JP2011241015A - Method for conveying strip-like flexible support, and method of manufacturing organic electronics element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for conveying a strip-like flexible support by which conveyance fault due to buckling does not occur when conveying the strip-like flexible support by holding both ends of the strip-like flexible support using, as conveying rolls, the conveying rolls each having a stepped-up part on both ends thereof in the environment isolated from outside air, and to provide a method of manufacturing the organic electronics element using the method of conveying the strip-like flexible support.SOLUTION: There is provided the method for continuously conveying the strip-like flexible support bodies in which the strip-like flexible support is conveyed by holding both ends of the strip-like flexible support by receiving units using, as conveying rolls, the conveying rolls each having the stepped-up part as the receiving unit on both ends of a barrel thereof, in the environment isolated from outside air. Here, the flexible support is formed of a resin film, and a ratio of a height of the receiving unit of the conveying roll having the stepped-up parts from a surface of a central part of the barrel of the conveying roll having the stepped-up parts to a width of the receiving unit is 0.004 to 0.03.

Description

  The present invention relates to a method for transporting a strip-shaped flexible support by a stepped transport roll having receiving portions that hold both ends of the strip-shaped flexible support at both ends, and a method for manufacturing an organic electronics element using this transport method. More specifically, when a film-formed surface in an environment shielded from outside air is conveyed in a non-contact manner by a stepped conveyance roll having a receiving portion for holding both ends of the belt-like flexible support at both ends, the belt-like is allowed. The present invention relates to a transport method that prevents a transport stop due to buckling of a flexible support, and a method for manufacturing an organic electronics element using the transport method.

  Conventionally, as a transport method for transporting the belt-like flexible support that continuously travels in a non-contact manner, a transport method in which the belt-like flexible support is lifted and transported by blowing air, received at both ends holding the end of the belt-like flexible support. A transport method using a stepped transport roll having a section (hereinafter also simply referred to as a stepped transport roll) is known.

  The non-contact conveyance method avoids failures due to scratches and dust adhering to the coating surface, for example, optical films, ink jet recording paper, heat development recording materials, organic electroluminescence elements (hereinafter also referred to as organic EL elements). And organic thin film transistor elements, organic solar cell elements (hereinafter also referred to as organic PV elements), organic photoelectric conversion elements, and other various organic electronic elements.

  Organic electronics devices are devices that perform electrical operations using organic compounds, and are expected to exhibit features such as energy saving, low cost, and flexibility, and are attracting attention as a technology that replaces conventional inorganic semiconductors based on silicone. Has been. These organic electronics elements are elements that emit light, generate electric power, charge, or control current and voltage by passing a current through an electrode through a very thin film of an organic compound.

  An organic EL element has a structure in which a light emitting layer made of an organic compound thin film is sandwiched between electrodes, and emits light when a current is supplied between a first electrode (anode or cathode) and a second electrode (anode or cathode). Therefore, when a thin-film organic EL element is used as a light source, it is easy to reduce the size and weight, and the illuminating device has a faster light emission response speed than a fluorescent lamp and a relatively stable light amount immediately after lighting.

  The organic EL element is generally manufactured by film formation by a vapor deposition method, but it is desired to manufacture by an application method in order to improve productivity and reduce manufacturing costs.

  An organic PV element and an organic photoelectric conversion element are elements that generate power when irradiated with light, with a power generation layer made of a thin film of an organic compound sandwiched between a first electrode (anode or cathode) and a second electrode (anode or cathode). is there. Therefore, when a thin-film organic photoelectric conversion element is used as a solar cell, it can be easily reduced in size and weight, and has a relatively stable output even in a low illuminance environment or a high temperature environment as compared with an existing inorganic semiconductor solar cell. The solar cell can be obtained.

  For example, an organic EL element has a thin film layer of a nanometer unit such as an organic molecule, a polymer or an organometallic complex on a light transmissive electrode, for example, ITO (indium tin oxide), and finally a thin film electrode layer. It is obtained by forming. However, even if all the thicknesses of these thin films are combined, the total film thickness is less than 1.0 μm, and it is a very thin multilayer structure thin film, that is, a laminate of functional thin films. Therefore, excellent flatness is required for the support before forming the thin film. In addition, when an organic EL element is formed with foreign matters, protrusions, scratches, creases, cracks, etc. on the support, the light emission current increases or does not emit light due to a short (so-called leakage) when a voltage is applied. There is.

  For this reason, for example, Japanese Patent Application Laid-Open No. 2006-294536 discloses that at least a first electrode, a hole transport layer, a light emitting layer, and an electron injection layer are provided on a belt-like flexible support. In order to prevent the adhesion of foreign matters when manufacturing an organic EL device having a formed body of the second electrode and a sealing layer or a sealing film in this order by a roll-to-roll method, A method is disclosed in which a take-up auxiliary member is wound under an environmental condition of cleanliness class 5 or less in accordance with JIS B 9920. In WO 06/100908, when manufacturing an organic EL device having a configuration of a first electrode / organic compound layer / second electrode on a strip-shaped flexible support, a strip shape is used to prevent adhesion of foreign matters. Discharge process of the flexible support is disposed, the organic compound layer has a dew point temperature of −20 ° C. or less, conforms to JIS B 9920, has an environmental condition of cleanliness of class 5 or less, and a drying section and A method of forming under an atmospheric pressure condition of 10 ° C. to 45 ° C. except for the heat treatment part is disclosed.

  However, manufacturing with a small amount of foreign matter attached is expensive in equipment, and even if foreign matter is attached, a manufacturing method with little secondary influence such as scratches caused by the foreign matter has been demanded.

  Japanese Patent Application Laid-Open No. 2007-42315 discloses that a belt-like flexible support is conveyed in a non-contact manner in a process of forming an organic EL element by a roll-to-roll method.

  In addition, as a countermeasure against scratches, a guide roll mechanism that uses a stepped transport roll that does not cause scratches on the support or film formation surface in a production process in which a thin film is formed on a belt-like flexible support by a roll-to-roll method under vacuum. A built-in vacuum film forming apparatus and a method for producing a highly productive organic electroluminescence element with improved light emission lifetime using the same are disclosed (for example, see Patent Document 1).

However, it has been found that when the guide roll mechanism using the stepped transport roll described in Patent Document 1 is used, there are the following drawbacks.
1) One of the characteristics of the organic electronics element is that a conductive film having a different contraction rate from the resin film is patterned as an electrode on the belt-like flexible support, which is a resin film. As a result, the flatness of the belt-like flexible support deteriorates. For this reason, in order to maintain the flatness of the belt-like flexible support and to obtain a uniform film during film formation, it is necessary to carry it with a tension as high as possible. However, when tension is applied to the belt-shaped flexible support, the belt-shaped flexible support is sometimes buckled at the non-contact portion of the stepped transport roll, resulting in a conveyance failure.
2) A location where buckling has occurred becomes a breakage and causes abnormal performance.
3) In order to correct buckling, it is necessary to interrupt the conveyance and re-apply the buckling part. In accordance with this, the inert gas atmosphere or vacuum atmosphere is returned to the outside air (atmospheric environment), and restarting is necessary. It takes time to restore the original environment, and production efficiency decreases.
4) By returning to the atmospheric environment, not only the buckled part but also its peripheral part becomes defective. In some cases, the entire original winding being processed may become defective.

  When transporting while holding both ends of the belt-shaped flexible support using a stepped transport roll as a transport roll in an environment that is cut off from the outside air from such a situation, a transport failure due to buckling occurs. It is desired to develop a method for transporting a strip-shaped flexible support and a method for producing an organic electronic device using this transport method.

JP 2009-256709 A

  The present invention has been made in view of the above situation, and its purpose is to use a stepped transport roll as a transport roll in an environment cut off from the outside air while transporting while holding both ends of the belt-like flexible support. An object of the present invention is to provide a method for transporting a belt-like flexible support that does not cause a transport failure due to buckling, and a method for manufacturing an organic electronic device using this transport method.

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

1. Using the step-shaped transport roll having a belt-shaped flexible support as a transport roll and receiving portions for receiving the band-shaped flexible support at both ends of the body portion in an environment shielded from outside air, In the method of transporting the belt-shaped flexible support that holds both ends of the conductive support in the receiving portion and continuously transports the support,
The belt-like flexible support is a resin film;
The ratio of the height from the central part of the trunk part of the receiving part of the stepped transport roll and the width between the inner surface of the receiving part and the inner surface of the receiving part is 0.004 to 0.03. A method of transporting a belt-like flexible support as a feature.

  2. In the method for manufacturing an organic electronic element having a laminated film having a structure in which at least one organic functional layer is laminated between a first electrode and a second electrode on a belt-like flexible support, A method for producing an organic electronic element, wherein the flexible support is transported by the transport method described in 1 above.

  The present invention has been made in view of the above situation, and its purpose is to use a stepped transport roll as a transport roll in an environment cut off from the outside air while transporting while holding both ends of the belt-like flexible support. Thus, it is possible to provide a method for transporting a belt-like flexible support that does not cause a transport failure due to buckling, and a method for manufacturing an organic electronic device using this transport method.

Schematic of the process of applying a coating liquid with a die coater and forming a coating film while holding both ends of a belt-like flexible support using a stepped transport roll in an environment shut off from outside air It is. It is a schematic sectional drawing in alignment with AA 'of the stepped conveyance roll used as the conveyance roll shown in FIG.1 (b). It is the schematic of the other shape of the stepped conveyance roll used as the conveyance roll shown in FIG.1 (b). It is a schematic diagram which shows the state at the time of conveying a strip | belt-shaped flexible support body using a stepped conveyance roll. It is the schematic of the organic electronics element manufactured using the conveyance method of this invention. It is the schematic of the manufacturing process which manufactures an organic EL element among organic electronics elements using the coating method shown in FIGS.

  Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 to 4, but the present invention is not limited thereto.

  FIG. 1 shows a process of forming a coating film by applying a coating solution with a die coater while holding both ends of a belt-like flexible support using a stepped transport roll in an environment shut off from the outside air. FIG.

