thermal oxide film equivalent value). It is preferable to do.

  In addition, the gas barrier layer is substantially uniform in the film surface direction (direction parallel to the surface of the gas barrier layer) from the viewpoint of forming a layer that is uniform over the entire film surface and has excellent light distribution. It is preferable that they are uniform. The fact that the gas barrier layer is substantially uniform in the film surface direction means that the number of extreme values of the distribution curves of the elements at the respective measurement points is the same at any two locations on the film surface of the gas barrier layer, And the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the distribution curve is the same as each other, or the difference between the maximum value and the minimum value is within 5 at%.

(Silicon atom ratio, oxygen atom ratio, carbon atom ratio)
In the silicon distribution curve, oxygen distribution curve, and carbon distribution curve, in the region where the atomic ratio of silicon, the atomic ratio of oxygen, and the atomic ratio of carbon are 90% or more of the layer thickness of the gas barrier layer, It is preferable to satisfy the conditions represented. In this case, the atomic ratio of the silicon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 25 to 45 at%, and preferably 30 to 40 at%. Is more preferable from the viewpoint of improving gas barrier properties.

  The atomic ratio of the oxygen atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 33 to 67 at%, and is preferably 45 to 67 at%. It is more preferable from the viewpoint of improving barrier properties and translucency.

  Further, the atomic ratio of the carbon atom content to the total amount of silicon atoms, oxygen atoms and carbon atoms in the gas barrier layer is preferably 3 to 33 at%, and 3 to 25 at%. It is more preferable from the viewpoint of improving barrier properties and translucency.

(Gas barrier layer manufacturing apparatus and manufacturing method)
FIG. 9 is a schematic view showing an example of a production apparatus that can be suitably used for producing the gas barrier film according to the present invention.

  The manufacturing apparatus shown in FIG. 9 includes a delivery roller 31, transport rollers 32, 33, 34, and 35, film formation rollers 36 and 37, a gas supply pipe 38, a plasma generation power source 39, a film formation roller 36, and 37, magnetic field generators 41 and 42 installed inside 37, and a take-up roller 43 are provided. In such a manufacturing apparatus, a vacuum chamber in which at least film forming rollers 36 and 37, a gas supply pipe 38, a plasma generating power source 39, and magnetic field generators 41 and 42 made of permanent magnets are not shown. Is placed inside. Further, in such a manufacturing apparatus, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a plasma generation power source so that a pair of film-forming rollers (film-forming roller 36 and film-forming roller 37) can function as a pair of counter electrodes. 39. Therefore, in such a manufacturing apparatus, it is possible to discharge to the space between the film formation roller 36 and the film formation roller 37 by supplying electric power from the power source 39 for plasma generation. Plasma can be generated in the space between the roller 36 and the film forming roller 37. In this way, when the film forming roller 36 and the film forming roller 37 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 36 and 37) so that the central axis may become substantially parallel on the same plane. By arranging a pair of film forming rollers (film forming rollers 36 and 37) in this way, the film forming rate can be doubled and a film having the same structure can be formed. Can be at least doubled.

  Further, inside the film forming roller 36 and the film forming roller 37, magnetic field generators 41 and 42 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  Further, as the film forming roller 36 and the film forming roller 37, known rollers can be appropriately used. As such film forming rollers 36 and 37, it is preferable to use ones having the same diameter from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 36 and 37 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. When the diameter is larger than 300 mmφ, the plasma discharge space is not reduced, productivity is not deteriorated, and the total amount of heat of the plasma discharge can be prevented from being applied to the film in a short time. On the other hand, it is preferable that the diameter is smaller than 1000 mmφ because practicality can be maintained in terms of device design including uniformity of plasma discharge space.

  Moreover, a well-known roller can be used suitably as the sending-out roller 31 and the conveyance rollers 32, 33, 34, and 35 used for such a manufacturing apparatus. Further, the winding roller 43 is not particularly limited as long as it can wind the resin base material on which the gas barrier layer is formed, and a known roller can be appropriately used.

  As the gas supply pipe 38, a pipe capable of supplying or discharging a raw material gas at a predetermined speed can be used as appropriate. Further, as the plasma generating power source 39, a known power source for a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 39 supplies power to the film forming roller 36 and the film forming roller 37 connected thereto, and makes it possible to use these as counter electrodes for discharge. As such a plasma generation power source 39, since the plasma CVD method can be carried out more efficiently, it is possible to alternately reverse the polarity of the pair of film forming rollers (AC power source etc. ) Is preferably used. In addition, as such a plasma generating power source 39, it is possible to more efficiently perform the plasma CVD method, so that the applied power can be in the range of 100 W to 10 kW and the AC frequency is 50 Hz to It is more preferable that the frequency range is 500 kHz. As the magnetic field generators 41 and 42, known magnetic field generators can be used as appropriate.

  Using such a manufacturing apparatus shown in FIG. 9, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the transport speed of the resin substrate are determined. By appropriately adjusting, the gas barrier film according to the present invention can be produced. That is, using the manufacturing apparatus shown in FIG. 9, a plasma discharge is generated between a pair of film forming rollers (film forming rollers 36 and 37) while supplying a film forming gas (such as a source gas) into the vacuum chamber. As a result, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is plasma formed on the surface of the resin base material on the film forming roller 36 and on the surface of the resin base material on the film forming roller 37. It is formed by the CVD method. In such film formation, the resin base material is transported by the delivery roller 31 and the film formation roller 36, respectively, so that the surface of the resin base material is formed by a roll-to-roll continuous film formation process. The gas barrier layer is formed.

<Raw gas>
The source gas in the film forming gas used for forming the gas barrier layer according to the present invention can be appropriately selected and used depending on the material of the gas barrier layer to be formed. As such a source gas, for example, an organosilicon compound containing silicon is preferably used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethyl Examples thereof include silane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as gas barrier properties of the obtained gas barrier layer and handling in film formation. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types.

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

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

  When such a film-forming gas contains a source gas and a reactive gas, the ratio of the source gas and the reactive gas is the reaction gas that is theoretically necessary for completely reacting the source gas and the reactive gas. It is preferable not to make the ratio of the reaction gas excessive rather than the ratio of the amount. If the ratio of the reaction gas is excessive, it is difficult to obtain the gas barrier layer according to the present invention. Therefore, in order to obtain the desired performance as a gas barrier film, when the film-forming gas contains the organosilicon compound and oxygen, the total amount of the organosilicon compound in the film-forming gas is reduced. It is preferable that the amount be less than the theoretical oxygen amount necessary for complete oxidation.

As typical examples, hexamethyldisiloxane (organosilicon compound: HMDSO: (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas will be described below.

A film-forming gas containing hexamethyldisiloxane (HMDSO, (CH ₃ ) ₆ Si ₂ O) as a source gas and oxygen (O ₂ ) as a reaction gas is reacted by a plasma CVD method to form a silicon-oxygen system In the case of producing a thin film of the following reaction formula (1):
(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ (1)
The reaction shown by follows occurs to produce silicon dioxide. In such a reaction, the amount of oxygen required to completely oxidize 1 mol of hexamethyldisiloxane is 12 mol. Therefore, when the film forming gas contains 12 moles or more of oxygen with respect to 1 mole of hexamethyldisiloxane and is completely reacted, a uniform silicon dioxide film is formed. The ratio is controlled to a flow rate equal to or less than the raw material ratio of the complete reaction, which is the theoretical ratio, and the incomplete reaction is performed. That is, the amount of oxygen must be less than the stoichiometric ratio of 12 moles per mole of hexamethyldisiloxane.

  Note that in the actual reaction in the plasma CVD chamber, the raw material hexamethyldisiloxane and the reaction gas oxygen are supplied from the gas supply unit to the film formation region to form a film, so the molar amount of oxygen in the reaction gas ( Even if the flow rate is 12 times the molar amount (flow rate) of hexamethyldisiloxane as the raw material, the reaction cannot actually proceed completely. It is considered that the reaction is completed only when a large excess is supplied as compared with the stoichiometric ratio (for example, in order to obtain silicon oxide by complete oxidation by the CVD method, the molar amount (flow rate) of oxygen is changed to the hexamethyldioxide raw material. (It may be about 20 times or more the molar amount (flow rate) of siloxane.) Therefore, the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of the raw material hexamethyldisiloxane is preferably an amount of 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio. . By containing hexamethyldisiloxane and oxygen in such a ratio, carbon atoms and hydrogen atoms in hexamethyldisiloxane that have not been completely oxidized are taken into the gas barrier layer to form a desired gas barrier layer. This makes it possible to exhibit excellent barrier properties and flex resistance in the resulting gas barrier film. If the molar amount (flow rate) of oxygen with respect to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is too small, unoxidized carbon atoms and hydrogen atoms are excessively taken into the gas barrier layer. In this case, the transparency of the barrier film is lowered, and the gas barrier film cannot be used for a flexible substrate for a device requiring transparency such as an organic EL element or an organic thin film solar cell. From such a viewpoint, the lower limit of the molar amount (flow rate) of oxygen relative to the molar amount (flow rate) of hexamethyldisiloxane in the film forming gas is more than 0.1 times the molar amount (flow rate) of hexamethyldisiloxane. Preferably, the amount is more than 0.5 times.

<Degree of vacuum>
Although the pressure (degree of vacuum) in a vacuum chamber can be suitably adjusted according to the kind etc. of source gas, it is preferable to set it as the range of 0.5-100 Pa.

<Roller film formation>
In such a plasma CVD method, in order to discharge between the film forming rollers 36 and 37, an electrode drum connected to a plasma generating power source 39 (in this embodiment, the electrode drums are installed on the film forming rollers 36 and 37). The electric power to be applied can be adjusted as appropriate according to the type of source gas, the pressure in the vacuum chamber, etc., and cannot be generally stated, but may be in the range of 0.1 to 10 kW. preferable. If the applied power is in such a range, no generation of particles is observed, and the amount of heat generated during film formation is within the control. There is no generation of wrinkles during film formation. In addition, the possibility that the resin base material is melted by heat and a large current discharge is generated between the bare film forming rollers to damage the film forming roller itself.

  Although the conveyance speed (line speed) of the resin base material 1 can be suitably adjusted according to the kind of raw material gas, the pressure in a vacuum chamber, etc., it is preferable to set it as the range of 0.25-100 m / min, A range of 0.5 to 20 m / min is more preferable. When the line speed is within the above range, wrinkles due to the heat of the resin base material are hardly generated, and the thickness of the formed gas barrier layer can be sufficiently controlled.

[2.3] High Refractive Index Layer By further providing a functional layer containing an oxide of the following transition metal on the gas barrier layer containing an element such as silica (Si) described above, A composite oxide is formed, which is preferable because it can achieve higher gas barrier properties and an improvement in patterning efficiency to the organic EL device by adjusting the refractive index.

