JP2009268975A - Application method of organic compound layer forming coating liquid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an application method of applying an organic compound layer forming coating liquid on a belt-like base material held on a holding member and continuously transported to form at least one organic compound layer of a thin film having stable film thickness using a pre-measuring type coating system coating device in a non-contact state. <P>SOLUTION: In the application method of applying the organic compound layer forming coating liquid on a belt-like base material held on a holding member and continuously transported using the coating device in the non-contact state, wherein the pre-measuring type coating device for continuously discharging the coating liquid from a slit and a drying device are used, the drying device is arranged to start the drying of the belt-like base material being in contact with the holding member at least before coating, the holding member has a vibration means, the application of the organic compound layer forming coating liquid is carried out while vibrating the holding member by the vibration means and the drying is carried out with the start of the coating at the same time. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coating method in which coating is performed in a non-contact manner using a pre-weighing type coating device on a belt-like substrate continuously held and held by a holding member.

  Conventionally, the following two coating methods are known as a method of coating a coating liquid on a continuously running belt-like substrate. One is a post-measurement type coating method in which an excess coating solution is discharged onto the substrate in advance, and then the excess is removed by some scraping means. As a post-measuring type coating method, a blade coating method, an air knife coating method, a wire bar coating method, a gravure coating method, a reverse coating method, and a reverse roll coating method are known.

  The other is a pre-weighing type coating method in which the coating liquid is discharged by an amount that forms a necessary coating liquid film, and the coating liquid is coated on the support. As the pre-measuring type coating method, an extrusion coating method using an extrusion type coating device, a slide coating method using a slide type coating device, a curtain coating method, and a coating method using an inkjet head are known.

  The pre-measuring type coating method can cope with high coating accuracy, high quality, high speed, thin film, multi-layer coating suitability, etc., for example, photographic material, magnetic recording medium, optical film, inkjet recording paper It is used for the production of heat-developable recording materials, organic electroluminescence panels (hereinafter also referred to as organic EL panels) and the like.

  Furthermore, in recent years, there has been an increasing demand for higher functionality and thinner layers of equipment in the display field and the like, and there is a growing demand for uniform coating film thickness to be coated on a support.

  In general, when applying by the pre-weighing type coating method, factors that affect the uniformity of the coating film thickness include, for example, unevenness in the discharge rate of the coating liquid discharged from the slit port, and vibration associated with the conveyance of the substrate. And vibration of the coating device. Measures have been examined so far for making the film thickness uniform. For example, there is known a method of obtaining a stable coating film by suppressing the vibration of the coating apparatus during coating by arranging the coating apparatus on a base portion provided with a vibration damping device or a vibration isolation device (see Patent Document 1). .

  However, in the method described in Patent Document 1, vibration of the coating apparatus can be suppressed. Therefore, the film thickness unevenness caused by the vibration of the coating apparatus is effective to some extent. It has been found that countermeasures are insufficient for the accompanying film thickness unevenness and the film thickness unevenness associated with the pulsation of the coating liquid discharged from the coating apparatus.

  When applying a coating solution using a slot die on a web that is continuously supported by a backup roller, the unevenness of the coating film caused by vibration of the building (floor surface) or pulsation during liquid feeding is suppressed. In order to form a high-quality coating layer, a method is known in which the slot width d of the slot die is 250 μm or less and the ratio L / d of the slot length L to the slot width d is 300 or more ( (See Patent Document 2).

  However, the method described in Patent Document 2 shows an effect on vibration during coating and pulsation of the coating liquid, but lacks countermeasures against film thickness unevenness due to vibration of the substrate during coating. I found out.

  For stability when forming a liquid film with a die coater, agglomeration of the material to be coated is generated in the slit of the die coater, and it is formed between the die coater and the substrate due to the deposit of the material to be coated adhering to the lip of the slit. A method of applying ultrasonic vibration to a die coater is known in order to prevent streaks by forming beads stably (see Patent Document 3).

  However, the method described in Patent Document 3 shows an effect on the stability of the bead formed on the die coater and the base material at the time of application, but measures against uneven film thickness due to vibration of the base material at the time of application. Was found to be insufficient.

  Coating defects such as streaks due to biting of foreign matter or bubbles at the application part, living due to pressure instability in the application part, horizontal unevenness due to mechanical vibrations, moya unevenness due to hot air during the drying process, etc. that occur when applying paint In order to solve this problem, a method of applying vibration to the support after coating is known (see Patent Document 4).

  However, in the method described in Patent Document 4, when a solvent having low volatility is used for the coating solution, the coating film after coating retains a certain degree of fluidity. In the case where a high-performance solvent is used and the film thickness is thin, it has been found that there are insufficient measures for reducing the fluidity of the coating film accompanying the evaporation of the solvent.

From such a situation, when the coating solution for forming an organic compound layer for forming at least one organic compound layer is applied in a non-contact manner using a pre-weighing type coating system coating apparatus, Development is desired.
JP 2007-268385 A JP 2007-75797 A JP 2003-260399 A JP 2005-144414 A

  The present invention has been made in view of the above situation, and an object of the present invention is to form an organic compound layer that forms at least one organic compound layer on a belt-like base material held by a holding member and continuously conveyed. It is to provide a coating method in which the coating liquid is applied in a non-contact manner using a pre-measuring type coating apparatus and the film thickness is stable.

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

  1. At least one layer of organic material on a belt-like substrate that is held by a holding member and continuously conveyed using at least a pre-metering type coating device that continuously discharges a coating liquid from a slit and a drying device In the coating method of coating the organic compound layer forming coating solution for forming the compound layer in a non-contact manner using the coating device, the drying device is in contact with the holding member at least before the coating. The holding member has a vibrating means, and the coating liquid for forming the organic compound layer is applied while vibrating the holding member by the vibrating means; and Drying is performed simultaneously with the start of the coating, and the coating method of the coating solution for forming an organic compound layer is provided.

  2. 2. The coating method of the coating solution for forming an organic compound layer according to 1 above, wherein the drying is started while the belt-shaped substrate is in contact with the holding member.

  3. 3. The drying according to 1 or 2 above, wherein the coating film formed by applying the organic compound layer forming coating liquid on the belt-like substrate is vibrated until the constant rate drying process is completed. Application method of coating solution for forming organic compound layer.

  4). 4. The coating method for coating liquid for forming an organic compound layer according to any one of 1 to 3, wherein the organic compound layer is an organic compound layer of an organic electroluminescence panel.

  5). Any one of said 1-4 characterized by the thickness at the time of application | coating of the coating film formed by apply | coating the said coating liquid for organic compound layer formation on a base material, 2 micrometers-24 micrometers. The coating method of the coating liquid for organic compound layer formation of this.

  6). 6. The coating method of a coating liquid for forming an organic compound layer according to any one of 1 to 5, wherein the vibrating means is a piezo element.

  7. The amplitude of vibration by the vibrating means is 30% to 70% of the film thickness of the coating film immediately after coating to apply the organic compound layer forming coating liquid and form the formed organic compound layer The coating method of the coating liquid for organic compound layer formation of any one of 1-6.

  8). 8. The coating method of a coating liquid for forming an organic compound layer according to any one of 1 to 7, wherein the vibration frequency of the vibrating means is 1.0 kHz to 20.0 kHz.

  9. The coating device has an upstream side of the substrate transporting the decompression chamber, and when the coating solution for forming an organic compound layer is coated on the substrate by the coating device, the coating position of the strip-shaped substrate by the decompression chamber The coating method of the coating liquid for forming an organic compound layer according to any one of 1 to 8, wherein the pressure on the upstream side is reduced more than that on the downstream side.

  The organic compound layer-forming coating solution for forming at least one organic compound layer on the belt-like base material held by the holding member and continuously conveyed is non-contacted using a pre-weighing type coating system coating device. It was possible to provide a coating method with a thin film and a stable film thickness.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 7, but the present invention is not limited thereto. The application method of the present invention will be described when it is applied to application of an organic compound layer when manufacturing an organic electroluminescence panel (hereinafter also referred to as an organic EL panel).

  The organic EL panel is provided with an anode made of a transparent conductive film such as ITO (Indium tin oxide) on a transparent substrate, and an organic layer made of a hole transport layer and a light emitting layer, and an anode formed on the transparent substrate. A cathode made of aluminum or the like is provided in this order. For example, the light emitting layer is a very thin layer of a fluorescent organic compound. Usually, the organic substance is an insulator, but by making the thickness of the organic layer very thin, current injection becomes possible, and the organic EL element can be driven at a low voltage of 10 V or less. Organic EL panels are current-driven light-emitting elements that emit light when a very thin thin film of fluorescent organic compound is sandwiched between an anode and a cathode, and in recent years display devices such as flat displays, electrophotographic copying machines, and printers. Use for light sources such as these is under consideration.

  FIG. 1 is a schematic view showing an example of an organic EL panel used for illumination. FIG. 1A is a schematic perspective view showing an example of an organic EL panel. FIG.1 (b) is a schematic sectional drawing in alignment with AA 'of Fig.1 (a).

  In the figure, 1 indicates an organic EL panel. The organic EL panel 1 includes an anode (first electrode) 102, a hole transport layer 103, a light-emitting layer 104, an electron transport layer 105, and a cathode buffer layer (electron injection layer) sequentially on a flexible substrate 101. ) 106, a cathode (second electrode) 107, an adhesive layer 108, and a sealing member 109. A sealing layer is formed by the adhesive layer 108 and the sealing member 109. The organic EL panel 1 has an adhesion sealing structure that is sealed with an adhesive layer 108 except for an end portion of an extraction electrode 102a for the anode (first electrode) 102 and an extraction electrode 107a for the cathode (second electrode) 107. It has become. A gas barrier film (not shown) may be provided between the anode (first electrode) 102 and the flexible substrate 101. In the present invention, the state in which the second electrode 107 is sealed with the sealing member 109 via the adhesive layer 108 is referred to as an organic EL panel, and the state in which up to the second electrode is formed is referred to as an organic EL element.

  The layer configuration of the organic EL panel shown in this figure is an example, but the following configuration is another typical layer configuration between the anode (first electrode) and the cathode (second electrode). Can be mentioned.

(1) Anode (first electrode) / light emitting layer / cathode (second electrode)
(2) Anode (first electrode) / light emitting layer / electron transport layer / cathode (second electrode)
(3) Anode (first electrode) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode (second electrode)
(4) Anode (first electrode) / hole transport layer (hole injection layer) / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (second electrode)
(5) Anode (first electrode) / 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 (second electrode)
Each layer constituting the organic EL panel will be described later.

