JP2011049084A - Method of manufacturing organic electroluminescence panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an organic EL panel, using a roll-to-roll method for improving the performance of the organic EL panel to be produced with activating treatment while eliminating the application range of a material to be used for an organic function layer. <P>SOLUTION: The method of manufacturing the organic electroluminescence panel having a first electrode, at least one organic function layer, and a second electrode on a strip-shaped substrate, includes forming the organic function layer into a rolled shape once after applying and drying organic function layer forming application liquid thereto, and then applying heat treatment thereto. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing an organic electroluminescence panel (hereinafter also referred to as an organic EL panel) by a roll-to-roll method.

  In recent years, organic EL panels have attracted attention as self-luminous elements. An organic EL panel is an organic functional layer having a light emitting layer of an organic compound (hereinafter also referred to as an organic light emitting layer or an organic layer) on a base material such as glass between at least one organic light emitting layer between a negative electrode and a positive electrode. The panel emits light from the organic light emitting layer by supplying a current between the negative electrode and the positive electrode. Recently, an organic EL panel using a flexible base material such as a resin film has also appeared due to expansion of the use of the organic EL panel, for example, a roll described in International Publication No. 01/005194 pamphlet. An organic EL panel is also manufactured by a two-roll method.

  Here, the roll-to-roll manufacturing method refers to forming at least a part of an organic EL structure on a base material by rolling out a rolled base material, and forming at least a part of the organic EL structure. The manufacturing method of the form which winds up a base material on a roll again is called. Manufacturing by the roll-to-roll method has an advantage that production efficiency can be improved because continuous production is possible.

  As a recent trend, for example, organic EL panels have been required to have high luminous efficiency and long life, and the composition of the organic layer can be changed by heating under different conditions for each organic functional layer configured to cope with these. It is necessary to remove the impurities contained therein.

  That is, an organic functional layer formed by applying and drying an organic functional layer forming coating solution to form an organic functional layer and then performing an activation process has been enhanced.

  In roll-to-roll manufacturing, the organic functional layer is coated with a coating solution for forming an organic functional layer, dried, and subsequently activated for higher functionality (for example, higher luminous efficiency and longer life). Has been done. As the activation treatment, for example, a method of performing a heat treatment with a heating device is known (see, for example, Patent Document 1).

However, it has been found that the method described in Patent Document 1 has the following drawbacks.
1. Since the heat treatment is performed while conveying a long base material as the activation treatment, the entire process becomes long. Therefore, there is a limit to the heating time due to restrictions on process installation.
2. Since the process installation is restricted, the heat treatment is performed with a shortened process, so the heating time is shortened and the function of the original organic functional layer is not used, and it is difficult to improve the performance of the organic EL panel. It becomes.
3. When changing the heating conditions by changing the material to improve performance, it is necessary to change the length of the heating process, which involves a significant equipment change. Alternatively, the heating time is shortened due to restrictions on process installation, and the performance is degraded.
4). When the process speed is increased in order to improve productivity, it is necessary to change the heating process length, which involves a significant equipment change. Alternatively, the heating time is further shortened due to restrictions on process installation, and the performance is degraded.

  In such a facility, there is no restriction on the process installation from the situation, and it is a facility that can perform activation processing for a long time, and there is no need to change the activation condition or change the equipment by increasing the process speed, Development of a manufacturing method of an organic EL panel having high functionality by a roll-to-roll method is desired.

JP 2007-149589 A

  The present invention has been made in view of such a situation, and the purpose thereof is a facility that does not impose restrictions on process installation and that can perform activation processing for a long time, and changes in activation conditions. It is another object of the present invention to provide a method for producing an organic EL panel having high functionality by a roll-to-roll method, without changing equipment due to an increase in process speed.

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

1. In the manufacturing method of the organic electroluminescence panel having the first electrode, at least one organic functional layer, and the second electrode on the band-shaped substrate,
The organic functional layer is formed by applying a coating liquid for forming an organic functional layer and drying it, then forming a winding roll once, and performing an activation process.

  2. 2. The organic electroluminescence panel according to 1 above, wherein activation uniformizing means having air permeability is provided along at least both side edges in the width direction orthogonal to the conveying direction of the belt-shaped substrate. Manufacturing method.

  It is a facility that does not impose restrictions on process installation and can perform activation processing for a long time, and there is no need to change the activation conditions or change the equipment by increasing the process speed. The manufacturing method of the organic electroluminescent panel which has functionality was able to be provided.

It is a schematic sectional drawing which shows an example of the organic electroluminescent panel manufactured by the manufacturing method of the organic electroluminescent panel of this invention. It is a general | schematic process flowchart of the manufacturing method of the organic electroluminescent panel of this invention. FIG. 3 is a schematic plan view showing an example of a substrate provided with activation uniformizing means. FIG. 4 is a schematic enlarged view of a portion indicated by S in FIG. 3. It is a schematic plan view of the process of forming the convex object as an activation equalization means shown in FIG. FIG. 3 is a schematic view of an activation processing apparatus used in the activation processing step shown in FIG. 2. It is the schematic which shows the internal state which accommodated the roll body in the heat processing box shown in FIG.

  Hereinafter, modes for carrying out the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited to these.

  FIG. 1 is a schematic cross-sectional view showing an example of an organic EL panel manufactured by the method for manufacturing an organic EL panel of the present invention.

  This will be described with reference to (a).

  In the figure, 1 indicates an organic EL panel. 101 shows a base material. Reference numeral 102 denotes a first electrode (anode), and reference numeral 102 a denotes a first electrode external connection electrode of the first electrode (anode) 102. Reference numeral 104a denotes a second electrode external connection electrode. The second electrode external connection electrode 104a includes a lead portion 102b and a second electrode formed on the base material 101 at a position separated from the first electrode (anode) 102 when the first electrode (anode) 102 is formed. (Cathode) 104 is formed by bonding. Reference numeral 103 denotes an organic functional layer including a light emitting layer formed on and around the first electrode (anode) 102 except on the first electrode external connection electrode 102a. Reference numeral 104 denotes a second electrode (cathode) formed so as to cover the organic functional layer 103 and a part of the lead portion 102b. Reference numeral 105 denotes an adhesive layer provided on and around the second electrode (cathode) 104 except for a part of the first electrode external connection electrode 102a and the second electrode external connection electrode 104a. Reference numeral 106 denotes a sealing layer, for example, a sealing member attached via an adhesive layer 105.

  This will be described with reference to (b).