  Fig. 1 (a) shows an environment where the outside of the belt is shielded from the outside air, and a coating film is formed by applying a coating solution using a die coater while holding both ends of a belt-like flexible support with a stepped transport roll and continuously transporting it. It is the schematic of the process to do. FIG. 1B is an enlarged schematic perspective view of a portion indicated by V in FIG.

  In the figure, reference numeral 1 denotes a step of forming a coating film by applying a coating solution using a die coater while holding both ends of a belt-like flexible support with a stepped transport roll and continuously transporting it. Step 1 is in a state of being stored in the coating chamber 2. The inside of the coating chamber 2 is an environment that is blocked from outside air. The environment blocked from the outside air is, for example, an environment in which a film susceptible to the influence of oxygen or moisture is replaced with an inert gas when forming a film on the band-shaped flexible support, vapor deposition on the band-shaped flexible support, etc. The vacuum environment in the case of forming a film by the vacuum film forming method, the high clean environment in the case of forming a film susceptible to the influence of foreign matters on the belt-like flexible support, and the like. This figure has shown the case where the application | coating chamber is substituted by the inert gas when apply | coating to a strip | belt-shaped flexible support body.

  The process 1 has the supply process 1a of the strip | belt-shaped flexible support body 3, the application | coating process 1b, the drying process 1c, and the collection | recovery process 1d.

  The supply process 1a uses an accumulator 1a1 and a feeding device (not shown). The roll-shaped flexible support 3 attached to the feeding device (not shown) is fed out and can be applied to the coating process 1b. A flexible support 3 is supplied.

  The belt-like flexible support 3 may already have a film formed on the surface, or may form a film from this. There are no particular limitations on the type of film formed, and examples include a single-layer film, a film in which a plurality of films are stacked, and a film in which a conductive substance or the like is formed in a pattern.

  The formation method and pattern shape of the film formed in a pattern are not particularly limited and can be appropriately selected as necessary. Examples of the patterned film include the first electrode or the second electrode in the case of an organic electronics element.

  The coating process 1b uses a slit type die coater 1b1 and a back roll 1b2 that holds the belt-like flexible support 3. The coating solution is held on the back roll 1b2 by the slit type die coater 1b1 and continuously conveyed. It is applied to the belt-like flexible support 3 (in the direction of the arrow in the figure) to form a wet coating film.

  The drying process 1c uses the drying apparatus 1c1, and heats and drying the strip-like flexible support 3 on which the wet coating film applied in the coating process 1b is formed, thereby forming a dry coating film. There is no limitation in particular as drying apparatus 1c1, For example, a heater heating system, a heating air system, etc. are mentioned, It is possible to select suitably as needed.

  The collection step 1d uses an accumulator 1d1 and a winding device (not shown), and collects the strip-shaped flexible support 3 on which the coating film is formed in the form of a winding roll around the core.

  The coating film is formed on the surface of the strip-shaped flexible support fed from the supply step 1a, and the strip-shaped flexible support is held and transported by the transport roll until it is collected in the form of a winding roll on the winding core in the recovery step 1d. The In the present invention, the transport roll refers to a roll that abuts on a belt-like flexible support and contributes to transport. In this figure, rolls 1f to 1i used for the accumulator 1a1 and accumulator 1d1 correspond to the transport rolls.

  The stepped transport roll 1e has a shape having a receiving portion 1e2 at one end of the body portion 1e1 and a receiving portion 1e3 at the other end. The receiving portion 1e2 and the receiving portion 1e3 are strip-shaped. Both ends of the flexible support 3 are held, and the structure other than the both ends of the belt-like flexible support 3 is not in contact with the body 1e1. In addition, the trunk | drum 1e1 shows between the receiving part 1e2 and the receiving part 1e3.

  A conveyance roll having a structure as shown in this figure is called a stepped conveyance roll. The stepped transport roll shown in this figure may be used for all the transport rolls in the process, but in particular, it should be used at the surface where the film-shaped surface of the belt-shaped flexible support is in contact with the surface where the film is formed. Is preferred.

  By using a stepped transport roll, the coated surface or the coating film of the strip-shaped flexible support 3 is transported in a non-contact manner, which is suitable for preventing scratches and preventing foreign matter adhesion. However, there are the following problems.

  1) If the belt-shaped flexible support 3 is transported with a certain tension or more when it is transported, the belt-shaped flexible support 3 is buckled and poorly transported, so that it can be transported only with low tension. Since the conveyance stability is poor, the speed cannot be increased and the production efficiency decreases.

  2) When buckling occurs, it is necessary to stop the process and re-apply the buckled part. However, especially when the environment is shut off from the outside air, the process is once returned to the outside air (atmospheric environment). Therefore, it takes time to resume the original environment, and the production efficiency decreases.

  3) By returning the process to the atmospheric environment, not only the buckled portion but also its peripheral portion becomes defective. In some cases, the entire original winding being processed may become defective.

  In the present invention, buckling refers to a state in which the belt-like flexible support is bent and a crease is generated.

  The present invention relates to a transport method capable of eliminating a transport defect due to buckling even when a stepped transport roll is used for transport, and transporting it with peace of mind even in an environment blocked from outside air, and organic electronics using the transport method The present invention relates to a method for manufacturing an element.

  FIG. 2 is a schematic cross-sectional view along the line AA ′ of the stepped transport roll shown in FIG.

  In the drawing, 1e21 indicates the inner surface of the receiving portion 1e2. 1e31 shows the inner surface of the receiving portion 1e3. L shows the width | variety of the trunk | drum 1e1 between the inner surface 1e21 of the receiving part 1e2 of the stepped conveyance roll 1e, and the inner surface 1e31 of the receiving part 1e3. M indicates the height of the receiving portion 1e3 from the surface of the center N in the width direction of the body portion 1e1. The ratio between the height M of the receiving part and the width L of the body part is 0.004 to 0.03. The height of the receiving portion 1e2 is the same as the height M of the receiving portion 1e3, and the ratio between the height and the width L is also the same as the ratio between the height M of the receiving portion 1e3 and the body portion L.

  When the ratio of the height M of the receiving part to the width L of the body part (M / L) is less than 0.0004, the belt-like flexible support is placed on the body part of the stepped transport roll when transported at a low tension. It is not preferable because it is in contact and a non-contact effect cannot be obtained.

  When the ratio of the height M of the receiving part to the width L of the trunk part (M / L) exceeds 0.03, buckling occurs before the belt-like flexible support comes into contact with the stepped transport roll. In other words, it is not preferable because the process will not be restored unless the process is stopped and the buckled portion is repaired.

  FIG. 3 is a schematic view of another shape of the stepped transport roll shown in FIG. FIG. 3A is a schematic perspective view of another shape of the stepped transport roll shown in FIG. FIG. 3B is a schematic cross-sectional view along BB ′ shown in FIG.

  In the figure, 1e 'indicates a stepped transport roll. 1e'21 shows the inner surface of the receiving part 1e'2. 1e'31 shows the inner surface of the receiving part 1e'3. N ′ indicates the center of the body 1e′1. The body 1e′1 has a structure including a first body 1e′11, a second body 1e′4, and a third body 1e′12.

  The first body portion 1e'11 and the third body portion 1e'12 have a concave shape provided with the same width on both sides of the second body portion 1e'4. The second body portion 1e'4 is provided at the center N ', and has a width indicated by Q having the same width on both sides of the center N'.

  The receiving portion 1e'2 and the receiving portion 1e'3 hold both ends of the belt-like flexible support 3, and the body 1e'1 except for both ends of the belt-like flexible support 3 (see FIG. 1). It has a structure that does not come into contact with.

  When the belt-like flexible support 3 (see FIG. 1) is bent during the conveyance, the bending is brought into contact with the second body 1e'4 of the body 1e'1, so that the bending can be kept small. It does not lead to bending. When buckling does not occur, the belt-like flexible support 3 is returned to the horizontal state due to the elasticity of the belt-like flexible support 3, so that the production can be continued without interruption.

  The reason why the concave first barrel 1e'11 and the concave third barrel 1e'12 are formed on both sides of the second barrel 1e'4 of the stepped transport roll 1e 'is to prevent buckling. It is possible to restrict the bending of the second body portion 1e'4 only, and the other portions have a structure in which the belt-like flexible support 3 is released so as not to contact.

  O indicates the width of the body portion 1e'1 between the inner surface 1e'21 of the receiving portion 1e'2 of the stepped transport roll 1e 'and the inner surface 1e'31 of the receiving portion 1e'3. P indicates the height of the receiving portion 1e'3 from the surface of the second barrel portion 1e'4 of the barrel portion 1e'1.

  The ratio (P / O) between the height P of the receiving portion 1e'3 and the width O of the body portion is defined by the height M of the receiving portion 1e3 and the width L of the body portion of the stepped transport roll 1e shown in FIG. It is the same as the ratio (M / L) and is 0.004 to 0.03. The ratio between the height of the receiving portion 1e'2 and the width O of the body portion is also the same as the ratio between the height P of the receiving portion of the receiving portion 1e'3 and the width O of the body portion.

  Q indicates the width of the second body 1e'4. The width Q of the second body portion 1e'4 is preferably 10 mm to 20 mm in consideration of variations in the position of deflection, although it depends on the size of the stepped transport roll.

  Although the material used for the stepped conveyance roll shown by FIG.2 and FIG.3 is not specifically limited, For example, SUS, aluminum, etc. are mentioned.

  A resin film is mentioned as the strip | belt-shaped flexible support body 3 conveyed with the stepped conveyance roll shown by FIGS. 1-3. The film thickness of the resin film is preferably 50 μm to 250 μm in consideration of the transportability and retention of the resin film.

  FIG. 4 is a schematic diagram showing a state when a belt-shaped flexible support is transported using a stepped transport roll.

  (A) is the schematic which shows a strip | belt-shaped flexible support body state when conveying a strip | belt-shaped flexible support body using the stepped conveyance roll shown in FIG. The belt-like flexible support 3 may be bent at the center of the belt-like flexible support 3 during transportation. The amount of deflection contacts the center of the body 1e1 of the stepped transport roll 1e, but the ratio (M / L) between the height M of the receiving part 1e3 (receiving part 1e2) and the width L of the body 1e1 is 0.004. From 0.03 to 0.03, it is possible to suppress the bending to a small extent and not to buckle. When buckling is not reached, the belt-like flexible support 3 returns to the horizontal state due to the elasticity of the belt-like flexible support 3, so that it is possible to continue production without interrupting the conveyance.