  FIG. 2 is a schematic view showing an example of a production process for producing the organic EL panel shown in FIG. 1 using a belt-like substrate.

  In the figure, reference numeral 2 denotes a manufacturing process of the organic EL panel. The manufacturing process 2 includes a belt-shaped substrate supplying process 201, a first electrode forming process 202, a hole transport layer forming process 203, a light emitting layer forming process 204, an electron transport layer forming process 205, a cathode buffer layer ( An electron injection layer) forming step 206, a second electrode forming step 207, a sealing step 208, and a recovery step 209; In addition, as the collection step 209, a cutting device for obtaining individual organic EL panels from a strip-shaped substrate having a plurality of organic EL panels may be used, or a strip-shaped substrate having a plurality of organic EL panels is rolled. You may use the winding apparatus wound up to. When the winding device is used, after winding and collecting in a roll shape, a plurality of organic EL panels produced on the band-shaped substrate in another process may be cut as individual organic EL panels. .

  As shown in this figure, a method for producing an organic EL panel using a band-shaped substrate wound in a roll shape and sequentially performing a first electrode forming step 202 to a sealing step 208 is called a roll-to-roll method.

  In addition, although this figure has shown the case where the supply process 201-collection | recovery process 209 is continued, when the whole process becomes long and installation becomes difficult, a process will be divided | segmented suitably and a strip | belt-shaped base material will be wound up in roll shape. You may make it preserve | save and supply a strip | belt-shaped base material in roll shape to the next process again. Each step will be described with reference to FIGS.

  FIG. 3 is a schematic diagram up to the supplying step shown in FIG. 2 and the first electrode and second electrode extraction electrode forming step.

  In the figure, 201 shows the supply process of the strip | belt-shaped base material 3, 202 shows the extraction electrode formation process for 1st electrodes and 2nd electrodes. From the supply process 201, a roll-out belt-like substrate 301 is drawn out (not shown), and the belt-like substrate 3 is continuously applied to the first electrode and second electrode extraction electrode formation process 202 in the next process. It feeds out through the transport roller 201b. It is preferable to attach an alignment mark (not shown) for determining the position where the first electrode and the second electrode extraction electrode are formed in advance to the belt-like substrate 3.

  The first electrode and second electrode extraction electrode forming step 202 includes a first electrode forming device (also serving as a second electrode extraction electrode forming device) 202a, a first accumulator 202b, a second accumulator 202c, and a winding device. 202d is used. The first electrode forming apparatus (also serving as the second electrode extraction electrode forming apparatus) 202a has a vapor deposition apparatus 202a1 having an evaporation source container 202a2.

  The first accumulator 202b has a plurality of lower conveyance rollers 202b1 and a plurality of upper conveyance rollers 202b2, and is arranged for speed adjustment with the supply step 201. The second accumulator 202c has a plurality of lower conveyance rollers 202c1 and a plurality of upper conveyance rollers 202c2, and is arranged for speed adjustment by the winding device 202d.

  In the first electrode formation step 202, an alignment mark (not shown) attached to the belt-like substrate 3 continuously supplied from the supply step 201 is read by a detection device (not shown), and the detection device (not shown) According to the information, the first electrode (not shown, corresponding to the first electrode 102 in FIG. 1) and the first electrode having the extraction electrode at a position determined by the first electrode formation apparatus (also serving as the second electrode extraction electrode formation apparatus) 202a A two-electrode lead electrode (not shown, corresponding to the second electrode lead electrode 107a in FIG. 1) is formed into a mask pattern. The number of first electrodes and second electrode take-out electrodes to be formed can be appropriately determined from the width of the belt-like substrate, the size of the organic EL panel to be produced, and the like. The thickness of the first electrode and the second electrode extraction electrode is preferably 100 nm to 200 nm. After the first electrode and the second electrode take-out electrode are formed, the belt-like base material on which the first electrode and the second electrode take-out electrode are stacked is temporarily wound up by the winding device 202d through the transport roller 202d1 and then temporarily wound up. It is preferable to store. After the primary storage, it is sent to the hole transport layer forming step 203 (see FIGS. 2 and 4). In addition, when not winding up and storing, it is continuously sent to the hole transport layer forming step 203 (see FIGS. 2 and 4).

  The supplying step 201 and the first electrode positive forming step (also serving as the second electrode extraction electrode forming device) 202 are preferably performed in a vacuum environment. In addition, although this figure has shown the case where the 1st electrode formation process (it also serves as the extraction electrode formation apparatus for 2nd electrodes) is formed by a vapor deposition method, it does not specifically limit about a formation method, For example, sputtering method etc. are shown. Can be used.

  FIG. 4 is a schematic diagram of the hole transport layer forming step shown in FIG.

  The hole transport layer forming step 203 includes a feeding unit 203a, a coating unit 203b, a drying unit 203c, a pattern forming unit 203d, and a winding unit 203e. In the hole transport layer forming step 203, the hole transport layer forming coating solution is applied to the entire surface including the first electrode and the second electrode take-out electrode of the belt-like substrate 3 formed up to the first electrode, After forming a patterned hole transport layer (not shown, corresponding to the hole transport layer 103 in FIG. 1) through the drying unit 203c and the pattern forming step 203d, it can be wound up and stored once. Yes. Further, it may be transferred to the light emitting layer forming step 204 (see FIG. 2). The hole transport layer forming step 203 in this figure is arranged in an atmospheric pressure environment.

In the feeding portion 203a, the first electrode and the second electrode take-out electrode are already formed, and the belt-like substrate 3 wound in a roll wound around the winding core is supplied via the transport roller 203a1. It has become. An accumulator 203a2 and an antistatic means 203a3 can be disposed between the feeding unit 203a and the coating unit 203b as necessary. The accumulator 203a2 has a plurality of lower conveyance rollers 203a21 and a plurality of upper conveyance rollers 203a22, and is arranged for speed adjustment in the application unit 203b. The antistatic means 203a3 has a non-contact type antistatic device 203a31 and a contact type antistatic device 203a32. Examples of the non-contact type antistatic device 203a31 include a non-contact type ionizer. 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.

  As the contact-type antistatic device 203a32, a static eliminating roll or a conductive brush connected to the ground is used. 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 the contact with the belt-like substrate 3a. 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 neutralizing 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 203a31 is preferably used on the side of the hole transport layer formed on the belt-like substrate 3, and the contact type antistatic device 203a32 is preferably used on the back side of the belt-like substrate 3.

  The coating unit 203b uses a pre-weighing type coating device 203b1 and a backup roll 203b2 which is a holding member for holding the strip-shaped substrate 3 on which the first electrode (anode) and the second electrode take-out electrode are formed. The backup roll 203b2 has vibration means 203b3 (see FIG. 6). The hole transport layer forming coating solution by the pre-weighing type coating device 203b1 is formed on the first electrode (anode) and the second electrode take-out electrode while vibrating the backup roll 203b2 by the vibrating means 203b3 (see FIG. 6). Is applied to the entire surface of the belt-like substrate 3 on which the first electrode (anode) and the second electrode extraction electrode are formed in a non-contact manner. Details of the application unit 203b will be described with reference to FIG. The thickness of the hole transport layer is about 5 nm to 5 μm, preferably 5 to 200 nm.

  This figure shows a case in which an extrusion type coater is used as the pre-weighing type coating apparatus 203b1, but it is also possible to use a coating apparatus such as a slide type coater or an ink jet head. The use of these pre-measuring type coating apparatuses can be appropriately selected according to the material of the hole transport layer.

  The drying unit 203c includes a drying device 203c1 and a heat treatment device 203c2. The drying device 203c1 is arranged so that drying can be started at least before application, and drying is performed simultaneously with the start of application. The heat treatment device 203c2 is continuously disposed after the drying device 203c1, and the hole transport layer formed by evaporating the solvent in the drying device 203c1 is transferred from the back surface side of the belt-like substrate 3 by the back surface heat transfer method. It is supposed to be heated. As the heat treatment conditions for the hole transport layer in the heat treatment apparatus 203c2, the smoothness of the hole transport layer is improved, the residual solvent is removed, the hole transport layer is cured, and the glass transition temperature of the hole transport layer is considered. Therefore, 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 hole transport layer at -30 to + 30 ° C. Details of the drying device 203c1 will be described with reference to FIG.

  The pattern forming unit 203d includes a solvent application unit 203d1 and a removal unit 203d2. The solvent application unit 203d1 uses an application device 203d12 that applies a solvent that dissolves the hole transport layer. The solvent application unit 203d1 has a first electrode (anode), a second electrode extraction electrode, and a first electrode (anode). Apply to unnecessary parts around). Thereafter, the solvent applied in the removing unit 203d2 and the hole transport layer dissolved in the solvent are removed to form a patterned hole transport layer. The coating device 203d12 is preferable because the inkjet head can perform fine coating. Removal of the solvent and the hole transport layer dissolved in the solvent in the removing unit 203d2 includes a suction method and a method using a wiping member such as a sponge. 203d13 shows the mounting base of the base material 3 in which the positive hole transport layer conveyed from the drying part 203c was formed.

  The winding unit 203e includes an antistatic means 203e2 and an accumulator 203e3 as necessary between the pattern forming unit 203d and the winding device 203e1, and after the processing in the pattern forming unit 203d is finished, the patterned positive The belt-like base material 3 on which the hole transport layer is formed is wound up via the transport roll 203e4. The antistatic means 203e2 has a non-contact type antistatic device 203e21 and a contact type antistatic device 203e22, and it is preferable to use the same as the noncontact type antistatic device 203a31 and the contact type antistatic device 203a32. The accumulator 203e3 has a plurality of lower conveyance rollers 203e31 and a plurality of upper conveyance rollers 203e32, and is arranged for speed adjustment in the winding unit 203e.

  Since the light emitting layer forming step 204 (see FIG. 2) has the same configuration as the hole transport layer forming step 203 shown in FIG. 4, a detailed description thereof will be omitted, and the outline of the light emitting layer formation and the electron transport layer formation will be omitted. I will explain. Moreover, when forming an electron carrying layer by application | coating, it is preferable that the electron carrying layer formation process 205 (refer FIG. 2) becomes the same structure as the positive hole transport layer forming process 203 shown in FIG. When forming an electron carrying layer by vapor deposition, it is preferable that it is the same structure as the cathode buffer layer (electron injection layer) formation process shown in FIG.