  In the figure, 1 'indicates an organic EL panel. 101 'shows a base material. Reference numeral 102 'denotes a first electrode (anode), and 102'a denotes an external connection electrode for the first electrode of the first electrode (anode) 102'. Reference numeral 104'a denotes a second electrode external connection electrode. The second electrode external connection electrode 104′a is a lead portion formed on the base material 101 ′ at a position separated from the first electrode (anode) 102 ′ when the first electrode (anode) 102 ′ is formed. 102′b and the second electrode (cathode) 104 ′ are joined by a conductive layer 105 ′. Reference numeral 103 ′ denotes an organic functional layer including a light emitting layer formed on and around the first electrode (anode) 102 ′ except on the first electrode external connection electrode 102 ′. Reference numeral 104 ′ denotes a second electrode (cathode) formed on the organic functional layer 103 ′ in accordance with the size of the first electrode (anode) 102 ′. Reference numeral 107 ′ denotes a conductive layer, which is formed so as to join the second electrode 104 ′ and the lead portion 102′b.

  Reference numeral 105 'denotes the second electrode (cathode) 104' and the conductive layer 105 'and the surroundings except for a part of the first electrode external connection electrode 102'a and the second electrode external connection electrode 104'a. The adhesive layer provided in is shown. Reference numeral 106 ′ denotes a sealing layer, for example, a sealing member attached via an adhesive layer 105 ′.

  This will be described with reference to (c).

  In the figure, 1 "indicates an organic EL panel. 101" indicates a substrate. 102 ″ represents a first electrode (anode), 102 ″ a represents a first electrode external connection electrode for the first electrode (anode) 102 ″. 103 ″ represents a first electrode external connection electrode 102 ″ a. 2 shows an organic functional layer including a light emitting layer formed on and around the first electrode (anode) 102 ″ except for. 104 ″ denotes a second electrode (cathode) formed on the organic functional layer and the substrate 101 ″ in accordance with the size of the first electrode (anode) 102 ″. 104 ″ a indicates the second electrode (cathode). The negative electrode external connection electrode for the second electrode (cathode) is formed integrally with the negative electrode 104 ″. 105 ″ indicates the external connection electrode for the first electrode 102 ″ a and the external connection for the second electrode. An adhesive layer provided on and around the second electrode (cathode) 104 "except a part of the electrode 104" a is shown. 106 "indicates a sealing layer, for example, via an adhesive layer 105" It is the stuck sealing member.

  The present invention is a roll-to-roll system that can be activated for a long time without being restricted by process installation when producing the organic EL panel shown in FIGS. 1 (a), (b), and (c). The present invention relates to a method for producing an organic EL panel having high functionality.

  The organic functional layer may be a single layer or a multilayer, for example, hole injection / transport layer / light emitting layer / electron injection / transport layer. The configuration of the organic EL panel will be described later.

  FIG. 2 is a schematic process flow diagram of the method for producing an organic EL panel of the present invention. In addition, this figure shows the general | schematic process flowchart of the manufacturing method of the organic electroluminescent panel of the structure shown by (a) of FIG.

  In the figure, 2 indicates a production line of an organic EL panel. The production line 2 has five production lines including a first electrode formation line 2a, a coating line 2b, an activation treatment line 2c, a second electrode formation line 2d, and a sealing / cutting line 2e.

  The first electrode formation line 2 a includes a first base material supply process 201, a first electrode (anode) formation process 202, and a first recovery process 203.

  The coating line 2b includes a second base material supply step 204, an organic functional layer coating step 205, a drying step 206, an organic functional layer removal step 207, and a second recovery step 208.

  The activation processing line 2c has an activation processing step 209.

  The second electrode formation line 2d includes a third base material supply step 210, a second electrode (cathode) formation step 211, and a third recovery step 212.

  The sealing / cutting line 2e includes a fourth base material supply process 213, a sealing process 214, a cutting process 215, and a third recovery process 216. When there is a possibility that a speed difference may occur between processes, it is preferable to arrange an accumulator letter (not shown) between the processes.

  The first electrode forming line 2a includes a portion for forming a first electrode external connection electrode on the base material 101 supplied from the first base material supplying step 201 in the first electrode forming step 202. (Anode) 102 (see FIG. 1) and lead portion 102b (see FIG. 1) are formed in a patterned state. Even if the substrate having the first electrode (anode) formed on the entire surface is supplied from the first substrate supply step 201 and patterned in the first electrode formation step 202, the substrate from the first substrate supply step 201 A material may be supplied, and the first electrode (anode) may be formed in a pattern on the substrate in the first electrode forming step 202. The former includes etching after photolithography or resist printing and removal of unnecessary portions by laser, and the latter includes pattern formation by printing such as inkjet.

  After the first electrode (anode) 102 (see FIG. 1) and the lead portion 102b (see FIG. 1) are patterned in the first electrode forming step 202, they are wound and collected in a roll shape in the first collecting step 203. In addition, you may supply to the organic functional layer application | coating process 205 continuously, without winding up.

  In the coating line 2b, in the organic functional layer coating step 205, the first electrode 102 (see FIG. 1) including a portion for forming the first electrode external connection electrode 102a supplied from the second base material supply step 204; The organic functional layer forming coating solution is applied on the entire surface or pattern of the substrate 101 (see FIG. 1) on which the lead portions 102b (see FIG. 1) are formed.

  In the drying step 206, the base material 101 (see FIG. 1) in a state where the whole surface of the base material 101 (see FIG. 1) supplied from the organic functional layer coating step 205 or the organic functional layer forming coating liquid is applied in a pattern. The solvent is removed from the coating layer to form the organic functional layer 103 (see FIG. 1).

  In the organic functional layer removing step 207, an unnecessary region of the organic functional layer 103 (see FIG. 1) (for example, in the case of a light emitting layer, a portion for forming the first electrode external connection electrode as a non-light emitting region, a lead portion 102b ( When the organic functional layer 103 (see FIG. 1) is a multilayer, the organic functional layer 103 (see FIG. 1) may be removed for each layer or may be removed collectively. Examples of the organic layer removal method include a wiping method using a solvent that dissolves the organic functional layer (see Japanese Patent Application Publication No. 2007-515756), a known dry etching method, a laser removal method, and the like. From the point of view, a method of wiping and removing with an organic solvent is desirable. In addition, when apply | coating an organic functional layer with a pattern, the organic functional layer removal process 207 may be unnecessary.

  In the second recovery step 208, an unnecessary region of the organic functional layer is removed in the organic layer removal step 207, and the substrate on which the patterned organic functional layer 103 (see FIG. 1) is formed is wound up and recovered in a roll shape. .

