JPWO2017090577A1 - Light emitting device - Google Patents

Abstract

The subject of this invention is providing the light-emitting device which can be reduced in size at the time of carrying. The light emitting device of the present invention is a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element, or At least one of the organic light-emitting element and the back-side base material has a gas barrier layer mainly composed of an inorganic material, and the light-emitting device is supported by having a fixed part and a movable part on a support member. Furthermore, the curvature radius of the curved surface formed by the movable portion of the organic light emitting element when being carried has a curved surface portion within a range of 1.0 to 10.0 mm.

Description

  The present invention relates to a light emitting device, and more particularly to a light emitting device that can be miniaturized when carried.

  An organic electroluminescence element (hereinafter also referred to as “organic EL element”) using electroluminescence of an organic material (hereinafter also referred to as “EL”) can emit light at a low voltage of several V to several tens V. It is a thin film type complete solid-state device and has many excellent features such as high brightness, high luminous efficiency, thinness, and light weight. For this reason, it is applied as a backlight for various displays, display boards such as signboards and emergency lights, and surface light emitters such as illumination light sources.

  In particular, in recent years, a flexible organic EL element using a resin substrate having a thin and lightweight gas barrier layer has attracted attention, and is applied as a light source having a curved surface and high design properties.

  However, when a bending moment is applied to the organic EL element, shear stress is generated between the layers constituting the organic EL element, causing peeling of the layer. There is a demand for an organic EL element that does not generate odor, and various studies have been made.

  As one method, a method in which a gas barrier layer is formed on a glass substrate and then peeled and transferred to a resin base material has been studied (see Patent Document 1).

  However, the light-emitting device currently under investigation is only a prototype for verifying flexibility, and no specific configuration as a practical device has been presented. Therefore, a specific configuration of the light emitting device that suppresses the deterioration of the light emitting device has been demanded.

JP-A-2015-173249

  The present invention has been made in view of the above problems and situations, and a problem to be solved is to provide a light emitting device that can be miniaturized when being carried.

In order to solve the above problems, the present inventor has a gas barrier layer between a resin base material and an organic light emitting element of an organic light emitting element sandwiched between two resin base materials in the process of examining the cause of the above problem, etc. In the present invention, the present invention has found that the above-mentioned problems can be solved by setting the radius of curvature of the curved surface formed by the organic light-emitting element within the range of 1.0 to 10.0 mm when folding or winding the light-emitting device. It came.

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

  1. A light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element or between the organic light emitting element and the back surface side base At least one of the materials has a gas barrier layer containing an inorganic material as a main component, and the light emitting device is supported on a support member with a fixed portion and a movable portion. A light emitting device comprising a curved surface portion having a curved radius of curvature of 1.0 to 10.0 mm formed by the movable portion of the light emitting element.

  2. At the time of carrying, it has a folded form, the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable part of the organic light emitting element has its light emitting surface bent outward. A portion A and a portion B in which the light emitting surface is bent inward; the portion A and the portion B are continuously present via an inflection point of curvature; and the length of the movable portion is L And when the protruding length of the loop formed by the movable portion from the support member is C, C / L is 0.3 or more, and the part B with respect to the minimum curvature radius Ar of the part A 2. The light emitting device according to item 1, wherein the ratio value (Br / Ar) of the minimum curvature radius Br is in the range of 0.4 to 1.1.

  3. At the time of carrying, it has a winding form, and the back side substrate is installed on a rigid support member via a viscoelastic sheet-like member, and the light emitting surface side resin substrate is wound outside. The movable part that is taken and the end part on the outer side of the winding of the light emitting device is fixed so that the position is not relatively displaced, and the position of the inner side of the winding is relatively variable 2. The light-emitting device according to item 1, wherein

  4). 4. The light emitting device according to claim 1, wherein the total thickness of the gas barrier layer is in a range of 20 to 1000 nm.

  5. Any one of Items 1 to 4, wherein a radius of curvature of the curved surface formed by the movable portion of the organic light emitting element has a curved surface portion within a range of 1.0 to 5.0 mm. The light emitting device according to item.

  6). The gas barrier layer is a region containing the non-transition metal M1 and the transition metal M2 at least in the thickness direction, and the value of the atomic ratio of the transition metal M2 to the non-transition metal M1 (M2 / M1) is Item 6. The light-emitting device according to any one of Items 1 to 5, wherein a mixed region in the range of 0.02 to 49 is continuously 5 nm or more in the thickness direction.

  7). The gas barrier layer includes the mixed region between a region containing the transition metal M2 as a main component of the metal and a region containing the non-transition metal M1 as a main component of the metal. 7. The light emitting device according to item 6.

  8). The light emitting device according to claim 6 or 7, wherein the entire region in the thickness direction in the gas barrier layer is a mixed region containing the transition metal and the non-transition metal.

9. When the composition of the mixed region is expressed by the following chemical composition formula (1), the following relational expression (2) is satisfied: The light-emitting device according to any one of items 6 to 8 .
Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Wherein, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen,
x, y, z: stoichiometric coefficient, a: maximum valence of M1, b: maximum valence of M2. )
10. The light-emitting device according to any one of Items 6 to 9, wherein the non-transition metal is silicon.

  11. 11. The light emitting device according to any one of items 6 to 10, wherein the transition metal is selected from niobium (Nb), tantalum (Ta), and vanadium (V).

  12 The light-emitting device according to any one of Items 1 to 11, further comprising an organic electroluminescence element.

  With the above-described means of the present invention, a light-emitting device that can be miniaturized when being carried can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  Conventionally, flexible light-emitting elements have been known, but their specific configuration has not been known. In the present invention, it is considered that the size can be reduced because the stress on the light emitting element when folded, wound or taken up can be reduced.

An example of a cross-sectional view of a light emitting part of a light emitting device of the present invention An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a folded configuration An example of a schematic diagram illustrating a light-emitting device having a bent configuration Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal Conceptual diagram showing the thickness change of the adhesive during winding and withdrawal An example showing the preferred shape of the support member Example of graph for explaining element profile and mixed region when composition distribution of non-transition metal and transition metal is analyzed by XPS method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method Diagram explaining the peeling method

  The light emitting device of the present invention is a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element, or At least one of the organic light-emitting element and the back-side base material has a gas barrier layer mainly composed of an inorganic material, and the light-emitting device is supported by having a fixed part and a movable part on a support member. Furthermore, the curvature radius of the curved surface formed by the movable portion of the organic light emitting element when being carried has a curved surface portion within a range of 1.0 to 10.0 mm. This feature is a technical feature common to the inventions according to claims 1 to 12.

  As an embodiment of the present invention, when folded, the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable portion of the organic light emitting element emits light. A portion A whose surface is bent outward, and a portion B whose light emitting surface is bent inward, wherein the portion A and the portion B exist continuously via an inflection point of curvature, and When the length of the movable part is L and the protruding length of the loop formed by the movable part from the support member is C, C / L is 0.3 or more and the minimum of the part A It is preferable that the ratio value (Br / Ar) of the minimum curvature radius Br of the part B to the curvature radius Ar is in the range of 0.4 to 1.1. Thereby, the stress applied to the organic light-emitting element is small, and a small-sized folded light-emitting device can be obtained.

  As an embodiment of the present invention, when carrying, the light emitting surface side resin has a winding form, and the back side base material is installed on a rigid supporting member via a sheet-like member having viscoelasticity. The base is wound outside and the winding outer end of the light emitting device is fixed so that the position does not shift relatively, and the winding inner is relatively positioned. It is preferable that the movable part is variable. Thereby, since the shift of the positional relationship between the light emitting device and the support member due to the difference in winding diameter that occurs during winding can be reduced and the stress applied to the organic light emitting element can be reduced, it is possible to obtain a light emitting device with a small winding form. it can.

  Furthermore, in the present invention, the total thickness of the gas barrier layer is preferably in the range of 20 to 1000 nm. Thereby, the effect which makes favorable bending durability and gas barrier property compatible is acquired.

  In order to realize a small light emitting device, it is preferable that the curved surface formed by the movable portion of the organic light emitting element has a curved radius within a range of 1.0 to 5.0 mm.

  As an embodiment of the present invention, the gas barrier layer is a region containing the non-transition metal M1 and the transition metal M2 at least in the thickness direction, and has an atomic ratio of the transition metal M2 to the non-transition metal M1. It is preferable to have a mixed region having a value (M2 / M1) in the range of 0.02 to 49 continuously in the thickness direction by 5 nm or more. As a result, even if the gas barrier layer is a thin layer, an extremely high gas barrier property can be obtained. Therefore, by making the gas barrier layer thinner, it is possible to achieve both better bending durability and gas barrier property. Is obtained.

  In the embodiment, the gas barrier layer includes the mixed region between a region containing the transition metal M2 as a metal main component and a region containing the non-transition metal M1 as a metal main component. It is preferable to have

  Furthermore, it is preferable that the entire region in the thickness direction in the gas barrier layer is a mixed region containing the transition metal and the non-transition metal. Thereby, a very high gas barrier property is obtained.

  When the composition of the mixed region is expressed by the chemical composition formula (1), it is preferable that the relational expression (2) is satisfied. Thereby, better gas barrier properties can be obtained.

  Furthermore, in the present invention, the non-transition metal is preferably silicon.

  The transition metal is preferably selected from niobium (Nb), tantalum (Ta), and vanadium (V). This combination of metal elements provides the best gas barrier properties.

  The light emitting device of the present invention preferably includes an organic EL element.

  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 Light Emitting Device of the Present Invention >>
The light emitting device of the present invention is a light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element, or At least one of the organic light-emitting element and the back-side base material has a gas barrier layer mainly composed of an inorganic material, and the light-emitting device is supported by having a fixed part and a movable part on a support member. Furthermore, the curvature radius of the curved surface formed by the movable portion of the organic light emitting element when being carried has a curved surface portion within a range of 1.0 to 10.0 mm.

When the gas barrier property of the gas barrier layer according to the present invention is calculated using a laminate in which the gas barrier layer is formed on a substrate, the oxygen permeability measured by a method according to JIS K 7126-1987 is 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)) measured by a method based on JIS K 7129-1992 % RH) is preferably a high gas barrier property of 1 × 10 ⁻³ g / (m ² · 24 h) or less.

  FIG. 1 is an example of a cross-sectional view of a light emitting portion of a light emitting device of the present invention.

  The light emitting device has a light emitting portion L in which the light emitting surface side resin base material 2, the organic light emitting element 3 and the back surface side base material 4 are laminated in this order. In this example, the light emitting surface side resin base material 2 and the organic light emitting element 3, and between the organic light emitting element 3 and the back side substrate 4, a gas barrier layer 5 is provided. The organic light emitting element 3 may be, for example, an organic EL element, has an organic functional layer unit 7 including at least a light emitting layer via two electrodes 6, and is sealed with a sealing member 8. The light emitting surface side resin base material 2 or the base material 4 may have a hard coat layer on both sides, and may have an adhesive layer as an intermediate layer, and a protective film on the outermost layer via an adhesive layer. . The organic functional layer unit has a hole transport layer, an electron transport layer, and the like in addition to the light emitting layer.

  This light-emitting device has a curved surface portion having a curved radius of curvature of 1.0 to 10.0 mm formed by the movable portion of the organic light-emitting element 7 when carried. When the curvature radius Ar of the part A or the curvature radius Br of the part B is less than 1.0, the base material itself deteriorates due to repeated bending, which is not preferable. Further, if the curvature radius exceeds 10.0 mm, it is not suitable as a small light emitting device.

  Here, the fixed portion refers to a portion where the light emitting device is fixed on the support member and the positional relationship between the light emitting device and the support member does not change, and the movable portion refers to the light emitting device not fixed on the support member. When the light emitting device is folded, the positional relationship between the support member and the light emitting device is generated between the inner side and the outer side of the folding. A part that absorbs the deviation caused by the difference in winding diameter and slightly changes.

  Moreover, it is preferable that the organic light emitting element 3 is sandwiched between the two base materials 2 and 4, and it is more preferable that the two base materials have the same thickness and the same elastic modulus. It can be expected that the stress applied to the organic light emitting element 3 located at the center of bending is brought close to zero when the light emitting device is bent because the two base materials have the same thickness and the same elastic modulus. it can.

  The total thickness of the light emitting device is preferably in the range of 20 to 200 μm. More preferably, it exists in the range of 30-150 micrometers, More preferably, it exists in the range of 30-100 micrometers. It is considered that by reducing the thickness, the stress applied to the organic light emitting element 1 when bent can be further reduced.

  Further, the total thickness of the gas barrier layer 5 is preferably in the range of 20 to 1000 nm from the viewpoint of achieving both the gas barrier property and the bending resistance of the gas barrier layer.

  With such a light-emitting device, it is possible to reduce the size of the light-emitting device when carried. Preferred embodiments include a light-emitting device that is folded and a light-emitting device that is rolled up when carried.

