JP5055711B2 - Method for manufacturing organic EL element, organic EL element - Google Patents

Description

  The present invention relates to a method for producing an organic EL (electroluminescence) element used as a surface light source, a display panel, and the like, and an organic EL element produced by this method.

  In recent years, organic EL elements using organic substances have been promising for use as solid light-emitting inexpensive, large-area full-color display elements and writing light source arrays, and active research and development have been promoted. The organic EL device includes a first electrode (anode or cathode) formed on a substrate, an organic compound layer (single layer portion or multilayer portion) containing an organic light emitting material laminated thereon, that is, a light emitting layer, It is a thin film type element having a second electrode (cathode or anode) laminated on the light emitting layer. When a voltage is applied to such an organic EL element, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer. It is known that light is obtained by releasing energy as light when the electrons and holes recombine in the light emitting layer and the energy level returns from the conduction band to the valence band.

  As described above, since the organic EL element is a thin film type element, when an organic EL panel in which one or a plurality of organic EL elements are formed on a substrate is used as a surface light source such as a backlight, a surface light source. It is possible to easily make a device equipped with In addition, when a display device is configured using an organic EL panel in which a predetermined number of organic EL elements as pixels are formed on a substrate as a display panel, the liquid crystal display device has high visibility and no viewing angle dependency. There are benefits that cannot be obtained.

  On the other hand, when forming an organic compound layer of an organic EL element, as described in JP-A-9-102393 and JP-A-2002-170676, vapor deposition, sputtering, CVD, PVD, solvent Various methods, such as coating methods using a glass, can be used. Among these methods, manufacturing processes are simplified, manufacturing costs are reduced, workability is improved, flexible large-area elements such as backlights and illumination light sources, etc. It is known that a wet film forming method such as a coating method is advantageous from the standpoint of application to the above. For example, Japanese Patent Application Laid-Open No. 2002-170676 describes a method of forming an organic compound layer on a single wafer glass substrate by spin coating. Japanese Patent Application Laid-Open No. 2003-142260 describes a method of sequentially forming an organic compound layer on a single wafer substrate by an ink jet method. Since all of these methods use a single-wafer substrate as the substrate, the production of large-area full-color display elements has the disadvantage that the apparatus is large and the cost is high. Inexpensive manufacturing methods are being studied for organic EL elements that are promising for use as area full-color display elements and writing light source arrays. For example, as a method of manufacturing an organic EL display in which a plastic film is used as a light-transmitting substrate and a cathode, one or a plurality of light emitting layers made of an organic material, and an anode layer are provided on the plastic film, an organic material is used. A method is known in which patterning of one or a plurality of light-emitting layers made of and patterning of a cathode is made by a roll-to-roll method using a vacuum deposition method (see, for example, Patent Document 1). Also, organic light-emitting layer is made of a polymer material such as polystyrene, polymethyl methacrylate, polyvinyl carbazole or the like in which a low-molecular luminescent dye is dispersed or dissolved, or a polymer material such as polyphenylene vinylene derivative or polyalkylfluorene derivative. And the method of winding-up production by the apply | coating method by using a suitable solvent is known (for example, refer patent document 2).

  However, the production of the organic EL element by the roll-to-roll method described in Patent Document 1 and Patent Document 2 is a preferable method from the viewpoint of improving production efficiency, but has the following drawbacks. If the surface of the organic EL element is attached with a slight amount of dust or scratches, the part where the dust is attached or scratched leaks and short-circuits, causing a light emission failure. This is one of the reasons why the production efficiency does not increase because the winding tension and the winding speed are controlled so that the surface and the supporting surface are rubbed and the film surface of the organic EL element is not scratched.

From such a situation, when producing an organic EL element by a roll-to-roll method, the film surface of the organic EL element is prevented from being scratched, and no complicated winding management is required. Development is desired.
International Publication No. 01/5194 Pamphlet JP 2003-77669 A

  The present invention has been made in view of the above situation, and its purpose is to prevent the film surface of the organic EL element from being scratched when the organic EL element is produced by a roll-to-roll method, and to perform complicated winding management. It is providing the manufacturing method of the organic EL element which does not require.

  The above object of the present invention has been achieved by the following constitution.

(Claim 1)
An organic EL having at least a first electrode, a hole transport layer, a light emitting layer, an electron injection layer, a second electrode, and a sealing layer or a sealing film in this order on the belt-like flexible support. A method for manufacturing an element, comprising:
At least the step of supplying the strip-shaped flexible support;
A) a first electrode forming step for forming the first electrode;
B) a hole transport layer forming step of forming the hole transport layer;
C) a light emitting layer forming step of forming the light emitting layer;
D) an electron injection layer forming step of forming the electron injection layer;
E) a second electrode forming step for forming the second electrode;
F) a sealing layer forming step for forming the sealing layer or a sealing film attaching step for attaching the sealing film;
G) In the manufacturing method of the organic EL element which has the collection | recovery process of the said organic EL element,
When winding the belt-like flexible support that has undergone at least one of the steps of A) to G), a winding auxiliary member is provided at both ends in the width direction of the belt-like flexible support. A method for producing an organic EL device, wherein a flexible polymer film having a predetermined width is applied and wound.

(Claim 2)
The method of manufacturing an organic EL element according to claim 1, wherein the winding assisting member is processed by a cleaning unit and an antistatic unit.

(Claim 3)
3. The method of manufacturing an organic EL element according to claim 2, wherein the antistatic means includes a non-contact type antistatic device and a contact type antistatic device.

(Claim 4 )
The method for manufacturing an organic EL element according to any one of claims 1 to 3, wherein the winding assisting member has a water content measured according to JIS P 8127 of 1 to 10 mass%.

(Claim 5 )
The method for manufacturing an organic EL element according to any one of claims 1 to 4, wherein the winding assisting member has a thickness of 10 to 200% with respect to a total thickness of the organic EL element.

(Claim 6)
When taking imparted by winding the winding auxiliary member, according to claim 1, characterized in that the dew point temperature -9 0 to -20 ° C., cleanliness class measured according to JIS B 9920 is performed in 5 following environmental conditions The manufacturing method of the organic EL element of any one of -5.

(Claim 7 )
The organic EL element wound with the winding assisting member is stored in an environment having an oxygen concentration of 1 to 100 ppm and a water concentration of 1 to 100 ppm. The manufacturing method of the organic EL element of description.

(Claim 8 )
An organic EL device manufactured by the method for manufacturing an organic EL device according to claim 1.

  When producing an organic EL element by a roll-to-roll method, the film surface of the organic EL element can be prevented from being damaged, and a method for producing an organic EL element that does not require complicated winding management can be provided. High-quality organic EL elements can be manufactured, work efficiency can be improved, and production efficiency can be improved.

  Embodiments according to the present invention will be described with reference to FIGS. 1 to 7, but the present invention is not limited thereto.

  FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic EL element. FIG. 1A is a schematic cross-sectional view showing a constituent layer of an organic EL element on which a sealing film is formed. FIG. 1B is a schematic cross-sectional view showing a constituent layer of an organic EL element formed by attaching a sealing film via an adhesive.

  The layer structure of the organic EL element shown in FIG. In the figure, 1a represents an organic EL element. The organic EL element 1a includes a first electrode 102, a hole transport layer 103, a light emitting layer 104, an electron injection layer 105, a second electrode 106, and a sealing layer 107 in this order on a substrate 101. Have.

  The layer structure of the organic EL element shown in FIG. 1B will be described.

  In the figure, 1b represents an organic EL element. The organic EL element 1b includes a first electrode 102, a hole transport layer 103, a light emitting layer 104, an electron injection layer 105, a second electrode 106, an adhesive layer 108, and a sealing material on a substrate 101. The film 109 is provided in this order. In the organic EL element shown in this figure, a hole injection layer (not shown) may be provided between the first electrode 102 and the hole transport layer 103. Further, an electron transport layer (not shown) may be provided between the light emitting layer 104 and the electron injection layer 105. In the organic EL element 1a and the organic EL element 1b shown in this figure, a gas barrier film (not shown) may be provided between the first electrode 102 and the substrate 101.