  In the light emitting layer forming step 204 (see FIG. 2), the light emitting layer is formed on the entire surface of the hole transporting layer formed by the pre-weighing type coating apparatus on the belt-like substrate 3 on which the hole transporting layer is formed. The forming coating solution is applied in a non-contact manner while applying vibration by a vibrating means disposed on the backup roll. As the pre-weighing type coating apparatus, the same coating apparatus as that used for coating the hole transport layer forming coating solution can be used.

  In the pattern forming unit, a coating apparatus (for example, an ink jet head) that applies a solvent that dissolves the formed light emitting layer is used, over the extraction electrode for the first electrode (anode), over the extraction electrode for the second electrode, and Application is performed on unnecessary portions around the first electrode (anode). Thereafter, the solvent applied in the removing portion and the light emitting layer dissolved in the solvent are removed to form a patterned light emitting layer.

  In the case of the coating method, in the electron transport layer forming step 205 (see FIG. 2), the entire upper surface of the light emitting layer formed by the pre-weighing type coating method coating device on the belt-like substrate 3 on which the light emitting layer is formed. The coating solution for forming an electron transport layer is applied in a non-contact manner while applying vibration by a vibrating means disposed on a backup roll. As the pre-weighing type coating apparatus, the same coating apparatus as that used for coating the hole transport layer forming coating solution can be used.

  In the pattern forming unit, a coating apparatus (for example, an ink jet head) that applies a solvent that dissolves the formed electron transport layer is used, over the extraction electrode for the first electrode (anode) and over the extraction electrode for the second electrode. And it applies to the unnecessary part around the 1st electrode (anode). Thereafter, the solvent applied in the removing portion and the electron transport layer dissolved in the solvent are removed, and a patterned electron transport layer is formed.

  When the electron transport layer is formed by vapor deposition, in the electron transport layer formation step 205 (see FIG. 2), an alignment mark (not shown) attached on the belt-like substrate 3 on which the light emitting layer is formed is used. Read with a detection device (not shown), remove the electrode at a position determined by the vapor deposition device according to the information of the detection device (not shown), and mask the electron transport layer on the already formed patterned light emitting layer Form a film. The thickness of the electron transport layer is preferably in the range of 5 nm to 50 nm.

  FIG. 5 is a schematic diagram after the cathode buffer layer (electron injection layer) forming step shown in FIG. This figure shows a case in which a cutting device is used in the recovery process and a band-shaped substrate on which the electron transport layer is formed is used.

  The cathode buffer layer (electron injection layer) formation step 206 includes a feeding portion 206a of the belt-like substrate 3 on which a patterned electron transport layer wound up in a roll shape is formed, and an evaporation source container 206c. A device 206b and an accumulator 206d are used. The accumulator 206d has a plurality of lower conveyance rollers 206d1 and a plurality of upper conveyance rollers 206d2, and is disposed between the feeding unit 206a and the vapor deposition device 206b, and the feeding unit 206a and the vapor deposition device 206b. It is arranged for speed adjustment.

  In the cathode buffer layer (electron injection layer) forming step 206, the electron transport layer (not shown, corresponding to the electron transport layer 105 in FIG. 1) continuously supplied from the feeding portion 206a through the transport roller 206a1 is formed. The alignment mark (not shown) attached to the belt-like base material 3 is read with a detection device (not shown), and the take-out electrode is removed at a position determined by the vapor deposition device 206b according to the information of the detection device (not shown). A cathode buffer layer (electron injection layer) (not shown, corresponding to the electron injection layer 107 in FIG. 1) is formed as a mask pattern on the patterned electron transport layer that has already been formed. The thickness of the cathode buffer layer (electron injection layer) is preferably in the range of 0.1 nm to 5 μm.

  The second electrode forming step 207 uses a vapor deposition apparatus 207a having an evaporation source container 207b and an accumulator 207c. The accumulator 207c has a plurality of lower conveyance rollers 207c1 and a plurality of upper conveyance rollers 207c2, and is disposed between the cathode buffer layer (electron injection layer) formation step 206 and the second electrode formation step 207. The cathode buffer layer (electron injection layer) forming step 206 is provided for speed adjustment.

  In the second electrode forming step 207, the alignment from the cathode buffer layer (electron injection layer) forming step 206 to the cathode buffer layer (electron injection layer) continuously supplied is attached to the band-shaped substrate 3 already formed. A mark (not shown) is read by a detection device (not shown), and a second electrode (cathode) take-out electrode (not shown, FIG. 1) is positioned at a position determined by the vapor deposition device 207a according to information of the detection device (not shown). The second electrode (cathode) (not shown, corresponding to the second electrode (cathode) 107 in FIG. 1) is connected so as to be connected to the second electrode extraction electrode 107a) and to intersect the first electrode electricity. ) Is formed on the already formed cathode buffer layer (electron injection layer) (not shown, corresponding to the cathode buffer layer (electron injection layer) 106 in FIG. 1).

  The sheet resistance as the second electrode (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. At this stage, an organic EL device having a configuration of base material / first electrode (anode) / hole transport layer / light emitting layer / cathode buffer layer (electron injection layer) / second electrode (cathode) is completed.

  This figure shows the case where the cathode buffer layer (electron injection layer) forming step 206 and the second electrode (cathode) forming step 207 are vapor deposition apparatuses, but the cathode buffer layer (electron injection layer) and the second electrode (cathode). There is no particular limitation on the formation method, for example, dry sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma polymerization method, plasma CVD. For example, a laser CVD method, a thermal CVD method, or the like can be used. The cathode buffer layer (electron injection layer) can also use a wet coating method.

  The sealing step 208 includes a sealing member supply step 208b, and uses a sealant coating device 208a, a bonding device 208c, and an accumulator 208e. The sealing member 208b1 is sent from the sealing member supply step 208b. The accumulator 208e has a plurality of lower transport rollers 208e1 and a plurality of upper transport rollers 208e2, and is arranged for speed adjustment with the second electrode (cathode) forming step 207.

  The sealing member 208b1 is also provided with an alignment mark (not shown) at the same position as the alignment mark (not shown) attached to the belt-like base material 3 on which the second electrode has already been formed.

  In the sealing step 208, an alignment mark (not shown) attached to the belt-like base material 3 on which the second electrodes have already been formed is read by a detection device (not shown) and sealed according to information from the detection device (not shown). By the agent coating device 208a, the organic EL element is coated on and around the organic EL element except for the extraction electrode (not shown, corresponding to the extraction electrode 102a and the extraction electrode 107a in FIG. 1).

  Then, the alignment mark (not shown) attached to the strip | belt-shaped base material 3 which has the some organic EL element with which the sealing agent was coated and formed by the bonding apparatus 208c, and the alignment mark (not shown) of sealing member 208b1 The organic EL element is closely sealed together. At this stage, an organic EL panel is manufactured. Since a plurality of organic EL panels manufactured at this stage are continuously connected, they are cut into individual organic EL panels in the recovery step 209.

  The collection step 209 uses a cutting device 209a, an accumulator 209b, and a collection box 209c. The accumulator 209 b has a plurality of lower conveyance rollers 209 b 1 and a plurality of upper conveyance rollers 209 b 2, and is arranged for speed adjustment with the sealing step 208. In the cutting device 209a, an alignment mark (not shown) attached to the band-shaped substrate 3 on which a plurality of organic EL panels are formed or an alignment mark (not shown) of the sealing member 208b1 is read by a detection device (not shown). Then, punching and cutting is performed in accordance with information from a detection device (not shown), and the individual organic EL panel 6 is collected in the collection box 209c. Reference numeral 209d denotes a skeleton wound in a roll shape from which an organic EL panel is punched. The cut organic EL panel 6 has the same configuration as the organic EL panel shown in FIG.

  FIG. 6 is an enlarged schematic view of a portion indicated by X in FIG. FIG. 6A shows a case where the drying device is disposed so as to cover up to the vicinity of the application point of the belt-like substrate 3 held on the backup roll. FIG. 6B shows a case where the drying device is disposed so as to cover the coating device.

  In the figure, reference numeral 203b12 designates a supply pipe for supplying a coating solution for forming an organic compound layer to the coating device 203b1. The viscosity of the coating solution for forming an organic compound layer to be used is preferably 0.2 mPa · s to 3 mPa · s in consideration of the solubility and coating properties of the material to be used.

  The boiling point of the solvent used in the coating solution for forming an organic compound layer is preferably 50 ° C. to 150 ° C. in consideration of drying properties, drying load, solubility of materials used, and the like.

  Reference numeral 203b13 denotes a decompression chamber disposed on the lower side of the coating apparatus 203b1 (upstream side with respect to the belt-like substrate 3 being conveyed). Reference numeral 203b131 denotes a suction pipe for reducing the pressure in the decompression chamber 203b13 and is connected to a suction pump (not shown). Reference numeral 203b132 denotes a discharge pipe for discharging the coating liquid discharged from the coating apparatus 203b1 at the start or end of coating. When the coating solution for forming an organic compound layer is applied onto the belt-shaped substrate by the decompression chamber 203b13, it is preferable to depressurize the upstream side relative to the downstream side with respect to the coating position P of the belt-shaped substrate. The degree of vacuum on the upstream side is preferably −5 Pa to −500 Pa in consideration of the stability of the coating film when the coating speed is increased relative to the downstream side. Application | coating in the application position P of a strip | belt-shaped base material is performed non-contact by the coating device 203b1.

  The backup roll 203b2 which is a holding member is rotatably supported by a support member 203b5 via a bearing box 203b4. Reference numeral 203b3 denotes a vibration means 203b3 disposed on the support member 203b5. In this figure, the vibration means 203b3 is disposed on the support member of the backup roll 203b2, but in the present invention, the holding member has the vibration means includes such a state of arrangement.

  Application of the organic compound layer forming coating solution onto the belt-like substrate by the coating device 203b1 is performed while applying vibration to the backup roll 203b2 by the vibration means 203b3. When vibration is not applied, unevenness due to film shrinkage occurs before drying due to insufficient leveling, which is not preferable.

  The vibration frequency of the vibration means 203b3 is preferably 1 kHz to 20 kHz in consideration of film stability.

  The amplitude of vibration by the vibration means 203b3 is 30% to 70% with respect to the film thickness of the coating film that forms the organic compound layer formed by applying the organic compound layer forming coating solution. Preferably there is.