  In the activation treatment line 2c, in the activation treatment step 209, the substrate 101 (see FIG. 1) on which the patterned organic functional layer 103 (see FIG. 1) wound in a roll shape is wound is wound up. Thus, the activation process of the organic functional layer 103 (see FIG. 1) is performed.

  In the present invention, the activation treatment refers to treatment aimed at enhancing the functionality of the organic functional layer (for example, external extraction quantum efficiency (high light emission efficiency), long life, reduction of driving voltage).

  Examples of the activation treatment include irradiation with active energy rays, heating, irradiation with active energy rays and heating, and the conditions for the activation treatment are appropriately selected depending on the type of organic material used for the organic functional layer 103 (see FIG. 1). It is possible to do.

As an example of the activation treatment, for example, 5 wt% dopant material Ir (ppy) ₃ is dissolved in 1,2-dichloroethane in a host material polyvinyl carbazole (PVK) in a light emitting layer to form a 1% solution. When the forming coating solution is used, the heating temperature is 220 ° C. and the time is 30 minutes.

  If the organic functional layer 103 (see FIG. 1) is multi-layered and the activation treatment step 209 needs to be performed for each layer under the conditions required for each layer, the application / drying / winding of each layer and each layer are performed. The activation process under the conditions required is repeated. In addition, when the activation process can be performed at once after the multilayer is applied, it is of course possible to perform the activation process at once.

  In the case of multilayer application of the organic functional layer and activation processing for each layer, single layer coating on the coating line 2b and activation processing on the activation processing line 2c are repeated for the number of organic functional layers.

  In the case of performing multilayer application and batch activation processing of organic functional layers, activation processing is performed on the activation processing line 2c after a plurality of coatings are performed on the coating line 2b by the number of organic functional layers.

  In the second electrode formation line 2d, the first electrode (anode) formed on the substrate 101 (see FIG. 1) supplied from the third substrate supply step 210 in the second electrode (cathode) formation step 211. ) On the organic functional layer 103 (see FIG. 1) on the 102 (see FIG. 1) so as to be joined to the lead portion 102b (see FIG. 1) in accordance with the size of the first electrode (anode) 102 (see FIG. 1). A second electrode (cathode) 104 (see FIG. 1) is formed. The lead portion 102b (see FIG. 1) is joined to the second electrode (cathode) 104 (see FIG. 1) to become the second electrode external connection electrode 104a (see FIG. 1).

  In the third recovery step 212, the base material 101 (see FIG. 1) on which the second electrode 104 (see FIG. 1) and the second electrode external connection electrode 104a (see FIG. 1) are formed is rolled up and collected. Is done. In addition, you may supply to the sealing process 214 continuously, without winding up.

  In the sealing / cutting line 2e, the first electrode external connection electrode 102a formed on the base material 101 (see FIG. 1) supplied from the fourth base material supply step 213 in the sealing step 214. (See FIG. 1) and an adhesive layer 105 (see FIG. 1) provided on and around the second electrode 104 (see FIG. 1) except for a part of the second electrode external connection electrode 104a (see FIG. 1). 1), a plurality of organic EL panels (configuration of FIG. 1A) in which a sealing layer 106 (see FIG. 1) having a sealing member attached thereto is continuously connected are formed. An organic EL panel continuum is produced.

  In the cutting step 215, the organic EL panel is cut from the band-shaped organic EL panel continuous body supplied from the sealing step 214.

  In the collecting step 216, the organic EL panels cut in the cutting step 215 are collected and collected.

  In addition, although this figure shows the case where the sealing process 214 and the cutting process 215 are continued, the unit required in another process after the strip-shaped organic EL panel formed in the sealing process 214 is collected in a roll shape You may cut it to

The present invention is characterized in that after applying a coating liquid for forming an organic functional layer as shown in the figure, the drying process and the activation process are separated and the activation process is performed in a roll state. The following effects can be obtained.
1. Since the activation process is performed in a roll state, the overall length of the process is shorter than the case where the activation process is performed while transporting.
2. Even if the activation process time is changed, there is no need to change the length of the activation process and no major equipment change is required.
3. Even if the process speed is increased to improve productivity, there is no need to change the length of the activation process, and no major equipment changes are required.

  Next, the first electrode formation line 2a, the coating line 2b, the activation treatment line 2c, the second electrode formation line 2d, the sealing / cutting of the organic EL panel production line 2 shown in FIG. An example of the work flow in the line 2e is shown.

  FIG. 3 is a schematic plan view showing an example of a substrate provided with an activation uniformizing means used for the activation process in a wound state.

  The activation uniformizing means is a means for uniformizing the transfer of heat from the end to the end of the winding core, during winding, and outside of the winding core when heated for roll-up activation processing. There is no limitation as long as it can be wound in a non-contact state between the base materials in a state that allows ventilation, for example, a convex material is provided at both ends of the base material, and a tape made of a foam base material at both ends of the base material is used. Winding together a breathable spacer. Examples of the air-permeable spacer tape include Toyobo Crisper.

  (A) shows the case where the activation uniformization means is provided along the both-sides edge part of the width direction orthogonal to the winding direction of a base material.

  (B) shows the case where the activation uniformization means is provided along the center part and both side edge part of the width direction orthogonal to the winding direction of a base material.

  A description will be given of the base material provided with the activation uniformizing means shown in (a).

  In the figure, 2a indicates a substrate. 2a1 indicates a heating uniformizing means provided along one side edge in the width direction orthogonal to the winding direction of the substrate 2a (the arrow direction in the figure), and 2a2 indicates the other side edge of the substrate 2a. The heating uniformization means provided along the part is shown.

  A description will be given of the base material provided with the activation uniformizing means shown in (b).

  In the figure, 2b represents a substrate. Reference numeral 2b1 denotes activation uniformizing means provided along one side edge in the width direction orthogonal to the conveyance direction (arrow direction in the figure) of the base material 2b, and 2b2 denotes the conveyance direction (figure of the figure). The heating uniformizing means provided along the center part of the width direction orthogonal to the arrow direction in the middle), 2b3 is the other of the width direction orthogonal to the winding direction of the substrate 2b (arrow direction in the figure) The activation uniformizing means provided along the side edge part is shown.

  The position and number of the activation homogenizing means can be appropriately selected depending on the width of the substrate to be used, and the arrangement of the heating homogenizing means shown in (a) is suitable for a substrate having a narrow width. The arrangement of the heating homogenizing means shown in (b) is suitable for a wide substrate.

  FIG. 4 is a schematic enlarged view of a portion indicated by S in FIG. FIG. 4A is a schematic enlarged plan view of a portion indicated by S in FIG. FIG. 4B is a schematic enlarged cross-sectional view along AA ′ of FIG.