  The present invention relates to a method for producing the organic EL element 1a (1b) shown in FIGS. 1A and 1B and an organic EL element produced by these production methods.

  The layer configuration of the organic EL element shown in this figure shows an example, but the following configuration can be given as a layer configuration of another typical organic EL element.

(1) Base material / anode / light emitting layer / electron transport layer / cathode / sealing layer (2) Base material / anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode / sealing layer (3) substrate / anode / hole transport layer (hole injection layer) / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer (4) substrate / Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer Each layer is described later.

  FIG. 2 is a schematic view showing an example of a production apparatus for producing an organic EL element.

  FIG. 2A is a schematic diagram showing an example of a process for producing an organic EL element. FIG. 2B is an enlarged schematic view of a portion indicated by G in FIG. In the description of the manufacturing apparatus shown in the figure, as an example of an organic EL element, a gas barrier layer, a first electrode, a hole transport layer, a light emitting layer, an electron injection layer, a second electrode, The case of the organic EL element for illumination (surface emitting) formed in the order of the sealing layers is performed. In this figure, since the gas barrier layer and the first electrode already formed on the belt-like flexible support are used, the first electrode forming step is omitted.

  In the figure, reference numeral 2a denotes an organic EL device manufacturing apparatus. The manufacturing apparatus 2a includes a strip-shaped flexible support supplying step 3, a hole transport layer forming step 4 for forming a hole transport layer, a light emitting layer forming step 5 for forming a light emitting layer, and an electron injection layer. An electron injection layer forming step 6, a second electrode forming step 7 for forming a second electrode, a sealing layer forming step 8 for forming a sealing layer, and a recovery step 9. The manufacturing apparatus shown in the figure continuously performs a supply process 3 to a light emitting layer formation process 5 under atmospheric pressure conditions, and after winding up, continuously performs an electron injection layer formation process 6 to a recovery process 9. This shows the case of performing under reduced pressure conditions.

The supply process 3 includes a feeding unit 301 and a surface treatment unit 302. In the feeding portion 301, a strip-shaped flexible support 301a (hereinafter referred to as strip-shaped flexible support A) in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core. Supplied in a roll state. 301a1 shows the former roll of the strip | belt-shaped flexible support body 301a. The surface treatment unit 302 includes a cleaning surface modification apparatus 302a and first antistatic means 302b. The cleaning surface modification processing device 302a cleans and modifies the surface of the first electrode (not shown) of the strip-shaped flexible support A sent from the supply step 301 before applying the hole transport layer forming coating solution. For example, it is preferable to use a low-pressure mercury lamp, an excimer lamp, a plasma cleaning apparatus, or the like. As conditions for the cleaning surface modification treatment using a low-pressure mercury lamp, for example, a cleaning surface modification treatment is performed by irradiating a low-pressure mercury lamp with a wavelength of 184.2 nm at an irradiation intensity of 5 to ²⁰ mW / cm ² and a distance of 5 to 15 mm. Conditions are mentioned. For example, atmospheric pressure plasma is preferably used as the condition for the cleaning surface modification treatment by the plasma cleaning apparatus. Examples of the cleaning conditions include conditions in which a gas containing oxygen of 1 to 5% by volume is used for argon gas, and the cleaning surface modification treatment is performed at a frequency of 100 KHz to 150 MHz, a voltage of 10 V to 10 KV, and an irradiation distance of 5 to 20 mm.

The first antistatic means 302b has a non-contact type static elimination prevention device 302b1 and a contact type static elimination prevention device 302b2. Examples of the non-contact type static elimination preventing device 302b1 include a non-contact type ionizer, and the type of ionizer is not particularly limited, and the ion generation method may be either an AC method or a DC method. An AC type, a double DC type, a pulsed AC type, and a soft X-ray type can be used, but the AC type is particularly preferable from the viewpoint of precise static elimination. Air or N ₂ is used as the injection gas required when using the AC type, but it is preferable to use N ₂ with sufficiently high purity. From the viewpoint of in-line operation, the blower type or the gun type is selected.

  The contact type static elimination preventing device 302b2 is performed using a static elimination roll or a conductive brush connected to the ground. The static elimination roll as the static eliminator is grounded and removes the surface charge by rotatingly contacting the neutralized surface. Such static elimination rolls include rolls made of elastic plastic or rubber mixed with conductive materials such as carbon black, metal powder, and metal fibers in addition to rolls made of metal such as aluminum, copper, nickel, and stainless steel. used. In particular, an elastic material is preferable in order to improve contact with the belt-like flexible continuous sheet. Examples of the conductive brush connected to the earth include a neutralizing bar or a neutralizing yarn structure having a brush member made of conductive fibers arranged in a line or a linear metal brush. The neutralization bar is not particularly limited, but a corona discharge type is preferably used. For example, SJ-B manufactured by Keyence Corporation is used. There is no particular limitation on the static elimination yarn, but usually a flexible yarn is preferably used. For example, 12/300 × 3 manufactured by Naslon can be cited as an example.

  The non-contact type antistatic device 302b1 is preferably used on the first electrode surface side of the belt-like flexible support A, and the contact-type antistatic device 302b2 is preferably used on the back surface side of the belt-like flexible support A. The first antistatic means removes the charge of the base material and prevents the adhesion of the dust and the dielectric breakdown, thereby improving the yield of the elements.

  In the hole transport layer forming step 4, a backup roll 401a holding the strip-shaped flexible support A and a coating solution for forming a hole transport layer are applied to the strip-shaped flexible support A held by the backup roll 401a. The first wet coater 401b, the first drying device 401c for removing the solvent of the hole transport layer a formed on the first electrode (not shown) on the strip-shaped flexible support A, and the solvent are removed. A first heat treatment device 401d for heating the hole transport layer a and a second antistatic means 401e.

  The coating liquid for forming a hole transport layer by the first wet coater 401b is applied onto the first electrode except for a part of one end of the already formed first electrode.

  The second antistatic means 401e has a non-contact type antistatic device 401e1 and a contact type antistatic device 401e2. The non-contact type antistatic device 401e1 is preferably used on the hole transport layer side, and the contact type antistatic device 401e2 is preferably used on the back side of the belt-like flexible support. The second antistatic means removes the charge on the hole transport layer surface and the back surface of the belt-like flexible support, and prevents dust adhesion and dielectric breakdown, thereby improving the device yield. The non-contact type antistatic device 401e1 and the contact type antistatic device 401e2 used for the second antistatic unit 401e are the same as the non-contact type antistatic device 302b1 and the contact type antistatic device 302b2 used for the first antistatic unit 302b. Those are preferred.

  The first drying device 401c includes a dry air supply header 401c1 having a discharge port 401c3 for discharging dry air, a dry air supply port 401c2, an exhaust port 401c4, and a transport roll 401c5. The first heat treatment apparatus 401d includes an apparatus main body 401d1, a plurality of heating rollers 401d2 for heating the hole transport layer a from the back surface side of the belt-like flexible support on which the hole transport layer a is formed, by a back surface heat transfer method, have.

  The light emitting layer forming step 5 includes a second wet coater 502b for applying a light emitting layer forming coating solution to a belt-like flexible support having the hole transport layer a held by the backup roll 502a, and a hole transport layer a. The second drying device 502c for removing the solvent of the light emitting layer b formed thereon, the second heat treatment device 502d for heating the light emitting layer c from which the solvent has been removed, the third antistatic means 502e, and the first winding And a take-up portion 502f.

  The second wet coater 502b is preferably of the same type as the first wet coater 401b. In this figure, since the organic EL element used for illumination is taken as an example, the second wet coater 402b is of a full-surface coating type. However, when the organic EL element is a full color system, it is patterned. For example, an inkjet method, a flexographic printing method, an offset printing method, a gravure printing method, a screen printing method, and a mask are used to apply a light emitting layer on the first electrode in accordance with the pattern of the first electrode formed It is possible to use various coating devices used for conventional spray coating methods.