  The vibration means 203b3 is not particularly limited, and various electric and hydraulic actuators can be used. Among these, a piezoelectric element is preferable in that a desired frequency can be easily obtained.

  The thickness of the coating film formed by coating the coating solution for forming an organic compound layer on the belt-like substrate with the coating device 203b1 is the characteristics of the organic compound layer, the solid content concentration of the coating solution for forming the organic compound layer, the viscosity, etc. Is preferably 50 μm to 100 μm. The thickness of the coating film immediately after coating is a value obtained by calculation from the supply amount of the coating liquid for forming an organic compound layer, the coating width, and the coating speed.

  The drying device 203c1 includes a main body 203c11, a dry air blowing header 203c12, and a conveying roller 203c13. Reference numeral 203c121 denotes a dry air supply pipe, and 203c122 denotes a dry air exhaust pipe. Reference numeral 203c123 denotes a discharge port for dry air.

  The drying by the drying device 203c1 takes into consideration the uniformity of the coating film, the fluidity of the coating film, the wettability of the coating liquid for forming the organic compound layer on the strip substrate, and the backup roll in which the strip substrate 3 is a holding member. It is preferable to start while touching.

  The drying device 203c1 shown in FIG. 6A starts drying immediately after the coating device 203b1 applies the organic compound layer forming coating solution onto the belt-like substrate 3 in contact with the backup roll. ing. The drying apparatus 203c1 shown in FIG. 6B is a backup of the band-shaped substrate 3 including before the coating liquid for forming the organic compound layer is applied onto the band-shaped substrate 3 in contact with the backup roll by the coating apparatus 203b1. Drying is started when it comes into contact with the roll.

  In addition, drying of the coating film formed by applying onto the belt-like substrate 3 conveyed away from the backup roll 203b2 which is the holding member by the drying device 203c1 is performed until the constant rate drying process is completed. It is preferable to give the same vibration as the vibration applied to the backup roll 203b2 at the time of application in consideration of the uniformity of the film and the fluidity of the coating film. The method for applying vibration is not particularly limited. For example, a piezoelectric element may be provided on the transfer roller 203c13 provided in the constant rate drying process of the main body 203c11 to apply vibration to the transfer roller 203c13.

  The constant rate drying process refers to a process in which the solvent evaporates at a constant rate from the surface of the coating film when the drying condition is constant when the coating film containing the solvent formed on the substrate is dried. . The end of the constant rate drying process is the point at which the coating surface temperature is observed with time and the coating surface temperature starts to rise. The coating surface temperature is preferably measured by contact with a radiation thermometer. For example, an infrared thermocouple IRt / c manufactured by EXERGEN can be used.

  The coating by the coating device 203b1 and the drying by the drying device 203c1 shown in FIGS. 6A and 6B are preferably performed in an inert gas atmosphere in consideration of safety.

  Examples of the coating solution for forming an organic compound layer used in the description of this figure include a coating solution for forming a hole transport layer, a coating solution for forming a light emitting layer, and a coating solution for forming an electron transport layer. After the hole transport layer is formed on the band-shaped substrate on which the first electrode is formed using the coating device 203b1 and the drying device 203c1 shown in FIG. 6, by the same method as the formation of the hole transport layer, A light emitting layer is formed on the hole transport layer, and the electron transport layer can be sequentially laminated by the same method.

  FIG. 7 is a schematic flow diagram showing patterning of the hole transport layer in the hole transport layer forming step shown in FIG. Hereinafter, the patterning of the hole transport layer formed on the entire surface of the belt-like flexible substrate on which the first electrode (anode) is formed will be described with reference to the flowchart.

  Step 1 is a state in which the first electrode (anode) 102 having a plurality of extraction electrodes 102a and the second electrode extraction electrode 107a are formed in the first electrode and second electrode extraction electrode formation step 202 (see FIG. 2). The strip-shaped base material 3 is shown. The right side is a schematic cross-sectional view along the line BB 'in the drawing shown in Step 1.

  In Step 2, the hole transport layer 103 is formed on the entire surface including the first electrode (anode) 102 having the extraction electrode 102a and the second electrode extraction electrode 107a in the hole transport layer formation step 203 (see FIG. 2). However, the belt-like base material 3 in a state in which both ends are excluded) is shown. The right side is a schematic cross-sectional view along the line CC 'in the drawing shown in Step 2.

  In Step 3, the extraction electrode 102a of the first electrode (anode) 102, the extraction electrode 107a for the second electrode, the first electrode, and the first electrode by the solvent application device 203d12 (see FIG. 4) of the pattern forming unit 203d (see FIG. 4). A state in which a solvent (good solvent) for dissolving the hole transport layer 103 is applied to an unnecessary portion around the (anode) 102 (portion indicated by diagonal lines in the drawing). The right side is a schematic cross-sectional view along the line DD 'in the drawing shown in Step 3.

  Step 4 shows a state in which the solvent that dissolves the hole transport layer 103 and the hole transport layer dissolved by the solvent are removed by the removing unit 203d2 (see FIG. 4). At the time when Step 4 is completed, the extraction electrode 102a of the first electrode (anode) 102, the extraction electrode 107a for the second electrode, and the belt-like substrate 3 around the first electrode (anode) 102 are exposed. The right side is a schematic cross-sectional view along the line FF ′ in the figure shown in Step 4.

  Thereafter, a patterned light emitting layer is formed on the hole transport layer 5 according to the flow of Step 1 to Step 4, and the patterned electron transport layer is similarly formed on the light emitting layer patterned according to the flow of Step 1 to Step 4. Is done.

As a typical example, the coating method of the present invention is shown in FIGS. 1 to 7 when used for an organic compound layer constituting an organic EL panel. The following effects can be obtained by the coating method of the present invention.
1. Even when a highly volatile solvent is used for the coating solution and the film thickness is thin, the leveling of the coating film is stabilized, and a thin film with a stable film thickness can be formed.

  Hereinafter, the materials constituting the organic EL panel mentioned as an example using the coating method of the present invention will be described.

(Strip-shaped substrate)
A resin film is mentioned as a strip | belt-shaped 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, poly Cycloolefin resins such as ether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Apel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

(Gas barrier film)
When using a resin film, it is preferable that a gas barrier film is formed on the surface of the resin film as 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, it is preferable that the water vapor permeability is 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 barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. 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 gas 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 polymerization method. 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.

(First electrode (anode))
As the first electrode (anode), 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 electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ .ZnO) that can form a transparent conductive film may be used. Alternatively, a coatable substance such as an organic conductive compound can be used. For the first electrode (anode), these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or the pattern accuracy is not so required. (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. In the case where light emission is extracted from the first electrode (anode), it is desirable that the transmittance be greater than 10%, and the sheet resistance as the first electrode (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.

(Hole injection layer (anode buffer layer))
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 for lowering the driving voltage and improving the luminance of light emission. “Organic EL panel and its industrialization front line (NTT, November 30, 1998) 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 Nos. 9-45479, 9-260062, and 8-288069. Specific examples thereof include copper phthalocyanine. Examples thereof include a phthalocyanine buffer layer, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.

(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, 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. Further, 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. These materials are preferably used to obtain a light emitting element with higher efficiency.

  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 panel with lower power consumption can be produced.

(Light emitting layer)
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 among 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. A white element can be manufactured by forming a light emitting layer in multiple 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 nm to 480 nm, 510 nm to 550 nm, and 600 nm to 640 nm. If it is three or more layers, there is no restriction 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 nm to 480 nm is referred to as a blue light emitting layer, a layer in the range of 510 nm to 550 nm is referred to as a green light emitting layer, and a layer in the range of 600 nm 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, a blue light emitting layer may be used by mixing a blue light emitting compound having a maximum wavelength of 430 nm to 480 nm and a green light emitting compound having a maximum wavelength of 510 nm 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 preferably contains a known host material and a known dopant material (a phosphorescent compound (also referred to as a phosphorescent compound)) in order to increase the light emission efficiency of the light emitting layer.

  The host material is a material 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 material. The phosphorescence quantum yield is preferably less than 0.01. A plurality of host materials may be used in combination. By using a plurality of types of host materials, 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 dopant materials, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of dopant material and the doping amount, and it can also be applied to illumination and backlight.

(Host material)
As the host material, a material that has a hole transporting ability and an electron transporting ability, prevents the emission of light from becoming longer, and has a high Tg (glass transition temperature) is preferable. Known host materials 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 No. 2002-338579, No. 2002-105445, No. 2002-343568, No. 2002-141173, No. 2002-352957, No. 2002-203683, No. 2002-363227, 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002 -29960, 2002-302516, 2002-305083, 2002-305084, 2002-308837, 2007-59119, 2007-251096, 2007- And compounds described in Japanese Patent No. 250501.

  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 material and obtaining high luminance. Phosphorescence emission energy refers to the 0-0 band peak energy of phosphorescence emission measured by measuring the photoluminescence of a deposited film of 100 nm on a substrate with a host compound.

  The host material has a phosphorescence energy of 2.9 eV or more and a Tg of 90 ° C. or more in consideration of deterioration of the organic EL element over time (decrease in luminance and film properties) and market needs as a light source. 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.

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

  The dopant material (phosphorescent compound (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 dopant material in principle. One is an energy transfer type in which recombination of carriers occurs on the host material to which carriers are transported to generate an excited state of the host material, and this energy is transferred to the dopant material to obtain light emission from the dopant material. is there. The other is a carrier trap type in which the dopant material becomes a carrier trap, and recombination of carriers occurs on the dopant material, and light emission from the phosphorescent compound is obtained. In any case, the condition is that the excited state energy of the dopant material is lower than the excited state energy of the host material.

  The dopant material can be appropriately selected from known materials used for the light emitting layer of the organic EL element. The dopant material 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, a platinum compound (platinum complex compound), or a rare earth complex. Among them, the most preferable is an iridium compound.

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

  The color emitted from the material used for the light emitting layer of the organic EL element is shown in FIG. 4.16 on page 108 of the “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). -1000 (manufactured by Konica Minolta Sensing Co., Ltd.) is determined by the color when the result of fitting to the CIE chromaticity coordinates.

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

  The light emitting layer formed by drying is a layer that emits light by recombination of electrons and holes injected from the electrode or electron injection layer and hole transport layer, and the light emitting part is within the layer of the light emitting layer. Even the interface between the light emitting layer and the adjacent layer may be used.