  In the figure, reference numeral 2a11 denotes a convex object of the activation uniformizing means provided along the side edge in the width direction orthogonal to the conveying direction of the substrate 2a. The convex object 2a11 may be the application surface side or the back surface side of the belt-like substrate 2a, or both surfaces of the application surface side and the back surface side, and can be appropriately selected as necessary. In addition, the convex-shaped object 2a11 shown by this figure may be simultaneously formed in the side edge part 2a1 and the side edge part 2a2 (refer FIG. 3), and may be provided in one side edge part alternately.

  For example, in the case where a convex object is provided along both side edges as shown in FIG. 3 (a), an area where a convex object is provided on one side edge is not provided. A convex object is formed so as to have a region. On the other hand, in the other side edge part which opposes, it says that a convex object is not provided in the area | region in which the convex object was provided, and a convex object is provided in the area | region in which the convex object is not provided.

  The shape of the convex object 2a11 is not particularly limited, and examples thereof include a dome shape, a rectangle, and a trapezoidal cross section. Among these, the dome shape is preferable from the viewpoint of manufacturing.

  The arrangement of the protrusions 2a11 is not particularly limited, and examples thereof include a staggered arrangement in the conveyance direction (arrow direction in the drawing) of the band-shaped substrate 2a, an alignment arrangement in the conveyance direction / width direction, and a random arrangement.

  F shows the width | variety in which the convex-shaped object 2a11 is provided. The position and number of the protrusions 2a11 can be appropriately selected according to the width of the base material to be used, and the total width of the protrusions 2a11 is relative to the width of the belt-like base material. In consideration of air permeability (heating uniformity), effective area of the substrate (material yield), winding property, unwinding property, etc., 2% to 20% is preferable.

  In the case where a spacer tape is used as the activation uniformizing means, the ratio of the total tape width to the width of the belt-shaped substrate corresponds to this.

  Specifically, when the convex objects are disposed along both side edges of the belt-like base material, it is preferable that the widths for arranging the convex objects on both side edges are the same. Further, when providing convex objects on both side edges and in the middle, it is preferable to divide them appropriately in the range of 2% to 20%.

  G shows the height of the convex body 2a11 from the base material 2a. The height G is preferably 60 μm to 300 μm in consideration of air permeability (heating uniformity), adhesive strength of convex objects, handleability (rolling diameter) of roll products, and the like. Height G shows the value measured using the thickness measuring machine (Mitutoyo Co., Ltd. Thickness gauge).

  H represents the diameter of the convex 2a11. In consideration of air permeability (heating uniformity), winding property, unwinding property, etc., the diameter H of the convex object 2a11 is 60 μm to 300 μm in the case of the dome-shaped convex object 2a11. It is preferable. The measurement of diameter H shows the value measured using the dimension measurement microscope (Mitutoyo Co., Ltd. measurement microscope + two-dimensional data processing apparatus).

The density of the convex object 2a11 is 2 / cm ^{2 in} the case of the dome-shaped convex object 2a11 having a diameter H of 60 μm and a height of G 80 μm in consideration of air permeability (heating uniformity), winding property, unwinding property, and the like. The number is preferably 200 / cm ² .

  I indicates the pitch between the adjacent convex objects 2a11. The pitch I is preferably 1 mm to 10 mm in the case of the dome-shaped convex 2a11 having a diameter H of 60 μm and a height of G 80 μm in consideration of air permeability (heating uniformity), winding property, unwinding property, and the like.

  The height, volume, width, density, and interval of the activation homogenizing means shown in this figure are the same as those of the activation homogenizing means 2a2 in FIG. 3A and the activation homogenizing means 2b1 in FIG. 3B. It is possible to apply to 2b3.

  The height and the like of the activation homogenizing unit vary depending on the type of base material, heating conditions, and the type of activation homogenizing unit. It is sufficient if the roll-shaped substrate is kept in a non-contact state and the purpose of the activation treatment by passing the heated air can be achieved.

  The method of disposing the activation uniformizing means 2a11 is not particularly limited. For example, a method of forming irregularities by pressing a rough surface formed with a large number of projections such as an embossing ring and a knurling roller, a coating method by ink jet, a ventilation For example, a method of attaching a spacer tape having a property. Among these, considering the deformation of the substrate itself, the height of the convex, the suitability for a thin substrate, productivity, air permeability, etc., the convex by the coating method using an inkjet head is used. Formation is preferred. FIG. 5 shows a method for forming a convex object using a shear mode type (piezo type) ink jet head.

  FIG. 5 is a schematic plan view of a process of forming a convex as the activation uniformizing means shown in FIG.

  In the figure, reference numeral 3 denotes a convex forming process. The convex object forming step 3 uses an inkjet head 301. The inkjet head 301 includes an inkjet head 301A and an inkjet head 301B. The ink jet head 301A is disposed to form a convex object 2a11 (see FIG. 4) on the side edge 2a1 on the left side (upper side in the drawing) with respect to the conveying direction of the belt-like substrate 2a (the arrow direction in the drawing). Has been. The inkjet head 301B forms the same convex object as the convex object 2a11 on the side edge 2a2 on the right side (lower side of the drawing) with respect to the conveyance direction (arrow direction in the figure) of the flexible strip-shaped substrate 2a. It is arranged.

  Reference numeral 305 denotes a supply tank that supplies a convex-form-forming coating liquid to the inkjet head 301 (301A, 301B). Reference numeral 306 denotes a control unit for driving the piezoelectric substrate of the inkjet head 301 (301A, 301B), which is connected to each inkjet head 301 (301A, 301B) via a connector. The control unit 306 selects the operation strength and frequency of the piezoelectric substrate when the coating liquid is ejected.

  The arrangement of the inkjet heads 301A (301B) is not particularly limited. For example, the inkjet heads 301A (301B) are arranged and tilted so that the direction in which the nozzle rows are arranged is orthogonal to the conveyance direction (arrow direction in the figure) of the belt-like substrate 2a May be arranged. Further, the number of inkjet heads to be arranged may be arranged in accordance with the width of the side edge portion forming the convex object and the pattern of the convex object.

  The portion where the convex object shown in the figure is formed may be on the application surface side or the back surface side of the belt-like base material 2a, or both surfaces of the application surface side and the back surface side, as appropriate. It is possible to select. In addition, the convex object knurling part 201a and the knurling part 201b shown in this figure may be simultaneously formed on both side edges, or may be alternately provided on one side edge.