<< Light-emitting device having a folded form >>
When the light emitting device having a folded configuration is carried, the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable portion of the organic light emitting element is bent outward. A portion A and a portion B in which the light emitting surface is bent inward; the portion A and the portion B are continuously present via an inflection point of curvature; and the length of the movable portion is L And when the protruding length of the loop formed by the movable portion from the support member is C, C / L is 0.3 or more, and the part B with respect to the minimum curvature radius Ar of the part A The ratio value (Br / Ar) of the minimum curvature radius Br is preferably in the range of 0.4 to 1.1. Here, in the case of a light-emitting device having a folded configuration, the movable portion usually has a plurality of curved surfaces, and therefore the radius of curvature of the portion A and the portion B uses the minimum radius of curvature. The minimum curvature radii of the part A and the part B are the minimum ones among the curvature radii of a plurality of curved surfaces of the organic light emitting element when bent.

  2A to 2C are examples of schematic diagrams illustrating a light-emitting device having a folded configuration.

  FIG. 2A shows a state in which the light-emitting device supported by the support housing 10 and the support housing 11 as two support members is bent. The bent light emitting device 1 has a portion A where the light emitting surface is bent outward and a portion B where the light emitting surface is bent inward via an inflection point. A portion where the light emitting portion L is supported by the support housing 10 and the support housing 11 is a fixed portion, and a portion A and a portion B are movable portions.

  FIG. 2C shows a state when the light emitting device 1 is opened. The hinge portion 12 having the hinge portion 12 between the support housings 10 and 11 has a function of protecting the light emitting device together with the support housings 10 and 11. When the light emitting device 1 is opened, the hinge portion 12 does not need to be in contact with the light emitting portion L.

  Conventionally, the form which makes a bending part U shape is known. However, in the case of the U-shaped form, in order to reduce the size, if the gap between the light emitting surface side resin base materials is less than 2 mm, the stress applied to the light emitting device at the time of bending increases, and there is a drawback that problems such as bending durability are likely to occur. was there.

In order to reduce this stress and enable miniaturization, the present invention has a portion A in which the light emitting surface is bent outward and a portion B in which the light emitting surface is bent inward. C / L is 0.3 or more, and the minimum curvature of the part A, where L is the length of the part and C is the protruding length of the loop formed by the movable part from the support member The ratio value (Br / Ar) of the minimum curvature radius Br of the portion B to the radius Ar is preferably in the range of 0.4 to 1.1. More preferably, it exists in the range of 0.6-1.1, More preferably, it exists in the range of 0.8-1.05. This is because, when the length of the hinge portion 12 is constant, the configuration in which the curvature when the light emitting surface is bent inward and the curvature when the light emitting surface is bent outward is approximate is the method for maximizing the minimum curvature. It is.
Thus, in order to make the curvature radius of the curved surface which the site | part A and the site | part B form close, it is preferable that the light emission part L is being fixed on the support member with high rigidity. In the case of a light emitting device having a folded configuration, specifically, the light emitting portion L other than the hinge portion 12 needs to be fixed to the support housing as a support member. The hinge portion is not fixed to the support housing so that it can be folded freely.

  When the light emitting device is folded in the absence of the hinge portion 12, a portion with a small radius of curvature is generated as shown in FIG. 2B (the minimum radius of curvature Br becomes small), but the hinge portion 12 is appropriately pushed into the fixed portion side. (Pressing the hinge portion 12 to the left in FIG. 2A) makes it possible to make the curved surface formed by the portion B close to a circle. However, if pushed too much, C / L becomes small. In this case, the loop has a shape extending up and down, and the compactness of the movable part is impaired. The B part is preferably substantially circular, and the C / L is more preferably 0.35 or more because the minimum curvature radius of the part A is not too small with respect to the minimum curvature radius of the part B. The above is more preferable. The upper limit of C / L may be adjusted so that the value of Br / Ar falls within the range of the present invention.

  In addition, the protrusion length C from a support member means the length of A + B in FIGS. In the above figure, if the positions in contact with the movable parts 10 and 11 are different (the lengths of A and B are different on the top and bottom of the loop in the figure), C is the average value.

  In this way, by approximating the curvature radii of the part A and the part B, the stress on the light emitting part L of the light emitting device applied to the part A and the part B can be reduced.

  The length of the hinge part 12 is preferably in the range of 4 to 17 mm.

  Usually, since the minimum curvature radius of the part A is larger than the minimum curvature radius of the part B, it is preferable to have means for adjusting the minimum curvature radii of the part A and the part B. In the method of adjusting the minimum curvature radius, it is preferable that the value of the ratio of the minimum curvature radius Br of the part B to the minimum curvature radius Ar of the part A is within the above range. For example, when it is bent, it can be adjusted by pressing from behind the light emitting device using a member constituting a hinge portion that supports the bent portion of the light emitting device from behind.

  Of course, in the light emitting device of this embodiment, the smaller the minimum curvature radius Ar and the minimum curvature radius Br, that is, the emphasis on making the shape of the folding part that is the movable part more compact, the respective minimum curvature radii are: As the light emitting device is designed to approach 1.0 mm, the damage to the movable part due to repeated folding increases. However, even in an apparatus having such a design, by having a movable part that falls within the scope of the present invention, an effect of improving folding durability can be obtained with respect to an apparatus having a movable part outside the scope of the present invention.

<< Light-emitting device having winding form >>
At the time of carrying, the back side resin base material is installed on a rigid support member having a winding form through a sheet-like member having viscoelasticity, and the light emitting surface side resin base material is wound outward. And the outer end of the light emitting device is fixed so that the position does not relatively shift (hereinafter also referred to as a fixed end), and the inner side of the winding is a movable part. The end portion is preferably a free end whose position can be relatively changed. That is, it is preferable that a part of the back side substrate of the light emitting unit of the light emitting device is fixed on a support member having high rigidity. In the case of a light emitting device having a winding form, specifically, an end portion far from the winding shaft on the outer side of the light emitting device is fixed. It is preferable that the support member has high rigidity capable of supporting the light emitting portion.

  FIG. 3 is an example of a schematic diagram illustrating a light emitting device having a winding form.

  In the light-emitting device 1 having a winding form, the back-side base material of the light-emitting portion L is installed on a rigid support member 21 via a sheet-like adhesive 22 having viscoelasticity, and the light-emitting surface-side resin base material It is structured to wind around the winding member 24 in the housing 23 with the outer side facing out. And the end part far from the winding shaft outside the winding of the light emitting device 1 is a fixed part fixed so as not to be relatively displaced. For example, it is fixed to the control unit 26. And the winding inner side is a movable part whose position can change relatively.

  When the light emitting portion L formed on the support member 21 is taken up in a winding form, the positional relationship between the light emitting portion L and the support member 21 is shifted due to a difference in winding diameter. In the present invention, one end of the light emitting portion L of the light emitting device is fixed to the support member. By fixing in this way, the wiring of the light emitting device can be secured. The other end of the light emitting portion L is a movable portion whose relative position can be changed with respect to the support member, so that stress can be reduced even if the radius of curvature formed by the movable portion of the light emitting portion L is reduced. .

  By installing the back side base material of the light emitting part L via a sheet-like adhesive having viscoelasticity, the stress caused by winding is taken up because the adhesive deforms and absorbs due to shear elongation due to shearing elongation. Is considered to be difficult to be transmitted to the light emitting device. When the winding is performed as the inside of the light emitting device, the above-described elongation relationship is reversed, and the free end may not be fixed on the support member.

  The sheet-like pressure-sensitive adhesive 22 preferably has viscoelasticity because it not only supports the light-emitting portion L on the support member 21 but also has a function of absorbing a shift that occurs during winding. As the adhesive having viscoelasticity, an acrylic or silicon adhesive can be used.

  Furthermore, the magnitude of the shift between the support member 21 and the light emitting portion L that occurs during winding increases as the winding proceeds. In order to make the shearing deformation applied to the adhesive during winding constant and to average the stress applied to the light emitting portion L, it is preferable that the thickness of the adhesive after winding is constant. Therefore, it is preferable that the adhesive on the free end side is thicker than the adhesive on the fixed end side.

  4A to 4D are conceptual diagrams showing changes in the thickness of the pressure-sensitive adhesive during winding and drawing. For example, as shown in FIG. 4A, a light emitting part L having a length of 100 mm and a thickness of 60 μm is installed on a support member having a thickness of 100 μm via a pressure-sensitive adhesive having a thickness of 100 μm, and this is wound around a radius of 5 mm. When wound in a casing having a take-up member, as shown in FIG. 4B, the positions of the support member and the light-emitting device at the free end are shifted by about 3 mm, and the thickness of the adhesive is considered to be about 70% of the original. The drawing at the time of winding is a schematic diagram in which the free end is flat for comparison.

  As shown in FIG. 4C, when pulling out, the thickness of the pressure-sensitive adhesive is inclined to increase the free end side, and the pressure-sensitive adhesive is formed so that the thickness of the pressure-sensitive adhesive is constant during winding. At the time of taking, the stress concerning the light emitting part L can be reduced, which is preferable.

  Furthermore, as shown to FIG. 4D, the form which can align the free end of an organic light emitting element and an adhesive at the time of winding may be sufficient.

  Further, in order to smoothly pull out and wind up, the support member preferably has a shape in which the edge is bent and the planar shape is maintained when being pulled out.

  FIG. 5 is an example showing a preferable shape of the support member in the winding form. The support member maintains a flat surface in the wound state, and has a shape in which the edge bends as shown in the drawing when pulled out in the direction of the arrow.

  In addition, it is preferable to use a metal plate such as a steel plate as the support member in order to increase rigidity.

  The configuration of the present invention will be described in detail below.

<Gas barrier layer>
The gas barrier layer according to the present invention has a mixed region containing a non-transition metal M1 and a transition metal M2 at least in the thickness direction, and has an atomic ratio of the transition metal M2 to the non-transition metal M1 in the mixed region. The gas barrier layer is characterized in that a region having a value (M2 / M1) within a range of 0.02 to 49 is continuously 5 nm or more in the thickness direction.

  Furthermore, as the gas barrier layer, a region A containing a transition metal of Group 3 to Group 11 as the main component a of metal, and a non-transition metal of Group 12 to Group 14 as the main component b of metal. It is a preferable embodiment to have a mixed region containing a compound derived from the main component a and the main component b between the B region to be contained.

  Moreover, in the gas barrier layer according to the present invention, it is also a preferable embodiment that the mixed region is formed over the entire region in the layer.

  In this mixed region, transition metal, non-transition metal, and oxygen are preferably contained. In addition, the mixed region preferably includes at least one of a mixture of a transition metal oxide and a non-transition metal oxide, or a composite oxide of a transition metal and a non-transition metal. More preferably, a composite oxide of a transition metal and a non-transition metal is contained.

  In addition, when the composition of the mixed region is represented by the following chemical composition formula (1), it is preferable that at least a part of the mixed region satisfies the condition defined by the following relational formula (2).

Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
In the above formulas, M1 represents a non-transition metal, M2 represents a transition metal, O represents oxygen, and N represents nitrogen. x, y, and z are stoichiometric coefficients, respectively, a represents the maximum valence of M1, and b represents the maximum valence of M2.

  Hereinafter, the details of the gas barrier layer according to the present invention will be further described.

[Each area constituting the gas barrier layer]
Although the area | region which comprises the gas barrier layer based on this invention is demonstrated, the definition of the technical term used below is demonstrated previously.

  In the present invention, the “region” means a plane that is substantially perpendicular to the thickness direction of the gas barrier layer (that is, a plane parallel to the outermost surface of the gas barrier layer), and the gas barrier layer has a constant or arbitrary thickness. This is a three-dimensional range (region) between two opposing surfaces formed when divided by 1. The composition of components in the region changes gradually even if the composition is constant in the thickness direction. It may be what you do.

  The “constituent component” in the present invention means a compound constituting a specific region of the gas barrier layer and a simple substance of metal or nonmetal. In addition, the “main component” in the present invention refers to a component having the maximum content as an atomic composition ratio. For example, “metal main component” refers to a metal component having the maximum content as an atomic composition ratio among the metal components in the constituent components.

  The “mixture” in the present invention refers to a product in a state where the constituent components in the regions A and B are mixed without being chemically bonded to each other. For example, a state in which niobium oxide and silicon oxide are mixed without being chemically bonded to each other.

  In the present invention, the “compound derived from the main component a and the main component b” refers to the main component a and the main component b themselves, and a composite compound formed by the reaction between the main component a and the main component b.

  A “composite oxide” will be described as a specific example of the composite compound. The “composite oxide” is a compound (oxide) formed by chemically bonding the constituent components in the regions A and B to each other. Say. For example, a compound having a chemical structure in which a niobium atom and a silicon atom form a chemical bond directly or through an oxygen atom. In the present invention, a complex formed by physically bonding the constituent components of the regions A and B to each other by intermolecular interaction or the like is also included in the “composite oxide” according to the present invention. And

  Next, each region will be described in detail.

(Transition metal-containing region: A region)
The A region which is a transition metal-containing region refers to a region containing a transition metal as the main component a of the metal.

  The transition metal (M2) 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, Y , Zr, Nb, Mo, Tc, Ru, Rh, 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 these, Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, etc. are mentioned as a transition metal (M2) from which a favorable gas barrier property is obtained. Among these, Nb, Ta, and V, which are Group 5 elements, are preferably used from the viewpoint of easy binding to the non-transition metal (M1) contained in the gas barrier layer, based on various examination results. it can.