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

  Conventionally, in the case of a single electron transport layer and a plurality of layers, an electron transport material (also serving as a hole blocking material) used for an electron transport layer adjacent to the light emitting layer on the cathode side is injected from the cathode. As long as it has a function of transferring electrons to the light-emitting layer, any material can be selected and used from the conventionally known compounds, such as nitro-substituted fluorene derivatives and diphenylquinone derivatives. Thiopyrandioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane 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, and 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 ₃ ), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) Aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., 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. In addition, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as an electron transporting material, and an inorganic semiconductor such as n-type-Si, n-type-SiC, etc., like the hole injection layer and the hole transporting layer. Can also be used as an electron transporting material.

  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 nm-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

(Cathode buffer layer (electron injection layer))
The cathode buffer layer (electron injection layer) is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense. The cathode buffer layer (electron 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 panel and the forefront of its industrialization (November 30, 1998) (Issued by TS Co., Ltd.) ”, Chapter 2“ Electrode Materials ”(pages 123 to 166) in the second volume. The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. A metal buffer layer typified by lithium fluoride, an alkali metal compound buffer layer typified by lithium fluoride, an alkaline earth metal compound buffer layer typified by magnesium fluoride, an 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.

  In addition, 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.

(Second electrode (cathode))
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 panel is transparent or translucent, the light emission luminance is improved, which is convenient.

  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.

(Sealing agent)
Examples of the sealant include a liquid sealant and a thermoplastic resin. As a liquid sealant, acrylic acid oligomers, photocuring and thermosetting sealants having a reactive vinyl group of methacrylic acid oligomers, moisture curable sealants such as 2-cyanoacrylate, etc., Examples thereof include epoxy-based heat- and chemical-curing type (two-component mixed) sealing agents, cationic curing type ultraviolet curing epoxy resin sealing agents, and the like. It is preferable to add a filler to the liquid sealant as necessary. The addition amount of the filler is preferably 5 to 70% by volume in consideration of adhesive strength. Moreover, the magnitude | size of the filler to add considers adhesive strength, the sealing agent thickness after bonding pressure bonding, etc., and 1 micrometer-100 micrometers are preferable. The kind of filler to be added is not particularly limited, and examples thereof include soda glass, non-alkali glass, or silica, titanium dioxide, antimony oxide, titania, alumina, zirconia, tungsten oxide, and other metal oxides.

  As the thermoplastic resin, a thermoplastic resin having a melt flow rate of JIS K 7210 specified in a range of 5 to 20 g / 10 min is preferable, and a thermoplastic resin of 6 to 15 g / 10 min or less is more preferably used. This is because if a resin having a melt flow rate of 5 (g / 10 min) or less is used, the gap caused by the step of the lead 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.

(Flexible sealing member)
Examples of the flexible sealing member include a material in which a barrier layer is formed on a support made of a flexible resin film such as polyethylene terephthalate or nylon by a vapor deposition method or a coating method, or a material using a metal foil as the barrier layer. Examples of the barrier layer include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O _3. , Y ₂ O ₃ , TiO _{2 and} other metal oxides deposited on the material. Moreover, as a material of the metal foil, for example, a metal material such as aluminum, copper, or nickel, or an alloy material such as stainless steel or an aluminum alloy can be used, but aluminum is preferable in terms of workability and cost. The film thickness is about 1 to 100 μm, preferably about 10 to 50 μm. In order to facilitate handling during production, a film such as polyethylene terephthalate or nylon may be laminated in advance. In the case of using a resin film for the flexible sealing member, it is preferable to have a thermoplastic adhesive resin layer on the side in contact with the liquid sealing agent.

The water vapor permeability of the flexible sealing member is preferably 0.01 g / m ² · day or less, and the oxygen permeability is preferably 0.1 ml / m ² · day · MPa or less. The water vapor permeability is a value measured mainly by the MOCON method by a method based on JIS K7129B method (1992), and the oxygen permeability is a value measured mainly by the MOCON method by a method based on JIS K7126B method (1987). is there. The Young's modulus of the flexible sealing member is 1 × 10 ⁻³ GPa in consideration of adhesion between the flexible sealing member, the first pressure-bonding member, and the second pressure-bonding member, prevention of spreading of the sealant, and the like. It is -80GPa, and it is preferable that thickness is 10 micrometers-500 micrometers.

  The external extraction efficiency at room temperature of light emission of the organic EL panel produced by the method for producing a functional thin film 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 panel / the number of electrons sent to the organic EL panel × 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 panel into multiple colors using a phosphor. In the case of using a color conversion filter, the λmax of light emission of the organic EL panel is preferably 480 nm or less.

  The organic EL panel produced by the method for producing a functional thin film 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 panel 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 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 method 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 the substrate, the transparent electrode layer, and the light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951).

  When an organic EL panel is produced by the method for producing a functional thin film of the present invention, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitting layer, or a substrate, a transparent electrode layer or a light emitting layer. A method of forming a diffraction grating between any layers (including between the substrate and the outside) can be suitably used.

  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 uses 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 or second-order diffraction. Of these, light that cannot be emitted outside due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode) It tries to take out light. 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 grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

  Further, in the organic EL panel manufactured by the method for manufacturing a functional thin film of the present invention, in order to efficiently extract light generated in the light emitting layer, a structure on a microlens array, for example, is provided on the light extraction side of the substrate. By processing or combining with a so-called condensing sheet, the luminance in a specific direction can be increased by condensing light in a specific direction, for example, 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, the substrate may be formed with a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded, and the pitch is randomly changed. The shape may be other shapes. 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 strip-shaped substrate>
A polyethylene terephthalate film (Teijin-DuPont film, hereinafter abbreviated as PET) having a thickness of 100 μm, a width of 200 mm, and a length of 500 m was prepared. In addition, in order to indicate the position where the first electrode and the second electrode take-out electrode are formed in advance, the alignment mark is placed on the same position on the surface on which the first electrode is formed and the opposite surface. Provided.

(Formation of first electrode and second electrode extraction electrode)
Using the apparatus shown in FIG. 3, an alignment mark attached to the prepared PET is detected, and according to the position of the alignment mark, ITO (indium having a thickness of 120 nm is formed on the PET under a vacuum environment condition of 5 × 10 ⁻¹ Pa. Tin oxide) is formed into a mask pattern by sputtering, and a 12 mm × 5 mm first electrode having a takeout electrode and a 10 mm × 3 mm second electrode takeout electrode are continuously arranged in 12 rows at regular intervals. Was formed and temporarily wound up and stored.

(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. The viscosity of the coating liquid for forming a hole transport layer was 0.7 mPa · s. The viscosity is a value measured at 20 ° C. using a digital viscometer LVDV-I manufactured by Brookfield.

(Formation of hole transport layer)
Using the apparatus shown in FIG. 4 and FIG. 6A, after the prepared roll-shaped PET on which the first electrode and the second electrode take-out electrode are formed is subjected to charge removal treatment, the PET held on the backup roll On the entire upper surface (excluding 10 mm at both ends), use the prepared coating liquid for forming the hole transport layer as a pre-weighing type coating device, using an extrusion coating machine, and a backup roll using a piezoelectric element placed on the backup roll. The coating was carried out in a non-contact manner under the conditions shown below while applying a vibration of 10 kHz. At the same time as the start of coating, drying and heat treatment were performed in the drying section under the following conditions, and then the hole transport layer on the extraction electrode portion of the first electrode and the extraction electrode for the second electrode was removed and patterned. A PET with a hole transport layer formed was prepared and Table 1 shows 1-i. After forming the hole transport layer, it was wound up and stored once.

  For comparison, all of the samples except that the coating liquid for forming the hole transport layer was applied to the backup roll without applying vibration was No. A PET having a hole transport layer formed by coating and drying under the same conditions as in 1-i was prepared. Table 1 shows 1-b. In addition, in the apparatus shown in FIG. 6 (a), all except for using an apparatus in which the drying section is arranged downstream from the coating position so that the drying section can be started 5 seconds after the start of coating. A PET having a hole transport layer formed by coating and drying under the same conditions as in 1-i was prepared. It is shown in Table 1 as 1-C.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the first electrode formation side, and a contact type antistatic device was used on the back side. As the non-contact type antistatic device, a flexible AC ionizing bar MODEL4100V manufactured by Hugle Electronics Co., Ltd. was used. The contact-type antistatic device was a conductive guide roll ME-102 manufactured by Miyako Roller Industry Co., Ltd.

(Application conditions of the coating liquid for forming the hole transport layer)
As the coating conditions, the supply amount of the coating liquid for forming the hole transport layer is 18 ml / min, the coating speed is 5 m / min, the coating width is 180 mm, the temperature at the coating of the coating liquid for forming the hole transport layer is 25 ° C., and the dew point temperature − It was carried out under an atmospheric pressure of N ₂ gas environment of 20 ° C. or less and with a cleanliness class 5 or less (JIS B 9920). The thickness of the coating film immediately after application was 20 μm. The amplitude of vibration applied to the backup roll was 60% with respect to the thickness of the coating film immediately after coating. The thickness of the coating film immediately after coating indicates a value obtained by calculation from the supply amount of the coating liquid for forming the hole transport layer, the coating speed, and the coating width. The amplitude indicates a value measured using a laser displacement sensor LK-G15 manufactured by Keyence Corporation. The degree of pressure reduction on the upstream side when coating was set to −100 Pa with respect to the downstream side. The degree of vacuum indicates a value measured using a pressure sensor AP-C40 manufactured by Keyence Corporation.

  The conveyance speed was 5 m / min. The conveyance speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.

Drying and Heating Treatment Conditions Drying and heating treatment conditions for the coating film for forming the hole transport layer are as follows: After applying the coating liquid for forming the hole transport layer, the drying apparatus shown in FIG. After removing the solvent at a height of 100 mm from the slit nozzle type discharge port of the drying apparatus toward the film formation surface, a discharge wind speed of 1 m / s, a wide wind speed distribution of 5%, and a temperature of 120 ° C., a heat treatment apparatus is then continued. Then, a heat treatment of the back surface heat transfer method was performed at a temperature of 150 ° C. to form a hole transport layer.

(Pattern of hole transport layer)
According to the flow shown in FIG. 7, the alignment mark attached to the PET is detected, and the hole transport layer formed on the PET according to the position of the alignment mark, on the extraction electrode portion of the first electrode, for the second electrode After applying the solvent which melt | dissolves a positive hole layer on the extraction electrode and the unnecessary part of the circumference | surroundings of a 1st electrode with an inkjet, the positive hole transport layer was removed by the method of wiping off.