  The second drying device 502c has the same structure as the first drying device 501c. The second heat treatment apparatus 502d has the same structure as the first heat treatment apparatus 501d, and the light emitting layer b formed on the hole transport layer b is transferred from the back surface side of the belt-like flexible support to the back surface heat transfer method. It is supposed to be heated with.

  The third antistatic means 502e has a non-contact type antistatic device 502e1 and a contact type antistatic device 502e2. The non-contact type antistatic device 502e1 is preferably used on the light emitting layer side, and the contact type antistatic device 502b2 is preferably used on the back surface side of the belt-like flexible support. The third antistatic means removes the charge on the light emitting layer surface and the back surface of the belt-like flexible support, and when the first winding portion 502f winds up, failure due to dust adhering or the like is prevented, so that the device yield. Is improved. The non-contact type antistatic device 502e1 and the contact type antistatic device 502e2 used for the third antistatic unit 502e are the same as the noncontact type antistatic device 302b1 and the contact type antistatic device 302b2 used for the first antistatic unit 302b. Those are preferred.

  The hole transport layer forming step 4 shown in this figure shows a case where there is one wet coating apparatus, one drying apparatus, and one heat treatment apparatus, but it can be increased as necessary. The light emitting layer forming step 5 also shows the case where there is one wet coating apparatus, one drying apparatus, and one heat treatment apparatus, but it can be increased as necessary.

  In the first winding portion 502f, the belt-like flexible support body on which the light emitting layer b is formed is wound on the winding core with the light emitting layer b inside, and the belt-like flexible support body 502g (hereinafter referred to as the belt-like flexible carrier). It is referred to as a support B).

  The electron injection layer formation step 6 includes a supply unit 601 and an electron injection layer formation unit 602. In the supply unit 601, the strip-shaped flexible support B produced in the previous step is fed out and supplied to the electron injection layer forming unit 602. In the electron injection layer forming unit 602, the electron injection layer c is formed on the light emitting layer b. Reference numeral 602a denotes a vapor deposition apparatus, and 602b denotes an evaporation source container. The belt-like flexible support on which the electron injection layer c is formed is subsequently sent to the second electrode forming step 7.

  In the second electrode formation step 7, the second electrode d is formed on the electron injection layer c formed by the electron injection layer formation unit 602 in the second electrode formation unit 701. Reference numeral 701a denotes a vapor deposition apparatus, and 701b denotes an evaporation source container. The strip-shaped flexible support on which the second electrode d is formed is subsequently sent to the sealing layer forming step 8.

  The sealing layer forming step 8 is a band shape in which the sealing layer e is formed on the sealing layer forming apparatus 801a on the second electrode d except for the end of the second electrode d formed in the second electrode forming step 7. A flexible support C (illumination (surface emitting) organic EL element) is produced. The sealing layer forming step 8 includes a sealing layer forming device 801a and a fourth antistatic means 801b. The fourth antistatic means 801b has a non-contact type antistatic device 801b1 and a contact type antistatic device 801be2. The non-contact type antistatic device 801b1 is preferably used on the sealing layer d side, and the contact type antistatic device 801b2 is preferably used on the back side of the belt-like flexible support. The fourth antistatic means 801b removes the charge on the sealing layer surface and the back surface of the belt-like flexible support member, and when the collecting unit 10 winds up, failure due to adhesion of dust or the like is prevented, so that the yield of elements can be reduced. Improvement is achieved. The non-contact type antistatic device 801b1 and the contact type antistatic device 801b2 used for the fourth antistatic unit 801b are the same as the non-contact type antistatic device 302b1 and the contact type antistatic device 302b2 used for the first antistatic unit 302b. Those are preferred.

The recovery process 9 includes a winding assisting member supply unit 9a and a winding unit 9b.
The winding assisting member supply unit 9a supplies the winding assisting member 902 to the winding unit 9b when the strip-shaped flexible support C (illumination (surface emitting) organic EL element) is wound by the winding unit 9b. It is a process and has a take-up assisting member feeding portion 9a1, a cleaning means 9a2, and a fifth antistatic means 9a3. Reference numeral 903 denotes an original winding roll of the winding auxiliary member 902. The winding assisting member supply unit 9a will be described in detail with reference to FIG.

  The belt-like flexible support C treated by the fourth antistatic means 801b is provided with the winding auxiliary member 902 supplied from the take-up assisting member supply portion 9a to the belt-like flexible support C. A roll-shaped strip-like flexible support 901 is produced by being wound together with the flexible support C.

  The winding tension when the winding auxiliary member 9a4 is applied to the belt-shaped flexible support C (illumination (surface emitting) organic EL element) in the collecting step 9 and wound is depending on the collapse, transportation, and handling. Considering the occurrence of scratches on the film surface of the organic EL element due to the rust between the organic EL element surface and the back surface of the belt-like flexible support, the occurrence of scratches on the film surface of the organic EL element due to winding, etc. A width of 000 N / m is preferred.

  The collected roll-shaped strip-shaped flexible support C (illumination (surface emitting) organic EL element) is considered to maintain performance, dark spots (non-light emitting portions), etc., and has an oxygen concentration of 1 to 100 ppm and a moisture concentration of 1 It is preferable to store in an environment of ˜100 ppm.

  In this figure, the case where the electron injection layer forming step 6 and the second electrode forming step 7 are vapor deposition apparatuses is shown, but the method for forming the electron injection layer and the second electrode is not particularly limited. Reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD method, laser CVD method, thermal CVD method, coating method, etc. may be used. I can do it.

  Further, instead of the sealing layer shown in the figure, a method of sticking a sealing film may be used. However, in this case, it is preferable that the supply portion, the sticking portion, and the recovery portion of the sealing film are continuously performed under atmospheric pressure conditions.

  FIG. 3 is an enlarged schematic perspective view of a portion indicated by H in FIG.

  The cleaning means 9a2 is preferably contact-type cleaning means such as an adhesive roll and a scraping blade since the supply process 9 of the take-up auxiliary member is disposed under reduced pressure conditions. Particularly, the take-up auxiliary member is damaged. An adhesive roll that is difficult to give and easy to manage is preferred. This figure has shown the case where the front surface of the winding auxiliary member 902 is sandwiched between the adhesive rolls 9a21 and the back is sandwiched between the adhesive rolls 9a22. The fifth antistatic means 9a3 includes a non-contact type antistatic device 9a31 and a contact type antistatic device 9a32. It is preferable to use the same as the first antistatic means 302b (see FIG. 2). For the winding auxiliary member 902, either a non-contact type antistatic device or a contact type antistatic device can be used, and can be appropriately used in accordance with the characteristics of the winding auxiliary member 902 to be used. Other symbols are the same as those in FIG.

  FIG. 4 is a schematic view showing another example of a manufacturing apparatus for producing an organic EL element. In addition, the difference between the manufacturing apparatus shown in this figure and the manufacturing apparatus 2a shown in FIG. 2 is as follows: 1) When winding at the first winding part after the light emitting layer forming step, a winding auxiliary member is provided and wound. For this purpose, the supply of the take-up auxiliary member is provided, 2) the recovery part of the take-up auxiliary member is provided in the supply part of the electron injection layer forming step, and 3) the second electrode is formed in the second electrode forming step. 4) Arrangement of the winding part for applying and winding the winding auxiliary member 4) Arrangement of the sealing film attaching process instead of the sealing layer forming process 5) In the supply part of the sealing film attaching process Arrangement of the collecting part of the winding assisting member, 6) Application of the winding assisting member cleaned by a different method of the cleaning means in the collecting part, and the others are the same as in FIG. Only those parts will be described.