  The portion where the belt-like flexible support 3 contacts the center of the body portion 1e1 of the stepped transport roll 1e may become defective due to scratches or the like due to the contact, but can be extracted and discarded in a subsequent inspection step. It is a good product after returning to level with elasticity.

  (B) is the schematic which shows the strip | belt-shaped flexible support body state when conveying a strip | belt-shaped flexible support body using the stepped conveyance roll shown in FIG.

  The belt-like flexible support 3 may bend at the center of the belt-like flexible support 3 until buckling at the time of conveyance. However, the bending is caused by the body portion 1e′1 of the stepped conveyance roll 1e ′. The height P of the receiving portion 1e'3 from the surface of the second barrel portion 1e'4 (see FIG. 3) and the width O of the barrel portion 1e'1 are in contact with the second barrel portion 1e'4. The ratio (P / O) is the same as the ratio (M / L) between the height M and the width L of the receiving portion 1e3 of the stepped transport roll 1e shown in FIG. Can be kept small and does not lead to buckling. When buckling is not reached, the belt-like flexible support 3 returns to the horizontal state due to the elasticity of the belt-like flexible support 3, so that it is possible to continue production without interrupting the conveyance.

  The portion where the belt-like flexible support 3 contacts the second body 1e'4 of the body 1e'1 of the stepped transport roll 1e 'may become defective due to scratches or the like due to contact, It can be extracted and discarded in the inspection process, and is elastic after returning to level with elasticity.

  (C) is the schematic which shows the strip | belt-shaped flexible support body state when transporting a strip | belt-shaped flexible support body using the conventional stepped conveyance roll.

  The width of the trunk portion 1e "1 between the receiving portions 1e" 2 and the receiving portion 1e "3 of the stepped transport roll 1e", the receiving portion 1e "2 from the surface of the trunk portion 1e" 1, and the receiving portion Since the ratio of the height of the portion 1e ″ 3 is higher than that of the stepped transport roll 1e shown in FIG. 5A and the stepped transport roll 1e ′ shown in FIG. The buckling occurs before the deflection generated in the central portion of 3 reaches the surface of the body 1e ″ 1. As a result of buckling, a crease is formed at the center of the belt-like flexible support 3 and this portion becomes a defective product, and the portion where the buckling has occurred is not restored and the buckling is repaired. Therefore, it is necessary to temporarily stop the conveyance and apply the buckled portion again.

  The tension when transporting the belt-like flexible support using the stepped transport roll shown in FIGS. 4A to 4C is unambiguously determined because it is affected by the width of the belt-like flexible support. However, for example, when the width is 250 mm, it is possible to carry in the range of 10N to 30N of the normal carrying tension. When the width of the belt-like flexible support to be used is different, it is usually necessary to change the tension in proportion to the width of the support.

  As shown in FIG. 1 to FIG. 4, the belt-like flexible support made of a resin film having a film on a base material in an environment shielded from outside air, the stepped transport roll shown in FIG. 2 or FIG. 3. The following effects can be obtained by continuously transporting the belt-like flexible support using the belt-like flexible support.

  1. It became possible to apply tension to the conveyance, and the conveyance was stable, so the speed could be increased and the production efficiency could be improved.

  2. Eliminating the conveyance failure caused by buckling, it has become possible to produce continuously in an environment that is shut off from the outside air, thereby improving production efficiency.

  3. Even if a belt-like flexible support with poor planarity with patterned electrodes is applied, it becomes possible to stably hold the belt-like flexible support on the back roll and to correct the flatness by applying tension to the conveyance. Application became possible.

  4). In a belt-like flexible support made of a resin film having a thickness of 50 μm to 250 μm, which is used in a roll-to-roll method, there is no conveyance failure due to buckling and no quality defect due to buckling, and organicity in the roll-to-roll method Adaptation to the production of electronics elements has become possible.

  Various transport methods including an organic EL device, an organic thin film transistor device, an organic solar cell device (hereinafter also referred to as an organic PV device), and an organic photoelectric conversion device using the transport method of the present invention shown in FIGS. It is possible to use organic electronics elements or the like for production in a roll-to-roll system.

  In the case of organic electronics elements, a patterned film made of a conductive material having a heat shrinkage rate different from the heat shrinkage rate of the belt-like flexible support on the belt-like flexible support made of a resin film Is formed. Such a belt-like flexible support has the following characteristics.

  1. The flatness of the belt-like flexible support is determined by performing heat treatment such as drying after cleaning after forming the membrane or drying after coating, drying after coating, and the like. Since the material has a different thermal contraction rate from the film, the surface of the belt-like flexible support becomes uneven.

  2. In addition, when applying a tension of a certain level or more to correct the flatness of such a belt-like flexible support, foreign matter adheres to the surface, and there is a high risk of scratches due to rubbing with the transport roll. It must be transported without contact.

  3. In order to carry it in a non-contact manner, if it is carried with tension applied by a stepped carrying roll, buckling occurs and a conveyance failure occurs.

  4). Since the process consists of a vapor deposition process, a process that requires cleanliness, and a process in which the coating liquid uses an organic solvent and is replaced with an inert gas, once buckling occurs, Although it is stopped and repaired, it takes time to return to the original state for restarting, so the production efficiency is lowered.

  5. In order to prevent the occurrence of buckling by using a stepped transport roll, it is necessary to transport with a minimum tension, which takes time for processing and decreases production efficiency.

  6). Since tension cannot be applied, it becomes difficult to stably hold the belt-like flexible support on the back roll and to correct the flatness, and it becomes difficult to apply stably.

  Next, using a strip-like flexible support on which a patterned film composed of a conductive material as described above is formed, it is attached to a method for manufacturing an organic electronic device by the transport method of the present invention. explain.

  FIG. 5 is a schematic view of an organic electronic device manufactured using the transport method of the present invention. FIG. 5A is a schematic perspective view of the organic electronics element of the present invention. FIG. 5B is a schematic cross-sectional view along CC ′ of FIG.

  In the figure, 4 indicates an organic electronics element. The organic electronics element 4 includes a first electrode (anode) 402, a functional layer 403, a second electrode (cathode) 404, and a sealing member 406 fixed via an adhesive layer 405 sequentially on the base material 401. Thus, the sealing structure is tightly sealed.

  Reference numeral 402 a denotes an extraction electrode of the first electrode (anode) 402, and 404 a denotes an extraction electrode of the second electrode (cathode) 404. A gas barrier film (not shown) may be provided between the first electrode (anode) 402 and the substrate 401.

  The thickness of the sealing member 406 is preferably 5 μm to 500 μm in consideration of productivity associated with the occurrence of claw breakage, flexibility of the organic electronics element itself, and the like.

  The thickness of the adhesive layer 405 is preferably 10 μm to 50 μm in consideration of adhesiveness, moisture resistance, and the like.

  Examples of the functional layer include a structure in which a hole transport layer / organic layer (light-emitting layer or photoelectric conversion layer) / electron transport layer are sequentially stacked on the first electrode.

  In addition, it is also possible to arrange a plurality of organic electronics elements shown in this figure into a large organic electronics element. In addition, a plurality of stacked bodies each including a first electrode having an extraction electrode formed on a substrate and a functional layer formed on the first electrode are arranged, and a second electrode common to all the stacked bodies is stacked. It is also possible to provide an organic electronic element by being tightly sealed with an adhesive layer 405 and a sealing member 406 as shown in FIG.

  The organic electronics element 4 shown in the figure emits light from the base material when an organic EL element is supplied with direct current from the extraction electrode 402a and the extraction electrode 404a. In the organic PV element, a direct electromotive force is generated by irradiating light from the base material, and power is extracted from the extraction electrode 402a and the extraction electrode 404a.

  Next, an organic electronics element will be described.

  Among the organic electronics elements shown in this figure, the layer structure of the organic EL element shows an example by a laminating method. The typical layer structure of the organic EL element is as follows (1) to (5). The structure shown is mentioned.

(1) Base material / first electrode (anode) / organic layer (light emitting layer) / second electrode (cathode) / adhesive / sealing member (2) base material / first electrode (anode) / organic layer (light emission) Layer) / electron transport layer / second electrode (cathode) / adhesive / sealing member (3) substrate / first electrode (anode) / hole transport layer / organic layer (light emitting layer) / hole blocking layer / Electron transport layer / second electrode (cathode) / adhesive / sealing member (4) substrate / first electrode (anode) / hole transport layer / organic layer (light emitting layer) / hole blocking layer / electron transport layer / Cathode buffer layer (electron injection layer) / second electrode (cathode) / adhesive / sealing member (5) substrate / first electrode (anode) / anode buffer layer / hole transport layer / organic layer (light emitting layer) ) / Hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / second electrode (cathode) / adhesive / sealing member The light emitting layer is injected from the electrode or the electron transport layer or the hole transport layer. Come a layer in which electrons and holes are recombined to emit light, the portion which emits light may be the interface between even within the layer of the light-emitting layer and the light emitting layer adjacent layer. The light emitting layer is not particularly limited in its configuration as long as the light emitting material included satisfies the above requirements. Further, there may be a plurality of layers having the same emission spectrum and emission maximum wavelength. It is preferable to have a non-light emitting intermediate layer between each light emitting layer.

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

  The film thickness of each light emitting layer is preferably adjusted in the range of 1 nm to 50 nm, more preferably in the range of 1 nm to 20 nm. There is no particular limitation on the relationship between the film thicknesses of the blue, green and red light emitting layers.

  Here, the light emitting layer preferably contains at least two kinds of light emitting materials having different emission colors, and a single layer or a light emitting layer unit composed of a plurality of light emitting layers may be formed.

  For the production of the light emitting layer, a light emitting material or a host compound can be formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method.

  Among the organic electronics elements shown in this figure, the layer structure of the organic photoelectric conversion element (organic thin film solar cell) is an example of the lamination method, but the layer structure of the organic photoelectric conversion element (organic thin film solar cell) Typical layer configurations include the following configurations (I) to (IV). The following structure is mentioned as a typical layer structure of a functional layer.