(Preparation of light emitting layer forming coating solution)
Dicarbazole derivative (CBP) 1.00% by mass
Iridium complex (Ir (ppy) ₃ ) 0.05% by mass
Toluene 98.95% by mass
The viscosity of the light emitting layer forming coating solution was 0.59 mPa · s. The viscosity is a value measured at 20 ° C. using a Brookfield Digital Viscometer LVDV-I.

(Formation of light emitting layer)
Using the same apparatus as the apparatus shown in FIG. 4 and the apparatus shown in FIG. After the 1-a is charged and removed, the prepared light emitting layer forming coating solution is exposed as a pre-weighing type coating device at a temperature of 25 ° C. on the entire upper surface of PET (except 10 mm at both ends) under the following conditions. It applied | coated, applying the vibration of 10 kHz to a backup roll with the piezo element arrange | positioned to the backup roll non-contactingly using the rouge application | coating machine. After coating, after drying and heat treatment in the drying section under the conditions shown below, the light emission on the extraction electrode portion of the first electrode and the extraction electrode for the second electrode is removed to form a patterned emission layer A PET was prepared and Table 1 shows 1-a. After forming the light emitting layer, it was wound up and stored.

  As a comparison, a roll-shaped PET having a prepared hole transport layer and a No. 1 layer was formed. No. 1 except that the light emitting layer forming coating liquid was applied without applying vibration to the backup roll after the charge removal treatment of 1-b. A PET having a light emitting layer formed under the same conditions as in 1-a was prepared. It is shown in Table 2 as 1-b. In addition, PET having a hole transport layer formed therein, No. Other than using 1-c after the electrification removal treatment, the apparatus shown in FIG. 6A uses a device in which the drying unit is arranged downstream from the coating position so that the drying unit can be started 5 seconds after the start of coating. No. A PET having a light emitting layer formed under the same conditions as in 1-a was prepared. It is shown in Table 2 as 1-c.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the hole transport layer side, and a contact type antistatic device was used on the back side. The non-contact type antistatic device and the tactile type antistatic device were the same as those used for forming the hole transport layer.

(Application conditions of the light emitting layer forming coating solution)
As the coating conditions, the supply amount of the light emitting layer forming coating solution is 18 ml / min, the coating speed is 5 m / min, the coating width is 180 mm, the temperature at the time of coating the light emitting layer forming coating solution is 25 ° C., and the dew point temperature is −20 ° C. or lower. It was carried out under the atmospheric pressure of N ₂ gas environment and with a cleanliness class of 5 or less (JIS B 9920). It was applied so that the thickness of the coating film immediately after application was 20 μm. The thickness of the coating film immediately after coating indicates a value obtained by calculation from the supply amount of the coating solution for forming the light emitting layer, the coating speed, and the coating width. The amplitude of vibration applied to the backup roll was 60% with respect to the thickness of the coating film immediately after coating. The amplitude indicates a value measured using a laser displacement sensor LK-G15 manufactured by Keyence Corporation. The degree of pressure reduction on the upstream side when coating was set to −100 Pa with respect to the downstream side. The degree of vacuum indicates a value measured using a pressure sensor AP-C40 manufactured by Keyence Corporation.

  The conveyance speed was 5 m / min. The conveyance speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.

Drying and Heating Treatment Conditions Drying and heating treatment conditions for the light emitting layer forming coating film were applied with the light emitting layer forming coating solution, and then the drying device shown in FIG. 6A was used. After removing the solvent at a height of 100 mm from the slit nozzle type discharge port toward the film-forming surface, a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 120 ° C., the temperature is subsequently 150 ° C. by a heat treatment apparatus. Then, a heat treatment of the back surface heat transfer method was performed to form a light emitting layer.

(Light emitting layer patterning)
The alignment mark attached to the PET is detected according to the flow shown in FIG. 7, and the second electrode extraction electrode is formed on the first electrode extraction electrode portion of the light emitting layer formed on the PET according to the position of the alignment mark. After applying a solvent for dissolving the light emitting layer on the top and the periphery of the first electrode by inkjet, the light emitting layer was removed by wiping, and the light emitting layer was patterned.

(Production of organic EL panel)
Using the process shown in FIG. 5, PET No. 1 formed up to the light emitting layer prepared under the conditions shown below. An electron transport layer, a cathode buffer layer (electron injection layer), a second electrode, and a sealing layer are sequentially formed on the light emitting layers 1-a to 1-c and cut to produce an organic EL panel. 101-103.
(Formation of electron transport layer)
The roll-shaped PET No. 1 formed up to the prepared patterned light emitting layer was formed. Alignment marks attached to 1-a to 1-c are detected, and, according to the position of the alignment mark, except for the extraction electrode for the first electrode and the extraction electrode for the second electrode, 5 is deposited on the light emitting layer by a vapor deposition apparatus. The electron transport layer was formed under vacuum environment conditions of × 10 ⁻⁴ Pa. A mask pattern was formed by vapor deposition using Alq ₃ as a forming material, and an electron transport layer having a thickness of 40 nm was laminated.

(Formation of cathode buffer layer (electron injection layer))
A roll-shaped PET No. in which the prepared light emitting (electron transporting) layer is prepared. Alignment marks attached to 1-a to 1-c are detected, and on the light emitting (electron transport) layer, except for the extraction electrode for the first electrode and the extraction electrode for the second electrode, according to the position of the alignment mark, In a vacuum environment condition of 5 × 10 ⁻⁴ Pa in a vapor deposition apparatus, LiF was used as a cathode buffer layer (electron injection layer) layer forming material, a mask pattern was formed by vapor deposition, and a 0.5 nm thick cathode buffer A layer (electron injection layer) was laminated.

(Formation of second electrode)
Subsequently, an alignment mark attached to the PET formed up to the cathode buffer layer (electron injection layer) is detected, and the size of the first electrode is formed on the cathode buffer layer (electron injection layer) formed according to the position of the alignment mark. The aluminum is used as the second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa in accordance with the size that can contact the second electrode and the second electrode, and the second electrode is formed on the first electrode and the second electrode. A mask pattern was formed by vapor deposition so as to be connected, and a second electrode having a thickness of 100 nm was laminated to produce an organic EL element.

(Applying adhesive)
An alignment mark affixed to the PET of the produced organic EL element is detected, and an ultraviolet curable type is formed around the light emitting region and the light emitting region except for the end portions of the first electrode and the second electrode extraction electrode according to the position of the alignment mark. A liquid adhesive (epoxy resin type) was used, and the coating was applied at a thickness of 30 μm.

(Pasting of sealing member)
Thereafter, the belt-like sheet sealing member shown below was prepared by stacking on the adhesive-coated surface of the organic EL element by a roll laminator method, and after roll-bonding at a pressure of 0.1 MPa in an atmospheric pressure environment, a wavelength of 365 nm The high-pressure mercury lamp was irradiated and adhered for 1 minute at an irradiation intensity of 5 to ²⁰ mW / cm ² and a distance of 5 to 15 mm, and a plurality of organic EL panels were continuously connected.

(Preparation of sealing member)
A two-layer belt-like sheet sealing member using a PET film (manufactured by Teijin DuPont) as the sealing member and using an inorganic film (SiN) as a barrier layer was prepared. The thickness of PET was 100 μm, and the thickness of the barrier layer was 200 nm. Incidentally, the barrier layer of the PET film was formed by a sputtering method. The water vapor permeability measured by the MOCON method mainly by the method based on JIS K-7129B method (1992) was 0.01 g / m ² · day. The oxygen permeability measured mainly by the MOCON method by a method based on JIS K7126B method (1987) was 0.1 ml / m ² · day · MPa.

(Cutting)
In the state in which a plurality of prepared organic EL panels are continuously connected, the alignment mark attached to the PET in the size of the individual organic EL panel was detected, and cut according to the position of the alignment mark.

Evaluation Each sample No. 101 to 103, samples were extracted from the beginning 5 m and the end 5 m, the leakage current characteristics and the light emission unevenness (luminance unevenness) were tested by the following test methods, and the results evaluated according to the following evaluation rank Table 3 shows.

Test Method for Leakage Current Characteristics Using a constant voltage power source, a reverse voltage (reverse bias) was applied at 5 V for 5 seconds, and the current flowing through the organic EL element at that time was measured. Measurement was performed on the light emission region of 10 samples, and the maximum current value was defined as a leakage current.

Evaluation rank of leakage current characteristics A: Maximum current value is less than 1 × 10 ⁻⁶ A ○: Maximum current value is 1 × 10 ⁻⁶ A or more and less than 1 × 10 ⁻⁵ A Δ: Maximum current value is 1 × 10 ^{− 5} A or more, less than 1 × 10 ⁻³ A ×: Maximum current value is 1 × 10 ⁻³ A or more Measuring method of light emission unevenness (luminance unevenness) Using a constant voltage power supply, DC 5 V is applied to the organic EL panel, The luminance difference at the six light emitting portions in the center of the sample was visually observed.

Evaluation rank of light emission unevenness (brightness unevenness) A: There is no difference in brightness.

○: The luminance at one location is different among six locations. Δ: The luminance at two locations or more and less than four locations is different among six locations. X: The luminance at four locations or more is different in six cells.

  The coating liquid for forming the hole transport layer and the coating liquid for forming the light-emitting layer were applied while applying vibration to the backup roll, and drying was started simultaneously with the application to the PET in contact with the backup roll. No. 101 has been confirmed to be capable of producing a stable organic EL panel having good leakage current characteristics and little light emission unevenness (luminance unevenness).

  The organic EL panel No102 produced by applying the hole transport layer forming coating liquid and the light emitting layer forming coating liquid without applying vibration to the backup roll and starting drying simultaneously with the application to the PET in contact with the backup roll. As a result, the leak current characteristics were inferior to those of the organic EL panel No. 101, and there were many light emission irregularities (luminance irregularities).

  The coating liquid for forming the hole transport layer and the coating liquid for forming the light-emitting layer were applied while applying vibration to the backup roll, and drying was started 5 seconds after the application, and then the organic EL panel No. 1 was prepared. 103 is an organic EL panel No. The results showed that there were more leakage current characteristics and light emission unevenness (luminance unevenness) than 101. The effectiveness of the present invention was confirmed.

Example 2
<Preparation of strip-shaped substrate>
The same belt-like substrate as in Example 1 was prepared.

(Formation of the first electrode)
Using the apparatus shown in FIG. 3, the prepared first PET electrode having the extraction electrode and the second electrode extraction electrode were continuously formed under the same conditions as in Example 1 using the prepared PET, and then wound up and stored.