  In addition, one ink jet head 301 is arranged at the center and both side edges of the belt-like substrate 2a so that the conveying direction of the belt-like substrate 2a and the direction in which the nozzle rows are arranged are orthogonal to each other. You may form in a convex part in the center part of the base material 2a, and a both-sides edge part (refer FIG.3 (b)). Also in this case, it may be the application surface side or the back surface side of the band-shaped substrate 2a, or both surfaces of the application surface side and the back surface side, and can be appropriately selected as necessary.

  The following effect is mentioned by arrange | positioning the heating equalization means shown in FIG. 3, FIG. 4 in a base material.

  1) When heating in the form of a roll in the activation treatment step, a space is created between the substrates by the activation homogenizing means, which allows heat to enter uniformly between the substrates and in the width direction of the substrates. Heating became possible.

  2) By eliminating performance fluctuations at the roll core, inside, and outside, it became possible to produce an organic EL panel with stable performance.

  3) By eliminating performance fluctuations at the center, inside, and outside of the roll, the yield is increased and the production efficiency can be improved.

  FIG. 6 is a schematic view of an activation processing apparatus used in the activation processing step shown in FIG. FIG. 6A is a schematic perspective view of the activation processing apparatus used in the activation processing step shown in FIG. FIG. 6B is a schematic perspective view showing the inside of the activation processing apparatus shown in FIG.

  In the figure, 4 indicates a heat treatment apparatus of the activation treatment apparatus. The heat treatment apparatus 4 includes a heat treatment box 401 and a heated air supply device 402. The heat treatment box 401 has a main body 401a and a lid 401b.

  The heat treatment box 401 has a roll body 5 (see FIG. 7) in which a base material 101 (see FIG. 1) on which a patterned organic functional layer 103 (see FIG. 1) is formed on a main body 401a is wound up in a roll shape. After being housed in a state, the lid body 401b is covered and heat-treated. The activation treatment in the present invention means a heat treatment.

  The main body 401a has a heated air supply box 401a1 on the bottom surface and an outer wall 401a2 on the peripheral surface of the heated air supply box 401a, and has an open top structure. Reference numeral 401 a 3 denotes a heated air supply pipe that supplies heated air to the heated air supply box 401 a 1, and is connected to the heated air supply device 402. A blower pump (not shown) is disposed between the heated air supply device 402 and the heated air supply box 401a1, and the amount of heated air blown can be adjusted.

  The heating air for activating the organic functional layer 103 differs depending on the organic functional layer to be activated, and is usually heated with low humidity nitrogen or air, but it does not deteriorate the organic functional layer 103. It is not limited to that.

  A roll body 5 (see FIG. 7) in which a base material 101 (see FIG. 1) on which a patterned organic functional layer 103 (see FIG. 1) is formed is rolled up on the upper surface 401a11 of the heated air supply box 401a1. A hole 401a12 corresponding to the diameter of the winding core 5a (see FIG. 7) is provided in order to be housed in the main body 401a in a standing state. The number of holes 401a12 can be appropriately set according to the number of roll bodies 5 (see FIG. 7) to be accommodated. A plurality of heating air supply holes 401a13 are arranged on the upper surface 401a11 with which the end surface of the roll body 5 (see FIG. 7) comes into contact with the diameter of the roll body 5 (see FIG. 7).

  The lid body 401b has a heated air exhaust box 401b1 and an outer wall 401b2 on the peripheral surface of the heated air exhaust box 401b1, and has a box structure in which the side facing the main body 401a is opened.

  Reference numeral 401b3 denotes a heated air exhaust pipe that exhausts heated air sent from the heated air supply box 401a1 via the roll body 5 (see FIG. 7), and is connected to the heated air supply device 402 to reheat and adjust moisture. It is possible to circulate to the heated air supply box 401a1. An exhaust pump (not shown) is disposed between the heated air exhaust box 401b1 and the heated air supply device 402, and the exhaust amount can be adjusted in accordance with the amount of heated air blown.

  In the lower surface 401b11 (see FIG. 7) of the heated air exhaust box 401b1, the diameter of the hole 401b12 and the roll body 5 (see FIG. 7) is adjusted to the position of the hole 401a12 disposed in the upper surface 401a11 of the heated air supply box 401a1. A plurality of heating air exhaust holes 401b13 (see FIG. 7) are arranged.

  FIG. 7 is a schematic view showing an internal state in which a roll body is stored in the heat treatment box shown in FIG. Fig.7 (a) is a schematic perspective view which shows the internal state which accommodated the roll body in the heat processing box shown in FIG. FIG. 7B is a schematic cross-sectional view along the line AA ′ in FIG.

  In the figure, reference numeral 5 denotes a roll body in which a base material 101 (see FIG. 1) on which a patterned organic functional layer 103 (see FIG. 1) is formed is wound into a roll shape. 5a represents a winding core, 5a1 represents one end of the winding core 5a, and 5a2 represents the other end. The roll body 5 houses the end 5a1 in a hole 401a12 (see FIG. 6) disposed in the upper surface 401a11 of the heated air supply box 401a1, and the other end 5a2 is the lower surface 401b11 (FIG. 7) of the heated air exhaust box 401b1. In the heat treatment box 401 in a state of being accommodated in the hole 401b12 provided in the reference).

  After being housed in the heat treatment box 401 in the state as shown in the figure, the heated air is supplied from the heated air supply pipe 401a3 so that the heated air is supplied to the upper surface 401a11 of the heated air supply box 401a1. From 401a13, passes through the base material of the roll body 5, passes through the heated air exhaust hole 401b13 provided on the lower surface 401b11 of the heated air exhaust box 401b1, and returns to the heated air supply device 402 via the heated air exhaust pipe 401b3. It has become. The arrows in the figure indicate the flow of heating air.

  The heat treatment apparatus shown in FIGS. 6 and 7 shows the case where the heat treatment is performed in a state where the roll body is set up, but the heat treatment method is not particularly limited as long as heat is uniformly transmitted between the base materials of the roll body. For example, it may be placed horizontally. However, in the case of horizontal installation, it is necessary to prevent the gap between the substrates from becoming narrow due to the weight of the roll body.

  Next, the structure of the organic EL panel according to the method for manufacturing the organic EL panel of the present invention will be described.

(Organic EL panel configuration)
An organic EL panel has a structure in which one or a plurality of organic functional layers are laminated between electrodes. In general, a hole injection / transport layer / light emission as an organic functional layer on the first electrode (anode). A layer / electron injection / transport layer is laminated, and a second electrode (cathode) is laminated thereon. Other typical layer structures include the following structures.