(I) Substrate / first electrode (anode) / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / second electrode (cathode) / adhesive / sealing member (II ) Substrate / first electrode (anode) / hole transport layer having electron blocking ability / photoelectric conversion layer / electron transport layer having hole blocking ability / cathode buffer layer / second electrode (cathode) / adhesive / sealing Stopping member (III) Base material / first electrode (anode) / anode buffer layer / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / second electrode (cathode) / adhesive / Sealing member (IV) substrate / first electrode (anode) / anode buffer layer / hole transport layer / electron block layer / photoelectric conversion layer / hole block layer / electron transport layer / cathode buffer layer / second electrode (Cathode) / Adhesive / Sealing member Photoelectric conversion layer (layer in which p-type semiconductor and n-type semiconductor are mixed, bar Click heterojunction layer, also referred to as i layer) is located at least one layer is a layer for generating electric current when exposed to light.

  Like the organic EL device, the organic photoelectric conversion device can increase the efficiency of extracting holes and electrons to the anode / cathode by sandwiching the photoelectric conversion layer between the hole transport layer and the electron transport layer. It is preferable to have the configuration. Also, the photoelectric conversion layer itself has a configuration in which the photoelectric conversion layer is sandwiched between layers made of a p-type semiconductor material and a single n-type semiconductor material in order to improve the rectification of holes and electrons (selection of carrier extraction) (p- (also referred to as an i-n configuration). Moreover, in order to improve the utilization efficiency of sunlight, the structure which absorbs sunlight of a different wavelength with each photoelectric converting layer may be sufficient. The thickness of the photoelectric conversion layer is preferably adjusted in the range of 50 nm to 400 nm, more preferably in the range of 80 nm to 300 nm.

  For the production of the photoelectric conversion layer, a p-type semiconductor material and an n-type semiconductor material are formed by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. I can do it.

  FIG. 6 is a schematic view of a manufacturing process for manufacturing an organic EL element used for illumination among the organic electronic elements using the coating method shown in FIGS.

  In the figure, reference numeral 5 denotes a manufacturing process of the organic EL element. The manufacturing process 5 includes a first supply process 501, a hole transport layer formation process 502, a light emitting layer formation process 503, an electron transport layer formation process 504, a first recovery process 505, a second supply process 506, It has the 2nd electrode formation process 507, the 2nd collection | recovery process 508, the 3rd supply process 509, the sealing member bonding process 510, and the cutting process 511.

  The first supply step 501 uses a feeding device (not shown) for the strip-shaped flexible support 6 wound up in a roll shape and an accumulator 501a. In the forming step 502, the belt-like flexible support 6 is fed out through the transport rolls 501b and 501c. The accumulator 501a is provided for speed adjustment with the hole transport layer forming step 502 of the next step. The strip-shaped flexible support 6 is formed with a first electrode (anode) (not shown) formed by patterning using indium tin oxide (ITO). An alignment mark (not shown) indicating the position of the first electrode (anode) is preferably provided. The thickness of the first electrode (anode) was 120 nm.

  As a patterning method, an electrode material 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 (100 μm) when pattern accuracy is not so required. As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. Or when using the substance which can be apply | coated like an organic electroconductive compound, it is also possible to use wet film forming methods, such as a printing system and a coating system.

  In the 1st supply process 501, the stepped conveyance roll shown in FIG. 2 is used for the conveyance rolls 501b and 501c and the accumulator 501a.

  The hole transport layer forming step 502 includes a coating step 502a and a drying step 502b, and uses an accumulator 502c. In the hole transport layer forming step 502, a hole transport layer forming coating solution is applied to the entire upper surface of the band-shaped flexible support 6 on which the first electrodes are formed.

  Thereafter, a hole transport layer is formed through a drying step 502b and conveyed to the next light emitting layer forming step 503. The accumulator 502c is provided for speed adjustment with the light emitting layer forming step 503 in the next step.

  In the hole transport layer forming step 502, the stepped transport rolls shown in FIG. 2 are used for the transport rolls 502f and 502g and the accumulator 502c.

  The coating step 502a is performed by a pre-measuring type coating method. Examples of the pre-metering type coating method include an extrusion coating method using a slit type die coater, a slide coating method using a slit type die coater, and a curtain coating method. And a coating method using an inkjet head. Use of these pre-weighing type coating devices can be appropriately selected according to the material of the hole transport layer. This figure uses a slit-type die coater 502a1 and a back roll 502a2 holding the belt-like flexible support 6 as a pre-weighing type coating apparatus.

  The hole transport layer forming coating solution by the slit type die coater 502a1 is applied to the entire surface including the first electrode formed on the strip-like flexible support 6. In the coating step 502a, the hole transport layer forming coating solution coated on the entire surface of the strip-shaped flexible support 6 is removed in an unnecessary portion of the coating film after the coating is completed in a removing step (not shown). . The removal method is not particularly limited, and examples thereof include a wiping method using a solvent used in the coating solution. Unnecessary portions include an external extraction electrode (not shown) for the first electrode, an external extraction electrode (not shown) for the second electrode (not shown), and an adjacent first electrode (not shown). There is an interval.

  The drying process 502b uses a drying device 502b1 and a heat treatment device 502b2. The drying device 502b1 and the heat treatment device 502b2 are not particularly limited, and examples thereof include a heating method and a heating air method, which can be appropriately selected as necessary.

  The heat treatment apparatus 502b2 heats a coating film (not shown) for forming a hole transport layer from the back surface side of the belt-like flexible support 6 by a back surface heat transfer method. As the heat treatment conditions for the hole transport layer (not shown) in the heat treatment apparatus 502b2, the hole transport layer is configured in consideration of improvement in smoothness of the hole transport layer, removal of residual solvent, curing of the hole transport layer, and the like. 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 with respect to the glass transition temperature of the resin that is −30 ° C. to + 30 ° C. .

  It is preferable to dispose antistatic means 502d between the drying step 502b and the light emitting layer forming step 503 as necessary.

The antistatic means 502d has a non-contact type antistatic device 502d1 and a contact type antistatic device 502d2. Examples of the non-contact type antistatic device 502d1 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. Also, it is selected from a blower type or a gun type from the viewpoint of performing inline.

  As the contact-type antistatic device 502d2, 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, in order to improve contact with the belt-like flexible support 6, an elastic material is preferable. Examples of the conductive brush connected to the earth include a neutralizing bar or a neutralizing yarn structure having a brush member made of conductive fibers arranged in a line or a linear metal brush. The neutralization bar is not particularly limited, but a corona discharge type is preferably used. For example, SJ-B manufactured by Keyence Corporation is used. There is no particular limitation on the static elimination yarn, but usually a flexible yarn is preferably used. For example, 12/300 × 3 manufactured by Naslon can be cited as an example.

  The non-contact type antistatic device 502d1 is used on the hole injection layer surface side formed on the belt-like flexible support 6, and the contact-type antistatic device 502d2 is used on the back surface side of the belt-like flexible support 6. It is preferable to do.

  The thickness of the hole transport layer is preferably from 0.1 nm to 100 nm, more preferably from 5 nm to 70 nm, and most preferably from 10 nm to 50 nm.

  The light emitting layer forming step 503 includes a coating step 503a and a drying step 503b, and uses an accumulator 503c. The accumulator 503c is provided for speed adjustment with the electron transport layer forming step 504 in the next step. In the light emitting layer forming step 503, a light emitting layer forming coating solution is applied to the entire upper surface of the belt-like flexible support 6 on which the hole transport layer is formed.

  Thereafter, a light emitting layer is formed through a drying step 503b and conveyed to an electron transport layer forming step 504 in the next step. The accumulator 503c is provided for speed adjustment with the electron transport layer forming step 504 in the next step.

  In the light emitting layer forming step 503, the stepped transport rolls shown in FIG. 2 are used for the transport rolls 503e to 503g and the accumulator 503c.

  The coating process 503a is performed by the same pre-measuring type coating method as the coating process 502a of the hole transport layer forming process 502, and the same slit-type die coater 503a1 as that of the coating process 502a as a pre-measuring type coating apparatus A back roll 503 a 2 that holds the flexible support 6 is used. The light emitting layer forming coating solution by the slit type die coater 503 a 1 is applied to the entire surface including the hole transport layer formed on the belt-like flexible support 6. In the coating step 503a, the coating liquid for forming the hole transport layer applied on the entire surface of the belt-like flexible support 6 is removed in the removing step (not shown) after the coating is completed. . The removal method and unnecessary portions are the same as those in the hole transport layer.

  In the drying step 503b, a drying device 503b1 and a heat treatment device 503b2 are used. The drying device 503b1 and the heat treatment device 503b2 are the same as the drying device 502b1 and the heat treatment device 502b2 used in the drying step 502b of the hole transport layer forming step 502, and thus description thereof is omitted.

  It is preferable to dispose antistatic means 503d between the drying step 503b and the electron transport layer forming step 504 as necessary. Since the antistatic means 503d is the same as the antistatic means 502d used in the hole transport layer forming step 502, description thereof is omitted.

  When the light emitting layer (not shown) is a multilayer, it is necessary to arrange an application process and a drying process according to the number of layers. For example, a white element can be manufactured by forming a light emitting layer in multiple layers. In the present invention, the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer. Also, when four or more light emitting layers are provided, for example, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting from the order close to the anode. Layered / green light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer / green light emitting layer / red light emitting layer, etc. It is preferable for improving luminance stability.

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

  The electron transport layer forming step 504 includes a coating step 504a and a drying step 504b, and uses an accumulator 504c. The accumulator 504c is provided for speed adjustment with the first recovery step 505 of the next step. In the electron transport layer forming step 504, the electron transport layer forming coating solution is applied to the entire upper surface of the belt-like flexible support 6 on which the light emitting layer is formed. Thereafter, an electron transport layer is formed through a drying step 504b, and is transported to the first recovery step 505 of the next step and once recovered.

  In the electron transport layer forming step 504, the stepped transport rolls shown in FIG. 2 are used for the transport rolls 504e to 504g and the accumulator 504c.