(Preparation of coating solution for hole transport layer formation)
A coating liquid for forming a hole transport layer having the same composition as in Example 1 was prepared.

(Formation of hole transport layer)
Using the apparatus shown in FIG. 4 and FIG. 6A, after removing the charged PET in the form of the prepared first electrode up to the first electrode, the thickness immediately after coating is changed as shown in Table 4. Other than the above, PET No. 1 formed up to the hole transport layer of Example 1 was used. After applying the prepared coating solution for hole transport layer formation under the same conditions as in 1-a, drying with and without vibration until the constant rate drying process with a drying apparatus, and performing heat treatment, the first electrode On the extraction electrode portion, the hole transport layer of the second electrode extraction electrode was removed, and a PET having a patterned hole transport layer was prepared. 2-a to 2-n. After forming the hole transport layer, it was wound up and stored once.

(Charge removal treatment)
PET in which the hole transport layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as in 1-a.

(Application conditions of the coating liquid for forming the hole transport layer)
As coating conditions, PET having a hole transport layer up to Example 1 and No. 1 were formed. The conditions were the same as for 1-i. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Drying and heat treatment conditions)
As a drying treatment condition for the coating film for forming the hole transport layer, after applying the coating liquid for forming the hole transport layer, drying was started immediately after coating using the drying apparatus shown in FIG. In the case of applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used, and vibration of 10 kHz was applied. The other conditions were as follows: PET having a hole transport layer up to Example 1; The test was performed under the same conditions as in 1-i. The heating conditions were PET No. 1 up to the hole transport layer of Example 1. The test was performed under the same conditions as in 1-i.

(Pattern of hole transport layer)
In the same manner as in Example 1, unnecessary hole transport layers on the extraction electrode portion of the first electrode, on the second electrode extraction electrode, and around the hole transport layer were removed and patterned.

(Preparation of light emitting layer forming coating solution)
A light emitting layer forming coating solution having the same composition as in Example 1 was prepared.

(Formation of light emitting layer)
Rolled PET having a prepared hole transport layer up to the prepared hole transport layer, After the electrification removal treatment of 2-a to 2-n, as shown in Table 5, except that the thickness immediately after coating was changed, PET having the light emitting layer of Example 1 formed thereon, After applying the light-emitting layer-forming coating solution prepared under the same conditions as 1-a, drying with and without vibration until the constant rate drying process with a drying apparatus, and performing heat treatment, the extraction electrode portion of the first electrode On the other hand, the luminescent layer of the second electrode take-out electrode was removed, and a PET having a patterned luminescent layer was prepared. 2-A to 2-N. After forming the light emitting layer, it was wound up and stored.

(Charge removal treatment)
PET on which the light emitting layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as 1-a.

(Application conditions of the light emitting layer forming coating solution)
As coating conditions, PET having the light emitting layer of Example 1 formed, The conditions were the same as for 1-a. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Drying and heat treatment conditions)
As drying conditions for the light-emitting layer-forming coating film, after applying the light-emitting layer-forming coating solution, drying was started immediately after coating using the drying apparatus shown in FIG. In the case of applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used, and vibration of 10 kHz was applied. Other conditions were as follows: PET No. 1 formed up to the light emitting layer of Example 1. It was performed under the same conditions as 1-a. The heating conditions were PET No. 1 up to the light emitting layer of Example 1. It was performed under the same conditions as 1-a.

(Light emitting layer patterning)
The same method as in Example 1 was performed, and the light-emitting layer on the extraction electrode portion of the first electrode, the extraction electrode for the second electrode, and unnecessary portions around the first electrode was removed and patterned.

(Production of organic EL panel)
Using the process shown in FIG. 5, PET No. 1 in which up to the light emitting layer prepared under the same conditions as in Example 1 was formed. A cathode buffer layer (electron injection layer), a second electrode, and a sealing layer are sequentially formed on the light emitting layers 2-A to 2-N and cut to produce an organic EL panel. 201-214.

Evaluation Each sample No. 201 to 214, samples are extracted from the beginning 5 m and end 5 m, leakage current characteristics and emission unevenness (luminance unevenness) are tested by the same test method as in Example 1, and according to the same evaluation rank as Example 1. Table 6 shows the evaluation results.

  The thickness of the coating film for forming the positive hole transport layer and the coating film for forming the light emitting layer immediately after coating is applied to the PET of the belt-like substrate held on the backup roll using an extrusion coating machine as the pre-metering type coating device. Sample No. 2 was prepared by applying while applying vibration with a piezoelectric element of vibration means arranged on the backup roll instead of 24 μm. Nos. 203 to 212 were able to produce organic EL panels that were stable in both leakage current characteristics and light emission unevenness (luminance unevenness). In addition, even when drying, sample No. 1 produced by applying vibration to the constant rate drying process. Nos. 203, 205, 207, 209, and 211 are sample Nos. Produced without applying vibration until the constant rate drying process. For 204, 206, 208, 210, and 212, it was confirmed that an organic EL panel having more stable leakage current characteristics and light emission unevenness (luminance unevenness) can be manufactured. Sample No. 1 was prepared with the thickness of the coating film for forming the hole transport layer and the coating film for forming the light emitting layer immediately after coating being 26 μm. In Nos. 213 and 214, the drying load was increased, resulting in some poor drying, and both leakage current characteristics and light emission unevenness (luminance unevenness) were somewhat affected. The effectiveness of the present invention was confirmed.

Example 3
<Preparation of strip-shaped substrate>
The same belt-like substrate as in Example 1 was prepared.

(Formation of first electrode and second electrode extraction electrode)
Using the apparatus shown in FIG. 3, the prepared first PET electrode having the extraction electrode and the second electrode extraction electrode were continuously formed under the same conditions as in Example 1 using the prepared PET, and then wound up and stored.

(Preparation of coating solution for hole transport layer formation)
A coating liquid for forming a hole transport layer having the same composition as in Example 1 was prepared.

(Formation of hole transport layer)
Using the apparatus shown in FIG. 4 and FIG. 6A, after the prepared roll-shaped PET formed up to the first electrode and the second electrode take-out electrode is subjected to charge removal treatment, as shown in Table 7 Other than changing the amplitude of vibration applied to the backup roll, PET No. 1 formed up to the hole transport layer of Example 1 was used. After applying the prepared coating solution for hole transport layer formation under the same conditions as in 1-a, drying with and without vibration until the constant rate drying process with a drying apparatus, and performing heat treatment, the first electrode The hole transport layer on the take-out electrode portion and the second electrode take-out electrode was removed, and a PET having a patterned hole transport layer was prepared. 3-a to 3-j. After forming the hole transport layer, it was wound up and stored once.

(Application conditions of the coating liquid for forming the hole transport layer)
As coating conditions, PET having a hole transport layer up to Example 1 and No. 1 were formed. The conditions were the same as for 1-i. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Charge removal treatment)
PET in which up to the hole transport layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as in 1-a.

(Drying and heat treatment conditions)
As a drying treatment condition for the coating film for forming the hole transport layer, after applying the coating liquid for forming the hole transport layer, drying was started immediately after coating using the drying apparatus shown in FIG. In the case of applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used, and vibration of 10 kHz was applied. The other conditions were PET No. 1 up to the hole transport layer of Example 1. The test was performed under the same conditions as in 1-i. The heating conditions were PET No. 1 up to the hole transport layer of Example 1. The test was performed under the same conditions as in 1-i.

(Pattern of hole transport layer)
The same method as in Example 1 was performed, and the hole transport layer on the extraction electrode portion of the first electrode, the extraction electrode for the second electrode, and unnecessary portions around the first electrode were removed and patterned.

(Preparation of light emitting layer forming coating solution)
A light emitting layer forming coating solution having the same composition as in Example 1 was prepared.

(Formation of light emitting layer)
PET in which the prepared hole transport layer is formed, No. After the electrification removal treatment of 3-a to 3-j, as shown in Table 8, except for changing the amplitude of vibration to be applied to the backup roll, PET No. 3 in which the light emitting layer of Example 1 was formed was formed. After applying the prepared light emitting layer forming coating solution under the same conditions as 1-a, drying with and without vibration until a constant rate drying process with a drying apparatus, and performing heat treatment, the extraction electrode of the first electrode The PET layer on which the light emitting layer on the part and the extraction electrode for the second electrode was removed to form a patterned light emitting layer was prepared. 3-A to 3-J. After forming the light emitting layer, it was wound up and stored.

(Application conditions of the light emitting layer forming coating solution)
As coating conditions, PET having a light-emitting layer up to Example 1 and No. 1 were formed. The conditions were the same as for 1-a. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Charge removal treatment)
PET in which up to the light emitting layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as 1-a.

(Drying and heat treatment conditions)
As a drying process condition of the light emitting layer forming coating film, after applying the light emitting layer forming coating solution, drying was started immediately after coating using the drying apparatus shown in FIG. In the case of applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used, and vibration of 10 kHz was applied. Other conditions were as follows: PET No. 1 in which up to the light emitting layer of Example 1 was formed. It was performed under the same conditions as 1-a. The heating conditions were PET No. 1 in which up to the light emitting layer of Example 1 was formed. It was performed under the same conditions as 1-a.

(Light emitting layer patterning)
The same method as in Example 1 was performed, and the light emitting layer was removed and patterned on the extraction electrode portion of the first electrode, the extraction electrode for the second electrode, and unnecessary portions around the first electrode.

(Production of organic EL panel)
Using the process shown in FIG. 5, PET No. 1 in which up to the light emitting layer prepared under the same conditions as in Example 1 was formed. An electron transport layer, a cathode buffer layer (electron injection layer), a second electrode, and a sealing layer are sequentially formed on the light emitting layers 3-A to 3-J, and cut to produce an organic EL panel. 301 to 310.

Evaluation Each sample No. 301 to 310, samples are extracted from the beginning 5m and end 5m, and leakage current characteristics and light emission unevenness (luminance unevenness) are tested by the same test method as in Example 1, and according to the same evaluation rank as in Example 1. Table 9 shows the evaluation results.