  The transition metal is not particularly limited, and any transition metal can be used alone or in combination. Here, the transition metal refers to a Group 3 element to a Group 11 element in the long-period periodic table, and the transition metal includes Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn Y, Zr, Nb, Mo, Tc, Ru, Pd, Ag, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta , W, Re, Os, Ir, Pt, and Au.

  Among them, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like are listed as transition metals that can provide good gas barrier properties. Among these, Nb, Ta, and V, which are Group 5 elements, are particularly preferable from the results of various investigations because they easily bond to silicon atoms that are non-transition metals contained in the gas barrier layer.

  In particular, when the transition metal is a Group 5 element (particularly Nb) and the non-transition metal described above is Si, a significant gas barrier property improvement effect can be obtained. This is presumably because the bond between Si and the Group 5 element (particularly Nb) is particularly likely to occur. Furthermore, from the viewpoint of optical properties, the transition metal is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

  In that case, it is preferable to adjust the refractive index difference between the gas barrier layer of the first gas barrier film and the functional layer in contact with the gas barrier layer to 1.5 or less.

  As a result of examination, this is due to the following reasons.

When the first gas barrier film is irradiated with ultraviolet rays having an incident angle of 45 ° in the air, the above-mentioned perhydropolysilazane (PHPS: refractive index n ₁ = 1. 62; λ 385 nm measurement), and when a high refractive index layer (niobium oxide Nb ₂ O ₅ , n ₂ = 2.27) is laminated thereon, the average transmittance of P-polarized light and S-polarized light at the interface is Fresnel formula Calculated as 97.1%, and the Fresnel loss was small.

  However, if the Fresnel loss exceeds 10%, the amount of ultraviolet light necessary for deactivation of the organic functional layer decreases, so that it is necessary to extend the integrated light irradiation time, and the tact time and power charge increase.

  FIG. 10 shows the result of calculating the average transmittance of the interface with respect to the difference Δn between the refractive index of the gas barrier layer of the first gas barrier film and the refractive index of the functional layer in contact therewith.

  The ray angle is ultraviolet light having an incident angle of 45 ° in the air and a wavelength of 385 nm. It can be seen that the transmittance decreases as Δn increases. It can be seen that Δn ≦ 1.5 needs to be satisfied because the transmittance at the boundary surface of the gas barrier layer needs to be 90% or more. More preferably, the transmittance at the boundary surface is 95% or more. In this case, Δn ≦ 0.92 is desirable.

  The adjustment of the refractive index can be controlled by the type and content of the material contained in the high refractive index layer.

  The formation of the layer containing the oxide of the transition metal is not particularly limited. For example, a conventionally known vapor deposition method using an existing thin film deposition technique can efficiently form a composite composition region. It is preferable from the viewpoint.

  These vapor phase film forming methods can be used by known methods. The vapor deposition method is not particularly limited, and examples thereof include physical vapor deposition (PVD) methods such as sputtering, vapor deposition, ion plating, and ion assisted vapor deposition, plasma CVD (chemical vapor deposition), and ALD. Examples thereof include a chemical vapor deposition (CVD) method such as an (Atomic Layer Deposition) method. In particular, it is possible to form a film without damaging the functional element, and since it has high productivity, it is preferably formed by a physical vapor deposition (PVD) method, and more preferably formed by a sputtering method. preferable.

  For the film formation by sputtering, bipolar sputtering, magnetron sputtering, dual magnetron sputtering (DMS) using an intermediate frequency region, ion beam sputtering, ECR sputtering, or the like can be used alone or in combination of two or more. The target application method is appropriately selected according to the target type, and either DC (direct current) sputtering or RF (high frequency) sputtering may be used.

  A reactive sputtering method using a transition mode that is intermediate between the metal mode and the oxide mode can also be used. By controlling the sputtering phenomenon so as to be in the transition region, a metal oxide film can be formed at a high film formation speed, which is preferable. As the inert gas used for the process gas, He, Ne, Ar, Kr, Xe, or the like can be used, and Ar is preferably used. Furthermore, by introducing oxygen, nitrogen, carbon dioxide, and carbon monoxide into the process gas, a thin film of a non-transition metal and transition metal composite oxide, nitride oxide, oxycarbide, or the like can be formed. Examples of film formation conditions in the sputtering method include applied power, discharge current, discharge voltage, time, and the like, which can be appropriately selected according to the sputtering apparatus, the material of the film, the layer thickness, and the like.

  The sputtering method may be multi-source co-sputtering using a plurality of sputtering targets including a transition metal (M2) alone or its oxide. Regarding the method for producing these sputtering targets and the method for producing a thin film made of a complex oxide using these sputtering targets, for example, JP 2000-160331 A, JP 2004-068109 A, JP The description of 2013-043761 gazette etc. can be referred suitably. The film forming conditions for carrying out the co-evaporation method include the ratio of the transition metal (M2) and oxygen in the film forming raw material, the ratio of the inert gas to the reactive gas during the film forming, and the film forming process. One or two or more conditions selected from the group consisting of the gas supply amount, the degree of vacuum during film formation, and the power during film formation are exemplified, and these film formation conditions (preferably oxygen content) By adjusting the pressure, a thin film made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the high refractive index layer using the co-evaporation method as described above, most of the formed region in the thickness direction can be made the composite composition region. For this reason, according to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the composite composition region. In addition, what is necessary is just to adjust the film-forming time at the time of implementing a co-evaporation method, for example, in order to control the thickness of a composite composition area | region.

[2.4] Adhesive layer, pressure-sensitive adhesive layer The first gas barrier film and the second gas barrier film according to the present invention are preferably bonded together via an adhesive or a pressure-sensitive adhesive. The agent may form a layer as an adhesive layer or an adhesive layer.

  The adhesive is not particularly limited as long as it is optically transparent and can adhere the first gas barrier film and the second gas barrier film, and a general adhesive can be used. However, among them, a synthetic resin adhesive is preferable.

  Moreover, it is also preferable to use a well-known adhesive as an adhesive based on this invention, and it is preferable that it is a synthetic resin adhesive in that case.

  As the synthetic resin adhesive, for example, a pressure sensitive adhesive, a thermosetting adhesive, and a photocurable adhesive can be used. For example, epoxy resin, acrylic resin, ionomer resin, urethane resin, ethylene vinyl acetate Examples thereof include an adhesive containing a polymerized resin.

  Examples of the synthetic resin adhesive include acrylic adhesive, rubber adhesive, silicone adhesive, and active energy ray-curable adhesive.

  As an acrylic adhesive, what has a (meth) acrylic acid ester type | system | group (co) polymer as a main component is mentioned. Examples of the (meth) acrylic acid ester monomer used when synthesizing the (meth) acrylic acid ester (co) polymer include (meth) acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group. It is done.

  Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. , Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate , Palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.

  As rubber-based adhesives, natural rubber, modified natural rubber-based adhesives obtained by graft polymerization of one or more monomers selected from (meth) acrylic acid alkyl ester, styrene, and (meth) acrylonitrile on natural rubber Agents; rubber-based adhesives made of isoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, urethane rubber, polyisobutylene resin, polybutene resin, and the like. Among these, polyisobutylene resins are preferable.

  Examples of the silicone pressure-sensitive adhesive include those having dimethylsiloxane as a main component.

  As the active energy ray-curable pressure-sensitive adhesive, acrylate oligomers are useful, and polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyol acrylate oligomers, polybutadiene acrylate oligomers, silicone acrylate oligomers, and the like. Can be mentioned.

Moreover, the adhesive marketed as a sheet-like adhesive laminated body can also be used preferably. Such a sheet-like adhesive laminate can be obtained from Mitsui DuPont Polychemical Co., 3M Co., Ajinomoto Co., Tessa Co., etc. In particular, “Nucleel (registered trademark)” manufactured by Mitsui DuPont Polychemical Co., Ltd. , N1214, AN4221C, N1560, N0200H, AN4213C, N035C) and 3M's “3MTM Optically Clear Adhesive”
(As product numbers, 8171, 8172, 8172P, 8171CL, 8172CL, etc.) can be preferably used.

  Moreover, as a commercially available adhesive, for example, SK Dyne series (for example, SK Dyne 2950 as a product number) manufactured by Soken Chemical Co., Ltd. is preferable.

[2.5] Ultraviolet Absorber The second gas barrier film, adhesive layer or pressure-sensitive adhesive layer according to the present invention contains an ultraviolet absorber in order to shield unnecessary ultraviolet rays irradiated to the organic EL element. It is preferable.

  Examples of ultraviolet absorbers include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like, but benzophenone compounds with little coloration. And benzotriazole-based compounds are preferred. In addition, ultraviolet absorbers described in JP-A-10-182621 and JP-A-8-337574 and polymer ultraviolet absorbers described in JP-A-6-148430 are also preferably used.

  The addition amount of the ultraviolet absorber is preferably in the range of 0.1 to 5.0 mass% with respect to the resin, adhesive or pressure-sensitive adhesive of the base material of the second gas barrier film, 0.5 to More preferably, it is in the range of 5.0% by mass.

  Specific examples of the ultraviolet absorber applicable to the present invention include, for example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H- Benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., and tinuvin 109, There are tinuvins such as tinuvin 171, tinuvin 234, tinuvin 326, tinuvin 327, tinuvin 328, and tinuvin 928, all of which are commercially available from BASF Japan, and can be preferably used.

  Moreover, the product by which the ultraviolet absorber is previously kneaded with the PET film used as a base material can also be used (Teijin DuPont UV cut PET film, HB). The organic EL device using the Teijin DuPont UV-cut PET film as the base material of the second gas barrier film had a long life due to small damage to the device due to ultraviolet rays even when exposed to sunlight.

[2.6] Hard Coat Layer It is preferable that a hard coat layer is disposed on the surface of the first gas barrier film according to the present invention opposite to the surface on which the organic EL element is formed. The hard coat layer used in the present invention is provided on the side opposite to the gas barrier layer from the viewpoint of flattening the rough surface of the substrate on which protrusions and the like are present and improving the adhesion when the mask is adhered to the film substrate. It is desirable to provide a clear hard coat layer.

  In addition, there are cases where the first gas barrier film substrate itself contains moisture and the like, and in order to suppress the influence of the moisture on the organic functionality, the gas barrier layer side is arranged on the organic functional layer side. It is preferable to do.

  Examples of the material of the hard coat layer 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, and polyester. Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicone resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples thereof include a thermosetting urethane resin composed of a coat, an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicone resin. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the hard coat layer is not particularly limited, but is preferably formed by a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a dry coating method such as a vapor deposition method.

  In the formation of the hard coat layer, additives such as an antioxidant and a plasticizer can be added to the above-described resin as necessary.

  The thickness of the hard coat layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm, from the viewpoint of improving the heat resistance of the substrate.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less.