  The coating process 504a is performed by the same pre-measuring type coating method as the coating process 502a of the hole transport layer forming process 502, and the same slit type die coater 504a1 as the pre-measuring type coating apparatus 502a and the strip-like flexible The back roll 504a2 that holds the conductive support 6 is used. The coating liquid for forming an electron transport layer by the slit type die coater 504a1 is applied to the entire surface including the light emitting layer formed on the belt-like flexible support 6. In the coating step 504a, the coating solution for forming the electron transport layer applied on the entire surface of the belt-like flexible support 6 is removed in the removing step (not shown) after the coating is completed. The removal method and unnecessary portions are the same as those in the hole transport layer.

  The drying step 504b uses a drying device 504b1 and a heat treatment device 504b2. Since the drying device 504b1 and the heat treatment device 504b2 are the same as the drying device 502b1 and the heat treatment device 502b2 used in the drying step 502b of the hole transport layer forming step 502, description thereof is omitted.

  It is preferable to arrange an antistatic means 504d between the drying step 504b and the first recovery step 505 as necessary. Since the antistatic means 504d is the same as the antistatic means 502d used in the hole transport layer forming step 502, description thereof is omitted.

  The preferred film thickness range of the electron transport layer is preferably from 0.1 nm to 100 nm, more preferably from 5 nm to 80 nm, and most preferably from 10 nm to 60 nm.

  The second supply step 506 uses a feeding device (not shown) of the belt-like flexible support 6 formed up to the electron transport layer and wound up in a roll shape, and an accumulator 506a. In the electrode forming step 507, the belt-like flexible support 6 on which the layers up to the electron transport layer are formed is fed out. The accumulator 506a is provided for speed adjustment with the second electrode forming step 507 of the next step.

  In the 2nd supply process 506, the stepped conveyance roll shown in FIG. 2 is used for the conveyance roll 506b and the accumulator 506a.

  The second electrode forming step 507 includes a vapor deposition apparatus 507a having an evaporation source container 507b and an accumulator 507c. The accumulator 507c is provided for speed adjustment with the second recovery step 508 of the next step.

  In the second electrode forming step 507, an alignment mark (not shown) attached to the belt-like flexible support 6 on which the electron transport layer supplied from the second supply step 506 is formed is detected by a detection device (not shown). The second electrode (cathode) (not shown) is masked on the already formed electron injection layer (not shown) at a position determined by the vapor deposition device 507a according to the information of the detection device (not shown). A pattern is formed. 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 nm to 200 nm. At this stage, the belt-like flexible support 6 having the structure of the base material / first electrode (anode) / hole transport layer / light emitting layer / electron injection layer / second electrode (cathode) is completed.

  The method for forming the second electrode (cathode) is not particularly limited. For example, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, 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.

  The thickness of the second electrode is usually 10 nm to 5 μm, preferably 50 nm to 200 nm.

  In the second electrode forming step 507, the stepped transport rolls shown in FIG. 2 are used for the transport rolls 507c to 507e and the accumulator 507c.

  In the second recovery step 508, the band-shaped flexible support 6 in which the structure of the base material / first electrode (anode) / hole transport layer / light emitting layer / electron injection layer / second electrode (cathode) is formed is a roll. It is wound up and collected.

  In the third supply step 509, a feeding device (not shown) is used, and the belt-like flexible support 6 formed up to the second electrode (cathode) recovered in the second recovery step 508 is continuously formed. It is set out to the sealing member bonding step 510 of the next step.

  In the 3rd supply process 509, the stepped conveyance roll shown in FIG. 2 is used for the conveyance roll 509a.

  The sealing member bonding step 510 uses an adhesive application device 510a and a sealing member bonding 510b. The adhesive applicator 510a uses the second electrode except for the extraction electrode 402a (see FIG. 5) of the first electrode 402 (see FIG. 5) and the extraction electrode 404a (see FIG. 5) of the second electrode 404 (see FIG. 5). An adhesive is applied on and around the electrode 404 (see FIG. 5), and the sealing member 510c is bonded.

  In the cutting step 511, the alignment mark attached to the belt-like flexible support 6 formed with the second electrode (cathode) sent from the sealing member bonding step 510 is detected using the cutting device 511a. The individual organic EL elements shown in FIG. 5 are manufactured by detecting and cutting with an apparatus (not shown).

  This figure shows one example of a manufacturing process in which the stepped transport roll shown in FIG. 2 is used for the transport roll of each process, and the transport system is determined by the arrangement of each process constituting the manufacturing process. Because of the difference, it is preferable to use a stepped transport roll shown in FIG. 2 according to the transport system.

  In particular, it is preferable to use the stepped transport roll shown in FIGS. 2 and 3 for the transport roll in contact with the surface on which the film is formed and the surface on which the film is formed.

  Of the manufacturing steps shown in this figure, the first supply step 501, the first recovery step 505, the third supply step 509, and the sealing member bonding step 510 are JIS B in order to avoid adhesion of foreign matters. The cleanliness class measured according to 9920 is an environmental condition of 5 or less.

  In each of the hole transport layer forming step 502, the light emitting layer forming step 503, and the electron transport layer forming step 504, the coating liquid used uses an organic solvent, so that it is blocked from the outside air and replaced with an inert gas. Environment.

  The second supply process 506, the second electrode formation process 507, and the second recovery process 508 are in a vacuum environment.

  In addition, conveyance tension | tensile_strength of the strip | belt-shaped flexible support body in the manufacturing process shown by this figure was conveyed with the tension | tensile_strength of 10N to 20N when the strip | belt-shaped flexible support body is 250 mm width. When the width of the belt-like flexible support is different, it is usually necessary to change the tension in proportion to the width of the support.

  Since this figure manufactures an organic EL element, each coating process 502a, coating process 503a, and coating process 504a are full-coated slit type die coaters. For example, an inkjet system, a flexographic printing system, Various coating devices used for an offset printing method, a gravure printing method, a screen printing method, a spray coating method using a mask, and the like can be used.

  This figure shows the case where the light-emitting layer forming process is divided into the electron transport layer forming process and the second electrode forming process, but it is also possible to continue from the hole injection transport layer forming process to the second electrode forming process. It is.

  In addition, in the manufacturing process which manufactures the organic EL element shown to this figure, the organic photoelectric conversion element which has the structure of a base material / 1st electrode / hole transport layer / photoelectric conversion layer / electron injection layer / second electrode, for example When manufacturing, the transport method of the present invention using the stepped transport roll shown in FIGS. 1 to 3 can be used for forming the hole transport layer and the photoelectric conversion layer which are organic functional layers. However, when the electron injection layer is formed by a vapor deposition method, it is preferable to form the photoelectric conversion layer, and after winding and storing it, the electron injection layer and the second electrode are formed by the vapor deposition method.

  Next, materials used for the organic EL element and the organic PV element among the organic electronic elements related to the method for producing the organic electronic element using the coating method of the present invention will be described.

(Light emitting layer of organic EL element)
Organic light-emitting materials contained in the light-emitting layer include aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, polyarylenes, aromatic condensed polycyclic compounds, aromatic heterocondensed compounds. Examples thereof include a ring compound, a metal complex compound, and the like, and a single oligo body or a composite oligo body thereof. However, the present invention is not limited to this, and widely known materials can be used.

  In the light emitting layer (film forming material), a dopant of preferably about 0.1% by mass to 20% by mass may be included in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). A complex compound such as an orthometalated iridium complex represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like is similarly contained in an amount of about 0.1 to 20% by mass.

  The phosphorescent light emitting method is a preferable embodiment in the present invention in which uneven light emission hardly occurs due to the fact that the light emitting layer has a light emitting region. The thickness of the light emitting layer is preferably in the range of 1 nm to several hundred nm.

(P-type semiconductor material for organic PV elements)
Examples of the p-type semiconductor material used for the photoelectric conversion layer (bulk heterojunction layer) include various condensed polycyclic aromatic low molecular compounds and conjugated polymers / oligomers.

  Examples of the condensed polycyclic aromatic low-molecular compound include pentacene and derivatives thereof, porphyrin and phthalocyanine, copper phthalocyanine and derivatives thereof.

  Examples of the conjugated polymer include polythiophene such as poly-3-hexylthiophene (P3HT) and oligomers thereof, polythiophene-thienothiophene copolymer, polythiophene-diketopyrrolopyrrole copolymer, polythiophene-thiazolothiazole copolymer, Nature Mat. vol. 6 (2007), p497 described in PCPDTBT, etc., polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, Examples thereof include polymer materials such as σ-conjugated polymers such as polysilane and polygermane.

(N-type semiconductor material for organic PV elements)
The n-type semiconductor material used for the photoelectric conversion layer (bulk heterojunction layer) is not particularly limited. For example, fullerene, octaazaporphyrin, and other p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), Examples thereof include aromatic carboxylic acid anhydrides such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, and perylenetetracarboxylic acid diimide, and polymer compounds containing an imidized product thereof as a skeleton. .

  A common material used for the configuration of the organic EL panel and the organic PV panel will be described.

(Transport layer, electron block layer)
Examples of materials used for the hole transport layer and the electron blocking layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylenedioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like. A high-molecular material such as a conductive polymer is also used in the light-emitting layer, for example, a carbazole-based light-emitting material such as 4,4′-dicarbazolylbiphenyl, 1,3-dicarbazolylbenzene, Di) Low molecular light emitting materials typified by pyrene-based luminescent materials such as azacarbazoles, 1,3,5-tripyrenylbenzene, polymer light emission typified by polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, etc. Materials and the like.

(Electron injection / transport layer, hole blocking layer)
Various n-type materials can be used as the electron injection / transport layer material. Examples of materials that can be preferably used in the organic electronic device of the present invention include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinato) zinc, or the following nitrogen-containing five-membered rings. There are derivatives. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  In addition to the above-mentioned compounds, fullerenes, carbon nanotubes, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), and n-type inorganic oxides such as titanium oxide, zinc oxide, gallium oxide, etc. It is also preferable in the present invention to use.

  In the present invention, an electron injection layer and an electron transport layer may be laminated according to the purpose, and an optimal material may be selected in connection with electron transport properties and electrodes.

  In the present invention, a material that has a function of blocking electrons as reverse carriers and improves the selectivity of charges may be selected.