  In particular, when the transition metal (M2) is a Group 5 element (particularly Nb) and the non-transition metal (M1), which will be described in detail later, is Si, a significant gas barrier property improvement effect can be obtained. A particularly preferred combination. 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 (M2) is particularly preferably Nb or Ta from which a compound with good transparency can be obtained.

  The thickness of the A region is preferably in the range of 2 to 50 nm, more preferably in the range of 4 to 25 nm, and more preferably in the range of 5 to 15 nm from the viewpoint of achieving both gas barrier properties and optical properties. More preferably it is.

(Non-transition metal-containing region: B region)
The B region, which is a non-transition metal-containing region, refers to a region containing a non-transition metal as a metal main component b. The “compound” here, that is, the “non-transition metal compound” means a compound containing a non-transition metal, for example, a non-transition metal oxide.

  As the non-transition metal (M1), a non-transition metal selected from metals of Groups 12 to 14 of the long-period periodic table is preferable. The non-transition metal is not particularly limited, and any metal of Group 12 to Group 14 can be used alone or in combination. Examples thereof include Si, Al, Zn, In, and Sn. . Especially, it is preferable that Si, Sn, or Zn is included as the non-transition metal (M1), Si is more preferable, and Si alone is particularly preferable.

  The thickness of the B region is preferably in the range of 10 to 1000 nm, more preferably in the range of 20 to 500 nm, and in the range of 50 to 300 nm from the viewpoint of achieving both gas barrier properties and productivity. More preferably it is.

(Mixed area)
The mixed region according to the present invention includes a non-transition metal (M1) selected from metals of Group 12 to Group 14 of the long-period periodic table and a transition metal selected from metals of Group 11 to Group 3 elements. (M2) is a region containing a mixed region in which the value (M2 / M1) of the atomic number ratio of the transition metal M2 to the non-transition metal M1 is in the range of 0.02 to 49. This is a region having 5 nm or more continuously in the vertical direction.

  Here, the mixed region may be formed as a plurality of regions having different chemical compositions of the constituent components, or may be formed as a region in which the chemical compositions of the constituent components are continuously changed. .

  The region other than the mixed region of the gas barrier layer may be a region such as a non-transition metal (M1) oxide, nitride, oxynitride, or oxycarbide, or a transition metal (M2) oxide. It may be a region of nitride, oxynitride, oxycarbide, or the like.

(Oxygen deficient composition)
In the present invention, it is preferable that a part of the composition contained in the mixed region has a non-stoichiometric composition (oxygen deficient composition) in which oxygen is lost.

In the present invention, the oxygen deficient composition is defined by the following relational expression (2) when at least a part of the composition of the mixed region is expressed by the following chemical composition formula (1). It is defined as satisfying the condition. In addition, as the oxygen deficiency index indicating the degree of oxygen deficiency in the mixed region, the minimum value obtained by calculating (2y + 3z) / (a + bx) in the certain mixed region is used.
Chemical composition formula (1)
(M1) (M2) _x O _y N _z
Relational expression (2)
(2y + 3z) / (a + bx) <1.0
In the above formulas, M1 represents a non-transition metal, M2 represents a transition metal, O represents oxygen, N represents nitrogen, and x, y, and z represent stoichiometric coefficients, respectively. a represents the maximum valence of M1, and b represents the maximum valence of M2.

  Hereinafter, when no special distinction is required, the composition represented by the chemical composition formula (1) is simply referred to as the composition of the composite region.

As described above, the composition of the composite region of the non-transition metal (M1) and the transition metal (M2) according to the present invention is represented by (M1) (M2) _x O _y N _z which is the formula (1). As is clear from this composition, the composition of the composite region may partially include a nitride structure, and it is more preferable to include a nitride structure from the viewpoint of gas barrier properties.

  Here, the maximum valence of the non-transition metal (M1) is a, the maximum valence of the transition metal (M2) is b, the valence of O is 2, and the valence of N is 3. When the composition of the composite region (including a part of the nitride) is a stoichiometric composition, (2y + 3z) / (a + bx) = 1.0. This formula means that the total number of bonds of non-transition metal (M1) and transition metal (M2) is equal to the total number of bonds of O and N. In this case, non-transition metal (M1) And the transition metal (M2) are bonded to either O or N. In the present invention, when two or more kinds are used together as the non-transition metal (M1), or when two or more kinds are used together as the transition metal (M2), the maximum valence of each element is set to The composite valence calculated by performing the weighted average according to the existence ratio is adopted as the values of a and b of each “maximum valence”.

  On the other hand, in the mixed region according to the present invention, when (2y + 3z) / (a + bx) <1.0 shown by the relational expression (2), a bond between the non-transition metal (M1) and the transition metal (M2) This means that the total number of O and N bonds is insufficient with respect to the total, and such a state is the above-mentioned “oxygen deficiency”.

  In the oxygen deficient state, the remaining bonds of the non-transition metal (M1) and the transition metal (M2) have the possibility of bonding to each other, and the metals of the non-transition metal (M1) and the transition metal (M2) When they are directly bonded, it is considered that a denser and higher-density structure is formed than when bonded between metals via O or N, and as a result, gas barrier properties are improved.

  In the present invention, the mixed region is a region where the value of x satisfies 0.02 ≦ x ≦ 49 (0 <y, 0 ≦ z). This is defined as a region where the value of the number ratio of transition metal (M2) / non-transition metal (M1) is in the range of 0.02 to 49 and the thickness is 5 nm or more. It is the same definition as that.

  In this region, since both the non-transition metal (M1) and the transition metal (M2) are involved in the direct bonding between the metals, a mixed region that satisfies this condition exists in a thickness of a predetermined value or more (5 nm). Therefore, it is thought that it contributes to the improvement of gas barrier properties. In addition, since it is considered that the closer the abundance ratio of the non-transition metal (M1) and the transition metal (M2), the more the gas barrier property can be improved, the mixed region is a region satisfying 0.1 ≦ x ≦ 10. It is preferable to include a thickness of 5 nm or more, more preferably include a region satisfying 0.2 ≦ x ≦ 5 at a thickness of 5 nm or more, and a region satisfying 0.3 ≦ x ≦ 4 to a thickness of 5 nm or more. It is further preferable to contain.

  Here, as described above, if there is a region satisfying the relationship of (2y + 3z) / (a + bx) <1.0 represented by the relational expression (2) within the range of the mixed region, the effect of improving the gas barrier property is obtained. Although it was confirmed that the mixed region exhibits at least a part of the composition, (2y + 3z) / (a + bx) ≦ 0.9, and (2y + 3z) / (a + bx) ≦ 0.85 in the mixed region. It is more preferable to satisfy | fill, and it is still more preferable to satisfy | fill (2y + 3z) / (a + bx) <= 0.8. Here, the smaller the value of (2y + 3z) / (a + bx) in the mixed region, the higher the gas barrier property, but the greater the absorption in visible light. Therefore, in the case of a gas barrier layer used for applications where transparency is desired, 0.2 ≦ (2y + 3z) / (a + bx) is preferable, and 0.3 ≦ (2y + 3z) / (a + bx). Is more preferable, and it is further preferable that 0.4 ≦ (2y + 3z) / (a + bx).

In the present invention, the thickness of the mixed region where good gas barrier properties can be obtained is 5 nm or more as a sputtering thickness in terms of SiO 2 in the XPS analysis method described later, and this thickness is 8 nm or more. Preferably, it is 10 nm or more, more preferably 20 nm or more. The thickness of the mixed region is not particularly limited from the viewpoint of gas barrier properties, but is preferably 100 nm or less, more preferably 50 nm or less, and further preferably 30 nm or less from the viewpoint of optical characteristics. preferable.
A gas barrier layer having a mixed region having a specific configuration as described above exhibits a very high gas barrier property that can be used as a gas barrier layer for an electronic device such as an organic EL element.

(Composition analysis by XPS and measurement of the thickness of the mixed region)
About the composition distribution in the gas barrier layer according to the present invention, the composition distribution in the A region and the B region, the thickness of each region, and the like, X-ray photoelectron spectroscopy (abbreviation: XPS) described in detail below. It can obtain | require by measuring by.

  Hereinafter, a method for measuring the mixed region, the A region, and the B region by XPS analysis will be described. Specifically, the element concentration distribution curve (hereinafter referred to as “depth profile”) in the thickness direction of the gas barrier layer according to the present invention is the element concentration of the non-transition metal M1 (for example, silicon), the transition metal M2 ( For example, the element concentration of niobium, oxygen (O), nitrogen (N), carbon (C) element concentration, etc. can be measured by combining X-ray photoelectron spectroscopy measurement with rare gas ion sputtering such as argon. It can be created by sequentially performing surface composition analysis while exposing the interior from the surface of the barrier layer.

A distribution curve obtained by such XPS depth profile measurement can be created, for example, with the vertical axis as the atomic ratio of each element (unit: atom%) and the horizontal axis as the etching time (sputtering time). In addition, in the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer in the layer thickness direction, As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement Can be adopted. In addition, as a sputtering method employed for such XPS depth profile measurement, a rare gas ion sputtering method using argon (Ar ⁺ ) as an etching ion species is employed, and the etching rate (etching rate) is 0.05 nm / It is preferable to set to sec (SiO ₂ thermal oxide film conversion value).

An example of specific conditions of XPS analysis applicable to the composition analysis of the gas barrier layer according to the present invention is shown below.
・ Analyzer: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement is repeated at a predetermined thickness interval with a SiO ₂ equivalent sputtering thickness to obtain a depth profile in the depth direction. The thickness interval was 1 nm (data every 1 nm is obtained in the depth direction).
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. Data processing uses MultiPak manufactured by ULVAC-PHI. The analyzed elements are non-transition metal M1 (for example, silicon (Si)), transition metal M2, oxygen (O), nitrogen (N), and carbon (C).

The composition ratio is calculated from the obtained data, the non-transition metal (M1) and the transition metal (M2) coexist, and the value of the atomic ratio of the transition metal (M2) / non-transition metal (M1) is , 0.02 to 49 is obtained, this is defined as a mixed region, and its thickness is obtained. The thickness of the mixed region represents the sputter depth in XPS analysis in terms of SiO ₂ .

  In the present invention, a “mixed region” is determined when the thickness of the mixed region is 5 nm or more. From the viewpoint of gas barrier properties, there is no upper limit of the thickness in the mixed region, but from the viewpoint of optical properties, it is preferably in the range of 5 to 100 nm, more preferably in the range of 8 to 50 nm, Preferably, it exists in the range of 10-30 nm.

  Below, the specific example of the mixing area | region in the gas barrier layer which concerns on this invention is demonstrated using figures.

  FIG. 6 is an example of a graph for explaining the element profile and the mixed region when the composition distribution of the non-transition metal and the transition metal in the thickness direction of the gas barrier layer is analyzed by the XPS method. In FIG. 6, elemental analysis of non-transition metal (M1), transition metal (M2), O, N, and C is performed in the depth direction from the surface of the gas barrier layer (the left end portion of the graph), and the horizontal axis represents spattering. It is the graph which showed the content rate (atom%) of a non-transition metal (M1) and a transition metal (M2) on the vertical axis | shaft with depth (layer thickness: nm).

  From the right side, the B region which is an elemental composition having a non-transition metal (M1, for example, Si) as the main component of the metal is shown, and on the left side, the transition metal (M2, for example, niobium) is the main component of the metal. A region which is an elemental composition is shown. The mixed region is a region where the value of the atomic ratio of transition metal (M2) / non-transition metal (M1) is indicated by an element composition within a range of 0.02 to 49, and part of A region and B region Is a region that overlaps with a part of the region and has a thickness of 5 nm or more.

[Method of forming each region]
(Transition metal-containing region: formation of region A)
Examples of the transition metal (M2) according to the present invention include Nb, Ta, V, Zr, Ti, Hf, Y, La, Ce, and the like from the viewpoint of obtaining good gas barrier properties as described above. In particular, Nb, Ta, and V, which are Group 5 elements, can be preferably used because they are likely to be bonded to the non-transition metal (M1) contained in the gas barrier layer.

  The formation of the layer containing the transition metal (M2) oxide is not particularly limited. For example, a conventionally known vapor deposition method using an existing thin film deposition technique can be used to make the mixed region efficient. It is preferable from a viewpoint of forming.

  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 any of DC (direct current) sputtering, DC pulse sputtering, AC (alternating current) sputtering, and 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, thin films of non-transition metal (M1) and transition metal (M2) composite oxides, nitride oxides, oxycarbides, etc. are formed. can do. 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 a multi-source simultaneous sputtering method using a plurality of sputtering targets including a single transition metal (M2) or an oxide thereof. 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 methods and conditions described in JP 2013-047361 A can be referred to as appropriate.

  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 gas concentration during the film forming. Examples include one or more conditions selected from the group consisting of supply amount, degree of vacuum during film formation, and power during film formation. These film formation conditions (preferably oxygen partial pressure) are By adjusting, a mixed region made of a complex oxide having an oxygen deficient composition can be formed. That is, by forming the gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. According to such a method, a desired gas barrier property can be realized by an extremely simple operation of controlling the thickness of the mixed 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 mixing area | region.

(Non-transition metal-containing region: formation of B region)
In the gas barrier layer according to the present invention, the method for forming the B region containing the non-transition metal (M1) is not particularly limited, and for example, a vapor deposition method can be used by a known method. 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. A non-transition metal is formed by a sputtering method. It can be used as a target.