  In the figure, reference numeral 2b denotes an organic EL device manufacturing apparatus. In the drawing, reference numeral 502f1 denotes a first winding assisting member supply unit provided in the winding unit 502f. Reference numeral 503 denotes a winding auxiliary member, and 503a denotes an original winding roll of the winding auxiliary member. The first winding assisting member supply unit 502f1 includes a first cleaning unit 502f11 and an antistatic unit 502f12. In the first winding portion 502f, the belt-like flexible support B on which the light emitting layer b is formed is taken up together with the take-up auxiliary member 503 to produce a roll-like belt-like flexible support B.

  Reference numeral 601a denotes a collection unit that collects the winding auxiliary member 503 that has been wound together when the belt-like flexible support B is unwound by the supply unit 601.

  The second electrode forming step 7 includes a second electrode forming portion 701, an antistatic means 702, and a second winding portion 703. The second winding unit 703 includes a second winding assisting member supply unit 703b having a cleaning unit 703b1 and an antistatic unit 703b2. Reference numeral 703c1 denotes an original winding roll of the winding auxiliary member 703c. In the second winding portion 703, the belt-shaped flexible support body on which the second electrode d is formed and the winding auxiliary member 703c are wound together to form a roll-shaped belt-shaped flexible support body 703a (hereinafter referred to as a belt-shaped flexible substrate). A support D).

  11 shows a sealing film sticking process. The sealing film sticking process 11 has the supply part 11a of the strip | belt-shaped flexible support body D, and the sticking part 11b. Reference numeral 11a1 denotes a collection unit that collects the winding auxiliary member 703c wound together when the belt-shaped flexible support D on which the second electrode d is formed is unwound by the supply unit 11a. The sticking part 11b has a coating device 11b1 for applying an adhesive on the second electrode, a sealing film supply part 11b2, a pressure-bonding roll 11b3, and a curing processing part 11b4. 11b5 shows the former roll of the sealing film 11b6.

  After being unwound from the supply unit 11a and the adhesive is continuously applied on the second electrode except for a part of the end of the second electrode of the strip-shaped flexible support 703a by the coating device 11b1, The sealing film 11b6 is continuously bonded and passes through the pressure-bonding roll 11b3, whereby the sealing film is continuously bonded onto the second electrode via an adhesive. After the sealing film 11b6 is pasted via an adhesive, the curing process of the adhesive is performed by the curing unit 11b4. A strip-like flexible support D (illumination (surface emitting) organic EL element) protected by the sealing film 11b6 is produced at the stage where the adhesive curing process is completed, and is sent to the recovery step 12.

  The collection process 12 includes an antistatic means 12a, a third winding assisting member supply unit 12b, and a winding unit 12c. The third winding auxiliary member supply unit 12b supplies the winding auxiliary member to the winding unit 12c when the belt-shaped flexible support D (illumination (surface emitting) organic EL element) is wound by the winding unit 12c. And includes a take-up assisting member feeding portion 12b1, a cleaning means 12b2, and an antistatic means 12b3. The winding assisting member supply unit 12b will be described in detail with reference to FIG. A winding auxiliary member 12b4 supplied from the feeding portion 12b1 is applied to the band-shaped flexible support C on the band-shaped flexible support D processed by the antistatic means 12a, and the belt-shaped flexible support D is wound together with the band-shaped flexible support D. A roll-shaped strip-shaped flexible support 1201 (roll-shaped lighting (surface emitting) organic EL element) is produced. 12b5 shows the former roll of winding auxiliary member 12b4.

  The winding tension when the winding auxiliary member 12b4 is applied to the belt-shaped flexible support C (illumination (surface emitting) organic EL element) in the collecting step 12 and wound is the same as that in the collecting step 9 shown in FIG. Same as the case. Other symbols are the same as those in FIG.

  The first winding assisting member supply unit 502f1 shown in this figure can be applied to the winding assisting member supplying unit shown in FIGS. 3, 5, and 6, and is preferably selected and used as appropriate. . It is preferable to apply the winding assisting member supply unit shown in FIG. 3 to the second winding assisting member supply unit 703b.

  FIG. 5 is an enlarged schematic perspective view of a portion indicated by I in FIG.

  In the figure, reference numeral 12b11 denotes a former winding roll of the winding auxiliary member 12b4. The winding assisting member 12b4 has the same width as the band-like flexible support (illumination (surface emitting) organic EL element) to which the sealing film is attached, and contacts the sealing film surface from the supply unit 12b1. Then, it is wound up together with a belt-like flexible support (illumination (surface emitting) organic EL element) on which the sealing film is attached. The cleaning means 12b2 has a gas blowing part 12b21 and a suction part 12b22. Reference numeral 12b23 denotes a gas supply pipe. The gas supplied from the gas supply pipe 12b23 is directed toward the take-up auxiliary member 12b4 from a slit (not shown) provided on the surface of the gas blowing portion 12b21 facing the take-up auxiliary member 12b4 side. Erupted. The pressure of the gas to be ejected is preferably 1 to 20 kPa in consideration of the cleanliness, thickness, type, width and the like of the winding assist member.

  The suction unit 12b22 is supplied by the gas blowing unit 12b21, and sucks the gas containing dust, so that the suction amount is 100 to the gas supply amount in consideration of reattachment to the film surface, scattering, and the like. 105% is preferred. Note that suction is performed via a suction pipe (illustrated) connected to a suction pump attached to the suction portion 12b22. The cleaning means 12b2 is preferably performed in a chamber (not shown) closed from the outside in order to avoid scattering of dust and reattachment to the film surface.

  It is preferable to use the same antistatic means 12b3 as the first antistatic means 302b (see FIG. 2). Either a non-contact type antistatic device or a contact type antistatic device can be used, and can be appropriately used in accordance with the characteristics of the winding assisting member 12b4 to be used. Instead of the take-up assisting member supply portion 12b shown in this figure, it is possible to use the take-up assisting member supply portion shown in FIG.

  FIG. 6 is a schematic perspective view when a narrow winding auxiliary member is wound around both ends instead of the wide winding auxiliary member of FIG.

  In the drawing, reference numeral 12b12 denotes an original winding roll of the narrow winding auxiliary member 12b5. Other symbols are synonymous with FIG. As shown in this figure, when using a narrow winding assisting member, it is necessary to wind it in the left and right positions.

  FIG. 7 is an enlarged schematic partial cross-sectional view of the roll-like belt-like flexible support (illumination (surface emitting) organic EL element) of FIGS. 5 and 6. FIG. 7A is an enlarged schematic partial sectional view taken along the line AA ′ of FIG. FIG. 7B is an enlarged schematic partial sectional view taken along the line BB ′ of FIG.

  In the figure, reference numeral 13 denotes a belt-like flexible support, and reference numeral 14 denotes a constituent layer constituting an organic EL element formed on the belt-like flexible support 13. Reference numeral 13 a denotes an end portion where the constituent layer 14 constituting the organic EL element of the strip-shaped flexible support 13 is not provided, and is provided at both ends of the strip-shaped flexible support 13. For this reason, in the case of (a) in FIG. 7, a gap corresponding to the thickness of the constituent layer 14 is formed at both ends of the winding assisting member 12 b 4 and the strip-like flexible support 13. In the case of FIG. 7B, since the winding auxiliary member 12b5 is wound around both ends of the belt-like flexible support 14, the thickness of the constituent layer 14 is subtracted from the thickness of the winding auxiliary member 12b5. Are formed between the surface of the constituent layer 14 and the back side of the belt-like flexible support 13. The winding position in the case of using the narrow winding assisting member 12b5 is not particularly limited, and is the same position from the center in the width direction of the band-shaped flexible support on which the constituent layer 14 constituting the organic EL element is formed. It is preferable to do. The method shown in (a) of FIG. 5 and (b) of FIG. 5 can be appropriately selected as necessary.