[3] Details of Organic EL Element Details of main layers constituting the organic EL element capable of performing the above-described patterning method according to the present invention and a manufacturing method thereof will be described below.

Examples of typical element structures that can be used in the organic EL element according to the present invention include the following structures, but are not limited thereto.
(1) Anode / light emitting layer / cathode (2) Anode / light emitting layer / electron transport layer / cathode (3) Anode / hole transport layer / light emitting layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode ( 7) Anode / hole injection layer / hole transport layer / (electron blocking layer /) luminescent layer / (hole blocking layer /) electron transport layer / electron injection layer / cathode Among the above, the configuration of (7) is preferable. Although used, it is not limited to this.

  An organic EL device comprising the first and second gas barrier films according to the present invention will be described with reference to the drawings.

  FIG. 11 is a schematic view of an organic EL device comprising the first gas barrier film and the second gas barrier film according to the present invention.

  In the structure of the representative element 200 described above, the first electrode 215 is formed on the first gas barrier film 211, and then the organic functional layer 216 having a light emitting property which is a layer excluding the anode and the cathode, and the second An electrode 217 is formed. In the organic EL device according to the present invention, the first electrode 215 or the second electrode 217 constitutes an anode or a cathode, respectively.

  On the 2nd electrode, the sealing member 221 and the sealing layer 222 which seal the whole organic EL element are formed.

  A second gas barrier film 213 is bonded to the surface of the first gas barrier film 211 opposite to the surface on which the organic EL element is formed via an adhesive 212.

<Organic functional layer>
In the above structure, the light emitting layer is formed of a single layer or a plurality of layers. When there are a plurality of light emitting layers, a non-light emitting intermediate layer may be provided between the light emitting layers.

  If necessary, a hole blocking layer (hole blocking layer), an electron injection layer (cathode buffer layer), or the like may be provided between the light emitting layer and the cathode, and between the light emitting layer and the anode. An electron blocking layer (electron barrier layer), a hole injection layer (anode buffer layer), or the like may be provided.

  The electron transport layer is a layer having a function of transporting electrons. The electron transport layer includes an electron injection layer and a hole blocking layer in a broad sense. Further, the electron transport layer may be composed of a plurality of layers.

  The hole transport layer is a layer having a function of transporting holes. The hole transport layer includes a hole injection layer and an electron blocking layer in a broad sense. The hole transport layer may be composed of a plurality of layers.

<Tandem structure>
The organic functional layer may be a so-called tandem element in which a plurality of organic functional layers including at least one light emitting layer are stacked.

As typical element configurations of the tandem structure, for example, the following configurations can be given. (1) Anode / first organic functional layer / intermediate functional layer / second organic functional layer / cathode (2) anode / first organic functional layer / intermediate functional layer / second organic functional layer / intermediate functional layer / third organic Functional layer / cathode Here, the first organic functional layer, the second organic functional layer, and the third organic functional layer may all be the same or different. Further, the two organic functional layers may be the same, and the remaining one may be different.

  Moreover, each organic functional layer may be laminated | stacked directly, or may be laminated | stacked through the intermediate functional layer. The intermediate functional layer is composed of, for example, an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, or an intermediate insulating layer. The intermediate functional layer has electrons in the anode side adjacent layer and holes in the cathode side adjacent layer. A known material structure can be used as long as the layer has a function of supplying.

Examples of materials used for the intermediate functional layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO ₂ , TiN, ZrN, HfN, TiOX, VOX, CuI, InN, GaN, and CuAlO. ₂ , conductive inorganic compound layers such as CuGaO ₂ , SrCu ₂ O ₂ , LaB ₆ , RuO ₂ and Al, two-layer films such as Au / Bi ₂ O ₃ , SnO ₂ / Ag / SnO ₂ , ZnO / Ag / ZnO, Bi ₂ O ₃ / Au / Bi ₂ O ₃ , TiO ₂ / TiN / TiO ₂ , TiO ₂ / ZrN / TiO _{2 and} other multilayer films, C _{60 and} other fullerenes, conductive organic materials such as oligothiophene Examples include layers, conductive organic compound layers such as metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, and metal-free porphyrins. However, the present invention is not limited to these.

  Specific examples of the tandem type organic functional layer include, for example, US Pat. No. 6,337,492, US Pat. No. 7,420,203, US Pat. No. 7,473,923, US Pat. No. 6,872,472, US Pat. No. 6,107,734. No. 6, U.S. Pat. No. 6,337,492, International Publication No. 2005/009087, JP-A 2006-228712, JP-A 2006-24791, JP-A 2006-49393, JP-A 2006-49394 Gazette, JP 2006-49396 A, JP 2011-96679 A, JP 2005-340187 A, JP 4711424 A, JP 34966681, JP 3884564 A, Japanese Patent No. 4213169, JP 2010-A. No. 192719, JP2009-076 29, JP 2008-078414, JP 2007-059848, JP 2003-272860, JP 2003-045676, WO 2005/094130, etc. Although a constituent material etc. are mentioned, it is not limited to these.

<Light emitting layer>
The light emitting layer used in the organic EL device according to the present invention is a layer that provides a field in which electrons and holes injected from an electrode or an adjacent layer are recombined to emit light via excitons. In the light emitting layer, the light emitting portion may be within the layer of the light emitting layer or may be the interface between the light emitting layer and the adjacent layer.

  The total sum of the thicknesses of the light emitting layers is not particularly limited, and is determined from the viewpoint of the uniformity of the film to be formed, the voltage required at the time of light emission, the stability of the light emission color with respect to the driving current, and the like. For example, the total thickness of the light emitting layers is preferably adjusted to a range of 2 nm to 5 μm, more preferably adjusted to a range of 2 to 500 nm, and further preferably adjusted to a range of 5 to 200 nm. Further, the individual layer thickness of the light emitting layer is preferably adjusted to a range of 2 nm to 1 μm, more preferably adjusted to a range of 2 to 200 nm, and further preferably adjusted to a range of 3 to 150 nm.

  The light-emitting layer preferably contains a light-emitting dopant (a light-emitting dopant compound, a dopant compound, also simply referred to as a dopant) and a host compound (a matrix material, a light-emitting host compound, also simply referred to as a host).

<Luminescent dopant>
As the light emitting dopant used in the light emitting layer, a fluorescent light emitting dopant (also referred to as a fluorescent dopant or a fluorescent compound) and a phosphorescent light emitting dopant (also referred to as a phosphorescent dopant or a phosphorescent compound) are preferably used. Of these, at least one light emitting layer preferably contains a phosphorescent dopant.

  The concentration of the light-emitting dopant in the light-emitting layer can be arbitrarily determined based on the specific dopant used and the device requirements. The concentration of the photodopant may be contained at a uniform concentration in the thickness direction of the light emitting layer, or may have an arbitrary concentration distribution.

  In addition, the light emitting layer may contain a plurality of types of light emitting dopants. For example, a combination of dopants having different structures, or a combination of a fluorescent luminescent dopant and a phosphorescent luminescent dopant may be used. Thereby, arbitrary luminescent colors can be obtained.

  The color emitted by the organic EL device according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Society for Color Science, University of Tokyo Press, 1985). It is determined by the color when the result measured with Konica Minolta Co., Ltd. is applied to the CIE chromaticity coordinates.

  In the organic EL device according to the present invention, it is also preferable that one or a plurality of light-emitting layers contain a plurality of light-emitting dopants having different emission colors and emit white light. There are no particular limitations on the combination of the light-emitting dopants that exhibit white, and examples include blue and orange, and a combination of blue, green, and red.

As the white color in the organic EL device according to the present invention, the chromaticity in the CIE 1931 color system at 1000 cd / m ² is x = 0.39 ± 0. 09, preferably in the region of y = 0.38 ± 0.08.

<Phosphorescent dopant>
The phosphorescent dopant is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 0 at 25 ° C. .01 or more compounds. In the phosphorescent dopant used for a light emitting layer, a preferable phosphorescence quantum yield is 0.1 or more.

  The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. The phosphorescence quantum yield in a solution can be measured using various solvents. The phosphorescence emitting dopant used for the light emitting layer should just achieve the said phosphorescence quantum yield (0.01 or more) in any solvent.

  There are two types of light emission of the phosphorescent dopant in principle.

  First, an excited state of the host compound is generated by recombination of carriers on the host compound to which carriers are transported. It is an energy transfer type in which light is emitted from the phosphorescent dopant by transferring this energy to the phosphorescent dopant. The other is a carrier trap type in which a phosphorescent dopant becomes a carrier trap, carrier recombination occurs on the phosphorescent dopant, and light emission from the phosphorescent dopant is obtained. In any case, it is a condition that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent dopant can be appropriately selected from known materials used for the light emitting layer of the organic EL device according to the present invention.

  Specific examples of known phosphorescent dopants include compounds described in the following documents.

  Nature, 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. , 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. , 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, US Patent Publication No. 2006/020202194, US Patent Publication No. 2007/0087321. No., US Patent Publication No. 2005/0244673, Inorg. Chem. , 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. , 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. , 34, 592 (2005), Chem. Commun. , 2906 (2005), Inorg. Chem. , 42, 1248 (2003), International Publication No. 2009/050290, International Publication No. 2002/015645, International Publication No. 2009/000673, US Patent Publication No. 2002/0034656, and US Pat. No. 7,332,232. US Patent Publication No. 2009/0108737, US Patent Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Publication No. 2007/0190359, US Patent Publication No. 2006/0008670, US Patent Publication No. 2009/0165846, US Patent Publication No. 2008/0015355, US Pat. No. 7,250,226, US Pat. No. 7,396,598, US Patent Publication No. 2006 0263635 Pat, U.S. Patent Publication No. 2003/0138657, U.S. Patent Publication No. 2003/0152802, U.S. Patent No. 7090928, Angew. Chem. lnt. Ed. 47, 1 (2008), Chem. Mater. , 18, 5119 (2006), Inorg. Chem. 46, 4308 (2007), Organometallics, 23, 3745 (2004), Appl. Phys. Lett. , 74, 1361 (1999), International Publication No. 2002/002714, International Publication No. 2006/009024, International Publication No. 2006/056418, International Publication No. 2005/019373, International Publication No. 2005/123873, International Publication. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, U.S. Publication No. 2006/0251923, U.S. Publication No. 2005/0260441, U.S. Pat. No. 7,393,599. , U.S. Pat. No. 7,534,505, U.S. Pat. No. 7,445,855, U.S. Patent Publication No. 2007/0190359, U.S. Patent Publication No. 2008/0297033, U.S. Pat. No. 7,338,722, U.S. Pat. Release 200 No. 034984, U.S. Pat. No. 7,279,704, International Publication No. 2005/076380, International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011. No. 134013, International Publication No. 2011/157339, International Publication No. 2010/086089, International Publication No. 2009/113646, International Publication No. 2012/020327, International Publication No. 2011/051404, International Publication No. 2011/004639. International Publication No. 2011/073149, JP 2012-069737 A, JP 2012-195554 A, JP 2009-114086 A, JP 2003-81988 A, JP 2002-302671 A, JP 002-363552 issue is a Publication.