  The electron injection layer (buffer layer) has a structure in which halides containing ions such as lithium, potassium, sodium, and cesium, for example, lithium fluoride, potassium fluoride, and the like are stacked to improve the bonding with the electrode. Particularly preferred in the invention.

  When using these electron-injecting materials made of inorganic materials, it is preferable to form a film by patterning mainly by vapor deposition through a shadow mask, but if it can be formed as a solution, it should be formed by coating from the viewpoint of productivity. Is more preferable.

  In the case of a vapor deposition method, the manufacturing method which forms a vapor deposition film after performing the wiping patterning mentioned above is especially preferable in this invention.

(Solvent used for coating liquid for organic functional layer formation)
Each organic material has solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different, the concentration cannot be generally determined. However, the type of the solvent used in the present invention is suitable for the above conditions depending on the organic material to be deposited. May be selected from known solvents, for example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, Ether solvents such as dioxane and anisole, methanol, alcohol solvents such as ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, glycerin, benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbon solvents, paraffin solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amide solvents such as methylpyrrolidone, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvents such as pyridine, quinoline and aniline, nitrile solvents such as acetonitrile and valeronitrile, sulfur such as thiophene and carbon disulfide And system solvents. In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Of these, preferable examples of the good solvent for the material used in the organic electronics panel include, for example, aromatic solvents, halogen solvents, ether solvents, and preferably aromatic solvents, ether solvents. It is. Examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  In addition, when laminating | stacking these organic substance layers by application | coating etc., it is necessary to select a material and a solvent so that the lower layer may not be dissolved.

  For this reason, a structure in which the material of the organic layer is insolubilized by positively cross-linking or the like can be preferably used. For example, a polymer having a polymerizable group such as a vinyl group or a cross-linking group and forming a polymer or a cross-linked structure having the above structural units by heating or light irradiation can be used. As a result, dissolution of the film due to the multilayer, disturbance of the interface, and the like can be suppressed.

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

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

  The second electrode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.

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

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

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

(Support)
The support is preferably a member that can transmit emitted light or light for generating electromotive force, that is, a member that is transparent to the wavelength of the light. Preferred examples of the substrate that can be used in the present invention include a glass substrate and a resin substrate, but it is desirable to use a transparent resin film from the viewpoint of lightness and flexibility.

  There is no restriction | limiting in particular in a transparent resin film, About the material, a shape, a structure, thickness, etc., it can select suitably from well-known things. For example, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at ~800nm), can be preferably applied to a transparent resin film according to the present invention. Among these, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film, and biaxially stretched. More preferred are polyethylene terephthalate films and biaxially stretched polyethylene naphthalate films. The thickness of the transparent resin film used in the roll-to-roll method is desirably 50 μm to 250 μm from the viewpoint of conveyance stability.

  The support used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution. A conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment. Examples of the easy-adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.

  In order to suppress the permeation of oxygen and water vapor, a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer is formed in advance on the side where the transparent conductive layer is formed or on the opposite side. May be.

(Sealing)
In order to prevent the produced organic photoelectric conversion element from being deteriorated by oxygen, moisture, etc. in the atmosphere, it is preferable to seal the organic EL element and the organic PV element by a known method. For example, a method of sealing and bonding a plastic film on which a gas barrier layer such as a thin film of aluminum, silicon oxide, or aluminum oxide is formed and an organic electronics element with an adhesive, UV curable / thermosetting resin, etc., gas barrier properties Spin coating of organic polymer materials (polyvinyl alcohol, etc.) with high viscosity, sputtering methods and CVD methods for inorganic thin films (silicon oxide, aluminum oxide, etc.) or organic films (parylene, etc.) with high gas barrier properties under vacuum or air The method of depositing by these, the method of laminating | stacking these compositely, etc. can be mentioned.

  Furthermore, in the present invention, from the standpoint of improving the lifetime of the element, the entire organic electronics element including the base material may be laminated and sealed with two base materials with a barrier, and preferably a structure in which a moisture getter or the like is enclosed. It doesn't matter.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
(Preparation of strip-shaped flexible support)
As shown in Table 1, a strip-like flexible support having a width of 250 mm and a length of 500 m was prepared. 1-A to 1-F.

(Preparation of coating solution)
A commercially available dye, C.I. I. A coating solution in which 1.5 parts by mass of Acid Red 249 was dissolved was prepared, and the amount of polyvinyl butyrate (PVB) added was adjusted so that the viscosity was 1.0 mP · s to prepare a coating solution. The viscosity of the coating solution is a value measured at a temperature of 25 ° C. using an E-type viscometer VISCONIC ED type manufactured by Toki Sangyo Co., Ltd.

(Preparation of slit type die coater)
The slit type die coater shown below was prepared.

Slit die coater width 400mm
Slit gap O 20μm
Application width 150mm
(Preparation of stepped transport roll)
A stepped transport roll having the shape shown in FIG. 2 in which the ratio between the width of the trunk portion and the height of the receiving portion shown in Table 2 was changed was prepared. 1-a to 1-f.

Material: SUS + hard chrome plating Body diameter: 200mm
Body width (L in FIG. 2): 200 mm
Width of receiving part: 25mm
The change in the ratio between the width of the trunk portion and the height of the receiving portion (M in FIG. 2) was performed by changing the height of the receiving portion while keeping the diameter of the trunk portion constant.

(Application)
In the step of forming the coating film shown in FIG. 1-a to 1-f were used, and the prepared belt-like flexible support No. Using a slit type die coater from 1-A to 1-F, a coating solution prepared in a combination as shown in Table 3 was applied on a strip-like flexible support at a coating speed of 5 m / min, A coating film was formed and sample no. 101 to 128. The conveyance tension was set to 40N, which is higher than the normal conveyance tension (10N to 30N) in order to surely see the occurrence of buckling. The inside of the process was replaced with nitrogen gas having a moisture concentration of 10 ppm and an oxygen concentration of 10 ppm or less to create an environment that was blocked from the outside air.

  The coating speed was measured with a laser Doppler speedometer LV203 manufactured by Mitsubishi Electric Corporation.

Evaluation Each sample No. Table 3 shows the results of evaluation from 101 to 128, evaluated by the following method, with and without the occurrence of folds due to buckling.

(With or without buckling)
Visual observation from the start to the end of application confirmed the presence or absence of folds due to buckling.

Example 2
Each sample No. 1 prepared in Example 1 was used except that the transport tension was set to 15N which was the range of the normal transport tension. Samples were prepared in the same manner as in Nos. 101 to 128, and 201 to 228.

Evaluation Each sample No. Table 4 shows the results from 201 to 228 and evaluated by the following method with and without scratches.

(With or without scratches)
Visual observation from the start to the end of application confirmed the presence or absence of scratches.

  From the results shown in Table 3 of Example 1 and the results shown in Table 4 of Example 2, the belt-like flexible support was placed at the height of the convex portion and the width of the trunk portion in an environment blocked from outside air. Using a stepped transport roll with a ratio of 0.004 to 0.03, a belt-like flexible support made of resin film having a film thickness of 50 μm to 250 μm is transported higher than the normal transport tension (10 N to 30 N). Sample No. produced by applying the coating solution while being continuously conveyed at 40N. 102, 103, 106 to 109, 112, 113, 116, 117, 120 to 123, 126, and 127 were confirmed to have no folds due to buckling even when the tension was increased. In addition, sample No. 1 was prepared by applying the coating liquid while continuously transporting at 15N which is the range of normal transport tension. 202, 203, 206 to 209, 212, 213, 216, 217, 220 to 223, 226, and 227 were confirmed to be free from abrasion due to rubbing with the stepped transport roll.

  The belt-like flexible support is higher than the normal transport tension (10N to 30N) by using a stepped transport roll having a ratio between the height of the convex portion and the width of the body portion of 0.004 to 0.03. It was confirmed that there was no generation of folds due to buckling even at a conveyance tension of 40 N, and there was no generation of scratches even in the normal conveyance tension range.

  Resin having a film thickness of 50 μm to 250 μm using a stepped transport roll having a ratio of the height of the convex part to the width of the trunk part of 0.003 in the environment shielded from the outside air. Sample No. 1 was prepared by applying the coating liquid while continuously transporting the film-like flexible support made of film at a transport tension of 40N higher than the normal transport tension (10N to 30N). 101, 105, 111, 115, 119, and 125 were not found to be bent due to buckling, but were prepared by coating the coating solution while continuously transporting at 15N, which is the normal transport tension range. Sample No. In 201, 205, 211, 215, 219, and 225, the generation of scratches was observed.

  Resin having a film thickness of 50 μm to 250 μm using a stepped transport roll with a ratio of the height of the convex part to the width of the body part of 0.04 in the environment shielded from outside air. Sample No. 1 was prepared by applying the coating liquid while continuously transporting the film-like flexible support made of film at a transport tension of 40N higher than the normal transport tension (10N to 30N). Nos. 104, 110, 114, 118, 124, and 128 show the occurrence of folds due to buckling. Sample Nos. 10 and 10 were prepared by applying the coating solution while continuously transporting at 15N, which is the normal transport tension range. In 204, 210, 214, 218, 224, and 228, no scratch was observed. The effectiveness of the present invention was confirmed.

  In addition, each sample No. produced in Example 1 was used. When creating 101 to 128, each sample No. 1 produced in Example 2 was used. When creating 201 to 228, the sample was prepared in the same way as all except that the transport tension was changed to 10N, 20N, 30N, and the presence or absence of folds due to buckling, and the presence or absence of scratches. As a result of the evaluation, the same results as in Tables 3 and 4 were obtained.

Example 3
<Production of organic EL element>
A band-shaped organic EL device (base material / first electrode (anode) / hole transport layer / light emitting layer / electron transport layer / second electrode (cathode) / sealing material) is used in the production process shown in FIG. After producing by the method shown below, it cuts and produces an organic EL element, Sample No. 301. The hole transport layer, the light emitting layer, and the electron transport layer were formed by coating with a slit type die coater, and the first electrode (anode) and the second electrode (cathode) were formed by vapor deposition.

(Preparation of stepped transport roll A)
As the stepped transport roll, a stepped transport roll having the following configuration and having the shape shown in FIG. 2 was used.