  As a winding auxiliary member, adhesion between the constituent layer constituting the organic EL element and the winding auxiliary member, winding property, unwinding property, prevention of scratches on the constituent layer constituting the organic EL element, etc. In consideration of the above, the static friction coefficient measured according to JIS P 8147 preferably has a value of 0.1 to 0.5.

  The winding auxiliary member is uniform in winding, uniform supply, prevention of tightening, stabilization of winding torque, and prevention of scratches on the film surface and the back surface of the organic EL element. In view of the above, it is preferable that the Clark flexibility is 10 to 300.

  The take-up auxiliary member has a water content measured according to JIS P 8127 in consideration of generation of static electricity, generation of static at the time of winding and unwinding, stabilization of the quality of the organic EL element, and the like. It is preferable that

  The winding assisting member preferably has a thickness of 10 to 200% with respect to the total thickness of the organic EL element in consideration of handleability, prevention of enlargement of the winding diameter, and stabilization of torque during winding.

  As the winding assisting member according to the present invention, if the constituent layer of the organic EL element of the belt-like flexible continuous sheet can be suitably protected and the peelability from the forming surface (coating film) is good, The general configuration is not particularly limited, and may be made of an inexpensive material. For example, there is no particular limitation such as synthetic paper, kraft paper, fine paper, polypropylene, polyethylene (PE), polyester, vinyl chloride, PE laminated paper, etc., but PE laminated paper, polypropylene, polyethylene, A flexible polymer film such as polyester or vinyl chloride is preferred.

  The base paper that becomes the core of the winding assisting member may be a resin coated with a resin. Examples of the resin applied to the resin coating include polyethylene such as high density polyethylene, low density polyethylene, medium density polyethylene, and linear low density polyethylene; isotactic, syndiotactic, atactic, mixtures thereof, ethylene, and the like Polypropylene such as random copolymer or block copolymer of the above; other poly-3-methylpentene-1, polyethylene glycol terephthalate, polyvinyl chloride, polyvinylidene chloride, eval, polyisobutylene, ethylene vinyl acetate copolymer alone Or it can be used in combination.

Using the manufacturing apparatus shown in FIG. 2 to FIG. 4, the belt-like flexible support (illumination (surface emitting) organic EL element) on which the winding auxiliary member and the sealing layer are formed is wound together. The following effects can be obtained by forming a roll-like strip-shaped flexible support (illumination (surface emitting) organic EL element) having the cross-sectional shape shown in FIG.
1) The film surface of the organic EL element can be protected, and a stable quality organic EL element can be manufactured.
2) By applying a winding auxiliary member at the formation stage of each layer constituting the organic EL element and winding it, the film surface can be protected and the quality can be stably conveyed to the next process, and the production efficiency can be improved. It was.
3) Complex and strict winding management such as tension and speed during winding is not required, and production efficiency can be improved.
4) A roll auxiliary member is provided, and the wound roll body is given resistance to disturbances such as vibration during handling and external pressure, so that the width of the manufacturing method can be expanded. The gas barrier layer, the first electrode, the hole transport layer, the light emitting layer, the electron injection layer, the second electrode, the sealing layer and the like constituting the organic EL device according to the invention will be described.

  A transparent resin film is mentioned as a strip | belt-shaped flexible support body used for the strip | belt-shaped flexible support body in which the gas barrier layer concerning this invention and the 1st electrode were already formed. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned.

A gas barrier film is preferably formed on the surface of the resin film used as the belt-like flexible support, if necessary. Examples of the gas barrier film include an inorganic film, an organic film, or a hybrid film of both. As a characteristic of the gas barrier film, the water vapor permeability is preferably 0.01 g / m ² · day · atm or less. Furthermore, a high barrier film having an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the element. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times. The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

As the first electrode, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such an electrode substance 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. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern of a desired shape may be formed by photolithography, or if the pattern accuracy is not so high (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductive compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is taken out from the anode, it is desirable that the transmittance is greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

  A hole injection layer (anode buffer layer) may be present between the first electrode and the light emitting layer or the hole transport layer. The hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of light emission. “The organic EL element and the forefront of industrialization (November 30, 1998, NTS) The details are described in the second volume, Chapter 2, “Electrode Materials” (pages 123 to 166) of “The Company”. The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

The hole transport layer applied and formed by the first wet coater 401b is made of a hole transport material having a function of transporting holes, and in a broad sense, the hole injection layer and the electron blocking layer are also hole transport layers. include. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one 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 and 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, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine 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 (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-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials. A hole transport layer having a high p property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such a hole transport layer having a high p property because an organic EL element with lower power consumption can be produced.

  In the case where the light emitting layer formed by the second wet coater 402b is a multilayer, it is necessary to arrange the units of the coating / drying unit according to the number of layers to be stacked. For example, a white element can be manufactured by forming a light emitting layer in multiple layers. In the present invention, the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer. In the present invention, it is preferable that at least one blue light emitting layer is provided at a position closest to the anode in all the light emitting layers. Also, when four or more light emitting layers are provided, for example, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting from the order close to the anode. Layered / green light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer / green light emitting layer / red light emitting layer, etc. It is preferable for improving luminance stability.

  The total thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 2 nm to 5 μm, preferably 2 to 200 nm in consideration of the uniformity of the film and the voltage required for light emission. Furthermore, it is preferable that it exists in the range of 10-20 nm. A film thickness of 20 nm or less is preferable because it has the effect of improving the stability of the emission color with respect to the driving current as well as the voltage surface. The film thickness of each light emitting layer is preferably selected in the range of 2 to 100 nm, and more preferably in the range of 2 to 20 nm. Although there is no restriction | limiting in particular about the film thickness relationship of each light emitting layer of blue, green, and red, It is preferable that the blue light emitting layer (the sum total when there are two or more layers) is the thickest among three light emitting layers.

  The light emitting layer includes at least three layers having different emission spectra, each having an emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm. If it is three or more layers, there will be no restriction | limiting in particular. When there are more than four layers, there may be a plurality of layers having the same emission spectrum. A layer having an emission maximum wavelength in the range of 430 to 480 nm is referred to as a blue light emitting layer, a layer in the range of 510 to 550 nm is referred to as a green light emitting layer, and a layer in the range of 600 to 640 nm is referred to as a red light emitting layer. Moreover, in the range which maintains the said maximum wavelength, you may mix a several luminescent compound in each light emitting layer. For example, the blue light emitting layer may be used by mixing a blue light emitting compound having a maximum wavelength of 430 to 480 nm and a green light emitting compound having the same wavelength of 510 to 550 nm.

  The material used for the light emitting layer is not particularly limited, and examples thereof include the latest trends of Toray Research Center, Inc. flat panel displays, the current state of EL displays and the latest technological trends, and various materials as described on pages 228-332.

  The light emitting layer formed by applying the coating liquid for forming the light emitting layer with the second wet coater 206b and drying is recombined with the electrons and holes injected from the electrode or the electron injection layer and the hole transport layer. The light emitting portion may be in the light emitting layer or at the interface between the light emitting layer and the adjacent layer.

  Examples of the wet coater that can be used for the first wet coater 203b and the second wet coater 206b include a die coat method, a screen printing method, a flexographic printing method, an ink jet method, a Mayer bar method, a cap coat method, and a spray. It is possible to use a coating machine such as a coating method, a casting method, a roll coating method, a bar coating method, or a gravure coating method. The use of these wet coating machines can be appropriately selected according to the material of the organic compound layer.

  As drying conditions for removing the solvent of the hole transport layer in the first drying device 401c, in consideration of drying unevenness, blown rough surface of the coating film, etc., the discharge air speed of the dry air from the discharge port is 0.1 to 5 m / s, Airflow drying in which the wind speed distribution in the width direction is 0.1 to 10% can be mentioned. The drying conditions for removing the solvent of the light emitting layer in the second drying device 402c may be the same as the conditions of the first drying device 401c.