  Among these, preferable phosphorescent dopants include organometallic complexes having Ir as a central metal. More preferably, a complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, or a metal-sulfur bond is preferable.

<Fluorescent luminescent dopant>
The fluorescent light-emitting dopant is a compound that can emit light from an excited singlet, and is not particularly limited as long as light emission from the excited singlet is observed.

  Examples of the fluorescent light-emitting dopant include anthracene derivatives, pyrene derivatives, chrysene derivatives, fluoranthene derivatives, perylene derivatives, fluorene derivatives, arylacetylene derivatives, styrylarylene derivatives, styrylamine derivatives, arylamine derivatives, boron complexes, coumarin derivatives, Examples include pyran derivatives, cyanine derivatives, croconium derivatives, squalium derivatives, oxobenzanthracene derivatives, fluorescein derivatives, rhodamine derivatives, pyrylium derivatives, perylene derivatives, polythiophene derivatives, and rare earth complex compounds.

  In addition, a light emitting dopant using delayed fluorescence may be used as the fluorescent light emitting dopant.

  Specific examples of the luminescent dopant using delayed fluorescence include compounds described in, for example, International Publication No. 2011/156793, Japanese Patent Application Laid-Open No. 2011-213643, Japanese Patent Application Laid-Open No. 2010-93181, and the like.

<Host compound>
The host compound is a compound mainly responsible for charge injection and transport in the light emitting layer, and its own light emission is not substantially observed in the organic EL element.

  Preferably, it is a compound having a phosphorescence quantum yield of phosphorescence of less than 0.1 at room temperature (25 ° C.), more preferably a compound having a phosphorescence quantum yield of less than 0.01. Moreover, it is preferable that the mass ratio in the layer is 20% or more among the compounds contained in a light emitting layer.

  Moreover, it is preferable that the excited state energy of a host compound is higher than the excited state energy of the light emission dopant contained in the same layer.

  A host compound may be used independently or may be used in combination of multiple types. By using a plurality of types of host compounds, it is possible to adjust the movement of electric charges, and it is possible to increase the efficiency of the organic EL element.

  There is no restriction | limiting in particular as a host compound used for a light emitting layer, The compound used with the conventional organic EL element can be used. For example, a low molecular compound, a high molecular compound having a repeating unit, or a compound having a reactive group such as a vinyl group or an epoxy group may be used.

  As a known host compound, while having a hole transport ability or an electron transport ability, it prevents the light emission from becoming longer wavelength, and further, from the viewpoint of stability against heat generation during driving of the organic EL element at a high temperature or during element driving, It is preferable to have a high glass transition temperature (Tg). As a host compound, it is preferable that Tg is 90 degreeC or more, More preferably, it is 120 degreeC or more.

  Here, the glass transition point (Tg) is a value obtained by a method based on JIS K 7121-2012 using DSC (Differential Scanning Colorimetry).

  Specific examples of known host compounds used in the organic EL device according to the present invention include compounds described in the following documents, but the present invention is not limited thereto.

  JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, US 2003/0175553, US 2006/0280965, US Publication No. 2005/0112407, United States Patent Publication No. 2009/0017330, United States Patent Publication No. 2009/0030202, United States Patent Publication No. 2005/0238919, International Publication No. 2001/039234. International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. 2012/023947, Japanese Patent Application Laid-Open No. 2008-200347. No. 074939, JP 2007-254297, EP 2034538, and the like.

<Electron transport layer>
Electron transport in the organic EL device according to the present invention is performed by a material having a function of transporting electrons, and has a function of transmitting electrons injected from the cathode to the light emitting layer.

  The electron transport material may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular about the total layer thickness of an electron carrying layer, Usually, it is the range of 2 nm-5 micrometers, More preferably, it is 2-500 nm, More preferably, it is 5-200 nm.

  In the organic EL device according to the present invention, when the light generated in the light emitting layer is extracted from the electrode, the light extracted directly from the light emitting layer and the light reflected from the electrode that is opposite to the electrode from which the light is extracted are extracted. It is known that light causes interference. When light is reflected by the cathode, this interference effect can be efficiently utilized by appropriately adjusting the total thickness of the electron transport layer between several nanometers and several micrometers.

  On the other hand, when the layer thickness of the electron transport layer is increased, the voltage is likely to increase. Therefore, particularly when the layer thickness is thick, the electron mobility of the electron transport layer is preferably 10 −5 cm 2 / Vs or more.

  As a material used for the electron transport layer (hereinafter referred to as an electron transport material), any material that has either an electron injection property or a transport property or a hole barrier property may be used. Any one can be selected and used.

  Examples thereof include nitrogen-containing aromatic heterocyclic derivatives, aromatic hydrocarbon ring derivatives, dibenzofuran derivatives, dibenzothiophene derivatives and silole derivatives.

  Examples of the nitrogen-containing aromatic heterocyclic derivatives include carbazole derivatives, azacarbazole derivatives (one or more carbon atoms constituting the carbazole ring are substituted with nitrogen atoms), pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, pyridazine derivatives, triazine derivatives. Quinoline derivatives, quinoxaline derivatives, phenanthroline derivatives, azatriphenylene derivatives, oxazole derivatives, thiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, triazole derivatives, benzimidazole derivatives, benzoxazole derivatives, and benzthiazole derivatives.

  Examples of the aromatic hydrocarbon ring derivative include naphthalene derivatives, anthracene derivatives, and triphenylene.

In addition, a metal complex having a quinolinol skeleton or a dibenzoquinolinol skeleton as a ligand, for example, tris (8-quinolinol) aluminum (Alq ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7 -Dibromo-8-quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq) and the like and their metal complexes A metal complex in which the central metal is replaced with In, Mg, Cu, Ca, Sn, Ga, or Pb can also be used as the electron transport material.

  In addition, metal-free or metal phthalocyanine or those in which the terminal thereof is substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transport material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc. as in the case of the hole injection layer and hole transport layer Can also be used as an electron transporting material.

  Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  In the organic EL device according to the present invention, the electron transport layer may be doped as a guest material with a doping material to form an electron transport layer having a high n property (electron rich). Examples of the doping material include metal compounds such as metal complexes and metal halides, and other n-type dopants.

  Specific examples of the electron transport layer having such a structure include, for example, JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. , 95, 5773 (2004) and the like.

  Specific examples of known preferable electron transport materials used in the organic EL device according to the present invention include, but are not limited to, compounds described in the following documents.

  US Pat. No. 6,528,187, US Pat. No. 7,230,107, US Patent Publication No. 2005/0025993, US Patent Publication No. 2004/0036077, US Patent Publication No. 2009/0115316, US Patent Publication No. 2009/0101870, United States Patent Publication No. 2009/0179554, International Publication No. 2003/060956, International Publication No. 2008/132805, Appl. Phys. Lett. , 75, 4 (1999), Appl. Phys. Lett. 79, 449 (2001), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 81, 162 (2002), Appl. Phys. Lett. 79,156 (2001), U.S. Pat. No. 7,964,293, International Publication No. 2004/080975, International Publication No. 2004/063159, International Publication No. 2005/085387, International Publication No. 2006/067931, International Publication. 2007/088652, International Publication No. 2008/114690, International Publication No. 2009/066942, International Publication No. 2009/066779, International Publication No. 2009/054253, International Publication No. 2011/086935, International Publication No. 2010 No./150593, International Publication No. 2010/047707, EP23111826, JP2010-251675A, JP2009-209133A, JP2009-124114A, JP2008-277810A, JP2006. − 56445, JP 2005-340122, JP 2003-45662, JP-2003-31367, JP 2003-282270, JP-WO 2012/115034, and the like.

  More preferable electron transport materials include pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, azacarbazole derivatives, and benzimidazole derivatives.

<Hole blocking layer>
The hole blocking layer is a layer having a function of an electron transport layer in a broad sense. Preferably, it contains a material having a function of transporting electrons and a small ability to transport holes. By blocking holes while transporting electrons, the recombination probability of electrons and holes can be improved.

  Moreover, the structure of the above-mentioned electron carrying layer can be used as a hole-blocking layer as needed.

  The hole blocking layer provided in the organic EL device according to the present invention is preferably provided adjacent to the cathode side of the light emitting layer.

  In the organic EL device according to the present invention, the thickness of the hole blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

  As the material used for the hole blocking layer, the material used for the above-described electron transport layer is preferably used, and the material used as the above-described host compound is also preferably used for the hole blocking layer.

<Electron injection layer>
The electron injection layer (also referred to as “cathode buffer layer”) is a layer provided between the cathode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. An example of an electron injection layer is described in the second chapter, Chapter 2, “Electrode Materials” (pages 123 to 166) of “Organic EL devices and their industrialization front line (issued by NTT Corporation on November 30, 1998)”. Have been described.

  In the organic EL device according to the present invention, the electron injection layer is provided as necessary, and is provided between the cathode and the light emitting layer or between the cathode and the electron transport layer as described above.

  The electron injection layer is preferably a very thin film layer, and the layer thickness is preferably in the range of 0.1 to 5 nm although it depends on the material. Moreover, the layer which consists of a nonuniform film | membrane in which a constituent material exists intermittently may be sufficient.

  Details of the electron injection layer are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specific examples of materials preferably used for the electron injection layer include metals typified by strontium and aluminum, alkali metal compounds typified by lithium fluoride, sodium fluoride, and potassium fluoride, magnesium fluoride, and fluoride. Examples include alkaline earth metal compounds typified by calcium, metal oxides typified by aluminum oxide, metal complexes typified by lithium 8-hydroxyquinolate (Liq), and the like. Moreover, it is also possible to use the above-mentioned electron transport material.

  Moreover, the material used for said electron injection layer may be used independently, and may be used in combination of multiple types.

<Hole transport layer>
The hole transport layer is made of a material having a function of transporting holes. The hole transport layer is a layer having a function of transmitting holes injected from the anode to the light emitting layer.

  In the organic EL device according to the present invention, the total thickness of the hole transport layer is not particularly limited, but is usually in the range of 5 nm to 5 μm, more preferably 2 to 500 nm, and further preferably 5 to 200 nm. is there.

  A material used for the hole transport layer (hereinafter referred to as a hole transport material) may have any of a hole injection property or a transport property and an electron barrier property. As the hole transport material, an arbitrary material can be selected and used from conventionally known compounds. The hole transport material may be used alone or in combination of two or more.