  As another method, a method of forming by a wet coating method using a polysilazane-containing coating solution containing Si as a non-transition metal is also a preferable method.

In the present invention, “polysilazane” applicable to formation of the B region is a polymer having a silicon-nitrogen bond in the structure, and includes SiO ₂ , Si _{3 made of} Si—N, Si—H, N—H, or the like. N is ₄ and both of the intermediate solid solution _SiO x _N preceramic inorganic polymers, such as _y.

  In order to form the B region constituting the gas barrier layer using polysilazane so as not to impair the planarity of the above-described base material, as described in JP-A-8-112879, Polysilazanes that can be modified to silicon oxide, silicon nitride, or silicon oxynitride at low temperatures are preferred.

  Examples of such polysilazane include compounds having a structure represented by the following general formula (1).

In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

In the present invention, perhydropolysilazane (PHPS) in which all of R ¹ , R ² and R ³ are hydrogen atoms is particularly preferred from the viewpoint of the denseness of the B region constituting the resulting gas barrier layer as a thin film. .

  On the other hand, the organopolysilazane in which the hydrogen part bonded to Si is partially substituted with an alkyl group or the like has an alkyl group such as a methyl group, so that the adhesion to an adjacent substrate is improved and it may be hard. The ceramic film made of polysilazane can be tough, and even when the film thickness is increased, the generation of cracks is preferred.

These perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.
Perhydropolysilazane is presumed to have a structure in which a linear structure and a ring structure centered on a 6- or 8-membered ring coexist.

  The molecular weight of polysilazane is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), is a liquid or solid substance, and varies depending on the molecular weight. These polysilazane compounds are commercially available in the form of a solution dissolved in an organic solvent, and commercially available products can be used as they are as coating solutions containing polysilazane compounds.

  Other examples of polysilazanes that are ceramicized at a low temperature include silicon alkoxide-added polysilazanes obtained by reacting the above polysilazanes with silicon alkoxides (Japanese Patent Laid-Open No. 5-238827), and glycidol-added polysilazanes obtained by reacting glycidol (specially (Kaihei 6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (JP-A-6-240208), and a metal carboxylate-added polysilazane obtained by reacting a metal carboxylate (JP-A-6-299118). No. 1), acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (Japanese Patent Laid-Open No. 6-306329), metal fine particle-added polysilazane obtained by adding metal fine particles (Japanese Patent Laid-Open No. 19698 JP), and the like.

  In addition, for details of polysilazane, for example, paragraphs (0024) to (0040) of JP2013-255910A, paragraphs (0037) to (0043) of JP2013-188942A, JP Paragraphs (0014) to (0021) of JP2013-151123A, Paragraphs (0033) to (0045) of JP2013-052569A, Paragraphs (0062) to (0075) of JP2013-129557A. ), And the contents described in paragraphs (0037) to (0064) of JP2013-226758A can be applied.

<Coating liquid containing polysilazane>
As an organic solvent for preparing a coating liquid containing polysilazane, it is preferable to avoid using an alcohol or water-containing one that easily reacts with polysilazane. Suitable organic solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers. it can. Specific examples include hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, and ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to the purpose such as the solubility of polysilazane and the evaporation rate of the solvent, and a plurality of organic solvents may be mixed. The concentration of polysilazane in the coating liquid containing polysilazane varies depending on the film thickness of the target gas barrier layer and the pot life of the coating liquid, but is preferably about 0.2 to 35% by mass.

  In addition, an amine or metal catalyst may be added to the coating liquid containing polysilazane in order to promote modification to silicon oxide, silicon nitride, or silicon oxynitride. For example, a polysilazane solution containing a catalyst such as NAX120-20, NN120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, SP140 manufactured by AZ Electronic Materials Co., Ltd. as a commercial product is used. be able to. Moreover, these commercial items may be used independently and may be used in mixture of 2 or more types.

  In addition, in the coating liquid containing polysilazane, the addition amount of the catalyst is adjusted to 2% by mass or less with respect to polysilazane in order to avoid excessive silanol formation by the catalyst, decrease in film density, increase in film defects, and the like. It is preferable.

  In addition to polysilazane, the coating liquid containing polysilazane can contain an inorganic precursor compound. The inorganic precursor compound other than polysilazane is not particularly limited as long as a coating liquid can be prepared. For example, compounds other than polysilazane described in paragraphs “0110” to “0114” of JP2011-143577A can be appropriately employed.

(Additive elements)
An organometallic compound of a metal element other than Si can be added to the coating liquid containing polysilazane. By adding an organometallic compound of a metal element other than Si, the replacement of N atom and O atom of polysilazane is promoted in the coating and drying process, and the composition can be changed to a stable composition close to SiO2 after coating and drying. .

  Examples of metal elements other than Si include aluminum (Al), titanium (Ti), zirconium (Zr), zinc (Zn), gallium (Ga), indium (In), chromium (Cr), iron (Fe), Magnesium (Mg), tin (Sn), nickel (Ni), palladium (Pd), lead (Pb), manganese (Mn), lithium (Li), germanium (Ge), copper (Cu), sodium (Na), Examples include potassium (K), calcium (Ca), cobalt (Co), boron (B), beryllium (Be), strontium (Sr), barium (Ba), radium (Ra), thallium (Tl), and the like.

  In particular, Al, B, Ti and Zr are preferable, and among them, an organometallic compound containing Al is preferable.

  Examples of the aluminum compound applicable to the present invention include aluminum isopoloxide, aluminum-sec-butyrate, titanium isopropoxide, aluminum triethylate, aluminum triisopropylate, aluminum tritert-butylate, aluminum tri-n- Examples include butyrate, aluminum trisec-butyrate, aluminum ethyl acetoacetate / diisopropylate, acetoalkoxyaluminum diisopropylate, aluminum diisopropylate monoaluminum-t-butylate, aluminum trisethylacetoacetate, aluminum oxide isopropoxide trimer, etc. be able to.

  Specific commercial products include, for example, AMD (aluminum diisopropylate monosec-butyrate), ASBD (aluminum secondary butyrate), ALCH (aluminum ethyl acetoacetate / diisopropylate), ALCH-TR (aluminum trisethylacetate). Acetate), aluminum chelate M (aluminum alkyl acetoacetate / diisopropylate), aluminum chelate D (aluminum bisethylacetoacetate / monoacetylacetonate), aluminum chelate A (W) (aluminum trisacetylacetonate) Ken Fine Chemical Co., Ltd.), Preneact (registered trademark) AL-M (acetoalkoxy aluminum diisopropylate, Ajinomoto Fine Chemical Co., Ltd.), etc. It is possible.

  In addition, when using these compounds, it is preferable to mix with the coating liquid containing polysilazane in inert gas atmosphere. This is to prevent these compounds from reacting with moisture and oxygen in the atmosphere and causing intense oxidation. Moreover, when mixing these compounds and polysilazane, it is preferable to heat up to 30-100 degreeC, and to hold | maintain for 1 minute-24 hours, stirring.

The content of the additional metal element in the polysilazane-containing layer constituting the gas barrier film according to the present invention is preferably 0.05 to 10 mol%, more preferably 100 mol% of silicon (Si). Is 0.5-5 mol%.
In the formation of the B region using polysilazane, it is preferable to perform a modification treatment after forming the polysilazane-containing layer.

  The modification treatment is a treatment in which polysilazane is imparted with energy and part or all thereof is converted into silicon oxide or silicon oxynitride.

  For the modification treatment in the present invention, a known method based on the conversion reaction of polysilazane can be selected, and examples thereof include known plasma treatment, plasma ion implantation treatment, ultraviolet irradiation treatment, vacuum ultraviolet irradiation treatment and the like. In the present invention, a conversion reaction using plasma, ozone, or ultraviolet light that can be converted at a low temperature is preferable. Conventionally known methods can be used for plasma and ozone. In the present invention, a gas barrier layer is formed by providing a coating film of a polysilazane-containing coating liquid of a coating method on a substrate and applying a vacuum ultraviolet irradiation treatment in which a vacuum ultraviolet ray (VUV) having a wavelength of 200 nm or less is irradiated to perform a modification treatment. The forming method is preferred.

  As the vacuum ultraviolet light source, a rare gas excimer lamp is preferably used. For example, an excimer lamp (single wavelength of 172 nm, 222 nm, 308 nm, for example, manufactured by USHIO INC., Manufactured by M.D. Can be mentioned.

  The treatment by vacuum ultraviolet irradiation uses light energy 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 polysilazane, and the bonding of atoms is an action of only a photon called a photon process. Thus, a silicon oxide film or a silicon oxynitride film is formed at a relatively low temperature (about 200 ° C. or lower) by proceeding an oxidation reaction with active oxygen or ozone while directly cutting.

  For details of these reforming treatments, for example, paragraphs (0055) to (0091) of JP2012-086394A, paragraphs (0049) to (0085) of JP2012-006154A, JP The contents described in paragraphs (0046) to (0074) of 2011-251460 can be referred to.

  Although there is no restriction | limiting in particular in the thickness of B area | region, It exists in the range of 1-500 nm, More preferably, it exists in the range of 10-300 nm.

(Formation of mixed region)
As described above, the mixed region forming method is preferably a method of forming the mixed region between the A region and the B region by appropriately adjusting each forming condition when forming the A region and the B region. .
When the B region is formed by the above-described vapor deposition method, for example, the ratio of the non-transition metal (M1) and oxygen in the deposition raw material, the ratio of the inert gas and the reactive gas during the deposition, Mixing by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Regions can be formed.

  When forming the B region by the above-described coating film forming method, for example, a film forming raw material type (polysilazane type or the like) containing the non-transition metal (M1), a catalyst type, a catalyst content, a coating film thickness, and a drying temperature. A mixed region can be formed by adjusting one or more conditions selected from the group consisting of time, reforming method, and reforming conditions.

  In the case where the A region is formed by the above-described vapor deposition method, for example, the ratio of the transition metal (M2) and oxygen in the deposition material, the ratio of the inert gas and the reactive gas during the deposition, A mixed region by adjusting one or more conditions selected from the group consisting of the gas supply amount during film formation, the degree of vacuum during film formation, the magnetic force during film formation, and the power during film formation Can be formed.

  Note that, in order to control the thickness of the mixed region by the above-described method, the formation conditions of the method of forming the A region and the B region can be adjusted as appropriate. For example, when forming the A region by a vapor deposition method, a desired thickness can be obtained by controlling the deposition time. In addition to this, a method of directly forming a mixed region of a non-transition metal and a transition metal is also preferable.

  As a method for directly forming the mixed region, it is preferable to use a known co-evaporation method. As such a co-evaporation method, a co-sputtering method is preferable. The co-sputtering method employed in the present invention is, for example, a composite target made of an alloy containing both a non-transition metal (M1) and a transition metal (M2), or a composite of a non-transition metal (M1) and a transition metal (M2). One-way sputtering using a composite target made of oxide as a sputtering target may be used.

  In addition, the co-sputtering method in the present invention is multi-source simultaneous sputtering using a plurality of sputtering targets including a single non-transition metal (M1) or its oxide and a single transition metal (M2) or its oxide. May be. 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 gas barrier layer using the co-evaporation method as described above, almost all regions in the thickness direction of the formed gas barrier layer can be mixed regions. 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 mixed 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 mixing area | region.

<Transfer method of gas barrier layer>
The gas barrier layer according to the present invention is formed as a layer to be peeled through a release layer on a substrate such as glass, as in the peeling method described in JP-A-2015-173249, The peelable layer can be transferred to a plastic film to function as a gas barrier film. Moreover, it can transfer to electronic devices, such as an organic electroluminescent (EL) element, and can also function as a sealing layer.

  Such a method for forming a gas barrier layer makes it easy to manage the cleanliness of the process of forming a thin gas barrier layer or sealing layer in a light, thin, or flexible electronic device. It is preferable from the viewpoint of improving the yield.

  Specifically, a first step of forming a release layer with a thickness of 0.1 nm or more and less than 10 nm on a substrate and a layer to be peeled including a first layer in contact with the release layer are formed on the release layer. A gas barrier layer by a peeling method comprising: a second step of: separating a part of the peeling layer and the first layer; and a third step of separating the peeling layer and the layer to be peeled. It is preferable to form as a layer to be peeled. A step of forming a starting point of peeling may be provided between the second step and the third step.

  An example of the peeling method is shown below. 7A to 7F are diagrams illustrating a peeling method.

<Peeling method>
First, as a first step, a peeling layer 103 with a thickness of less than 10 nm is formed over a manufacturing substrate 101, and then, as a second step, a layer to be peeled 105 is formed on the peeling layer 103 (FIG. 7A). Here, an example in which an island-shaped release layer is formed is shown, but the present invention is not limited thereto. Alternatively, the layer to be peeled 105 may be formed in an island shape.

  In this step, when the layer to be peeled 105 is peeled from the manufacturing substrate 101, peeling occurs in the interface between the manufacturing substrate 101 and the peeling layer 103, the interface between the peeling layer 103 and the layer to be peeled 105, or the peeling layer 103. Select material. In this embodiment, the case where separation occurs at the interface between the separation layer 105 and the separation layer 103 is illustrated; however, the present invention is not limited to this depending on the combination of materials used for the separation layer 103 and the separation layer 105. Note that in the case where the layer to be peeled 105 has a stacked structure, a layer in contact with the peeling layer 103 is particularly referred to as a first layer.