  As a heat treatment condition of the hole transport layer in the first heat treatment unit 401d, the glass transition temperature of the hole transport layer is considered in consideration of improvement in smoothness of the hole transport layer, removal of residual solvent, curing of the hole transport layer, and the like. On the other hand, it is preferable to perform the back-surface heat transfer type heat treatment at −30 to + 30 ° C. and at a temperature not exceeding the decomposition temperature of the organic compound constituting the hole transport layer.

  As the heat treatment conditions of the light emitting layer in the second heat treatment unit 502d, considering the smoothness improvement of the light emitting layer, the removal of the residual solvent, the curing of the light emitting layer, etc., the glass transition temperature of the light emitting layer is −30 to + 30 ° C. In addition, it is preferable to perform the back surface heat transfer type heat treatment at a temperature not exceeding the decomposition temperature of the organic compound constituting the light emitting layer.

  When the coating liquid for forming the hole transport layer is applied by the first wet coater 401b, the variation in the conveyance speed of the belt-like flexible support, and when the coating liquid for forming the light emitting layer is applied by the second wet coater 502b The variation in the conveyance speed of the belt-like flexible support is preferably 0.2 to 10% with respect to the average conveyance speed in consideration of unevenness in light emission luminance associated with uneven coating thickness in the longitudinal direction.

The hole transport layer forming coating solution used in the first wet coater 401 and the light emitting layer forming coating solution used in the second wet coater 502b include at least one organic compound material and at least one solvent. The surface tension is preferably 15 × 10 ^{−3 to} 55 × 10 ⁻³ N / m in consideration of repelling during coating and uneven coating.

  The process of forming the hole transport layer and the light emitting layer, which are the constituent layers of the organic EL element shown in this figure, considers the maintenance of the performance of the hole transport layer and the light emitting layer, the prevention of failure defects due to foreign matter adhesion, Dew point temperature is −20 ° C. or lower, conforms to JISB 9920, measured cleanliness is class 5 or lower, and is formed under atmospheric pressure conditions of 10 to 45 ° C. excluding the first drying section and the second drying section. It is preferable. In the present invention, cleanliness of class 5 or less means class 3 to class 5.

  The storage period is preferably 1 hour to 200 hours in consideration of the removal of oxygen and trace moisture due to deterioration of the hole transport layer and the light emitting layer. In some cases, it may be stored in a heated environment.

  The electron injection layer formed in the electron injection layer forming step is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. The electron injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of the light emission. “Organic EL element and its forefront of industrialization (NST 30, November 30, 1998) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166). The details of the electron injection layer (cathode buffer layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, as an electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the light emitting layer side, it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. As a material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodisides. Examples include methane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group can also be used as the electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum. Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Distyrylpyrazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type-Si and n-type-SiC are also used as electron transport materials in the same manner as the hole injection layer and hole transport layer. I can do it. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  An electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such an electron transport layer having a high n property because an element with lower power consumption can be manufactured. The electron transport layer can also be formed by thinning the electron transport material by a known method such as wet coating or vacuum deposition.

As the second electrode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials 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 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the first electrode (anode) or the second electrode (cathode) of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

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

  As the sealing film to be used, a barrier film and a metal film made of the same material as the gas barrier film can be used. Specific examples of the adhesive include photo-curing and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, moisture-curing adhesives such as 2-cyanoacrylates, and epoxy. Heat- and chemical-curing type (two-component mixed) adhesives, polyamide-based, polyester-based, polyolefin-based hot-melt adhesives, cationic-curing type UV-curable epoxy resin adhesives, etc. I can do it.

  In addition, since the organic layer which comprises an element may deteriorate with heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print it like screen printing.

  When the sealing film is formed, it can be formed on the second electrode by using the materials and methods described in the gas barrier layer of the substrate.

  In the gap between the sealing member (sealing film and sealing film shown in FIG. 1) and the display area of the organic EL element, in the gas phase and the liquid phase, an inert gas such as nitrogen or argon, or fluorocarbon It is preferable to inject an inert liquid such as hydrogen or silicon oil. A vacuum can also be used. Moreover, a hygroscopic compound can also be enclosed inside. Examples of the hygroscopic compound include metal oxides (eg, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide), sulfates (eg, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate, etc.). Metal halides (eg, calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide, etc.), perchloric acids (eg, barium perchlorate, In particular, anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

  The light emitting layer constituting the organic EL device of the present invention contains a known host compound and a known phosphorescent compound (also referred to as a phosphorescent compound) in order to increase the luminous efficiency of the light emitting layer. Is preferred.

  The host compound is a compound contained in the light-emitting layer, the mass ratio in the layer is 20% or more, and the phosphorescence quantum yield of phosphorescence emission is 0.1 at room temperature (25 ° C.). Is defined as less than a compound. The phosphorescence quantum yield is preferably less than 0.01. A plurality of host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As these host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) are preferable. Known host compounds include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, Examples thereof include compounds described in 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837 and the like.

  In the case of having a plurality of light emitting layers, it is preferable that 50% by mass or more of the host compound in each layer is the same compound because it is easy to obtain a uniform film property over the entire organic layer. It is more preferable that the light emission energy is 2.9 eV or more because it is advantageous in efficiently suppressing energy transfer from the dopant and obtaining high luminance. Phosphorescence emission energy means the peak energy of the 0-0 band of phosphorescence emission when the photoluminescence of a deposited film of 100 nm is measured on a substrate with a host compound.

  The host compound has a phosphorescence emission energy of 2.9 eV or more and a Tg of 90 ° C. or more in consideration of deterioration of the organic EL device over time (decrease in luminance and film properties), market needs as a light source, and the like. Preferably there is. That is, in order to satisfy both luminance and durability, it is preferable that phosphorescence emission energy is 2.9 eV or more and Tg is 90 ° C. or more. Tg is more preferably 100 ° C. or higher.

  A phosphorescent compound (phosphorescent compound) is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. The compound is 0.01 or more at ° C. When used in combination with the host compound described above, an organic EL device with higher luminous efficiency can be obtained.

  The phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more. The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen), 4th edition, Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the phosphorescence quantum yield in any solvent.

  There are two types of light emission of the phosphorescent compound in principle. One is the recombination of the carrier on the host compound to which carriers are transported, and an excited state of the host compound is generated, and this energy is generated by the phosphorescent compound. The energy transfer type is to obtain light emission from the phosphorescent compound by moving to the other, and the other is that the phosphorescent compound becomes a carrier trap, and carrier recombination occurs on the phosphorescent compound, and the phosphorescent compound emits light. Although it is a carrier trap type in which light emission can be obtained, in any case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device. The phosphorescent compound is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), rare earth Of these, iridium compounds are the most preferred.

  In the present invention, the phosphorescence emission maximum wavelength of the phosphorescent compound is not particularly limited, and can be obtained in principle by selecting a central metal, a ligand, a ligand substituent, and the like. The emission wavelength can be changed.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

The white element referred to in the present invention means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X = 0.33 ± 0.07 when the front luminance at 2 ° C. viewing angle is measured by the above method. It is in the region of Y = 0.33 ± 0.07.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

  The organic EL device of the present invention preferably uses the following method in combination in order to efficiently extract light generated in the light emitting layer. The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and only about 15% to 20% of the light generated in the light emitting layer can be extracted. It is generally said that there is no. This is because the light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the element, or the transparent electrode or light emitting layer and the transparent substrate This is because the light undergoes total reflection between them, the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side surface of the device.

  As a technique for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435). A method for improving efficiency by providing a substrate with a light condensing property (JP-A-63-314795). A method of forming a reflective surface on the side surface of an element (Japanese Patent Laid-Open No. 1-220394). A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between a substrate and a light emitter (Japanese Patent Laid-Open No. 62-172691). A method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter (Japanese Patent Laid-Open No. 2001-202827). There is a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer, and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951).