(1) Substrate / first electrode (anode) / light emitting layer / second electrode (cathode) / adhesive layer / sealing layer (2) substrate / first electrode (anode) / light emitting layer / electron transport layer / Second electrode (cathode) / adhesive layer / sealing layer (3) substrate / first electrode (anode) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / second electrode (cathode) / Adhesive layer / Sealing layer (4) Base material / first electrode (anode) / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) ) / Second electrode (cathode) / adhesive layer / sealing layer (5) substrate / first electrode (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) / second electrode (cathode) / adhesive layer / sealing layer Main components constituting the organic EL panel will be described below.

(Base material)
A transparent resin film is mentioned as a strip | belt-shaped flexible base material used for a base material. 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.

(Gas barrier layer)
Examples of the gas barrier layer provided on the surface of the belt-like flexible substrate include inorganic and organic coatings or a hybrid coating of both. As a characteristic of the gas barrier film, the water vapor permeability is preferably 0.01 g / m ² · day or less. Furthermore, a high barrier film having an oxygen permeability of 0.1 ml / m ² · day · MPa or less and a water vapor permeability of 10 ⁻⁵ g / m ² · day or less is preferable. As a material for forming the gas barrier film, any material may be used as long as it has a function of suppressing intrusion of an element such as moisture or oxygen that causes 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, and for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable. The material used for these gas barrier layers can also be used for the second strip-shaped flexible substrate and the strip-shaped flexible adhesive member.

(First electrode)
The first electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element structure, but preferably a transparent electrode is used as the anode. For example, when used as an anode, it is preferably an electrode that transmits light from 380 nm to 800 nm. A material having a work function larger (deep) than 4 eV is suitable. For example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, and metal thin films such as gold, silver and platinum Metal nanowires, carbon nanotubes, and the like can be used.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. 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, as well as 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.

(Light emitting layer)
The material used for the light emitting layer is not particularly limited, and examples thereof include various materials as described on pages 228 to 332 of “Today Research Center, Inc.“ Current Trends of Flat Panel Displays, Current Status and Latest Trends of EL Displays ”. .

  The light emitting layer preferably contains a known host compound and a known phosphorescent compound (also referred to as a phosphorescent compound) in order to increase the light emission efficiency of the light emitting layer. 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 uniform film properties over the entire organic layer, and further phosphorescence emission of the host compound. It is more preferable that the energy is 2.9 eV or more because energy transfer from the dopant is effectively suppressed and high luminance is obtained. Phosphorescence emission energy refers to 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 preferably has a phosphorescence quantum yield of 0.1 or more. The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 version, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. 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 the carrier is transported to generate an excited state of the host compound, and this energy is transferred to 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.

  The phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited. In principle, the emission wavelength obtained by selecting a central metal, a ligand, a ligand substituent, etc. is changed. I can do it.

  The color emitted by the compound is shown in Fig. 4.16 on page 108 of the "New Color Science Handbook" (Edited by the Japan Color Society, The University of Tokyo Press, 1985). Spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) It is determined by the color when the measurement result is applied to the CIE chromaticity coordinates.

(Electron transport layer)
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 the 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 derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an 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 metal of these metal complexes is 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 transport 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 to 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 be formed by forming the electron transport material into a thin film by a known method such as a wet method or a dry method.

(Second electrode)
The second electrode is not particularly limited to a cathode and an anode, and can be selected depending on the element configuration, but preferably a transparent electrode is used as the anode. For example, when used as a cathode, it is preferable to use a metal, an alloy, an electrically conductive compound having a work function of 4 eV or less (shallow), and a mixture thereof as an electrode material. 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 viewpoint of electrical bonding with the organic functional layer and durability against oxidation, etc., these metals and the second metal, which is a stable metal having a larger (deep) work function value than this, Mixtures such as magnesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum alone and the like are suitable.

  The second electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 nm to 200 nm.

  If a highly reflective metal material is used as the second electrode, for example, in an organic EL element, a part of the emitted light can be reflected and taken out to the outside, and the organic PV element passes through a photoelectric conversion layer. The effect of increasing the optical path length can be obtained by reflecting the reflected light and returning it to the photoelectric conversion layer again, and in any case, improvement of the external quantum efficiency can be expected.

  Furthermore, it may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.) or a nanoparticle, nanowire, or nanostructure made of carbon. A highly dispersible paste is preferable because a transparent and highly conductive counter electrode can be formed by a coating method or a printing method.

  Further, when the counter electrode side is made light transmissive, for example, a conductive material suitable for the counter electrode such as aluminum and aluminum alloy, silver and silver compound is formed with a thin film thickness of about 1 nm to 20 nm, and then the above-mentioned By providing a film of the conductive light-transmitting material mentioned in the description of the transparent electrode, a light-transmitting electrode can be obtained.

(Adhesive layer)
Examples of the adhesive used for the adhesive layer include a liquid adhesive, a sheet-like adhesive, and a thermoplastic resin. Examples of the liquid adhesive include photo-curing and thermosetting sealing agents having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, moisture-curing adhesives such as 2-cyanoacrylate, epoxy-based adhesives, etc. 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. . 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. Moreover, it is preferable that the above-mentioned gas barrier layer is formed on the back surface side of the adhesive layer of the belt-like flexible adhesive member as necessary.

  The sheet-like adhesive refers to an adhesive that is non-flowable at room temperature (about 25 ° C.) and exhibits fluidity in the range of 50 ° C. to 100 ° C. when heated and is formed into a sheet shape. As an adhesive to be used, for example, a photocurable resin mainly composed of a compound having an ethylenic double bond at the terminal or side chain of a molecule and a photopolymerization initiator can be mentioned. In use, for example, it is preferable to use it at a normal temperature (about 25 ° C.) or less by pasting it on the sealing member side in advance.

  As the thermoplastic resin, a thermoplastic resin having a melt flow rate of 5 to 20 g / 10 min as defined in JIS K 7210 is preferable, and a thermoplastic resin having a viscosity of 6 to 15 g / 10 min or less is more preferable. This is because if a resin having a melt flow rate of 5 (g / 10 min) or less is used, the gap formed by the steps of the extraction electrode of each electrode cannot be completely filled, and a resin of 20 (g / 10 min) or more cannot be filled. This is because if used, the tensile strength, stress cracking resistance, workability and the like are lowered. These thermoplastic resins are preferably formed into a film and bonded to a flexible sealing member (a strip-shaped flexible sealing member or a single-sheet flexible sealing member). The laminating method can be made by using various generally known methods such as a wet laminating method, a dry laminating method, a hot melt laminating method, an extrusion laminating method, and a thermal laminating method.