  The thickness of the peeling layer 103 may be, for example, less than 10 nm, preferably 8 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. The thinner the release layer 103 is, the better the release yield can be improved. In addition, the thickness of the release layer 103 may be, for example, 0.1 nm or more, preferably 0.5 nm or more, more preferably 1 nm or more. A thicker release layer 103 is preferable because a uniform film can be formed. For example, the thickness of the release layer 103 is preferably 1 nm or more and 8 nm or less. In this embodiment, a tungsten film with a thickness of 5 nm is used.

  Note that, as an example, the thickness of the release layer 103 is desirably as described above over the entire layer. Note that one embodiment of the present invention is not limited to this. For example, the peeling layer 103 may have a region with the above thickness at least in part. Alternatively, the release layer 103 may have a region with the above-described thickness in a region of 50% or more of the release layer, more preferably in a region of 90% or more of the release layer. That is, in one embodiment of the present invention, part of the peeling layer 103 may have a region with a thickness of less than 0.1 mm or a region with a thickness of 10 nm or more.

  As the manufacturing substrate 101, a substrate having heat resistance that can withstand at least a processing temperature in the manufacturing process is used. As the manufacturing substrate 101, for example, a glass substrate, a quartz substrate, a sapphire substrate, a semiconductor substrate, a ceramic substrate, a metal substrate, a resin substrate, a plastic substrate, or the like can be used.

  Note that a large glass substrate is preferably used as the formation substrate 101 in order to improve mass productivity. For example, the third generation (550 mm × 650 mm), the third generation (600 mm × 720 mm, or 620 mm × 750 mm), the fourth generation (680 mm × 880 mm, or 730 mm × 920 mm), the fifth generation (1100 mm × 1300 mm), 6th generation (1500 mm × 1850 mm), 7th generation (1870 mm × 2200 mm), 8th generation (2200 mm × 2400 mm), 9th generation (2400 mm × 2800 mm, 2450 mm × 3050 mm), 10th generation (2950 mm × 3400 mm), etc. A glass substrate or a glass substrate larger than this can be used.

  In the case where a glass substrate is used as the manufacturing substrate 101, an insulating film such as a silicon oxide film, a silicon oxynitride film, a silicon nitride film, or a silicon nitride oxide film is formed as a base film between the manufacturing substrate 101 and the separation layer 103. It is preferable because contamination from the glass substrate can be prevented.

  The separation layer 103 includes an element selected from tungsten (W), molybdenum (Mo), titanium, tantalum, niobium, nickel, cobalt, zirconium, zinc, ruthenium, rhodium, palladium, osmium, iridium, and silicon, and the element. An alloy material or a compound material containing the element can be used. The crystal structure of the layer containing silicon may be any of amorphous, microcrystalline, and polycrystalline. Alternatively, a metal oxide such as aluminum oxide, gallium oxide, zinc oxide, titanium dioxide, indium oxide, indium tin oxide, indium zinc oxide, or In—Ga—Zn oxide may be used. It is preferable to use a refractory metal material such as tungsten, titanium, or molybdenum for the separation layer 103 because the degree of freedom in the formation process of the separation layer 105 is increased.

  The release layer 103 is formed by, for example, sputtering, CVD (Chemical Vapor Deposition) (plasma CVD, thermal CVD, MOCVD (Metal Organic CVD), etc.), ALD (Atomic Layer Deposition), coating (spin coating, (Including a droplet discharge method, a dispensing method, and the like), a printing method, a vapor deposition method, and the like.

  In the case where the separation layer 103 has a single-layer structure, a tungsten film, a molybdenum film, or a film containing a mixture of tungsten and molybdenum is preferably formed. Alternatively, a film containing tungsten oxide or oxynitride, a film containing molybdenum oxide or oxynitride, or a film containing an oxide or oxynitride of a mixture of tungsten and molybdenum may be formed. Note that the mixture of tungsten and molybdenum corresponds to, for example, an alloy of tungsten and molybdenum. For example, an alloy film of molybdenum and tungsten such as Mo: W = 3: 1 [atomic ratio], Mo: W = 1: 1 [atomic ratio], or Mo: W = 1: 3 [atomic ratio]. It may be used. The alloy film of molybdenum and tungsten is, for example, Mo: W = 49: 51 [wt%], Mo: W = 61: 39 [wt%], Mo: W = 14.8: 85.2 [wt%]. ] Can be formed by a sputtering method using a metal target having the composition.

By changing the surface state of the tungsten film, adhesion between the peeling layer 103 and a layer to be peeled later can be controlled. For example, the surface of a film containing tungsten is subjected to thermal oxidation treatment, oxygen plasma treatment, nitrous oxide (N ₂ O) plasma treatment, treatment with a solution having strong oxidizing power such as ozone water, and the like to form tungsten oxide. A containing film may be formed. Plasma treatment and heat treatment may be performed in oxygen, nitrogen, nitrous oxide alone, or a mixed gas atmosphere of the gas and other gases.

  In one embodiment of the present invention, by using a tungsten film with a thickness of less than 10 nm, it is possible to easily perform separation with a small separation force in the third step, so that the plasma treatment or the heat treatment is not performed. Good. This is preferable because it can simplify the peeling process and the manufacturing process of the apparatus.

  As the layer to be peeled 105, a gas barrier layer in contact with the peeling layer 103 is formed. Furthermore, you may produce a functional element on a gas barrier layer.

  Next, the layer to be peeled 105 and the substrate 109 are bonded together using the bonding layer 107, and the bonding layer 107 is cured (FIG. 7B). Here, FIG. 7B corresponds to a cross-sectional view taken along the dashed-dotted line A1-A2 in FIG. 7C. FIG. 7C is a plan view seen from the substrate 109 (not shown) side.

  Here, the bonding layer 107 is preferably disposed so as to overlap with the separation layer 103 and the separation layer 105. 7B and 7C, the end portion of the bonding layer 107 is preferably not positioned outside the end portion of the release layer 103.

  Next, a starting point of peeling is formed by laser light irradiation (step of forming a starting point of peeling) (FIGS. 7B and 7D).

  By using laser light irradiation, it is not necessary to cut the substrate or the like in order to form the separation starting point, and generation of dust or the like can be suppressed, which is preferable.

  Laser light is applied to a region where the cured bonding layer 107, the layer to be peeled 105, and the peeling layer 103 overlap (see arrow P1 in FIG. 7B).

  The laser light may be irradiated from either side of the substrate, but it is preferable to irradiate from the side of the manufacturing substrate 101 provided with the release layer 103 in order to suppress the scattered light from being irradiated to the functional element or the like. . Note that a material that transmits the laser light is used for the substrate on the laser light irradiation side.

  At least the first layer (the layer included in the layer to be peeled 105 and in contact with the peeling layer 103) is cracked (to cause film cracking or cracking), thereby removing a part of the first layer, A starting point can be formed (see the region enclosed by the dotted line in FIG. 7D). At this time, not only the first layer but also other layers of the layer to be peeled 105, the peeling layer 103, and part of the bonding layer 107 may be removed. By irradiation with laser light, a part of the film can be dissolved, evaporated, or thermally destroyed. Moreover, the formation method of the starting point of peeling does not ask | require. It is sufficient that at least a part of the first layer is peeled from the peeling layer, and a part of the first layer may not be removed.

  At the time of the peeling process, it is preferable that the force for separating the layer to be peeled 105 and the peeling layer 103 is concentrated on the starting point of peeling, so that the starting point of peeling is formed near the end rather than the central part of the cured bonding layer 107. Is preferred. In particular, it is preferable to form the separation starting point in the vicinity of the corner portion in the vicinity of the end portion, as compared with the vicinity in the side portion.

  In addition, it is preferable that the start of separation be formed in a solid line or a broken line by continuously or intermittently irradiating the vicinity of the end portion of the bonding layer 107 with a laser beam because peeling is easy.

  There is no particular limitation on the laser used to form the separation starting point. For example, a continuous wave laser or a pulsed laser can be used. Laser light irradiation conditions (frequency, power density, energy density, beam profile, and the like) are appropriately controlled in consideration of the thickness, material, and the like of the manufacturing substrate 101 and the separation layer 103.

  Then, the layer to be peeled 105 and the manufacturing substrate 101 are separated from the starting point of peeling formed (FIGS. 7E and 7F). Thus, the layer 105 to be peeled can be transferred from the manufacturing substrate 101 to the substrate 109. At this time, it is preferable to fix one substrate to an adsorption stage or the like. For example, the manufacturing substrate 101 may be fixed to an adsorption stage, and the layer to be peeled 105 may be peeled from the manufacturing substrate 101. Alternatively, the substrate 109 may be fixed to the suction stage and the manufacturing substrate 101 may be peeled from the substrate 109. Note that the bonding layer 107 formed outside the separation starting point remains on at least one of the manufacturing substrate 101 and the substrate 109. Although FIG. 7E and 7F show the example which remains on both sides, it is not restricted to this.

  For example, the layer to be peeled 105 and the manufacturing substrate 101 may be separated from the starting point of peeling by a physical force (a process of peeling with a human hand or a jig, a process of separating while rotating a roller, or the like).

  Alternatively, the manufacturing substrate 101 and the layer to be peeled 105 may be separated by infiltrating a liquid such as water into the interface between the peeling layer 103 and the layer to be peeled 105. The liquid can be easily separated by permeating between the peeling layer 103 and the peeled layer 105 by capillary action. In addition, static electricity generated at the time of peeling can be prevented from adversely affecting the functional elements included in the layer to be peeled 105 (such as a semiconductor element being destroyed by static electricity). The liquid may be sprayed in the form of mist or steam. As the liquid, pure water, an organic solvent, or the like can be used, and a neutral, alkaline, or acidic aqueous solution, an aqueous solution in which a salt is dissolved, or the like may be used.

  Note that the bonding layer 107 that does not contribute to adhesion between the layer to be peeled 105 and the substrate 109 remaining on the substrate 109 may be removed after the separation. By removing, it is possible to suppress adverse effects on the functional elements in the subsequent steps (mixing of impurities, etc.), which is preferable. For example, unnecessary resin can be removed by wiping, washing, or the like. In the peeling method of one embodiment of the present invention described above, a peeling starting point is formed by laser light irradiation, and the peeling layer 103 and the layer to be peeled 105 are easily peeled, and then peeling is performed. Thereby, the yield of a peeling process can be improved.

<Electronic device>
The gas barrier film according to the present invention as described above has excellent gas barrier properties, transparency, and bending resistance. Therefore, the gas barrier film according to the present invention is a gas barrier used for electronic devices such as packages such as electronic devices, photoelectric conversion elements (solar cell elements), organic electroluminescence (EL) elements, liquid crystal display elements, and the like. It can be used for various applications such as a conductive film and an electronic device using the same.

  As an example of the electronic device main body used for an electronic device, an organic electroluminescent element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV) etc. can be mentioned, for example. . From the viewpoint that the effects of the present invention can be obtained more efficiently, the electronic device body is preferably an organic EL element.

<Base material>
A plastic film is preferably used as the light emitting surface side resin base material and the back surface side base material used in the present invention. The plastic film used is not particularly limited in material, thickness and the like as long as it can hold an organic light emitting element, a gas barrier layer, and the like, and can be appropriately selected. Specific examples of the plastic film include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin, and polyetherimide. Resin, cellulose acylate resin, polyurethane resin, polyetheretherketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring-modified polycarbonate resin, alicyclic ring Examples thereof include thermoplastic resins such as modified polycarbonate resins, fluorene ring-modified polyester resins, and acryloyl compounds.

  The thickness of the resin base material is preferably about 10 to 100 μm, more preferably 15 to 50 μm.

  In addition, as for the type of the base material and the manufacturing method of the base material, the techniques disclosed in paragraphs “0125” to “0136” of JP2013-226758A can be appropriately employed.

  In particular, in the case of a light-emitting device in a winding form, it is preferable that the back substrate has high rigidity from the viewpoint of stably supporting the light-emitting device.

<Configuration and manufacturing method of organic functional layer unit>
Next, in the organic EL device as a light emitting device that can be preferably used in the present invention, as a representative example of the configuration of each layer of the organic functional layer unit formed on the transparent anode and the manufacturing method thereof, a charge injection layer, a light emitting layer The hole transport layer, the electron transport layer, and the blocking layer will be described in this order.

(Charge injection layer)
In the organic EL device according to the present invention, the charge injection layer is a layer provided between the electrode and the light emitting layer in order to lower the driving voltage and improve the light emission luminance. The details are described in Chapter 2, “Electrode Materials” (pp. 123-166) of Volume 2 of “November 30, 1998, issued by NTS Corporation”. There is.

  As a charge injection layer, generally, if it is a hole injection layer, it exists between a transparent anode and a light emitting layer or a hole transport layer, and if it is an electron injection layer, it exists between a cathode and a light emitting layer or an electron transport layer. Can be made.