  In the present invention, these methods can be used in combination with an organic EL element. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, a transparent electrode layer, A method of forming a diffraction grating between any layers of the light emitting layer (including between the substrate and the outside) can be suitably used. In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a low refractive index medium is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower. . Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less. The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate. The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method is generated from the light emitting layer by utilizing the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Of the light, the light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode) , Trying to extract light out. The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction gratings is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

  Furthermore, the organic EL device of the present invention is processed so as to provide, for example, a structure on the microlens array on the light extraction side of the substrate in order to efficiently extract light generated in the light emitting layer, or so-called condensing. By combining with the sheet, the luminance in the specific direction can be increased by collecting light in a specific direction, for example, in the front direction with respect to the element light emitting surface. As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, a substrate may be formed with a Δ-shaped stripe having an apex angle of 90 degrees and a pitch of 50 μm, or the apex angle is rounded and the pitch is changed randomly. Other shapes may be used. Moreover, in order to control the light emission angle from a light emitting element, you may use a light-diffusion plate and a film together with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the mode of the present invention is not limited to this.

Example 1
(Preparation of winding auxiliary member)
As shown in Table 1, a 40 μm thick PET having a different coefficient of static friction was prepared as a winding auxiliary member. 1-1 to 1-11. The static friction coefficient was changed by mechanically roughening the surface of PET. In addition, the width | variety of the winding assistance member was made into the same width as the strip | belt-shaped flexible support body which has each layer which comprises an organic EL element, and the Clark softness | flexibility was 100. The static friction coefficient is a value measured with a surface tester manufactured by Shinto Kagaku Co., Ltd. according to JIS P 8147. The Clark flexibility indicates a value measured by an automatic Clark stiffness tester manufactured by Kumagaya Riki Kogyo Co., Ltd. according to JIS P 8143.

<Preparation of strip-shaped flexible support having gas barrier layer and first electrode layer in this order>
Using a polyethylene terephthalate film having a thickness of 100 μm (a film made by Teijin-Deupon, hereinafter abbreviated as PET), a gas barrier layer and a first electrode are formed by the method described below, and a winding roll is formed on the winding core. A belt-like flexible support having a gas barrier layer and a first electrode in this order was prepared.

(Formation of a transparent gas barrier layer)
On the prepared PET, a transparent gas barrier layer having a thickness of about 90 nm was formed by an atmospheric pressure plasma discharge treatment method. As a result of measuring the water vapor transmission rate by a method based on JISk-7129B, it was 10 ⁻³ g / m ² / day or less. As a result of measuring the oxygen transmission rate by a method based on JISk-7126B, it was 10 ⁻³ g / m ² / day or less.

(Formation of the first electrode)
On the barrier layer thus formed, ITO (indium tin oxide) having a thickness of 120 nm was patterned by a vapor deposition method to form a first electrode.

(Formation of hole transport layer and light emitting layer)
Holes shown below on the first electrode of the strip-shaped flexible support having the gas barrier layer wound around the prepared core and the first electrode in this order using the step shown in FIG. The coating liquid for transport layer formation is applied and dried by a wet coating method using an extrusion coating machine, and then charged, and then the coating liquid for forming the light emitting layer is applied onto the hole transport layer by using an extrusion coating machine. After applying and drying by the wet application method used to form a light emitting layer, it was charged, cooled to the same temperature as room temperature, and then wound around the winding core. The conveyance speed was 2 m / min. The conveyance speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.

Before applying the coating liquid for forming the hole transport layer, the surface of the belt-like flexible support is subjected to a cleaning surface modification treatment using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. Carried out. The charge removal treatment was performed using a static eliminator with weak X-rays.

  The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm. The light emitting layer forming coating solution was applied so that the thickness after drying was 100 nm. The conveyance speed was 2 m / min.

Preparation of coating solution for forming hole transport layer Polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) diluted with pure water 65% and methanol 5% to form hole transport layer It was prepared as a coating solution. The surface tension of the coating liquid for forming a hole transport layer was 40 × 10 ⁻³ N / m (manufactured by Kyowa Interface Chemical Co., Ltd .: surface tension meter CBVP-A3).

Preparation of a coating solution for forming a light emitting layer 5% by mass of a dopant material Ir (ppy) 3 is dissolved in 1,2-dichloroethane in polyvinyl carbazole (PVK) as a host material to prepare a coating solution for forming a light emitting layer. did. The surface tension of the coating solution for forming the light emitting layer was 32 × 10 ⁻³ N / m (manufactured by Kyowa Interface Chemical Co., Ltd .: surface tension meter CBVP-A3). The glass transition temperature of the light emitting layer was 225 degreeC. In addition, although the material which has green light emission was used for this example, it is possible to produce a white organic EL element by laminating | stacking further using blue, red, and a dopant material.

Coating conditions The temperature at the time of application of the hole transport layer forming coating solution was 25 ° C., and the temperature at the time of coating of the light emitting layer forming coating solution was 25 ° C. in an atmospheric environment. The wet coating process was performed with a dew point temperature of −20 ° C. or lower and a cleanliness class 5 or lower (JIS B 9920).

Drying and Heat Treatment Conditions After coating the hole transport layer forming coating solution, the first drying device and the first heat treatment device shown in FIG. 2 are used. After removing the solvent at a height of 100 mm, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 100 ° C., a backside heat transfer system heat treatment is subsequently performed at a temperature of 200 ° C. in a first heat treatment apparatus. A hole transport layer was formed. After the light emitting layer forming coating solution is applied, the second drying device and the second heat treatment device shown in FIG. 2B are used. In the second drying device, the slit nozzle type discharge port is directed toward the film formation surface. After removing the solvent at a height of 100 mm, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C., a heat treatment was subsequently performed at a temperature of 220 ° C. in a second heat treatment apparatus to form a light emitting layer.

(Formation of electron injection layer and second electrode)
Subsequently, a cathode layer forming step and a sealing layer forming step shown in FIG. 2 are used on the formed light emitting layer, and a LiF layer (electron injection layer) having a thickness of 0.5 nm under 5 × 10 ⁻⁴ Pa vacuum. ) On the entire surface, and after forming a 100 nm thick aluminum layer (second electrode) with a width of 50 μm and a spacing of 30 μm so as to be orthogonal to the first electrode through a mask, the deposition method is continued. The sealing layer was formed by vapor deposition and cooled to room temperature.

(Production of roll organic EL element)
Subsequently, using the winding assisting member overlapping apparatus shown in FIG. 3, using the prepared winding assisting members 1-1 to 1-11, a winding roll-shaped organic EL element was produced on the winding core, and samples 101 to 111. The tension during winding was variable in accordance with the winding diameter in the range of 400 to 500 N / m width, and 150 m was wound. In addition, when the take-up assisting member was applied and taken up, the cleanliness class measured according to JIS B 9920 was performed at a dew point temperature of −35 ° under 5 environmental conditions.

Evaluation The produced sample No. Table 2 shows the results obtained by measuring the scratches according to the evaluation methods shown below according to the evaluation methods shown below.

Evaluation Method of Scratches Ten samples of 30 cm × 30 cm were sampled from a location 10 m from the beginning of winding, and the number of scratches having a length of 100 μm was visually measured with an 8 times loupe. The average number of 10 scratches was measured.

Evaluation rank of scratches ○: Average number of scratches is less than 5 Δ: Average number of scratches is 5 or more and less than 10 ×: Average number of scratches is 10 or more

  The effectiveness of the present invention was confirmed.

Example 2
Sample No. 1 prepared in Example 1 was used. When producing 1-4, a roll-shaped organic EL device was produced under the same conditions except that the Clark flexibility of the winding assisting member was changed as shown in Table 4, and used as samples 201-206. Note that the flexibility was changed by changing the thickness of the winding assisting member.

Evaluation The produced sample No. Table 3 shows the results of evaluation of the same evaluation items as in Example 1 with the same evaluation method, and evaluation according to the same evaluation rank.

  Sample No. Although 201 had no problem with scratches, it was found that handling was a problem and some countermeasures were required for practical use. The effectiveness of the present invention was confirmed.