  The thermoplastic resin is not particularly limited as long as it satisfies the above numerical values. For example, low density polyethylene (LDPE) which is a polymer film described in the new development of functional packaging materials (Toray Research Center, Inc.). ), HDPE, linear low density polyethylene (LLDPE), medium density polyethylene, unstretched polypropylene (CPP), OPP, ONy, PET, cellophane, polyvinyl alcohol (PVA), stretched vinylon (OV), ethylene-vinyl acetate copolymer A combination (EVOH), ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinylidene chloride (PVDC), or the like can be used. Among these thermoplastic resins, LDPE, LLDPE produced using LDPE, LLDPE and a metallocene catalyst, or a thermoplastic resin using a mixture of LDPE, LLDPE and HDPE films is preferably used.

(Sealing layer)
The base material of the sealing member used for the sealing layer is not particularly limited. For example, ethylene tetrafluoroethyl copolymer (ETFE), high density polyethylene (HDPE), expanded polypropylene (OPP), polystyrene (PS), poly (polyethylene). Thermoplastic resin film materials used for general packaging films such as methyl methacrylate (PMMA), stretched nylon (ONy), polyethylene terephthalate (PET), polycarbonate (PC), polyimide, polyether styrene (PES), glass, Metal foil or the like can be used. As these thermoplastic resin films, a multilayer film produced by coextrusion with a different film, a multilayer film produced by bonding with different stretching angles, etc. can be used as required. Further, it is naturally possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Production of organic EL panel)
The organic EL panel having the structure of the base material / first electrode (anode) / organic functional layer / second electrode (cathode) / adhesive layer / sealing member shown in FIG. Was made. In addition, it was set as the structure of a positive hole transport layer / light emitting layer / electron transport layer as an organic functional layer, and the positive hole transport layer, the light emitting layer, and the electron transport layer were formed with the wet apply | coating method.

<Preparation of base material>
As a base material, a strip-like polyethylene naphthalate film (Teijin-DuPont film, hereinafter abbreviated as PEN film) having a width of 200 mm and a length of 500 m and a thickness of 100 μm was prepared. A position designation mark was attached to the position where the alignment mark, the first electrode external connection electrode, and the lead portion were formed in accordance with the position of the first electrode (anode) formed in advance.

(Distribution of activation equalization means)
(Preparation of coating solution for convex product formation)
Dipentaerystol hexaacrylate (including dimer and trimer components)
100 parts by weight Photoreaction initiator (dimethoxybenzophenone) 4 parts by weight Propylene glycol monomethyl ether 30 parts by weight Methyl ethyl ketone 100 parts by weight (Coating of a coating solution for forming a convex product)
As shown in FIG. 3 (a), using the process of forming the convex object shown in FIG. 5, the convex object of the heating uniformizing means is sheared by the ink jet method along both side edges of the prepared PEN film. With a type (piezo type) ink jet head, 1000 droplets were landed at one place, dried at a temperature of 100 ° C. after 20 seconds, and then irradiated with ultraviolet rays at an irradiation intensity of 150 mJ / cm ² from a curing processing apparatus. The heating uniform means comprised with the dome-shaped convex thing as shown was provided.

Shear mode type (piezo type) ink jet head Nozzle outlet interval: 0.05 mm
Number of nozzle outlets: 500, Average ejection volume per drop: 50 pl (picoliter)
Arrangement of shear mode type (piezo type) ink jet heads: Arranged so that the direction in which nozzle discharge ports are arranged is orthogonal to the transport direction of the PEN film Distance between the nozzle surface and the surface of the PEN film: 1 mm
PEN film transport speed: 10 m / min
Percentage of the total width of both side edges of the PEN film on which the activation uniformizing means is disposed: 4%
Shape of dome-shaped convex object constituting activation uniformizing means Diameter of dome-shaped convex object: 60 μm
Height of dome-shaped convex object: 80 μm
Density of convex objects: 50 / cm ²
Pitch between adjacent dome-shaped convex objects: 2 mm
The height of the dome-shaped convex object indicates a value measured using a thickness measuring device (Sickness Gauge manufactured by Mitutoyo Corporation).

  The diameter of the dome-shaped convex object indicates a value measured using a dimension measurement microscope (measurement microscope + two-dimensional data processing device manufactured by Mitutoyo Corporation).

The density of the dome-shaped convex object is a value obtained by visually observing a 10 cm × 10 cm sample with a magnifying glass, counting the number of dome-shaped convex objects, and converting it to the number per 1 cm ² .

(Formation of the first electrode (anode))
On the prepared PEN film, the first electrode (anode) having a thickness of 120 nm, a width of 70 mm and a length of 100 mm and having an external connection electrode for the first electrode and the lead part are patterned by vapor deposition of ITO (indium tin oxide). Then, the first electrode and the lead part were formed in two rows with an interval of 20 mm in the length direction of the strip-shaped flexible support and 15 mm at both ends in the width direction with a spacing of 15 mm, and the winding core was formed into a winding roll shape.

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

(Application of coating liquid for hole transport layer formation)
The prepared coating solution for forming the hole transport layer is applied to the entire surface of the PEN film on which the prepared first electrode (anode) and the lead portion in the form of a roll are formed. After coating with min, the solvent is removed at a height of 100 mm toward the film forming surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 100 ° C. to form a 50 nm thick hole transport layer. The core was wound up and stored. Before applying the coating solution for forming the hole transport layer, the cleaning surface modification treatment of the PEN film was performed 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. The charge removal treatment was performed using a static eliminator with weak X-rays.

(Activation process)
Activation treatment (heat treatment) was performed by supplying dry air having a temperature of 120 ° C. for 30 minutes to the roll-shaped PEN film having been dried to form a hole transport layer.

<Formation of light emitting layer>
(Preparation of green luminescent layer forming coating solution)
A dopant material Ir (ppy) ₃ was dissolved in a host material polyvinyl carbazole (PVK) in 5% by mass in 1,2-dichloroethane to prepare a 1% solution, which was prepared as a coating solution for forming a green light emitting layer.

(Application of coating solution for green light emitting layer formation)
The prepared green light emitting layer-forming coating solution is applied to the entire surface of the PEN film formed up to the hole transport layer using an extrusion coater in a dry nitrogen gas atmosphere at a coating speed of 2 m / min. The solvent was removed at a height of 100 mm toward the surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. to form a light-emitting layer having a thickness of 100 nm, which was wound up and stored.

(Activation process)
Activation treatment (heat treatment) was performed by supplying dry nitrogen having a temperature of 220 ° C. for 30 minutes to the roll-shaped PEN film formed with a green light-emitting layer by drying.

<Formation of electron transport layer>
(Preparation of coating solution for electron transport layer formation)
The electron transport layer was prepared by dissolving Alq ₃ in 1,2-dichloroethane to obtain a 0.5 mass% solution as a coating solution for forming an electron transport layer.