  The details of the hole injection layer are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, etc. Examples of the material used for the hole injection layer include: , Porphyrin derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives, Inrocarbazole derivatives, isoindole derivatives, acene derivatives such as anthracene and naphthalene, fluorene derivatives, fluorenone derivatives, polyvinylcarbazole, aromatic amines introduced into the main chain or side chain Material or oligomer, polysilane, a conductive polymer or oligomer (e.g., PEDOT (polyethylene dioxythiophene): PSS (polystyrene sulfonic acid), aniline copolymers, polyaniline, polythiophene, etc.) and the like can be mentioned.

  Examples of the triarylamine derivative include benzidine type represented by α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), and MTDATA (4,4 ′, 4 ″). Examples include a starburst type represented by -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine) and a compound having fluorene or anthracene in the triarylamine-linked core.

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

  The details of the electron injection layer are 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 are as follows. Metals represented by strontium and aluminum, alkali metal compounds represented by lithium fluoride, sodium fluoride, potassium fluoride, etc., alkali metal halide layers represented by magnesium fluoride, calcium fluoride, etc. Examples thereof include an alkaline earth metal compound layer typified by magnesium, a metal oxide typified by molybdenum oxide and aluminum oxide, and a metal complex typified by lithium 8-hydroxyquinolate (Liq). Moreover, when the transparent electrode in this invention is a cathode, organic materials, such as a metal complex, are used especially suitably. The electron injection layer is desirably a very thin film, and although depending on the constituent material, the layer thickness is preferably in the range of 1 nm to 10 μm.

(Light emitting layer)
In the organic EL device according to the present invention, the light emitting layer constituting the organic functional layer unit preferably includes a phosphorescent light emitting compound as a light emitting material.

  This light emitting layer is a layer that emits light by recombination of electrons injected from the electrode or the electron transport layer and holes injected from the hole transport layer, and the light emitting portion is in the layer of the light emitting layer. Alternatively, it may be the interface between the light emitting layer and the adjacent layer.

  As such a light emitting layer, there is no restriction | limiting in particular in the structure, if the light emitting material contained satisfy | fills the light emission requirements. Moreover, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. In this case, it is preferable to have a non-light emitting intermediate layer between the light emitting layers.

  The total thickness of the light emitting layers is preferably in the range of 1 to 100 nm, and more preferably in the range of 1 to 30 nm because a lower driving voltage can be obtained. In addition, the sum total of the thickness of a light emitting layer is the thickness also including the said intermediate | middle layer, when a nonluminous intermediate | middle layer exists between light emitting layers.

  In this invention, the structure which laminated | stacked two or more light emitting layer units may be sufficient. The thickness of each light emitting layer is preferably adjusted in the range of 1 to 50 nm, more preferably in the range of 1 to 20 nm. When the plurality of stacked light emitting layers correspond to the respective emission colors of blue, green, and red, there is no particular limitation on the relationship between the thicknesses of the blue, green, and red light emitting layers.

  The light emitting layer as described above is prepared by using a light emitting material or a host compound described later, for example, a known method such as a vacuum deposition method, a spin coating method, a casting method, an LB method (Langmuir Brodget, Langmuir Blodgett method), an ink jet method, or the like. Can be formed.

  In the light emitting layer, a plurality of light emitting materials may be mixed, and a phosphorescent light emitting material and a fluorescent light emitting material (also referred to as a fluorescent dopant or a fluorescent compound) may be mixed and used in the same light emitting layer. The structure of the light-emitting layer preferably includes a host compound (also referred to as a light-emitting host) and a light-emitting material (also referred to as a light-emitting dopant compound), and emits light from the light-emitting material.

<Host compound>
As the host compound contained in the light emitting layer, a compound having a phosphorescence quantum yield of phosphorescence emission at room temperature (25 ° C.) of less than 0.1 is preferable. Further, the phosphorescence quantum yield is preferably less than 0.01. Moreover, it is preferable that the volume ratio in the layer is 50% or more among the compounds contained in a light emitting layer.

  As the host compound, a known host compound may be used alone, or a plurality of types of host compounds may be used. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the efficiency of the organic electroluminescent device can be improved. In addition, by using a plurality of kinds of light emitting materials described later, it is possible to mix different light emission, thereby obtaining an arbitrary light emission color.

  The host compound used in the light emitting layer may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (evaporation polymerizable light emitting host). )

  Examples of host compounds applicable to the present invention include, for example, JP-A Nos. 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 No. -75645, No. 2002-338579, No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002. 363 No. 27, No. 2002-231453, No. 2003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-260861, No. 2002-280183. No. 2002, No. 2002-299060, No. 2002-302516, No. 2002-305083, No. 2002-305084, No. 2002-308837, US Patent Application Publication No. 2003/0175553, US Patent Application Publication No. 2006/0280965, US Patent Application Publication No. 2005/0112407, US Patent Application Publication No. 2009/0017330, US Patent Application Publication No. 2009/0030202, US Patent Public application No. 2005/238919, 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 No./003898, International Publication No. 2012/023947, Japanese Patent Application Laid-Open No. 2008-074939, Japanese Patent Application Laid-Open No. 2007-254297, European Patent No. 2034538, and the like.

<Light emitting material>
As a light-emitting material that can be used in the present invention, a phosphorescent compound (also referred to as a phosphorescent compound, a phosphorescent material, or a phosphorescent dopant) or a fluorescent compound (both a fluorescent compound or a fluorescent material) is used. Say).

<Phosphorescent compound>
A phosphorescent compound is a compound in which light emission from an excited triplet is observed. Specifically, it is a compound that emits phosphorescence at room temperature (25 ° C.), and the phosphorescence quantum yield is 0 at 25 ° C. A preferred phosphorescence quantum yield is 0.1 or more, although it is defined as 0.01 or more compounds.

  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 the solution can be measured using various solvents, but when using a phosphorescent compound in the present invention, the phosphorescence quantum yield is 0.01 or more in any solvent. Should be achieved.

  The phosphorescent compound can be appropriately selected from known ones used in the light emitting layer of a general organic EL device, and preferably a group 8-10 metal in the periodic table of elements. It is a complex compound to be contained, more preferably an iridium compound, an osmium compound, a platinum compound (platinum complex compound) or a rare earth complex, and most preferably an iridium compound.

  In the present invention, at least one light emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light emitting layer varies in the thickness direction of the light emitting layer. It may be an embodiment.

  Specific examples of known phosphorescent compounds that can be used in the present invention 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 Application Publication No. 2006/835469, US Patent Application Publication No. 2006 /. Examples thereof include compounds described in US Patent No. 0202194, US Patent Application Publication No. 2007/0087321, US Patent Application Publication No. 2005/0244673, and the like.

  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 Application Publication No. 2002/0034656, and US Pat. No. 7,332,232. US Patent Application Publication No. 2009/0108737, US Patent Application Publication No. 2009/0039776, US Patent No. 6921915, US Patent No. 6,687,266, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2006/0008670, US Patent Application Publication No. 2009/0165846, US Patent Application Publication No. 2008/0015355, US Pat. No. 7,250,226, US Pat. No. 7,396,598 US patent Examples include compounds described in Japanese Patent Application Publication No. 2006/0263635, US Patent Application Publication No. 2003/0138657, US Patent Application Publication No. 2003/0152802, US Pat. No. 7090928, and the like. it can.

  Also, 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 No. 2005/123873, International Publication No. 2007/004380, International Publication No. 2006/082742, US Patent Application Publication No. 2006/0251923, US Patent Application Publication No. 2005/0260441, US Pat. No. 7,393,599. Description, US Pat. No. 7,534,505, US Pat. No. 7,445,855, US Patent Application Publication No. 2007/0190359, US Patent Application Publication No. 2008/0297033, US Pat. No. 7,338,722 , US special Examples include compounds described in Japanese Patent Application Publication No. 2002/0134984, US Patent No. 7279704, US Patent Application Publication No. 2006/098120, US Patent Application Publication No. 2006/103874, and the like. it can.

  Furthermore, International Publication No. 2005/076380, International Publication No. 2010/032663, International Publication No. 2008/140115, International Publication No. 2007/052431, International Publication No. 2011/134013, 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, Special JP 2012-069737 A, JP 2009-1114086 A, JP 2003-81988 A, JP 2002-302671 A, JP 2002-363552 A, and the like.

  In the present invention, preferred phosphorescent compounds include organometallic complexes having Ir as a central metal. Furthermore, a complex including at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond is preferable.

The phosphorescent compound described above (also referred to as a phosphorescent metal complex) is described in, for example, Organic Letter, vol. 16, 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. 8, 1685-1687 (1991), J. Am. Am. Chem. Soc. , 123, 4304 (2001), Inorganic Chemistry, Vol. 40, No. 7, 1704-1711 (2001), Inorganic Chemistry, Vol. 41, No. 12, 3055-3066 (2002) , New Journal of Chemistry. 26, 1171 (2002), European Journal of
It can be synthesized by applying the methods described in Organic Chemistry, Vol. 4, pages 695-709 (2004), and references in these documents.

<Fluorescent compound>
Fluorescent compounds include, for example, coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.

(Hole transport layer)
The hole transport layer is composed of a hole transport material having a function of transporting holes. In a broad sense, the hole injection layer and the electron blocking layer also have a function of a hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.

  The hole transport material has characteristics of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples include stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, and thiophene oligomers.

  As the hole transport material, those described above can be used, but in addition, porphyrin compounds, aromatic tertiary amine compounds and styrylamine compounds can be used, and in particular, aromatic tertiary amines. It is preferable to use a compound.

  Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′— Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (abbreviation: TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1 -Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis (4-di-p -Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, '-Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) c Audriphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N- Examples include diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole and the like.

  For the hole transport layer, known methods such as vacuum deposition, spin coating, casting, printing including ink jet, and LB (Langmuir Brodget, Langmuir Broadgett) are used as the hole transport material. Thus, it can be formed by thinning. Although there is no restriction | limiting in particular about the layer thickness of a positive hole transport layer, Usually, about 5 nm-5 micrometers, Preferably it is the range of 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

  Moreover, p property can also be made high by doping the material of a positive hole transport layer with an impurity. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175 and J.P. Appl. Phys. 95, 5773 (2004), and the like.

  Thus, it is preferable to increase the p property of the hole transport layer because an element with lower power consumption can be manufactured.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer structure or a stacked structure of a plurality of layers.

  In the electron transport layer having a single-layer structure and the electron transport layer having a multilayer structure, an electron transport material (also serving as a hole blocking material) constituting a layer portion adjacent to the light emitting layer is used as an electron transporting material. What is necessary is just to have the function to transmit. As such a material, any one of conventionally known compounds can be selected and used. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane, anthrone derivatives, and oxadiazole derivatives. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as a material for the electron transport layer. it can. Furthermore, a polymer material in which these materials are introduced into a polymer chain, or a polymer material having these materials as a polymer main chain can also be used.

In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (abbreviation: 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 (abbreviation: Znq), etc., and the central metal of these metal complexes A metal complex in which In, Mg, Cu, Ca, Sn, Ga, or Pb is replaced can also be used as the material for the electron transport layer.

  The electron transport layer can be formed by thinning the above material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an inkjet method, and an LB method. Although there is no restriction | limiting in particular about the layer thickness of an electron carrying layer, Usually, about 5 nm-5 micrometers, Preferably it exists in the range of 5-200 nm. The electron transport layer may have a single structure composed of one or more of the above materials.

(Blocking layer)
Examples of the blocking layer include a hole blocking layer and an electron blocking layer, which are provided as necessary in addition to the constituent layers of the organic functional layer unit described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). Hole blocking (hole block) layer and the like.

  The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes, and recombines electrons and holes by blocking holes while transporting electrons. Probability can be improved. Moreover, the structure of an electron carrying layer can be used as a hole-blocking layer as needed. The hole blocking layer is preferably provided adjacent to the light emitting layer.

  On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense. The electron blocking layer is made of a material that has the ability to transport holes and has a very small ability to transport electrons. By blocking holes while transporting holes, the probability of recombination of electrons and holes is improved. Can be made. Moreover, the structure of a positive hole transport layer can be used as an electron blocking layer as needed. The layer thickness of the hole blocking layer applied to the present invention is preferably in the range of 3 to 100 nm, more preferably in the range of 5 to 30 nm.

〔anode〕
As the anode in the organic EL element, a material having a work function (4 eV or more, preferably 4.5 eV or more) of a metal, an alloy, an electrically conductive compound, or a mixture thereof is preferably used. Specific examples of such electrode substances include metals such as Au, 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) capable of forming a transparent conductive film may be used.

  The anode may be formed by depositing a thin film of these electrode materials by vapor deposition or sputtering, and a pattern having a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

  Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less.

  The film thickness of the anode depends on the material, but is usually selected within the range of 10 nm to 1 μm, preferably 10 to 200 nm.

〔cathode〕
The cathode is an electrode film that functions to supply holes to the organic functional layer unit, and a metal, an alloy, an organic or inorganic conductive compound, or a mixture thereof is used. Specifically, gold, aluminum, silver, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum 1 mixture, magnesium / indium mixture, indium, lithium / aluminum mixture, rare earth metal, ITO, ZnO And oxide semiconductors such as TiO ₂ and SnO ₂ .

  The cathode can be produced by using these conductive materials and forming a thin film by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 5 nm to 5 μm, preferably 5 to 200 nm.