  Hole transport materials include, for example, porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, tria Reelamine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinyl carbazole, polymer materials having aromatic amine introduced in the main chain or side chain, or Oligomer, polysilane, conductive polymer or oligomer (for example, PEDOT: PSS, aniline copolymer, polyaniline, polythiophene, etc.) And the like.

  Examples of the triarylamine derivative include a benzidine type typified by α-NPD, a starburst type typified by MTDATA, and a compound having fluorene or anthracene in the triarylamine linking core part.

  In addition, hexaazatriphenylene derivatives described in JP-T-2003-519432 and JP-A-2006-135145 can also be used as the hole transport material.

  Furthermore, a hole transport layer having a high p property doped with impurities can also be used. For example, JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), etc., can also be applied to the hole transport layer.

JP-A-11-251067, J. Org. Huang et. al. It is also possible to use so-called p-type hole transport materials and inorganic compounds such as p-type-Si and p-type-SiC as described in the literature (Applied Physics Letters, 80 (2002), p. 139). . Further, ortho-metalated organometallic complexes having Ir or Pt as the central metal as typified by Ir (ppy) ₃ are also preferably used.

  Although the above-mentioned materials can be used as the hole transport material, a triarylamine derivative, a carbazole derivative, an indolocarbazole derivative, an azatriphenylene derivative, an organometallic complex, or an aromatic amine is introduced into the main chain or side chain. The polymer materials or oligomers used are preferably used.

  Specific examples of the hole transport material used in the organic EL device according to the present invention include, but are not limited to, the compounds described in the following documents in addition to the documents listed above.

  Appl. Phys. Lett. 69, 2160 (1996); Lumin. 72-74, 985 (1997), Appl. Phys. Lett. 78, 673 (2001), Appl. Phys. Lett. , 90, 183503 (2007), Appl. Phys. Lett. , 90, 183503 (2007), Appl. Phys. Lett. 51, 913 (1987), Synth. Met. , 87, 171 (1997), Synth. Met. 91, 209 (1997), Synth. Met. , 111, 421 (2000), SID Symposium Digest, 37, 923 (2006), J. Am. Mater. Chem. 3,319 (1993), Adv. Mater. 6, 677 (1994), Chem. Mater. , 15, 3148 (2003), US Patent Publication No. 2003/0162053, US Patent Publication No. 2002/0158242, US Patent Publication No. 2006/0240279, US Patent Publication No. 2008/0220265. U.S. Patent No. 5061569, International Publication No. 2007/002683, International Publication No. 2009/018009, EP650955, U.S. Patent Publication No. 2008/0124572, U.S. Patent Publication No. 2007/0278938, US Patent Publication No. 2008/0106190, US Patent Publication No. 2008/0018221, International Publication No. 2012/115034, Japanese Translation of PCT International Publication No. 2003-519432, Japanese Patent Laid-Open No. 2006-135145, US Patent Application Number 13/5 5981 issue, and the like.

<Electron blocking layer>
The electron blocking layer is a layer having a function of a hole transport layer in a broad sense. Preferably, it is made of a material having a function of transporting holes and a small ability to transport electrons. The electron blocking layer can improve the probability of recombination of electrons and holes by blocking electrons while transporting holes.

  Moreover, the structure of the above-mentioned hole transport layer can be used as an electron blocking layer of the organic EL device according to the present invention, if necessary. The electron blocking layer provided in the organic EL element is preferably provided adjacent to the anode side of the light emitting layer.

  The thickness of the electron blocking layer is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

  As the material used for the electron blocking layer, the materials used for the above-described hole transport layer can be preferably used. Moreover, the material used as the above-mentioned host compound can also be preferably used as the electron blocking layer.

<Hole injection layer>
The hole injection layer (also referred to as “anode buffer layer”) is a layer provided between the anode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. An example of the hole injection layer is “Organic EL device and its industrialization front line (November 30, 1998, issued by NTT)”, Chapter 2, Chapter 2, “Electrode material” (pages 123-166). It is described in.

  The hole injection layer is provided as necessary, and is provided between the anode and the light emitting layer or between the anode and the hole transport layer as described above.

  The details of the hole injection layer are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like.

  Examples of the material used for the hole injection layer include the materials used for the hole transport layer described above. Among them, phthalocyanine derivatives represented by copper phthalocyanine, hexaazatriphenylene derivatives as described in JP-T-2003-519432, JP-A-2006-135145, etc., metal oxides represented by vanadium oxide, amorphous Conductive polymers such as carbon, polyaniline (emeraldine) and polythiophene, orthometalated complexes represented by tris (2-phenylpyridine) iridium complex, and triarylamine derivatives are preferred.

  The materials used for the hole injection layer described above may be used alone or in combination of two or more.

<Additive>
The organic functional layer constituting the organic EL device according to the present invention may further contain other additives.

  Examples of the additive include halogen elements and halogenated compounds such as bromine, iodine and chlorine, alkali metals and alkaline earth metals such as Pd, Ca, and Na, transition metal compounds, complexes, and salts.

  The content of the additive can be arbitrarily determined, but is preferably 1000 ppm or less, more preferably 500 ppm or less, and further preferably 50 ppm or less with respect to the total mass% of the contained layer. .

  However, it is not within this range depending on the purpose of improving the transportability of electrons and holes or the purpose of favoring the exciton energy transfer.

<Method for forming organic functional layer>
A method for forming an organic functional layer (hole injection layer, hole transport layer, light emitting layer, hole blocking layer, electron transport layer, electron injection layer, etc.) of the organic EL device according to the present invention will be described.

  The method for forming the organic functional layer is not particularly limited, and can be formed by a conventionally known method such as a vacuum deposition method or a wet method (wet process).

  Examples of the wet method include a spin coating method, a casting method, an ink jet method, a printing method, a die coating method, a blade coating method, a roll coating method, a spray coating method, a curtain coating method, and an LB method (Langmuir-Blodgett method). From the standpoint of obtaining a uniform thin film and high productivity, a method having high suitability for a roll-to-roll method such as a die coating method, a roll coating method, an ink jet method, or a spray coating method is preferable.

  Examples of the liquid medium for dissolving or dispersing the organic functional layer material in the wet method include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, and xylene. Aromatic hydrocarbons such as mesitylene and cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin and dodecane, and organic solvents such as DMF and DMSO can be used.

  Moreover, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.

  When employing a vapor deposition method for forming each layer constituting the organic functional layer, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a degree of vacuum of 10 −6 to 10 −2 Pa, It is desirable to appropriately select a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a layer thickness of 0.1 to 5 μm, preferably 5 to 200 nm.

  In the formation of the organic EL device according to the present invention, it is preferable to consistently produce the organic functional layer to the cathode by one evacuation, but it may be taken out halfway and subjected to different film forming methods. In that case, it is preferable to perform the work in a dry inert gas atmosphere.

  Different formation methods may be applied for each layer.

<First electrode>
As the first electrode 215, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more, preferably 4.3 eV or more) is used. Specific examples of such an electrode substance include metals such as Au and Ag, alloys thereof, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) that can form a transparent conductive film may be used.

  For the first electrode, a thin film is formed by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape is formed by a photolithography method. Alternatively, when the pattern accuracy is not so high (about 100 μm or more), the pattern may be formed through a mask having a desired shape when the electrode material is formed by vapor deposition or sputtering.

  In the case of using a coatable material such as an organic conductive compound, a wet film forming method such as a printing method or a coating method can also be used.

  When the emitted light is extracted from the first electrode side, it is desirable that the transmittance be greater than 10%. The sheet resistance as the first electrode is several hundred Ω / sq. The following is preferred. Further, the thickness of the first electrode depends on the material, but is usually 10 nm to 1 μm, preferably 10 to 200 nm.

  In particular, the first electrode is a layer composed mainly of silver and is preferably composed of silver or an alloy composed mainly of silver. Examples of the method for forming the first electrode include a method using a wet process such as a coating method, an inkjet method, a coating method, a dip method, a vapor deposition method (resistance heating, EB method, etc.), a sputtering method, a CVD method, and the like. Examples include a method using a dry process. Of these, the vapor deposition method is preferably applied.

  As an example, the alloy mainly composed of silver (Ag) constituting the first electrode is silver magnesium (AgMg), silver copper (AgCu), silver palladium (AgPd), silver palladium copper (AgPdCu), silver indium (AgIn). Etc.

  The first electrode as described above may have a structure in which silver or an alloy layer mainly composed of silver is divided into a plurality of layers as necessary.

  Further, the first electrode preferably has a thickness in the range of 4 to 15 nm. A thickness of 15 nm or less is preferable because the absorption component and reflection component of the layer are kept low and the light transmittance of the first electrode is maintained. Further, when the thickness is 4 nm or more, the conductivity of the layer is also ensured.

  In the case where a layer composed mainly of silver is formed as the first electrode, another conductive layer containing Pd or the like, or an organic functional layer such as a nitrogen compound or a sulfur compound is used as a base layer for the first electrode. You may form as. By forming the base layer, it is possible to improve the film formation of a layer composed mainly of silver, to reduce the resistivity of the first electrode, and to improve the light transmittance of the first electrode 15.

<Second electrode>
As the second electrode 217, an electrode substance made of a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, or a mixture thereof is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, aluminum, rare earth metals and the like.

Among these, a mixture of an electron injecting metal and a second metal having a work function value larger and more stable than that of the electron injecting metal, for example, magnesium / Silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.

  The second electrode can be produced using the above electrode material by a method such as vapor deposition or sputtering. The sheet resistance of the second electrode is several hundred Ω / sq. The following is preferred. The thickness of the second electrode is usually in the range of 10 nm to 5 μm, preferably 50 to 200 nm.

  Moreover, after producing the metal with a thickness of 1 to 20 nm on the second electrode, a transparent transparent or translucent second electrode is produced by producing a conductive transparent material mentioned in the description of the first electrode on the second electrode. can do. By applying this, an element in which both the first electrode and the second electrode are transmissive can be manufactured.

<Sealing member>
As shown in FIG. 11, the organic EL element according to the present invention may be solid-sealed by bonding a sealing member 221 and a sealing layer 222 that cover the entire organic functional layer.

  The sealing member 221 is provided in a state of covering at least the organic functional layer, and is provided in a state of exposing the terminal portions (not shown) of the first electrode and the second electrode. Moreover, an electrode may be provided on the sealing member 221 so that the terminal portions of the first electrode and the second electrode of the organic EL element are electrically connected to this electrode.

  The sealing member 221 is made of a resin sealing material for bonding the second electrode 217 and the sealing layer 222. In addition to the resin sealing material, an inorganic sealing material may be used. For example, the organic functional layer may be covered with an inorganic sealing material, and then the sealing layer and the second electrode may be bonded with a resin sealing material.