Example 3
Sample No. 1 prepared in Example 1 was used. When producing 1-4, the winding auxiliary member was changed to low density polyethylene, and the thickness (%) with respect to the total thickness of the organic EL element of the winding auxiliary member was changed as shown in Table 4, and all the same conditions. Thus, a roll-shaped organic EL device was prepared as Samples 301 to 309.

Evaluation The produced sample No. Table 4 shows the results of evaluation of the same evaluation items as in Example 1 with the same evaluation method, and evaluation according to the same evaluation rank.

  Sample No. In No. 301, no generation of scratches was observed, but it became difficult to handle the winding assisting member, and it was confirmed that some measures were required. The effectiveness of the present invention was confirmed.

Example 4
Sample No. 1 prepared in Example 1 was used. When producing 1-4, a roll-shaped organic EL device was used under the same conditions except that a laminate paper obtained by laminating a winding auxiliary member with PE was used and the water content of the winding auxiliary member was changed as shown in Table 5. Were prepared as Samples 401-407. The water content was changed by performing a humidification process or a dehumidification process on the laminated paper. The water content is a value measured according to JIS P 8127.

Evaluation The produced sample No. Table 5 shows the results obtained by measuring dark spots (non-light-emitting portions) and scratches with reference to 401 to 407 by the evaluation method shown below and evaluating according to the evaluation rank shown below. The scratches were evaluated according to the same evaluation method and the same evaluation rank as in Example 1.

Dark Spot Evaluation Method Using a source measure unit 2400 type manufactured by Toyo Technica Co., Ltd., a direct current voltage was applied to the organic EL element to emit light. At this time, the number of dark spots (the number per pixel (50 μm × 150 μm)) when light was emitted at 100 cd / m ² was visually measured using a 100 times magnifier.

Dark spot evaluation rank ○: Less than 5 dark spots △: More than 5 dark spots Less than 10 ×: More than 10 dark spots

  The effectiveness of the present invention was confirmed.

Example 5
Sample No. 1 prepared in Example 1 was used. When producing 1-4, roll organic EL elements were produced under the same conditions except that the dew point temperature and cleanliness class of the process were changed as shown in Table 6 to obtain samples 501 to 509. The dew point temperature varied depending on the purity of the gas used for the atmospheric gas in the space (using N ₂ ) and the drying conditions when preparing the sample. The cleanliness class was changed by changing the air circulation system filter.

Evaluation The produced sample No. Table 6 shows the results of evaluation of the same evaluation items as in Example 1 by the same evaluation method, and evaluation according to the same evaluation rank, in 501 to 509.

  The effectiveness of the present invention was confirmed.

Example 6
Sample No. 1 prepared in Example 1 was used. When producing 1-4, a roll-shaped organic EL device was produced under the same conditions except that the winding tension was changed as shown in Table 7 to obtain samples 601 to 609. The winding tension was such that the winding tension taper when winding 150 m with respect to the initial winding tension was 80%. The initial winding tension indicates the tension when the winding diameter is zero. The winding tension taper indicates a ratio with the winding initial tension when winding 150 m.

Evaluation The produced sample No. Table 7 shows the results obtained by measuring the same evaluation items as those of Example 1 with the same evaluation method and evaluating according to the same evaluation rank, with reference to 601 to 609.

  Sample No. No scratches were observed in 601, but the winding was loose and handling was necessary. The effectiveness of the present invention was confirmed.

Example 7
Sample No. 1 prepared in Example 1 was used. Samples 701 to 714 were stored for 3 days under storage conditions in which the oxygen concentration and water concentration were changed as shown in Table 8 in Table 1-4. The oxygen concentration and water concentration are adjusted according to the purity of the atmospheric gas (using N ₂ ) when the closed space is once depressurized and brought into a vacuum state to sufficiently lower the water concentration and oxygen concentration and return to the atmosphere. did.
The oxygen concentration and the water concentration indicate values measured by a CIS100 closed ion source gas analysis system manufactured by Tokyo Instruments Co., Ltd.

Evaluation The produced sample No. Table 8 shows the results of measuring 701 to 714, measuring the same evaluation items as in Example 5 with the same evaluation method, and evaluating according to the same evaluation rank.

  The effectiveness of the present invention was confirmed.

It is a schematic sectional drawing which shows an example of the laminated constitution of an organic EL element. It is a schematic diagram which shows an example of the manufacturing apparatus which produces an organic EL element. It is an expansion schematic perspective view of the part shown by H of FIG. It is a schematic diagram which shows another example of the manufacturing apparatus which produces an organic EL element. It is an expansion schematic perspective view of the part shown by I of FIG. FIG. 6 is a schematic perspective view when a narrow winding auxiliary member is wound around both ends instead of the wide winding auxiliary member of FIG. 5. It is an expansion schematic fragmentary sectional view of the roll-shaped strip | belt-shaped flexible support body (illumination (surface emission) organic EL element) of FIG. 5, FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b Organic EL element 101 Base material 102 1st electrode 103 Hole transport layer 104 Light emitting layer 105 Electron injection layer 106 2nd electrode 107 Sealing layer 108 Adhesive layer 109 Sealing film 2a Manufacturing apparatus 3 Supply process 4 Hole Transport layer forming process 5 Light emitting layer forming process 502f1 First winding assisting member supply part 6 Electron injection layer forming process 7 Second electrode forming process 703b Second winding assisting member supplying part 8 Sealing layer forming process 9 Recovery process 9a Winding Winding auxiliary member supply unit 902 Winding auxiliary member 9a2, 12b2 Cleaning unit 9a3 Fifth antistatic unit 9a31 Non-contact type antistatic device 9a32 Contact type antistatic device 12b Third winding auxiliary member supply unit

Claims (8)

An organic EL having at least a first electrode, a hole transport layer, a light emitting layer, an electron injection layer, a second electrode, and a sealing layer or a sealing film in this order on the belt-like flexible support. A method for manufacturing an element, comprising:
At least the step of supplying the strip-shaped flexible support;
A) a first electrode forming step for forming the first electrode;
B) a hole transport layer forming step of forming the hole transport layer;
C) a light emitting layer forming step of forming the light emitting layer;
D) an electron injection layer forming step of forming the electron injection layer;
E) a second electrode forming step for forming the second electrode;
F) a sealing layer forming step for forming the sealing layer or a sealing film attaching step for attaching the sealing film;
G) In the manufacturing method of the organic EL element which has the collection | recovery process of the said organic EL element,
When winding the belt-like flexible support that has undergone at least one of the steps of A) to G), a winding auxiliary member is provided at both ends in the width direction of the belt-like flexible support. A method for producing an organic EL device, wherein a flexible polymer film having a predetermined width is applied and wound.   The method of manufacturing an organic EL element according to claim 1, wherein the winding assisting member is processed by a cleaning unit and an antistatic unit.   3. The method of manufacturing an organic EL element according to claim 2, wherein the antistatic means includes a non-contact type antistatic device and a contact type antistatic device.   The method for manufacturing an organic EL element according to any one of claims 1 to 3, wherein the winding assisting member has a water content measured according to JIS P 8127 of 1 to 10 mass%.   The method for manufacturing an organic EL element according to any one of claims 1 to 4, wherein the winding assisting member has a thickness of 10 to 200% with respect to a total thickness of the organic EL element. When taking imparted by winding the winding auxiliary member, according to claim 1, characterized in that the dew point temperature -9 0 to -20 ° C., cleanliness class measured according to JIS B 9920 is performed in 5 following environmental conditions The manufacturing method of the organic EL element of any one of -5.   The organic EL element wound with the winding assisting member is stored in an environment having an oxygen concentration of 1 to 100 ppm and a water concentration of 1 to 100 ppm. The manufacturing method of the organic EL element of description.   An organic EL device manufactured by the method for manufacturing an organic EL device according to claim 1.

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