  When applying while applying vibration to the PET of the belt-like base material held on the backup roll using an extrusion coating machine as a pre-weighing type coating device with the piezoelectric element of the vibration means arranged on the backup roll, the amplitude is applied immediately after coating. Sample No. produced with 30% to 70% of the coating thickness. Nos. 303 to 308 were able to produce organic EL panels having stable leakage current characteristics and light emission unevenness (luminance unevenness). In addition, even when drying, sample No. 1 produced by applying vibration to the constant rate drying process. Nos. 303, 305, and 307 are sample Nos. Produced without applying vibration until the constant rate drying process. It was confirmed that an organic EL panel having more stable leakage current characteristics and light emission unevenness (luminance unevenness) than 304, 306, and 308 can be manufactured. The effectiveness of the present invention was confirmed. The effectiveness of the present invention was confirmed.

Example 4
<Preparation of strip-shaped substrate>
The same belt-like substrate as in Example 1 was prepared.

(Formation of first electrode and second electrode extraction electrode)
Using the apparatus shown in FIG. 3, the prepared first PET electrode having the extraction electrode and the second electrode extraction electrode were continuously formed under the same conditions as in Example 1 using the prepared PET, and then wound up and stored.

(Preparation of coating solution for hole transport layer formation)
A coating liquid for forming a hole transport layer having the same composition as in Example 1 was prepared.

(Formation of hole transport layer)
Using the apparatus shown in FIG. 4 and FIG. 6A, after the prepared roll-shaped PET formed up to the first electrode and the second electrode take-out electrode is subjected to charge removal treatment, as shown in Table 10 Other than changing the frequency of vibration applied to the backup roll, PET No. 1 formed up to the hole transport layer of Example 1 was used. After applying the prepared coating solution for hole transport layer formation under the same conditions as in 1-a, drying with and without vibration until the constant rate drying process with a drying apparatus, and performing heat treatment, the first electrode The hole transport layer on the take-out electrode portion and the second electrode take-out electrode was removed, and a PET having a patterned hole transport layer was prepared. 4-a to 4-l. After forming the hole transport layer, it was wound up and stored once.

(Application conditions of the coating liquid for forming the hole transport layer)
As coating conditions, PET having a hole transport layer up to Example 1 and No. 1 were formed. The conditions were the same as for 1-i. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Charge removal treatment)
PET in which the hole transport layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as in 1-a.

(Drying and heat treatment conditions)
As drying treatment conditions for the coating film for forming the hole transport layer, after applying the coating liquid for forming the hole transport layer, drying was started immediately after the coating using the drying apparatus shown in FIG. When applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used to apply vibration of 10 kHz. The other conditions were PET No. 1 up to the hole transport layer of Example 1. The test was performed under the same conditions as in 1-i. The heating conditions were PET No. 1 up to the hole transport layer of Example 1. The test was performed under the same conditions as in 1-i.

(Pattern of hole transport layer)
The same method as in Example 1 was performed, and the hole transport layer of unnecessary portions on and around the first electrode extraction electrode portion and the second electrode extraction electrode and around the first electrode was removed and patterned.

(Preparation of light emitting layer forming coating solution)
A light emitting layer forming coating solution having the same composition as in Example 1 was prepared.

(Formation of light emitting layer)
The PET No. in which the prepared hole transport layer is formed. After the electrification removal treatment of 4-a to 4-l, as shown in Table 11, except for changing the amplitude of vibration applied to the backup roll, PET No. After applying the prepared light emitting layer forming coating solution under the same conditions as 1-a, drying with and without vibration until a constant rate drying process with a drying apparatus, and performing heat treatment, the extraction electrode of the first electrode The light emitting layer on the part and the second electrode take-out electrode was removed, and a PET having a patterned light emitting layer formed thereon was prepared. 4-A to 4-L. After forming the light emitting layer, it was wound up and stored.

(Application conditions of the light emitting layer forming coating solution)
As coating conditions, PET having a light-emitting layer up to Example 1 and No. 1 were formed. The conditions were the same as for 1-a. The thickness, vibration frequency, amplitude, the degree of pressure reduction on the upstream side when coating, and the conveyance speed were measured by the same method as in Example 1.

(Charge removal treatment)
PET in which up to the light emitting layer of Example 1 was formed, The charge removal treatment was performed under the same conditions as 1-a.

(Drying and heat treatment conditions)
As a drying process condition of the light emitting layer forming coating film, after applying the light emitting layer forming coating solution, drying was started immediately after coating using the drying apparatus shown in FIG. In the case of applying vibration up to the constant rate drying process, a piezoelectric element disposed on the transport roll was used, and vibration of 10 kHz was applied. Other conditions were as follows: PET No. 1 in which up to the light emitting layer of Example 1 was formed. It was performed under the same conditions as 1-a. The heating conditions were PET No. 1 in which up to the light emitting layer of Example 1 was formed. It was performed under the same conditions as 1-a.

(Light emitting layer patterning)
The same method as in Example 1 was performed, and the light emitting layer was removed and patterned on the extraction electrode portion of the first electrode, the extraction electrode for the second electrode, and unnecessary portions around the first electrode.

(Production of organic EL panel)
Using the process shown in FIG. 5, PET having a light emitting layer prepared under the same conditions as in Example 1 was formed. An electron transport layer, a cathode buffer layer (electron injection layer), a second electrode, and a sealing layer are sequentially formed on the light emitting layers of 4-A to 4-L, and cut to produce an organic EL panel. 401 to 412.

Evaluation Each sample No. Reference numerals 401 to 412, samples are extracted from the beginning 5m and end 5m, and leakage current characteristics and light emission unevenness (luminance unevenness) are tested by the same test method as in Example 1, and according to the same evaluation rank as in Example 1. Table 12 shows the evaluation results.

  When applying an application to a PET strip of a belt-like substrate held on a backup roll using a piezo element of a vibration means provided on the backup roll using an extrusion coater as a pre-weighing type coating apparatus, the vibration frequency is 1. Sample No. manufactured at 0 kHz to 20.0 kHz. Nos. 403 to 410 were able to produce organic EL panels that were stable in both leakage current characteristics and light emission unevenness (luminance unevenness). In addition, when drying, Sample No. produced by applying vibration to the constant rate drying process. Samples Nos. 403, 405, 407, and 409, which were prepared without applying vibration until the constant rate drying process when dried. It was confirmed that an organic EL panel having more stable leakage current characteristics and light emission unevenness (luminance unevenness) than that of 404, 406, 408, and 410 can be manufactured. Sample No. manufactured with a frequency of 0.8 kHz. 401 and 402 did not fully reflect the effect of vibration. In addition, the sample No. manufactured with a frequency of 30 kHz was used. In 411 and 412, the vibration was too strong, and the coating film was roughened, resulting in somewhat inferior results. The effectiveness of the present invention was confirmed.

It is the schematic which shows an example of the organic electroluminescent panel used for illumination. It is a schematic diagram which shows an example of the manufacturing process which manufactures the organic EL panel shown in FIG. 1 using a strip | belt-shaped base material. It is a schematic diagram until the supply process shown in FIG. 2, and the extraction electrode formation process for 1st electrodes and 2nd electrodes. It is a schematic diagram of the positive hole transport layer formation process shown in FIG. FIG. 3 is a schematic diagram after the cathode buffer layer (electron injection layer) forming step shown in FIG. 2. FIG. 5 is an enlarged schematic view of a portion indicated by X in FIG. 4. FIG. 5 is a schematic flow diagram showing patterning of a hole transport layer in the hole transport layer forming step shown in FIG. 4.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic electroluminescent panel 101 Flexible base material 102 Anode (1st electrode)
103 hole transport layer 104 light emitting layer 105 electron transport layer 106 cathode buffer layer (electron injection layer)
107 Cathode (second electrode)
DESCRIPTION OF SYMBOLS 108 Adhesive layer 109 Sealing member 2 Manufacturing process 202 1st electrode formation process 203 Hole transport layer formation process 203b1 Coating apparatus 203b2 Backup roll 203b3 Vibration means 203b13 Decompression chamber 203b131 Suction tube 203c1 Drying apparatus 203d Pattern formation part 204 Light emitting layer formation Process 205 Electron Transport Layer Forming Process 206 Cathode Buffer Layer (Electron Injection Layer) Forming Process 206b Vapor Deposition Device 206c Evaporation Source Container 207 Second Electrode Forming Process 208 Sealing Process

Claims (9)

At least one layer of organic material on a belt-like substrate that is held by a holding member and continuously conveyed using at least a pre-metering type coating device that continuously discharges a coating liquid from a slit and a drying device In a coating method in which a coating liquid for forming an organic compound layer for forming a compound layer is applied in a non-contact manner using the coating device,
The drying device is arranged so that drying of the belt-shaped substrate in contact with the holding member can be started at least before the application,
The holding member has vibration means,
The application of the organic compound layer forming coating solution is performed while vibrating the holding member by the vibrating means,
And the said drying is performed simultaneously with the start of the said application | coating, The coating method of the coating liquid for organic compound layer formation characterized by the above-mentioned. The said drying is started while the strip | belt-shaped base material is contacting the holding member, The coating method of the coating liquid for organic compound layer formation of Claim 1 characterized by the above-mentioned. 3. The drying according to claim 1, wherein the coating is formed by applying an organic compound layer-forming coating solution on a band-shaped substrate, and vibration is applied until the constant rate drying process is completed. Coating method for forming an organic compound layer. The said organic compound layer is an organic compound layer of an organic electroluminescent panel, The coating method of the coating liquid for organic compound layer formation of any one of Claims 1-3 characterized by the above-mentioned. The thickness at the time of application | coating of the coating film formed by apply | coating the said coating liquid for organic compound layer formation on a base material is 2 micrometers-24 micrometers, In any one of Claims 1-4 characterized by the above-mentioned. The coating method of the coating liquid for organic compound layer formation of description. 6. The coating method for a coating liquid for forming an organic compound layer according to claim 1, wherein the vibration means is a piezo element. The amplitude of vibration by the vibrating means is 30% to 70% of the film thickness of a coating film immediately after coating for applying a coating liquid for forming an organic compound layer and forming the formed organic compound layer. Item 7. A coating method of the coating solution for forming an organic compound layer according to any one of Items 1 to 6. The coating method of the coating liquid for forming an organic compound layer according to any one of claims 1 to 7, wherein the vibration frequency of the vibration means is 1.0 kHz to 20.0 kHz. The coating device has an upstream side of the substrate transporting the decompression chamber, and when the coating solution for forming an organic compound layer is coated on the substrate by the coating device, the coating position of the strip-shaped substrate by the decompression chamber The coating method of the coating liquid for forming an organic compound layer according to any one of claims 1 to 8, wherein the upstream side is depressurized more than the downstream side.

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