  The resin sealing material is used for fixing the sealing layer 222 to the second electrode 217 side. Moreover, it is used as a sealing material for sealing the organic functional layer sandwiched between the sealing member and the first electrode.

  In order to bond the sealing layer to the second electrode, it is preferable to bond the sealing layer using any curable resin sealing material. As the resin sealing material, a suitable adhesive can be appropriately selected from the viewpoint of improving the adhesion with the sealing member to be bonded.

  As such a resin sealing material, it is preferable to use a thermosetting resin.

  As the thermosetting adhesive, for example, a resin mainly composed of a compound having an ethylenic double bond at the molecular end or side chain and a thermal polymerization initiator can be used. More specifically, a thermosetting adhesive made of an epoxy resin, an acrylic resin, or the like can be used. Moreover, according to the bonding apparatus and hardening processing apparatus which are used by the manufacturing process of an organic EL element, you may use a fusion type thermosetting adhesive.

  Moreover, as such a resin sealing material, it is also preferable to use a photocurable resin. For example, photo-radically polymerizable resins mainly composed of various (meth) acrylates such as polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, epoxy, vinyl ether, etc. Examples thereof include a cationic photopolymerizable resin mainly composed of a resin and a thiol / ene addition type resin. Among these photo-curing resins, an epoxy resin-based photo-cationic polymerizable resin having a low shrinkage of the cured product, a small outgas, and excellent long-term reliability is preferable.

  In addition, as such a resin sealing material, a chemically curable (mixed two-component) resin can be used. Hot melt polyamide, polyester, and polyolefin can also be used. Moreover, a cationic curing type ultraviolet curing epoxy resin can be used.

  In addition, the organic material which comprises an organic EL element may deteriorate with heat processing. For this reason, it is preferable to use a resin sealing material that can be adhesively cured from room temperature to 80 ° C.

  The said inorganic sealing material is a member which seals the light emitting unit which consists of a 1st electrode, an organic functional layer, and a 2nd electrode with a resin sealing material. For this reason, it is preferable to use a material having a function of suppressing intrusion of moisture, oxygen, or the like that degrades the organic functional layer as the inorganic sealing material.

  In addition, since the inorganic sealing material has a configuration in direct contact with the organic functional layer, it is preferable to use a material having excellent bonding properties with the organic functional layer.

  The inorganic sealing material is preferably formed of a compound such as an inorganic oxide, inorganic nitride, or inorganic carbide having high sealing properties.

Specifically, it is formed of SiO _x , Al ₂ O ₃ , In ₂ O ₃ , TiO _x , ITO (tin / indium oxide), AlN, Si ₃ N ₄ , SiO _x N, TiO _x N, SiC, or the like. be able to.

  The inorganic sealing material can be formed by a known method such as a sol-gel method, a vapor deposition method, CVD, ALD (Atomic Layer Deposition), PVD, or a sputtering method.

  In addition, in the atmospheric pressure plasma method, the inorganic sealing material is selected from conditions such as an organometallic compound, a decomposition gas, a decomposition temperature, and an input power that are raw materials (also referred to as raw materials). Compositions such as mixtures of inorganic carbides, inorganic nitrides, inorganic sulfides and inorganic halides such as inorganic oxides or inorganic oxynitrides and inorganic oxide halides as the main component can be made.

  For example, if a silicon compound is used as a raw material compound and oxygen is used as the decomposition gas, silicon oxide is generated. Further, if silazane or the like is used as a raw material compound, silicon oxynitride is generated. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multi-step chemical reactions are accelerated very rapidly in the plasma space, and the elements in the plasma space are thermodynamically This is because it is converted into a stable compound in a very short time.

  As long as the raw material for forming such an inorganic sealing material is a silicon compound, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. In addition, since these dilution solvents are decomposed | disassembled into a molecule | numerator or an atom during a plasma discharge process, the influence can be almost disregarded.

  Examples of such silicon compounds include silane, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrat-butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane Bis (dimethylamino) methylvinylsilane, bis (ethylamino) dimethylsilane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) carbodiimide, die Ruaminotrimethylsilane, dimethylaminodimethylsilane, hexamethyldisilazane, hexamethylcyclotrisilazane, heptamethyldisilazane, nonamethyltrisilazane, octamethylcyclotetrasilazane, tetrakisdimethylaminosilane, tetraisocyanatosilane, tetramethyldisilazane , Tris (dimethylamino) silane, triethoxyfluorosilane, allyldimethylsilane, allyltrimethylsilane, benzyltrimethylsilane, bis (trimethylsilyl) acetylene, 1,4-bistrimethylsilyl-1,3-butadiyne, di-t-butylsilane, 1,3-disilabutane, bis (trimethylsilyl) methane, cyclopentadienyltrimethylsilane, phenyldimethylsilane, phenyltrimethylsilane, pro Rugyltrimethylsilane, tetramethylsilane, trimethylsilylacetylene, 1- (trimethylsilyl) -1-propyne, tris (trimethylsilyl) methane, tris (trimethylsilyl) silane, vinyltrimethylsilane, hexamethyldisilane, octamethylcyclotetrasiloxane, tetramethyl Examples thereof include cyclotetrasiloxane, hexamethylcyclotetrasiloxane, M silicate 51, and the like.

  In addition, as a decomposition gas for decomposing these silicon-containing source gases to obtain an inorganic sealing material, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, suboxide Examples thereof include nitrogen gas, nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, and chlorine gas.

  An inorganic sealing material containing silicon oxide, nitride, carbide, or the like can be obtained by appropriately selecting the source gas containing silicon and the decomposition gas.

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

  The discharge gas and the reactive gas are mixed and supplied to an atmospheric pressure plasma discharge generator (plasma generator) as a thin film forming (mixed) gas to form a film. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, the reactive gas is supplied with the ratio of the discharge gas being 50% or more with respect to the entire mixed gas.

<Sealing layer>
The sealing layer 222 covers the organic EL element. For example, a plate-like (film-like) sealing layer 222 is fixed to the second electrode side via the sealing member 221.

  Specific examples of the plate-like (film-like) sealing member include a glass substrate and a polymer substrate, and these substrate materials may be used in the form of a thin film. Examples of the glass substrate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

  Moreover, it is preferable to use the metal foil by which the resin film was laminated (polymer film) as a sealing layer. A metal foil laminated with a resin film cannot be used as a substrate on the light extraction side, but is a low-cost and low moisture-permeable sealing material. For this reason, it is suitable as a sealing layer which does not intend light extraction.

  The metal foil refers to a metal foil or film formed by rolling or the like, unlike a metal thin film formed by sputtering or vapor deposition, or a conductive film formed from a fluid electrode material such as a conductive paste. .

  As metal foil, there is no limitation in particular in the kind of metal, for example, copper (Cu) foil, aluminum (Al) foil, gold (Au) foil, brass foil, nickel (Ni) foil, titanium (Ti) foil, copper alloy Examples thereof include foil, stainless steel foil, tin (Sn) foil, and high nickel alloy foil. Among these various metal foils, a particularly preferred metal foil is an Al foil.

  The thickness of the metal foil is preferably 6 to 50 μm. In the case of 6 μm or more, depending on the material used for the metal foil, the required gas barrier properties (moisture permeability, oxygen permeability) can be obtained without any pinholes during use. When the thickness is 50 μm or less, an increase in cost due to the material used for the metal foil can be suppressed, and the organic EL element can be prevented from becoming too thick. Therefore, there is an advantage of using a film-shaped sealing member.

  In the metal foil laminated with the resin film, as the resin film, various materials described in the new development of functional packaging materials (Toray Research Center, Inc.) can be used. For example, polyethylene resin, polypropylene resin, polyethylene terephthalate resin, polyamide resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon Resin, vinylidene chloride resin and the like can be used. Resins such as polypropylene resins and nylon resins may be stretched and further coated with a vinylidene chloride resin. The polyethylene resin may be either low density or high density.

The sealing layer 222 has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and is measured by a method according to JIS K 7129-1992. Further, the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / m ² · 24 h or less.

  Moreover, you may use the above sealing layers processed into a concave plate shape. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

  Moreover, not only this but a metal material may be used. Examples of the metal material include one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum. By using such a metal material as a sealing layer in the form of a thin film, the entire light-emitting panel provided with the organic EL element can be thinned.

  Among them, since the element can be thinned, a polymer substrate (gas barrier film) having a gas barrier property in a thin film shape as the sealing layer can be preferably used.

The film-like polymer substrate has an oxygen permeability measured by a method in accordance with JIS K 7126-1987, measured by a method in accordance with JIS K 7129-1992, which is 1 × 10 ⁻³ mL / m ² · 24 h · atm or less. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) is preferably 1 × 10 ⁻³ g / m ² · 24 h or less.

  Further, the above substrate material may be processed into a concave plate shape and used as a sealing member. In this case, the above-described substrate member is subjected to processing such as sand blasting or chemical etching to form a concave shape.

<Extraction electrode>
The extraction electrode (not shown) is for electrically connecting the first electrode and the external power source, and the material thereof is not particularly limited and a known material can be preferably used. A metal film such as a MAM electrode (Mo / Al · Nd alloy / Mo) having a layer structure can be used.

<Auxiliary electrode>
The auxiliary electrode (not shown) is provided for the purpose of reducing the resistance of the first electrode, and is provided in contact with the electrode layer of the first electrode. The material for forming the auxiliary electrode is preferably a metal having low resistance such as gold, platinum, silver, copper, or aluminum. Since these metals have low light transmittance, a pattern is formed within a range not affected by extraction of emitted light from the light extraction surface.

  Examples of a method for forming such an auxiliary electrode include a vapor deposition method, a sputtering method, a printing method, an ink jet method, and an aerosol jet method. The line width of the auxiliary electrode is preferably 50 μm or less from the viewpoint of the aperture ratio for extracting light, and the thickness of the auxiliary electrode is preferably 1 μm or more from the viewpoint of conductivity.

<Protective film, protective plate>
The organic EL element may further include a protective film or a protective plate on the sealing material.

  The protective film or the protective plate mechanically protects the organic EL element body by sandwiching an organic EL element body (organic functional layer, various electrodes and wiring) and a sealing material between the protective film or the protective plate. In particular, when a sealing film is used as the sealing material, it is preferable that a protective film or a protective plate is provided because mechanical protection of the organic EL element body is not sufficient.

  As the protective film or protective plate, a glass plate, a polymer plate, a thin polymer film, a metal plate, a thin metal film, or a polymer material film or a metal material film is used. Among these, a polymer film is preferably used from the viewpoint of light weight and thinning of the element.

  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 otherwise indicated, "mass part" or "mass%" is represented.