  In the case where the organic EL element is a double-sided light emitting type in which emitted light is extracted also from the cathode side, a cathode with good light transmittance may be selected and configured.

(Sealing member)
The organic EL device according to the present invention is a sealing member for shielding a transparent conductive film (TF) including a transparent anode, a cathode, and an organic functional layer unit formed between the cathode and the transparent anode from the outside air. It is preferable to have a structure for sealing.

Examples of the sealing means used in the present invention include a method of bonding a sealing material and a constituent member of the organic EL element by forming a sealing resin layer with an adhesive.
As long as it is arranged so as to cover the display area of the organic EL element, it may be in the form of a concave plate or a flat plate. Further, transparency and electrical insulation are not particularly limited.

  Specific examples of the sealing material used for sealing include a glass plate, a polymer plate / film, and a metal plate / film. Examples of the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of 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.

In the present invention, a polymer film and a metal film can be preferably used because the organic EL element can be thinned. Furthermore, the polymer film is JIS K
The oxygen permeability measured by a method according to 7126-1987 is 1 × 10 ⁻³ cm ³ / (
m ² · 24 h · atm), the water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by a method according to JIS K 7129-1992 is 1 × 10 ⁻³ g. / (M ² · 24h) or less is preferable.

  For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

  Specific examples of the adhesive for forming the sealing resin layer include photocuring and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture curing such as 2-cyanoacrylates. Examples thereof include an adhesive such as a mold. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.

  In addition, since an organic EL element may deteriorate by heat processing, what can be adhesively cured in a temperature range from room temperature to 80 ° C. is preferable. A desiccant may be dispersed in the adhesive.

  Application | coating of the adhesive agent to a sealing material may use a commercially available dispenser, and may print it like screen printing.

<Other light emitting elements>
Note that although an organic EL element is described above as an example of a light-emitting element, one embodiment of the present invention is not limited thereto, and other display elements, light-emitting elements, semiconductor elements, or the like may be used.

  For example, in this specification and the like, a display element, a display device that is a device including a display element, a light-emitting element, and a light-emitting device that is a device including a light-emitting element have various forms or have various elements. I can do it. As an example of a display element, a display device, a light emitting element, or a light emitting device, an EL element (an EL element including an organic substance and an inorganic substance, an organic EL element, an inorganic EL element), an LED (white LED, red LED, green LED, blue LED, etc.) ), Transistor (transistor that emits light in response to current), electron-emitting device, liquid crystal device, electronic ink, electrophoretic device, grating light valve (GLV), plasma display panel (PDP), MEMS (micro electro mechanical system) ), Digital micromirror device (DMD), DMS (digital micro shutter), IMOD (interference modulation) element, electrowetting element, piezoelectric ceramic display, carbon nanotube, etc. Contrast, brightness, reflectance, etc. transmittance those having a display medium changes. An example of a display device using an EL element is an EL display. As an example of a display device using an electron-emitting device, there is a field emission display (FED), a SED type flat display (SED: Surface-Conduction Electron-Emitter Display), or the like. As an example of a display device using a liquid crystal element, there is a liquid crystal display (a transmissive liquid crystal display, a transflective liquid crystal display, a reflective liquid crystal display, a direct view liquid crystal display, a projection liquid crystal display) and the like. An example of a display device using electronic ink or an electrophoretic element is electronic paper.

  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
<< Production of organic EL element >>
[Production of Organic EL Element 1]
The organic EL element 1 was produced according to the following method.

[Preparation of transparent conductive film 1]
(Step 1-1: Preparation of resin base material)
As a resin base material, a polyethylene terephthalate film having a thickness of 23 μm and easily bonded on both sides (Teijin DuPont Films, KFL12W # 23, hereinafter abbreviated as PET) is used. The following hard coat was formed on both sides.

A clear hard coat layer having an antiblock function was formed on the surface opposite to the surface on which the gas barrier layer of PET was formed. Specifically, a UV curable resin (manufactured by Aika Kogyo Co., Ltd., product number: Z731L) was applied so that the dry film thickness was 0.5 μm, then dried at 80 ° C., and then in air, a high-pressure mercury lamp Was cured under the condition of an irradiation energy amount of 0.5 J / cm ² .

Next, a clear hard coat layer having a thickness of 2 μm was formed on the surface on which the gas barrier layer was to be formed. Specifically, UV curable resin OPSTAR (registered trademark) Z7527 manufactured by JSR Corporation was applied so as to have a dry film thickness of 2 μm, dried at 80 ° C., and then a high-pressure mercury lamp in air. It was used and cured under conditions of an irradiation energy amount of 0.5 J / cm ² . Thus, the resin base material was produced (Hereafter, the same base material is used about all the preparation examples.).

  Next, on the opposite surface of the surface of the resin base material on which the gas barrier layer is formed, an adhesive layer having an adhesive made of a heat-resistant acrylic resin having a thickness of 20 μm is used as a support film, and a thickness of 75 μm. A PET film was bonded and pressure-bonded with a nip roll to obtain a resin base material with a support film.

(Step 1-2: Formation of CVD gas barrier layer)
A gas barrier layer was formed on the resin substrate by the following plasma CVD method.

<Plasma CVD method>
Using a plasma CVD apparatus described in Japanese Patent Application Laid-Open No. 2007-307784, a gas barrier layer made of silicon oxide and having a thickness of 200 nm was formed on a resin substrate according to the following film formation conditions.

<Film formation conditions>
Feed rate of raw material gas (hexamethyldisiloxane, HMDSO): 30 sccm (Standard Cubic Centimeter per Minute)
Supply amount of oxygen gas (O ² ): 300 sccm
Degree of vacuum in the vacuum chamber: 3Pa
Applied power from the power source for plasma generation: 0.5 kW
Frequency of power source for plasma generation: 13.56 MHz
Conveying speed of flexible resin substrate: 0.4 m / min
(Step 1-3: Formation of coating gas barrier layer)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) at a ratio of 4: 1 (mass ratio), and further for dry film thickness adjustment Dilution with dibutyl ether prepared a coating solution having a solid content of 8% by mass.

  For the formation of the coating gas barrier layer, a roll-to-roll type coating apparatus capable of continuously performing coating surface side protective film peeling, coating, drying, excimer modification treatment, and coating surface side protective film bonding was used.

  The coating solution was coated on the substrate using a die coater so that the thickness after drying was 250 nm and dried at 80 ° C. in a dryer zone.

Subsequently, a vacuum ultraviolet ray irradiation treatment was performed on the dried coating film continuously in a vacuum ultraviolet ray irradiation zone having an Xe excimer lamp having a wavelength of 172 nm under the condition that the irradiation energy was 6.0 J / cm ^2. A barrier layer was formed. At this time, the irradiation atmosphere was replaced with nitrogen heated to 60 ° C., and the oxygen concentration was set to 0.1% by volume or less. Up to this point, there was no contact of the transport roll or the like on the coating surface.

  This process was further repeated twice to form three layers of a coating gas barrier layer having a thickness of 250 nm. Next, a self-adhesive OPP film (Futamura Chemical Co., Ltd., FSA010M) was bonded as a protective film to the coated surface, and then wound up.

  In this way, a gas barrier film substrate 1 having a gas barrier layer having a total thickness of 950 nm was obtained.

The water vapor permeability of the gas barrier film substrate 1 was measured using the Ca method. The measurement conditions were 40 ° C. and 90% RH. The water vapor transmission rate obtained was 8.2 × 10 ⁻⁶ g / (m ² · 24 h).

<Measurement of water vapor transmission rate by Ca method>
(Production of evaluation cell)
After the surface of the gas barrier layer of the gas barrier film was UV washed, a thermosetting sheet-like adhesive (epoxy resin) was bonded to the surface of the gas barrier layer with a thickness of 20 μm as a sealing resin layer. This was punched out to a size of 50 mm × 50 mm, then placed in a glove box and dried for 24 hours.

  One side of a 50 mm × 50 mm non-alkali glass plate (thickness 0.7 mm) was UV cleaned.

  Ca was vapor-deposited by the size of 20 mm x 20 mm through the mask in the center of the glass plate using the vacuum vapor deposition apparatus made from ALS Technology. The thickness of Ca was 80 nm.

  The glass plate on which Ca has been deposited is taken out into the glove box, placed so that the sealing resin layer surface of the gas barrier film to which the sealing resin layer is bonded and the Ca deposition surface of the glass plate are in contact with each other, and adhered by vacuum lamination. . At this time, heating at 110 ° C. was performed. Further, the adhered sample was placed on a hot plate set at 110 ° C. with the glass plate facing down, and cured for 30 minutes to produce an evaluation cell.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample using a quartz glass plate having a thickness of 0.2 mm was used instead of the gas barrier film sample as a comparative sample. Was stored under high temperature and high humidity at 40 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 500 hours.

(Measurement of water vapor transmission rate)
Using the evaluation cell, the amount of water that reacted with Ca was determined from the change in the permeation concentration of Ca before and after 500 hours, and the water vapor transmission rate was determined.

  For the transmission density measurement, a black and white transmission densitometer TM-5 manufactured by Konica Minolta was used. The transmission density was measured at any four points in the evaluation cell, and the average value was calculated.

[Production of organic EL elements]
(Step 1-4: Formation of transparent anode)
On the gas barrier layer from which the protective film of the obtained gas barrier film substrate 1 was peeled, a transparent anode composed of a silver thin film was formed according to the following method.

  The outer size of the organic EL element 1 is 60 mm × 150 mm, and the size of the light emitting portion is 40 mm × 130 mm.

  The gas barrier film substrate 1 was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and a resistance heating boat made of tungsten was charged with silver (Ag), and attached to the first vacuum chamber of the vacuum deposition apparatus.

Next, after depressurizing the first vacuum tank to 4 × 10 ⁻⁴ Pa, the resistance heating boat containing silver was energized and heated. Thus, a transparent anode made of silver having a thickness of 15 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second, and a transparent conductive film 1 was produced.

(Step 1-5: Formation of organic functional layer unit to cathode)
Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 shown below was deposited at a deposition rate of 0 while moving the transparent conductive film 1 formed up to the transparent anode. Evaporation was performed at a rate of 1 nm / second, and a 20 nm hole transport layer (HTL) was provided.

  Next, compound A-3 (blue light emitting dopant), compound A-1 (green light emitting dopant), compound A-2 (red light emitting dopant) and compound H-1 (host compound) shown below are converted into compound A-3. The vapor deposition rate is changed depending on the film formation region so that is linearly 35% to 5% by mass with respect to the film thickness. The deposition rate was changed depending on the film formation region so that the concentration of the compound H-1 was 64.6% by mass to 94.6% by mass at a deposition rate of 0.0002 nm / second so that the concentration was mass%. A light emitting layer was formed by co-evaporation so that the total layer thickness was 70 nm.

  Then, the following compound ET-1 was vapor-deposited with a film thickness of 30 nm to form an electron transport layer, and further potassium fluoride (KF) was formed with a thickness of 2 nm to form an organic functional layer unit. Subsequently, aluminum 110nm was vapor-deposited and the cathode was formed.

  In addition, the said compound HT-1, compound A-1 to 3, compound H-1, and compound ET-1 are the compounds shown below.

(Step 1-6: Sealing step)
Next, the gas barrier film base material 1 used for the production of the transparent conductive film 1 is used as a sealing base material, and a thermosetting adhesive (as a sealing resin layer on one side of the sealing base material ( A sealing member in which an epoxy resin) was bonded to a thickness of 20 μm was used to superimpose the sample up to the cathode. At this time, the sealing resin layer forming surface of the sealing member and the organic functional layer unit surface of the organic EL element were overlapped so that the end portions of the transparent anode and the lead electrode of the cathode were exposed.

  Next, the laminate is placed in a decompression device, and the sample formed between the laminated resin base material and the cathode and the sealing member is pressed under a decompression condition of 0.1 MPa at 90 ° C. Hold for a minute. Subsequently, the laminate was returned to the atmospheric pressure environment and further heated at 90 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under a nitrogen atmosphere having a moisture content of 1 ppm or less, a cleanliness measured in accordance with JIS B 9920, class 100, an atmospheric pressure having a dew point temperature of −80 ° C. or less and an oxygen concentration of 0.8 ppm or less. Went under. In addition, the description regarding formation of the extraction wiring from a transparent anode and a cathode is abbreviate | omitted.

  Next, the support film of the gas barrier film base 1 on the substrate side and the sealing side was peeled off.

  Thus, the organic EL element 1 which is a white light emitting device having a total thickness of about 75 μm was produced.

<< Production of Organic EL Element 2 >>
The organic EL element 2 was produced according to the following method.

[Preparation of transparent conductive film 1]
(Step 2-1: Preparation of resin base material)
The same as the organic EL element 1 was used.

(Step 2-2: Formation of coating gas barrier layer 1)
A dibutyl ether solution containing 20% by mass of perhydropolysilazane (manufactured by AZ Electronic Materials Co., Ltd., NN120-20) and an amine catalyst (N, N, N ′, N′-tetramethyl-1,6-diaminohexane (TMDAH) )) And a perhydropolysilazane 20 mass% dibutyl ether solution (manufactured by AZ Electronic Materials Co., Ltd., NAX120-20) at a ratio of 4: 1 (mass ratio), and further for dry film thickness adjustment Dilution with dibutyl ether prepared a coating solution having a solid content of 8% by mass.