Material: SUS + hard chrome plating Body diameter: 200mm
Body width (L in FIG. 2): 200 mm
Width of receiving part: 25mm
Height of receiving part (M in FIG. 2): 2 mm
Ratio between the width of the trunk (L in FIG. 2) and the height of the receiving part (M in FIG. 2): 0.01
(Preparation of transport roll B with comparison step)
Same as stepped transport roll A except that the height of the receiving part is 8 mm and the ratio of the width of the body part (L in FIG. 2) to the height of the receiving part (M in FIG. 2) is 0.04. A stepped transport roll was produced and used as a comparative stepped transport roll B.

<Preparation of strip-shaped flexible support with first electrode formed>
PEN was prepared as a strip-shaped flexible support having a thickness of 125 μm, a width of 250 mm, and a length of 500 m, and the prepared stepped transport roll A was used, and the thickness of 120 nm was measured under a vacuum environment condition of transport of 5 × 10 ⁻¹ Pa. A mask pattern is formed by sputtering of ITO (indium tin oxide), and 12 rows of first electrodes of 12 mm × 5 mm having takeout electrodes are continuously formed at regular intervals, wound up and stored once. A strip-shaped flexible support having one electrode formed thereon was produced. In the belt-like flexible support, an alignment mark was previously provided at the same position on the surface where the first electrode is formed and the opposite surface in order to indicate the position where the first electrode is formed. In addition, the stepped conveyance roll A was used as a conveyance roll of the process which forms a 1st electrode.

(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 prepared slit type die coater, the strip-shaped flexible support on which the first electrode is formed is subjected to charge removal treatment, and then the entire upper surface of the strip-shaped flexible support held by the backup roll (however, both ends After applying the prepared coating liquid for forming a hole transport layer under the conditions shown below, the extraction electrode forming portion of the first electrode and the periphery of the first electrode formed by patterning are applied. The hole transport layer was removed by wiping with acetone as a solvent. Thereafter, drying and heat treatment were subsequently performed to form a hole transport layer. In addition, the stepped conveyance roll A was used as a stepped conveyance roll of a positive hole transport layer formation process.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the first electrode forming 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 coating conditions, the hole transport layer forming coating solution has a transport tension of 15 N, a coating speed of 5 m / min, a coating width of 180 mm, a wet film thickness of 2 μm, and the temperature during coating of the hole transport layer forming coating solution is 25 ° C. The test was carried out under an atmospheric pressure of N ₂ gas environment having a dew point temperature of −20 ° C. or lower and a cleanliness class of 5 or lower (JIS B 9920). The coating speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.

(Drying and heat treatment conditions)
As conditions for drying and heat treatment of the coating film for forming the hole transport layer, after applying the coating liquid for forming the hole transport layer and passing through the preliminary drying step, the residual solvent was removed at 120 ° C. using a drying apparatus. Subsequently, a back surface heat transfer type heat treatment was performed at a temperature of 150 ° C. by a heat treatment apparatus to form a hole transport layer.

(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)
After the strip-shaped flexible support formed up to the prepared hole transport layer is electrified and removed, the entire upper surface of the hole transport layer (however, excluding 10 mm at both ends of the strip-shaped flexible support) Using a slit-type die coater, after applying the light emitting layer forming coating solution under the conditions shown below, the hole transport around the first electrode formed by patterning the extraction electrode forming portion of the first electrode and each pattern The layer was removed by wiping with acetone as solvent. Thereafter, a belt-like flexible support having a light emitting layer formed by subsequent drying and heat treatment was produced, and subsequently conveyed to the electron transport layer forming step.

  In addition, the stepped conveyance roll A was used as the stepped conveyance roll of a light emitting layer formation process.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the light emitting 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 light emitting layer forming coating liquid is transported at a tension of 15 N, the coating speed is 5 m / min, the coating width is 180 mm, the wet film thickness is 2 μm, the temperature during coating of the light emitting layer forming coating liquid is 25 ° C., and the dew point temperature − It was performed under atmospheric pressure in an N ₂ gas environment of 20 ° C. or lower and with a cleanliness of class 5 or lower (JIS B 9920). The coating speed was measured by the same measuring method as the coating speed of the hole transport layer.

Drying and heat treatment conditions Drying and heat treatment conditions for the coating film for forming the light emitting layer include applying a coating liquid for forming the light emitting layer, and then using a drying device. The drying condition is a slit nozzle type outlet of the drying device. After removing the solvent at a height of 100 mm toward the film-forming surface, an outlet air velocity of 1 m / s, a wide wind velocity distribution of 5%, and a temperature of 120 ° C., a heat treatment is then performed at 150 ° C. using a heat treatment device. Went.

(Preparation of coating solution for electron transport layer formation)
As a coating liquid for forming an electron transport layer, a 1-butanol solution containing 0.5% by mass of the electron transport material 1 was prepared.

(Formation of electron transport layer)
After the strip-shaped flexible support having the prepared light emitting layer formed thereon is subjected to charge removal treatment, the prepared slit die coater is used on the entire upper surface of the light emitting layer (except 10 mm at both ends of PET). After coating the prepared coating liquid for forming an electron transport layer under the conditions shown below, acetone is used as a solvent with the extraction electrode forming portion of the first electrode and the electron transport layer around each patterned first electrode formed as a pattern. And wiped away. Thereafter, drying and heat treatment were subsequently carried out in the drying section under the conditions shown below to form a patterned electron transport layer. After that, it was wound up and stored once. In addition, the stepped conveyance roll A was used as a stepped conveyance roll of an electron carrying layer formation process.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the electron 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.

(Coating conditions for the electron transport layer forming coating solution)
As the coating conditions, the electron transport layer forming coating liquid was transported at a tension of 15 N, the coating speed of 5 m / min, the coating width of 180 mm, the wet film thickness was 2 μm, and the temperature during coating of the electron transport layer forming coating liquid was 25 ° C. It was performed under an atmospheric pressure of N ₂ gas environment having a dew point temperature of −20 ° C. or lower and a cleanliness level of class 5 or lower (JIS B 9920). The coating speed was measured by the same measuring method as the coating speed of the hole transport layer.

Drying and heat treatment conditions The drying and heat treatment conditions for the coating film for forming the electron transport layer are as follows. After the coating liquid for forming the electron transport layer is applied, a drying apparatus is used. After removing the solvent from the outlet to the film formation surface at a height of 100 mm, outflow air velocity of 1 m / s, wide air velocity distribution of 5%, and a temperature of 120 ° C, the backside heat transfer method at a temperature of 150 ° C by a heat treatment device. The heat treatment was performed.

(Formation of second electrode)
Subsequently, the alignment mark attached to the belt-like flexible support formed up to the electron transport layer is detected, and it is taken out on the first electrode on the electron transport layer formed according to the position of the alignment mark. Except for the portion, the size of the first electrode and the size to form the second electrode extraction electrode, using aluminum as the second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa, by vapor deposition A mask pattern was formed, and a second electrode having a thickness of 100 nm was stacked. In addition, the stepped conveyance roll A was used as a conveyance roll of a 2nd electrode formation process.

(Production of organic EL element)
The strip-shaped flexible support formed up to the second electrode is sealed with a sealing member via an adhesive under the conditions shown below, and the individual organic EL elements are connected to each other. An organic EL element was prepared and sample No. 301. In addition, the stepped conveyance roll A was used as a conveyance roll of a sealing process.

(Applying adhesive)
An alignment mark attached to the belt-like flexible support is detected, and ultraviolet rays are detected on the second electrode and the periphery of the second electrode except for the end portions of the first electrode and the second electrode extraction electrode according to the position of the alignment mark. A curable liquid adhesive (epoxy resin type) was used, and the coating was applied to a thickness of 30 μm.

(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.

(Pasting of sealing member)
The prepared sealing member is stacked on the adhesive coating surface by a roll laminator method, and after pressure-bonding with a pressure of 0.1 MPa in an atmospheric pressure environment, a high-pressure mercury lamp with a wavelength of 365 nm is irradiated with an irradiation intensity of 20 mW / cm ^2. , Irradiated for 1 minute at a distance of 15 mm, fixed and pasted.

(Cutting)
The alignment mark attached to the belt-like flexible support was detected and cut according to the position of the alignment mark.

(Production of comparative organic EL element)
In addition, sample No. was changed except that the stepped transport roll B was used instead of the stepped transport roll A. A comparative organic EL element was prepared by the same method as in Sample 301, and Sample No. 302.

Evaluation Each sample No. As a result of visually observing from the start to the end of the application, whether or not there is a crease due to buckling, attached to 301 and 302. In 301, the occurrence of folds due to buckling was not confirmed. In 302, there was a crease due to buckling, and the process was temporarily stopped, and the part where the crease was caused by buckling was restored and manufactured. The production of 301 took much time and the production efficiency was lowered. The effectiveness of the present invention was confirmed.

Example 4
<Preparation of organic photoelectric conversion element>
A band-shaped organic photoelectric conversion element structure (base material / first electrode (anode) / hole transport layer / photoelectric conversion layer / electron injection layer / second electrode (cathode)) is used in the manufacturing process shown in FIG. After producing by the method shown below, it cuts and produces an organic photoelectric conversion element, sample No. 401. The hole transport layer and the photoelectric conversion layer were formed by coating with a slit type die coater, and the first electrode (anode), the electron injection layer, and the second electrode (cathode) were formed by vapor deposition.

(Preparation of stepped transport roll C)
As the stepped transport roll, a stepped transport roll having the following configuration and having the shape shown in FIG. 2 was used.

Material: SUS + hard chrome plating Body diameter: 200mm
Body width (L in FIG. 2): 200 mm
Width of receiving part: 25mm
Height of receiving part (M in FIG. 2): 2 mm
Ratio between the width of the trunk (L in FIG. 2) and the height of the receiving part (M in FIG. 2): 0.01
(Preparation of transport roll D with comparison step)
The stage prepared in Example 3 except that the height of the receiving portion is 8 mm and the ratio of the width of the trunk portion (L in FIG. 2) to the height of the receiving portion (M in FIG. 2) is 0.04. The same stepped transport roll as the stepped transport roll B was produced and used as a comparative stepped transport roll D.