Example 1
<Pattern No. of organic EL element 1>
[Production of organic EL elements]
(Production of substrate)
<Production of first gas barrier film>
Polyester film with a thickness of 125 μm (manufactured by Teijin DuPont Films Co., Ltd., ultra-low heat yield PET Q83; measured by a spectrophotometer, transmittance of UV light at a wavelength of 385 nm: 84%, spectrophotometer 3300) as a base material, and after forming a polysilazane coating film, a vacuum ultraviolet ray irradiation treatment was performed according to the following method to form a gas barrier layer having a thickness of 250 nm, which was repeated four times to obtain a total thickness. A first gas barrier film having a gas barrier layer of 1000 nm was produced, and the light transmittance in the wavelength range of 360 to 410 nm of the gas barrier film was 70% or more. This is a value measured using a photometer in an environment of 25 ° C. and 55% RH.

(Preparation of polysilazane-containing coating solution)
A dibutyl ether solution containing 20% by mass of non-catalytic perhydropolysilazane (manufactured by AZ Electronic Materials, Aquamica (registered trademark) NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-) Perhydropolysilazane 20% by weight dibutyl ether solution (AZ Electronic Materials Co., Ltd., Aquamica (registered trademark) NAX120-20) containing 5% by weight of 1,6-diaminohexane (TMDAH) In a solvent mixed so that the mass ratio of dibutyl ether and 2,2,4-trimethylpentane is 65:35, the coating solution is mixed so that the solid content of the coating solution is 5% by mass. Was diluted and prepared.

  The coating solution obtained above was formed on the PET substrate with a spin coater so that the thickness after modification was 250 nm, left for 2 minutes, and then heat-treated for 1 minute on an 80 ° C. hot plate. And a polysilazane coating film was formed.

  After drying, the substrate was gradually cooled to 25 ° C., and the coating surface was subjected to a modification treatment by irradiation with vacuum ultraviolet rays in a vacuum ultraviolet irradiation apparatus. As a light source of the vacuum ultraviolet irradiation device, an Xe excimer lamp having a double tube structure for irradiating vacuum ultraviolet rays of 172 nm was used.

<Modification processing equipment>
Ex. Irradiator MODEL: MECL-M-1-200, light wavelength 172 nm, lamp filled gas Xe
<Reforming treatment conditions>
Excimer light intensity 3J / cm ² (172nm)
Stage heating temperature 100 ° C
Oxygen concentration in the irradiation device 1000ppm
Next, a clear hard coat layer having a thickness of 2 μm was formed as follows on the surface of the substrate opposite to the surface on which the gas barrier layer was formed.

A UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied to a resin substrate so as to have a dry layer thickness of 2 μm, dried at 80 ° C., and then using a high-pressure mercury lamp in the air. Then, curing was performed under the condition of an irradiation energy amount of 0.5 J / cm ² .

The substrate has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ mL / m ² · 24 h · atm or less, and a water vapor permeability of 1 × 10 ⁻⁴ g / m. it was confirmed that the following gas-barrier substrate ² · 24h.

<Production of organic EL element>
(Formation of first transparent electrode)
On the formed substrate, ITO (Indium Tin Oxide: ITO) having a thickness of 150 nm is formed by sputtering using a commercially available sputtering apparatus, and patterned by photolithography. A transparent electrode was formed. The pattern was such that the light emission area was 50 mm square.

(Formation of organic light emitting layer)
(Formation of hole transport layer)
On the first transparent electrode, the following coating solution for forming a hole transport layer is applied with a spin coater in an environment of 25 ° C. and a relative humidity of 50% RH, and then dried and heated under the following conditions. And a hole transport layer was formed. The coating solution for forming the hole transport layer was applied so that the thickness after drying was 50 nm.

<Preparation of hole transport layer forming coating solution>
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

<Drying and heat treatment conditions>
After applying the hole transport layer forming coating solution, the solvent was removed at a temperature of 100 ° C. using a heat treatment apparatus having a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, and a wide air velocity distribution of 5%. Then, the heat processing of the back surface heat transfer system was continuously performed at the temperature of 150 degreeC using the said heat processing apparatus, and the positive hole transport layer was formed.

(Formation of light emitting layer)
On the hole transport layer formed above, the following coating solution for forming a white light emitting layer was applied with a spin coater under the following conditions, followed by drying and heat treatment under the following conditions to form a light emitting layer. . The white light emitting layer forming coating solution was applied so that the thickness after drying was 40 nm.

<White luminescent layer forming coating solution>
As a host material, 1.0 g of a compound represented by the following chemical formula HA, 100 mg of a compound represented by the following chemical formula DA as a dopant material, and 0.1 mg of a compound represented by the following chemical formula DB as a dopant material. 2 mg of a compound represented by the following chemical formula DC as a dopant material was dissolved in 0.2 mg and 100 g of toluene to prepare a white light emitting layer forming coating solution.

<Application conditions>
The coating process was performed in an atmosphere having a nitrogen gas concentration of 99% or more and the coating temperature was 25 ° C.

<Drying and heat treatment conditions>
After applying the white light emitting layer forming coating solution, after removing the solvent at a temperature of 60 ° C. using a heat treatment apparatus having a height of 100 mm toward the film formation surface, a discharge air velocity of 1 m / s, and a wide air velocity distribution of 5%. Subsequently, heat treatment was performed at a temperature of 130 ° C. using the heat treatment apparatus to form a light emitting layer.

(Formation of electron transport layer)
On the light emitting layer formed above, the following coating liquid for forming an electron transport layer was applied with a spin coater under the following conditions, and then dried and heated under the following conditions to form an electron transport layer. The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm.

<Application conditions>
The coating process was performed in an atmosphere with a nitrogen gas concentration of 99% or more, and the coating temperature of the electron transport layer forming coating solution was 25 ° C.

<Coating liquid for electron transport layer formation>
The electron transport layer was prepared by dissolving a compound represented by the following chemical formula EA in 2,2,3,3-tetrafluoro-1-propanol to obtain a 0.5 mass% solution as a coating liquid for forming an electron transport layer.

<Drying and heat treatment conditions>
After applying the electron transport layer forming coating solution, after removing the solvent at a temperature of 60 ° C. using a heat treatment device having a height of 100 mm toward the film forming surface, a discharge air velocity of 1 m / s, and a wide air velocity distribution of 5%. Subsequently, heat treatment was performed with the heat treatment apparatus at a temperature of 200 ° C. to form an electron transport layer.

(Formation of electron injection layer)
An electron injection layer was formed on the electron transport layer formed above. First, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. In advance, cesium fluoride prepared in a tantalum vapor deposition boat was heated in a vacuum chamber to form an electron injection layer having a thickness of 3 nm.

(Formation of second electrode (reflection electrode))
Aluminum (Al) is used as the second electrode forming material on the electron injection layer formed as described above, except for the portion to be the extraction electrode of the first transparent electrode, under a vacuum of 5 × 10 ⁻⁴ Pa. A mask pattern was formed so as to have a light emitting area of 50 mm square by vapor deposition so as to have an extraction electrode, and a second electrode having a thickness of 150 nm was laminated.

(Cutting)
As described above, each laminate including the second electrode was moved again to a nitrogen atmosphere, and cut to a specified size using an ultraviolet laser to produce an organic EL element.

(Electrode lead connection)
An anisotropic conductive film DP3232S9 manufactured by Sony Chemical & Information Device Co., Ltd. was used for the produced organic EL element, and a flexible printed board (base film: polyimide 12.5 μm, rolled copper foil 18 μm, coverlay: polyimide 12.5 μm). , Surface-treated NiAu plating).

  Pressure bonding conditions: Pressure bonding was performed at a temperature of 170 ° C. (ACF temperature 140 ° C. measured using a separate thermocouple), a pressure of 2 MPa, and 10 seconds.

(Sealing)
Using the first gas barrier film as a sealing substrate, the organic EL element was sealed according to the following procedure to produce an organic EL element 101.

As shown in FIG. 11, the first gas barrier film is used as the sealing layer 222, and an epoxy thermosetting adhesive (Elephant CS manufactured by Yodogawa Paper Co., Ltd.) is used as the sealing member 221 as an adhesive. In a glove box with an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less, under conditions of 80 ° C., 0.04 MPa load, reduced pressure (1 × 10 ⁻³ MPa or less) suction 20 seconds, press 20 seconds toward the organic EL element Then, vacuum pressing was performed so that the gas barrier layer of the first gas barrier film was on the element side.

  Thereafter, the adhesive layer was thermally cured by heating on a hot plate at 110 ° C. for 30 minutes in the glove box.

<Patterning of organic EL elements>
[UV irradiation]
Using the patterning apparatus shown in FIG. 2, the produced organic EL element was patterned. The patterning conditions are shown below.

<Glass mask>
A glass mask in which a black-and-white photosensitive material was baked by a photographic method so that a dark part and a bright part were equally divided into a glass substrate (quartz glass) having a thickness of 5 mm and a size of 60 × 60 mm was used.

  A glass mask was brought into close contact with the clear hard coat layer side of the organic EL element produced above, and patterning was performed by irradiating ultraviolet rays (light wavelength 385 nm) with non-parallel light using the following procedure and the apparatus shown in FIG.

<Case>
Dimensions: W250mm × D250mm × H450mm
Material: Aluminum inner wall reflector (thickness 1.5mm)
The gap between the reflective light guide housing and the glass mask: 5.0 mm
<Ultraviolet light emitting part>
Light source: UV-LED with a wavelength of 385 nm
Irradiance: 4 W / cm ²
Accumulated irradiation time: 10 minutes (40 cycles of irradiation 15 seconds, extinguishing 15 seconds)
<Air flow generator>
Using a slit-like laminar airflow generator, the blowing part was sprayed from the direction of both short sides in the center direction of the glass mask with the same air volume.

Slit position of spraying part: 3mm above glass
Angle of sprayed part of air flow generation part: parallel to glass mask (0 degree)
A pair of air flow generators was attached at a position facing the short side of the housing with a gap 18:40 mm between the air flow generator and the housing.

Air temperature: 25 ° C
Compressed air pressure: 0.2 MPa
Air consumption: 1000L / min
<Chiller>
A water-cooled tube having a diameter of 5 mmφ was provided inside an aluminum pattern forming body mounting table, and water at a temperature of 20 ° C. was circulated at a flow rate of 5 L / min.

<Lamination of second gas barrier film>
After performing the above patterning, the first gas barrier film is used as it is as the second gas barrier film, and the gas barrier layer of the second gas barrier film and the clear hard coat layer of the first gas barrier film are bonded. It adhered by vacuum-pressing so that it might contact through an agent layer.

Using an epoxy thermosetting adhesive (Elephan CS manufactured by Yodogawa Paper Co., Ltd.) as an adhesive, reduced pressure (1 × under a 0.04 MPa load at 80 ° C. in a glove box having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less. 10 ⁻³ MPa or less) The suction was performed for 20 seconds and the press was performed for 20 seconds. Thereafter, the adhesive layer was cured by heating on a hot plate at 110 ° C. for 30 minutes in the glove box.