  For the formation of the coating gas barrier layer, a roll-to-roll type coating apparatus capable of continuously performing coating surface side protective film peeling, coating, drying, excimer modification treatment, and coating surface side protective film bonding was used.

  The coating solution was coated on the substrate using a die coater so that the thickness after drying was 250 nm and dried at 80 ° C. in a dryer zone.

Subsequently, a vacuum ultraviolet ray irradiation treatment was performed on the dried coating film continuously in a vacuum ultraviolet ray irradiation zone having an Xe excimer lamp having a wavelength of 172 nm under the condition that the irradiation energy was 6.0 J / cm ^2. A gas barrier layer 1 was formed. At this time, the irradiation atmosphere was replaced with nitrogen heated to 60 ° C., and the oxygen concentration was set to 0.1% by volume or less. Up to this point, there was no contact of the transport roll or the like on the coating surface.

  Subsequently, it wound up, without bonding a protective film on the application surface.

(Step 2-3: Formation of transition metal-containing layer)
A niobium oxide layer, which is a transition metal-containing layer, was formed on the coating gas barrier layer obtained in Step 2-2 by using a roll-to-roll magnetron sputtering apparatus.

A commercially available oxygen deficient niobium oxide target was used as a target, and sputtering was performed by a DC pulse method. The power density was 4.0 kW / cm ² , the T-S distance was 100 mm, the film forming pressure was 0.2 Pa, argon and oxygen were used as process gases, and the oxygen ratio was 10%. Moreover, the conveyance speed was adjusted so that the film thickness was 15 nm.

(Step 2-4: Formation of coating gas barrier layer 2)
A coating solution was prepared in the same manner as the coating gas barrier layer 1 except that the solid content was 4% by mass. Also, the coating gas barrier layer 1 was formed in the same manner as the coating gas barrier layer 1 except that the thickness after drying was 110 nm.

  Next, a self-adhesive OPP film (Futamura Chemical Co., Ltd., FSA010M) was bonded as a protective film to the coated surface, and then wound up.

  In this way, a gas barrier film substrate 2 having a gas barrier layer having a total thickness of 375 nm was obtained.

The water vapor permeability of the gas barrier film substrate 2 was measured using the Ca method. The measurement conditions were set to 40 ° C. and 90% RH as in the measurement of the gas barrier film substrate 1. The obtained water vapor transmission rate was 6.8 × 10 ⁻⁶ g / (m ² · 24 h).

  Moreover, the composition profile in the thickness direction of the gas barrier was analyzed by the XPS method. Confirm that a mixed region containing Si and Nb is formed at the interface 1 between the coating gas barrier layer 1 and the transition metal-containing layer and at the interface 2 between the transition metal-containing layer and the coating gas barrier layer 2. did. Further, when the minimum value of the oxygen deficiency in the mixed region was obtained using the relational expression (2), it was 0.57 at the interface 1 and 0.60 at the interface 2.

<Measurement of composition distribution in the thickness direction of the gas barrier layer>
The composition distribution profile in the thickness direction of the gas barrier layer was measured by XPS analysis. The XPS analysis conditions are as follows.

<XPS analysis conditions>
・ Device: QUANTERASXM manufactured by ULVAC-PHI
・ X-ray source: Monochromatic Al-Kα
・ Sputtering ion: Ar (2 keV)
Depth profile: Measurement was repeated at a predetermined thickness interval with a SiO2 equivalent sputtering thickness, and a depth profile in the depth direction was obtained. The thickness interval was 1 nm (data for every 1 nm is obtained in the depth direction)
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area. For data processing, MultiPak manufactured by ULVAC-PHI was used. The analyzed elements are Si, Nb, Ta, Al, O, N, and C.

  However, in the sample prepared this time, Al was not detected in the region containing (M1) and (M2).

<Measurement of mixing area thickness>
Taking the case where the transition metal is Nb as an example, the composition of the gas barrier layer can be represented by (Si) (Nb) _x O _y N _z from the data obtained from the XPS composition analysis. In the aspect in which the first layer and the second layer are laminated, Si as a non-transition metal and Nb as a transition metal coexist in the interface region between the first layer and the second layer, and the transition metal Nb / Si. A region where the value x of the number ratio of atoms in the range of 0.02 ≦ x ≦ 50 was defined as a “mixed region”, and the presence / absence of the region and its thickness (nm) were measured and listed in the table. The same measurement was performed in the case where the gas barrier layer was formed as a composite oxide layer of Si, which is a non-transition metal, and Nb (or Ta), which is a transition metal, and the thickness (nm) of the region is listed in the table. did.

<Calculation of oxygen deficiency index in mixed region>
Using the XPS analysis data, a value of (2y + 3z) / (a + bx) at each measurement point was calculated. Here, since the non-transition metal is Si, a = 4, and since the transition metal is Nb or Ta, a = 5. The minimum value of the value of (2y + 3z) / (a + bx) was determined and listed in the table as an oxygen deficiency index. When (2y + 3z) / (a + bx) <1.0, this indicates an oxygen deficient state.

[Production of organic EL elements]
(Step 2-5: Formation of transparent anode)
The same procedure as in the organic EL element 1 was performed except that the gas barrier film substrate 2 was used.

(Step 2-6: Formation of organic functional layer unit to cathode)
The same procedure as in the organic EL element 1 was performed except that the gas barrier film substrate 2 was used.

(Step 2-7: Sealing step)
Next, it was made to be the same as that of the organic EL element 1 except that the gas barrier film substrate 2 was used as the sealing substrate.

  Thus, an organic EL element 2 which is a white light emitting device having a total thickness of about 73 μm was produced.

  In both the organic EL element 1 and the organic EL element 2, the initial light emission state was good and no dark spot was generated. Also, no dark spots were generated after storage for 100 hours in an environment of 85 ° C. and 85% RH.

Example 2
Evaluation assuming a light emitting device in a folded form was performed.

  A light emitting device simulating a light emitting device in a folded form as shown in FIGS. 2A and 2B was produced.

  At the time of folding, it has a portion A where the light emitting surface is bent outward and a portion B where the light emitting surface is bent inward, and the portion A and the portion B are continuously present via an inflection point of curvature. And, the value (Br / Ar) of the ratio of the curvature radius Br of the part B to the curvature radius Ar of the part A falls within the range of 0.4 to 1.0. A device having a hinge part to be peeled is a type (1) (FIG. 2A), and a device having no hinge part at a bent part is a type (2) (FIG. 2B). Eight types of light-emitting devices were produced by changing the radius of curvature of the part B to the values shown in Table 1. The length of the hinge part is 16 mm. In the case of the type (2) which is a device having no hinge part, the minimum curvature radius of the part B was less than 1 mm.

  For each light-emitting device, after performing folding to match the surface of the support housing 5000 times from a flat state and after performing folding 10,000 times, light is emitted to determine whether or not dark spots occur in the light-emitting portion at the hinge portion. Evaluation was made according to the following indices 1 to 5.

5: No occurrence of dark spots with a diameter of 100 μm or more 4: 1-2 occurrences of dark spots with a diameter of 100 μm or more 3: 3 occurrences of dark spots with a diameter of 100 μm or more 2: Dark spots with a diameter of 100 μm or more Generation: 6 to 10 1: Generation of dark spots with a diameter of 100 μm or more: 11 or more

  As shown in Table 1, the light emitting device of the present invention was good with almost no dark spots due to folding. In particular, a light emitting device using a gas barrier film having a mixed region of transition metal and non-transition metal in the gas barrier layer showed good results.

Example 3
Evaluation was made assuming a light-emitting device in a winding form.

  A steel sheet having a thickness of 100 μm is used as a supporting member, the organic EL element produced above is bonded to the steel sheet, the organic EL element is placed outside, and a winding shaft having a radius of 8 mm is wound in the longitudinal direction. Four types of devices simulating a light emitting device in a winding form were prepared.

  The type (3) apparatus has a short side 10 mm width on the side far from the take-up shaft attached to a steel sheet with a thermosetting adhesive (epoxy resin, 100 μm thickness), 90 ° C. for 30 minutes. Curing was performed to obtain a fixed portion (fixed end). The other part was bonded using a 100 μm thick acrylic adhesive sheet (manufactured by Nitto Denko Corporation), and the short side near the take-up shaft was a free end (see FIG. 4A. The right end is the fixed end) .)

  In the type (4) apparatus, the entire surface was adhered to a steel sheet with a thermosetting adhesive (epoxy resin, 100 μm thickness), and cured by 90 ° C. for 30 minutes and fixed.

  The light emitting devices 11 to 14 were prepared by combining the organic EL element and the device type, and each light emitting device was made to emit light after being wound and unwound 100 times, and the light emitting state was confirmed. The results are shown in Table 2.

  As shown in Table 2, the light-emitting device of the present invention maintained a good light-emitting state even when it was wound and rewound, and no dark spot was generated. On the other hand, in the light emitting device of the comparative example having no movable part, linear dark spots, which are thought to be caused by gas barrier layer cracks, formed by stretching the organic EL element by winding were frequently generated.

  The light-emitting device of the present invention can be miniaturized when being carried, and can be used in various applications such as electronic devices such as packages for electronic devices, photoelectric conversion elements (solar cell elements), organic EL elements, liquid crystal display elements, and the like. Can be used.

DESCRIPTION OF SYMBOLS 1 Light-emitting device 2 Light emission surface side resin base material 3 Organic light emitting element 4 Back side base material 5 Gas barrier layer 6 Electrode 7 Organic functional layer unit 8 Sealing member A The site | part where the light emission surface was bent outside B Light emission surface inside Bent part L Light emitting part 10, 11 Supporting housing 12 Hinge part 21 Supporting member 22 Adhesive 23 Housing 24 Winding member 25 Fixed part (fixed end)
26 Control Unit 27 Free End 101 Fabrication Substrate 103 Peeling Layer 105 Peeled Layer 107 Bonding Layer 109 Substrate

Claims (12)

  A light emitting device in which a light emitting surface side resin base material, an organic light emitting element, and a back surface side base material are laminated in this order, and between the light emitting surface side resin base material and the organic light emitting element or between the organic light emitting element and the back surface side base At least one of the materials has a gas barrier layer containing an inorganic material as a main component, and the light emitting device is supported on a support member with a fixed portion and a movable portion. A light emitting device comprising a curved surface portion having a curved radius of curvature of 1.0 to 10.0 mm formed by the movable portion of the light emitting element.   At the time of carrying, it has a folded form, the light emitting surface side resin bases face each other with a gap of less than 2 mm, and the curved surface formed by the movable part of the organic light emitting element has its light emitting surface bent outward. A portion A and a portion B in which the light emitting surface is bent inward; the portion A and the portion B are continuously present via an inflection point of curvature; and the length of the movable portion is L And when the protruding length of the loop formed by the movable portion from the support member is C, C / L is 0.3 or more, and the part B with respect to the minimum curvature radius Ar of the part A 2. The light emitting device according to claim 1, wherein the ratio value (Br / Ar) of the minimum curvature radius Br is in a range of 0.4 to 1.1.   At the time of carrying, it has a winding form, and the back side substrate is installed on a rigid support member via a viscoelastic sheet-like member, and the light emitting surface side resin substrate is wound outside. The movable part that is taken and the end part on the outer side of the winding of the light emitting device is fixed so that the position is not relatively displaced, and the position of the inner side of the winding is relatively variable The light emitting device according to claim 1, wherein:   4. The light emitting device according to claim 1, wherein a total thickness of the gas barrier layer is in a range of 20 to 1000 nm.   The curvature radius of the curved surface formed by the movable portion of the organic light emitting element has a curved surface portion within a range of 1.0 to 5.0 mm. The light emitting device according to item.   The gas barrier layer is a region containing the non-transition metal M1 and the transition metal M2 at least in the thickness direction, and the value of the atomic ratio of the transition metal M2 to the non-transition metal M1 (M2 / M1) is The light emitting device according to any one of claims 1 to 5, wherein the mixed region in the range of 0.02 to 49 has a thickness of 5 nm or more continuously in the thickness direction.   The gas barrier layer has the mixed region between a region containing the transition metal M2 as a main component of the metal and a region containing the non-transition metal M1 as a main component of the metal. 6. The light emitting device according to 6.   The light emitting device according to claim 6 or 7, wherein the entire region in the thickness direction in the gas barrier layer is a mixed region containing the transition metal and the non-transition metal. The light emitting device according to any one of claims 6 to 8, wherein when the composition of the mixed region is expressed by the following chemical composition formula (1), the following relational expression (2) is satisfied. .
Chemical composition formula (1): (M1) (M2) _x O _y N _z
Relational expression (2): (2y + 3z) / (a + bx) <1.0
(Wherein, M1: non-transition metal, M2: transition metal, O: oxygen, N: nitrogen,
x, y, z: stoichiometric coefficient, a: maximum valence of M1, b: maximum valence of M2. )   The light emitting device according to any one of claims 6 to 9, wherein the non-transition metal is silicon.   11. The light emitting device according to claim 6, wherein the transition metal is selected from niobium (Nb), tantalum (Ta), and vanadium (V).   The light-emitting device according to claim 1, further comprising an organic electroluminescence element.

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