<Preparation of band-shaped support with first electrode formed>
PET is prepared as a belt-like flexible support having a thickness of 125 μm, a width of 200 mm, and a length of 100 m, and a mask of 120 nm thick ITO (indium tin oxide) is formed by sputtering under a vacuum environment condition of 5 × 10 ⁻¹ Pa. A film was formed into a pattern, and a first electrode having a size of 50 mm × 50 mm having a takeout electrode was continuously formed at regular intervals, wound up and stored, and a first electrode-formed strip-shaped flexible support was produced. In addition, in order to show the position which forms a 1st electrode in advance in the strip | belt-shaped flexible support body, the alignment mark was provided in the same position of the surface in which a 1st electrode is formed, and the opposite surface. In addition, the stepped conveyance roll C was used as a conveyance roll of the process of forming the 1st electrode.

(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 prepared slit-type die coater, the prepared strip-shaped flexible support with the first electrode formed thereon is subjected to charge removal treatment, and then the entire upper surface of the strip-shaped flexible support held by the backup roll (however, , Except for 10 mm at both ends), the prepared coating liquid for forming a hole transport layer is applied under the following conditions, and then the extraction electrode forming portion of the first electrode and the first electrode formed by patterning are formed. The surrounding hole transport layer was removed by wiping with acetone as a solvent. Thereafter, drying and heat treatment were subsequently performed to form a hole transport layer. In addition, the stepped conveyance roll C was used as a conveyance roll of a positive hole transport layer formation process.

(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. It was.

(Application conditions of the coating liquid for forming the hole transport layer)
As the coating conditions, the hole transport layer forming coating solution is transported at a tension of 15 N, the coating speed is 5 m / min, the coating width is 180 mm, and the hole transport layer forming coating solution is applied so that the dry film thickness is 30 nm. The temperature was 25 ° C., the atmospheric pressure was N ₂ gas environment with a dew point temperature of −20 ° C. or lower, and the cleanliness was class 5 or lower (JIS B 9920). The coating speed was measured with a laser Doppler velocimeter LV203 manufactured by Mitsubishi Electric Corporation.

(Drying and heat treatment conditions)
The conditions for drying and heat treatment of the coating film for forming the hole transport layer include applying a coating solution for forming the hole transport layer and passing through the preliminary drying step, and then using the drying device, and using the slit nozzle type flow of the drying device. Residual solvent was removed from the outlet to the film formation surface at a height of 100 mm, outflow air velocity of 1 m / s, wide air velocity distribution of 5%, and a temperature of 120 ° C, and then backside heat transfer method at a temperature of 150 ° C by a heat treatment device. Then, the hole transport layer was formed.

(Preparation of coating liquid for photoelectric conversion layer formation)
P3HT (manufactured by Plextronics: regioregular poly-3-hexylthiophene) (Mw = 52000, polymer p-type semiconductor material) and PCBM (Mw = 911, low-molecular n-type semiconductor material) (photoelectric conversion layer coating solution) Frontier carbon: 6,6-phenyl _{-C 61} - butyric acid methyl ester) a as of 3.0 wt% 1: mixed solution was prepared in 1.

(Formation of photoelectric conversion layer)
After the strip-shaped flexible support formed up to the prepared hole transport layer is electrified and removed, the entire upper surface of the hole transport layer (however, excluding 10 mm at both ends of the strip-shaped flexible support) Using a slit type die coater, after applying the coating liquid for forming the photoelectric conversion layer under the conditions shown below, the extraction electrode forming portion of the first electrode and the holes around the first electrode formed by patterning The transport layer was removed by wiping with acetone as the solvent. After that, a belt-like flexible support having the layers up to the photoelectric conversion layer formed by subsequent drying and heat treatment was produced, and was temporarily wound and stored. In addition, the stepped conveyance roll C was used as the stepped conveyance roll of a photoelectric converting layer formation process.

(Charge removal treatment)
For the charge removal treatment, a non-contact type antistatic device was used on the photoelectric conversion 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.

(Coating conditions for the coating liquid for forming the photoelectric conversion layer)
As for the coating conditions, the photoelectric conversion layer forming coating liquid is transported at a tension of 15 N, the coating speed is 5 m / min, the coating width is 180 mm, and the temperature at the time of applying the photoelectric conversion layer forming coating liquid is such that the thickness after drying is 150 nm. It was carried out under an atmospheric pressure of N ₂ gas environment of 25 ° C. and dew point temperature of −20 ° C. or less, and the cleanliness was class 5 or less (JIS B 9920). The coating speed was measured by the same measuring method as the coating speed of the hole transport layer.

Drying and heat treatment conditions As the drying and heat treatment conditions of the coating film for forming the photoelectric conversion layer, after applying the coating liquid for forming the photoelectric conversion layer, a drying device is used, and the drying conditions are of the slit nozzle type of the drying device. After removing the solvent from the outlet to the film formation surface at a height of 100 mm, outflow air velocity of 1 m / s, wide air velocity distribution of 5%, and a temperature of 120 ° C, the backside heat transfer method at a temperature of 150 ° C by a heat treatment device. Then, the photoelectric conversion layer was formed.

(Formation of electron injection layer)
Each strip-shaped flexible support formed up to the prepared photoelectric conversion layer is subjected to an antistatic treatment, and then, on the formed photoelectric conversion layer, except for a portion that becomes a take-out electrode on the first electrode, 5 × LiF is used as a material for forming an electron injection layer under a vacuum environment condition of 10 ⁻⁴ Pa, and a LiF layer (electron injection layer) having a thickness of 0.5 nm is formed by a vapor deposition method except for a portion that becomes a takeout electrode of the first electrode Are stacked up to the electron injection layer. In addition, the stepped conveyance roll C was used as a conveyance roll of an electron injection layer formation process.

(Formation of second electrode)
Subsequently, the alignment mark attached to the belt-like flexible support formed up to the electron injection layer is detected, and it is taken out on the first electrode on the electron injection layer formed according to the position of the alignment mark. Except for the portion, the size of the first electrode and the size of the second electrode take-out electrode are formed, and aluminum is used as the second electrode forming material under a vacuum of 5 × 10 ⁻⁴ Pa. A mask pattern was formed in the same size as the first electrode by vapor deposition so as to have the extraction electrode at a position not overlapping with the extraction electrode, and a second electrode having a thickness of 100 nm was laminated. In addition, the stepped conveyance roll C was used as a conveyance roll of a 2nd electrode formation process.

(Production of organic photoelectric conversion element)
The strip-shaped flexible support formed up to the second electrode is sealed with a sealing member via an adhesive under the conditions shown below, and the individual organic photoelectric conversion elements are connected, and then cut. An individual organic photoelectric conversion element was prepared and sample No. 401. In addition, the stepped conveyance roll C was used as a conveyance roll of a sealing process.

(Applying adhesive)
An alignment mark attached to the belt-like flexible support is detected, and ultraviolet rays are detected on the second electrode and the periphery of the second electrode except for the end portions of the first electrode and the second electrode extraction electrode according to the position of the alignment mark. A curable liquid adhesive (epoxy resin type) was used, and the coating was applied to a thickness of 30 μm.

(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.

(Pasting of sealing member)
The prepared sealing member is stacked on the adhesive coating surface by a roll laminator method, and after pressure-bonding with a pressure of 0.1 MPa in an atmospheric pressure environment, a high-pressure mercury lamp with a wavelength of 365 nm is irradiated with an irradiation intensity of 20 mW / cm ^2. Then, irradiation was carried out for 1 minute at a distance of 15 mm, followed by bonding, and a plurality of organic EL panels were continuously connected.

(Cutting)
The alignment mark attached to the belt-like flexible support was detected and cut according to the position of the alignment mark.

(Production of comparative organic photoelectric conversion device)
In addition, sample No. was changed except that the stepped transport roll D was used instead of the stepped transport roll C. A comparative organic photoelectric conversion element was prepared by the same method as in Sample 301, and Sample No. 402.

Evaluation The produced sample No. As a result of visually observing from the start to the end of coating whether or not there is a crease due to buckling, the sample No. In 401, the occurrence of folds due to buckling was not confirmed. In No. 402, there was a crease due to buckling, and since the process was temporarily stopped and the part where the crease occurred due to buckling was restored, it was manufactured. The production of 401 took a lot of time and the production efficiency decreased. The effectiveness of the present invention was confirmed.

1 process 1a supply process 1b, 502a, 503a, 504a coating process 1c, 502b, 503b, 504b drying process 1d recovery process 1e, 1e ′, 1e ″, 501b, 501c, 502c, 502f, 502g, 503c, 503e, 503f, 503g, 504c, 504e, 504f, 504g, 506a, 506b, 507c, 507e, 509a Stepped transport rolls 1e1, 1e'1, 1e "1 Body 1e2, 1e'2, 1e" 2, 1e3, 1e'3, 1e ″ 3 receiving portion 1e′11 first body portion 1e′4 second body portion 1e′12 third body portion 3, 6 strip-shaped flexible support 4 organic electronics element 401 base material 402 first electrode (anode)
403 Functional layer 404 Second electrode (cathode)
405 Adhesive layer 406, 510c Sealing member 5 Manufacturing process 501 First supply process 502 Hole transport layer forming process 503 Light emitting layer forming process 504 Electron transport layer forming process 510 Sealing member bonding process 511 Cutting process

Claims (2)

Using the step-shaped transport roll having a belt-shaped flexible support as a transport roll and receiving portions for receiving the band-shaped flexible support at both ends of the body portion in an environment shielded from outside air, In the method of transporting the belt-shaped flexible support that holds both ends of the conductive support in the receiving portion and continuously transports the support,
The belt-like flexible support is a resin film;
The ratio of the height from the central part of the trunk part of the receiving part of the stepped transport roll and the width between the inner surface of the receiving part and the inner surface of the receiving part is 0.004 to 0.03. A method of transporting a belt-like flexible support as a feature.   In the method for manufacturing an organic electronic element having a laminated film having a structure in which at least one organic functional layer is laminated between a first electrode and a second electrode on a belt-like flexible support, A method for producing an organic electronic element, wherein the flexible support is transported by the transport method according to claim 1.

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