(Application of coating solution for electron transport layer formation)
The prepared coating liquid for forming an electron transport layer is extruded on a light-emitting layer of a PEN film formed up to the light-emitting layer in an atmosphere of dry nitrogen gas using an extrusion coater and applied at a coating speed of 2 m / min. The solvent was removed at a height of 100 mm toward the surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 60 ° C. to form an electron transport layer having a thickness of 30 nm, and wound and stored on a winding core.

(Activation process)
An activation treatment was performed by supplying dry nitrogen having a temperature of 200 ° C. for 30 minutes to the roll-shaped PEN film having been dried to form an electron transport layer.

(Waste treatment of unnecessary area of organic functional layer)
Acetone is used as a solvent for the unnecessary regions of the organic functional layer (hole transport layer / light emitting layer / electron transport layer) (the first electrode external connection electrode in the transport direction of the PEN film and the organic functional layer on the lead). It was wiped off and taken up on a roll core and stored.

(Formation of second electrode)
Except the first electrode external connection electrode part on the PEN film on which the first electrode external connection electrode, the lead part and the electron transport layer are formed, on the electron transport layer and part of the lead part A second electrode having a thickness of 100 nm is formed by using aluminum as a second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa, forming a mask pattern in the same size as the first electrode (anode) by vapor deposition. Were laminated. The lead portion becomes the second electrode external connection electrode by being connected to the second electrode.

(Pasting of sealing member)
A sealing member in which PET of 50 μm thickness, aluminum foil of 30 μm thickness as a moisture-proof layer, and 16X-098 made by ThreeBond Co., Ltd. as an adhesive is laminated on the PEN film formed up to the second electrode. They were stacked, bonded at a pressure of 0.5 MPa, and bonded and fixed at a temperature of 100 ° C. A band-shaped organic EL panel was produced.

(Punching cutting of belt-shaped machine EL panel)
A punching and cutting device equipped with a die and a punch that matches the shape of the die was prepared, and 400 individual organic EL panels were punched and cut at a cutting speed of 30 / min to produce individual organic EL panels. Sample No. 101.

(Production of comparative sample)
When forming the hole transport layer, the light emitting layer, and the electron transport layer as the organic functional layer, all of them are under the same conditions except that the drying process and the activation process are connected and the activation process is performed while transporting the substrate. An organic EL element was fabricated and sample No. 102.

Evaluation Each sample No. 101 and 102, and the performance (external extraction quantum efficiency, drive voltage, life) was evaluated according to the following evaluation method.

Sampling of evaluation sample Sample No. 101 is an evaluation sample obtained by sampling 10 individual organic EL panels from 5 m of each of the winding core, winding and unwinding when the activation treatment is performed in a roll shape.

  Sample No. 102, sample No. Ten individual organic EL panels were sampled from the same position as 101 and used as evaluation samples.

Method for Measuring External Extraction Quantum Efficiency An organic EL panel is lit at room temperature (about 23 to 25 ° C.) under a constant current condition of ^2.5 mA / cm ² , and light emission luminance (L) [cd / m ² immediately after the start of lighting] The external extraction quantum efficiency (η) was calculated. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used.

Measuring method of driving voltage The driving voltage was determined as a voltage when driving at ^2.5 mA / cm ² .

When driving at a constant current of ^2.5 mA / cm ² , the time required for the luminance to drop to half of the luminance immediately after the start of light emission (initial luminance) was measured, and this was calculated as the half-life time (τ 0.5) As an index of life. For the measurement, a spectral radiance meter CS-1000 (manufactured by Konica Minolta Sensing) was used.

  As a result, the sample No. 2 prepared by the method according to the activation process of the present invention was used. No. 101 is a sample No. 101 produced by a conventional method in which activation processing is performed while conveying a substrate in terms of performance (external extraction quantum efficiency, driving voltage, lifetime). It was confirmed that it showed the same performance as 102.

  In addition, each sample No. As a result of actual measurement according to the length of the activation treatment line used when producing 101 and 102, sample No. 10 prepared by the activation treatment method related to the method for producing the organic electroluminescence panel of the present invention was used. In the case of 101, it was 5 m. In addition, the activation treatment line related to the method for manufacturing the organic electroluminescence panel of the present invention can be used for one activation treatment line for the activation treatment of the hole transport layer, the light emitting layer, and the electron transport layer. It was 5m regardless of. It was confirmed that the production line can be made compact by the roll-to-roll method.

  Sample No. produced by a conventional activation method was used. In the case of 102, one layer was 50 m. In addition, the activation process line related to the conventional manufacturing method is arranged according to the number of layers to be stacked because the activation process of the hole transport layer, light emitting layer, and electron transport layer must be performed separately in the roll-to-roll method. It was confirmed that three 50m activation treatment lines were required as a whole, and the production line was lengthened. The effectiveness of the present invention was confirmed.

1, 1 ', 1 "organic EL panel 101, 101', 101", 2a base material 102, 102 ', 102 "first electrode (anode)
102a, 102'a, 102 "a External connection electrode for first electrode 102b, 102'b Lead portion 103, 103 ', 103" Organic functional layer 104, 104', 104 "Second electrode (cathode)
104a, 104′a, 104 ″ a External connection electrodes for second electrode 105, 105 ′, 105 ″ Adhesive layer 107 ′ Conductive layer 106, 106 ′, 106 ″ Sealing member 2 Manufacturing process of organic EL panel 201 First DESCRIPTION OF SYMBOLS 1 Substrate supply process 202 1st electrode (anode) formation process 203 1st collection | recovery process 204 2nd base material supply process 205 Organic functional layer application | coating process 206 Drying process 207 Organic functional layer removal process 208 2nd collection | recovery process 209 Activation process Process (heat treatment process)
210 Third substrate supply step 211 Second electrode (cathode) formation step 212 Third recovery step 213 Fourth substrate supply step 214 Sealing step 215 Cutting step 216 Fourth recovery step 2a1, 2a2, 2b1 to 2b3 Activation uniform 2a11 Convex object F Width G Height H Diameter I Pitch

Claims (2)

In the manufacturing method of the organic electroluminescence panel having the first electrode, at least one organic functional layer, and the second electrode on the band-shaped substrate,
The organic functional layer is formed by applying a coating liquid for forming an organic functional layer and drying it, then forming a winding roll once, and performing an activation process.   2. The organic electroluminescence according to claim 1, wherein activation uniformizing means having air permeability is provided along at least both side edges in the width direction perpendicular to the transport direction of the belt-shaped substrate. Panel manufacturing method.

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