  12A and 12B show schematic diagrams of the above layer configuration and patterning.

  In FIG. 12A, the organic EL element 200 includes a gas barrier layer 211a, a base material 211b, and a gas barrier of a first gas barrier film configured by a hard coat layer 214 on the surface of the base material opposite to the gas barrier layer. The first electrode 215, the light emitting unit layer 216, and the second electrode 217 are stacked on the layer 211a, sealed with the sealing member 221 and the sealing layer 222, and then irradiated with ultraviolet rays through the mask 5 for patterning. Then, in FIG. 12B, the second gas barrier film 213 composed of the gas barrier layer 213a and the base material 213b is bonded through the adhesive layer 212 to form a double barrier configuration. In this case, the outermost layer of the organic EL element 200 is the hard coat layer 214.

<Pattern No. of organic EL element 2>
Patterning No. of organic EL element The high refractive index layer (niobium oxide Nb ₂ O ₅ , refractive index n) is formed on the gas barrier layer (perhydropolysilazane modified film: refractive index n ₁ = 1.62) of the first gas barrier film prepared in 1. ₂ = 2.27) was patterned in the same manner except that the organic EL element was patterned by the following procedure.

<Lamination of high refractive index layer>
Using commercially available metal niobium (Nb), a film was formed by the following DC method. The oxygen partial pressure was 20%. The film formation time was set so that the layer thickness was 10 nm.

As the sputtering apparatus, a magnetron sputtering apparatus (manufactured by Canon Anelva: Model EB1100) was used. Ar and O ₂ were used as process gases, and a DC film was formed by a magnetron sputtering apparatus. The sputtering power source power was 5.0 W / cm ² and the film forming pressure was 0.4 Pa. Further, the oxygen partial pressure was adjusted under each film forming condition. It should be noted that, after film formation using a glass substrate in advance, the layer thickness change data with respect to the film formation time is taken, the layer thickness formed per unit time is calculated, and then the film is formed so that the set layer thickness is obtained. Set the time.

  The second gas barrier film has a patterning no. The second gas barrier film used in 1 was used.

<Pattern No. of organic EL element 3>
Patterning No. of organic EL element Instead of the first gas barrier film produced in step 1, a gas barrier film was produced by the following procedure, and the organic EL was similarly used except that it was used as the first gas barrier film and the second gas barrier film. The element was patterned.

<Production of gas barrier film by CVD method>
A gas barrier layer is formed on the PET film using a plasma CVD apparatus using plasma generated by applying a voltage between opposed roller electrodes having a magnetic field generating member for generating the magnetic field shown in FIG. A barrier film was prepared. Film formation was performed by roll-to-roll.

  Specifically, it is mounted on the apparatus so that the back surface of the PET film is in contact with the counter roller electrode, and the film formation process is continuously repeated 6 times under the following film formation conditions (plasma CVD conditions). The film was formed under the condition that the thickness of the gas barrier layer was 1000 nm.

[Film formation conditions]
Deposition gas mixing ratio (hexamethyldisiloxane (HMDSO) / oxygen): 1/10 (molar ratio)
Degree of vacuum in the vacuum chamber: 2.0Pa
Applied power from the power source for plasma generation: 25 W / cm
Frequency of power source for plasma generation: 80 kHz
Substrate conveyance speed: 10 m / min
・ Drawing roller diameter: 300mmφ
・ Film roller temperature: 60 ℃
-Number of times of film formation: 6 times <Pattern No. of organic EL element 4>
Patterning No. of organic EL element 1, after forming the organic EL element on the first gas barrier film, the second gas barrier film is bonded to the first gas barrier film, and then ultraviolet rays are similarly applied from the second gas barrier film side. Irradiation was performed to pattern the organic EL element.

<Pattern No. of organic EL element 5>
Patterning No. of organic EL element 4, benzotriazole UV absorber Tinuvin 928 (manufactured by BASF Japan Ltd.) is used as an epoxy thermosetting adhesive as an adhesive when the second gas barrier film is bonded to the first gas barrier film. The organic EL element was patterned in the same manner except that 2.0% by mass was added.

≪Evaluation≫
[1] Measurement of luminance ratio The organic EL element subjected to the above patterning is energized, light is adjusted by adjusting the current so that the luminance of the bright portion becomes 700 cd / m ^2, and the luminance of the dark portion at that time is measured. The ratio (bright / dark) was calculated. The luminance was measured using a spectral radiance meter CS-2000 manufactured by Konica Minolta. The target luminance ratio in the present invention is 200 or more.

[2] Amount of irradiation pattern deviation (δ) The organic EL element subjected to the above patterning is energized, and the current is adjusted so that the brightness of the bright portion becomes 700 cd / m ² to emit light. Using a possible luminance meter, the width dimension of the region where the luminance decreased from the bright part to the dark part was measured, and the irradiation pattern deviation δ was obtained. The luminance distribution was measured using a two-dimensional color luminance meter CA-2000 manufactured by Konica Minolta.

  Table 1 shows the patterning configuration of the organic EL element, the luminance ratio, and the result of the irradiation pattern deviation.

  From Table 1, it can be seen that the organic EL element patterning method according to the present invention enables patterning with a target luminance ratio and reduced irradiation pattern deviation.

  Patterning No. which is a comparative example and is patterned after laminating the second gas barrier film. 4, the luminance ratio is significantly lower than the target value, and the irradiation pattern shift amount is large. In addition, when the first gas barrier film and the second gas barrier film are bonded, a patterning No. 1 containing an ultraviolet absorbent in the adhesive is used. 5, it was found that the luminance ratio was extremely low, and almost no deactivation (patterning) of the organic EL element layer occurred.

Example 2
Patterning No. 1 of the organic EL element of Example 1 1, the organic EL element was patterned in the same manner except that the patterning was performed by the following method.

<Pattern No. of organic EL element by dot drawing 6>
Patterning No. of organic EL element 1, after forming an organic EL element on the first gas barrier film, using the apparatus shown in FIG. 5, patterning of the organic EL element by spot drawing with blue-violet light having a light wavelength of 405 nm is performed without using a glass mask. Went. At that time, the light spot is moved in the X direction and the Y direction on the organic EL element, and the ultraviolet spot is irradiated so as to divide the organic EL element into two equal parts as in the first embodiment. Was made.

  When the luminance ratio (bright part / dark part) was measured in the same manner as in Example 1, the luminance ratio was 200, and the patterning according to the present invention could be performed by patterning the organic EL element by dot drawing. I understood.

  On the other hand, patterning no. In FIG. 4, after the second gas barrier film was bonded, the patterning of the organic EL element was similarly performed by dot drawing. As a result, the transmittance of blue-violet light decreased due to the influence of the double gas barrier film. Under the irradiation conditions, the luminance ratio was 130. In order to increase the luminance ratio to 200 or more, it is necessary to further increase the irradiance or to extend the irradiation time, which is a result of an increase in cost and a decrease in production efficiency.

  The method for producing an organic electroluminescent element of the present invention is a method for patterning an organic electroluminescent element having a high gas barrier property, which suppresses an increase in cost and a decrease in production efficiency, and also performs patterning through a mask. Therefore, it is a suitable method for producing a highly accurate organic electroluminescence element with high productivity.

DESCRIPTION OF SYMBOLS 1 1st gas barrier film 2 2nd gas barrier film 3 Organic EL element 4 Sealing material 5 Mask 6 Non-parallel light 7 Light-shielding film 10 Patterning apparatus 11 Ultraviolet light emission part 11a Light source substrate 11b Light source 11c Lens array 12 Case (reflector)
DESCRIPTION OF SYMBOLS 13 Glass mask 14 Air flow 15 Air flow generation part 16 Organic EL element which used 1st gas barrier film as a board | substrate 17 The space | interval of a glass mask and a housing | casing 18 Distance of a housing | casing and an air flow generation | occurrence | production part 19 Pattern formation object mounting Stand (chiller)
19a Water-cooled tube (introduction)
19b Water-cooled pipe (discharge)
DESCRIPTION OF SYMBOLS 20 Light source part 21 Heat sink 22 Mask holding base 23 Elevating part 24 Support base 25 Mask alignment apparatus 26 Camera 27 Alignment part 28 Alignment mark 29 Alignment mark 30 Manufacturing apparatus 31 Delivery rollers 32, 33, 34, 35 Conveyance rollers 36, 37 Film roller 38 Gas supply pipe 39 Plasma generating power source 40 Film 41, 42 Magnetic field generator 43 Winding roller 100 Pattern forming device 101 Light source 102 Light irradiation unit 103 Collimator lens 104 Condensing lens 105 Beam splitter 106 Photo detector 107 Reflection Mirror 108 Adjusting unit 109 Moving unit 110 Control unit 200 Organic EL element 211 First gas barrier film 211a Gas barrier layer 211b Base material 212 Adhesive layer 213 Second gas barrier Film 213a gas barrier layer 213b substrate 214 hard coat layer 215 first electrode 216 light-emitting unit layer 217 second electrode 221 sealing member 222 sealing layer

Claims (8)

A method for producing an organic electroluminescence device comprising at least a laminate of a first gas barrier film and a second gas barrier film as a substrate,
After forming the organic electroluminescence element using the first gas barrier film as a substrate,
Patterning is performed by irradiating light to the organic electroluminescence element from the first gas barrier film side,
The second gas barrier film is bonded to the surface of the first gas barrier film opposite to the surface on which the organic electroluminescence element is formed via an adhesive layer or an adhesive layer, and the laminate. A method for producing an organic electroluminescence element, comprising:   The method for producing an organic electroluminescent element according to claim 1, wherein the wavelength of the light is in a range of 360 to 410 nm.   The method of manufacturing an organic electroluminescent element according to claim 1, wherein the light is irradiated as non-parallel light through a mask.   The manufacturing method of the organic electroluminescent element of Claim 1 or 2 which concentrates the said light, forms a light spot on the said organic electroluminescent element, and performs the said patterning by point drawing.   The thickness of the said 1st gas barrier film exists in the range of 20-500 micrometers, The manufacturing method of the organic electroluminescent element as described in any one of Claim 1- Claim 4 characterized by the above-mentioned.   6. The organic electroluminescent device according to claim 1, wherein the first gas barrier film has a light transmittance of 60% or more in a wavelength range of 360 to 410 nm. Manufacturing method.   The refractive index difference between the gas barrier layer of the first gas barrier film and the functional layer in contact with the gas barrier layer is 1.5 or less, and the refractive index difference is 1.5 or less. The manufacturing method of organic electroluminescent element of this.   8. The organic electroluminescent element according to claim 1, wherein the second gas barrier film, the adhesive layer, or the pressure-sensitive adhesive layer has ultraviolet light shielding properties. Production method.

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