TW201213160A - Printing board, method of making thin film using same, and method of making organic EL element - Google Patents

Abstract

Provided is a printing board, wherein the printing board further comprises a first film showing a better flexibility than a glass board, and the glass board is covered by the first film. The first film is disposed between the glass board and projections, and the projections are provided adjacent to the first film. The printing board further comprises a second film showing a better flexibility than the glass board, and the glass board is disposed between the first film and the second film, and the projections are provided on the first film. The first film and the second film are preferable to be constituted from a same material.

Description

201213160 VI. OBJECT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a printing plate, a method for producing a film using the printing plate, and a method for producing an organic EL (Electro Luminescence) device using a printing plate . [Prior Art] A letterpress printing method, a gravure printing method, or the like is known as a plate printing method in which an ink can be pattern-coated in a printed body. The surface of the printing plate used in the plate printing method is formed with irregularities of a specific pattern corresponding to the printed pattern. In the printing, the ink is first held in the convex portion or the concave portion of the printing plate, and then pressed onto the object to be printed, and the ink is applied in a pattern (see, for example, Patent Document 1). [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2006-252787 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) Now, in the printing method, printing using resin or rubber is commonly used. Version, but this printing plate will be slightly deformed when used, and its size will change. Therefore, even if a printing plate having a concave-convex pattern formed with high precision is used, the printed pattern sometimes deviates from the turning. Especially in the field of printing where fine pattern coating is required, even a slight deviation of the print is sometimes not allowed to deviate. For example, in the field of display devices using EL tl devices as pixel light sources, pattern coating with a high accuracy of 3,322,839 201213160 is required. In the display of the reduction, a plurality of organic & =1 direction pieces are arranged in a matrix shape with a slight interval therebetween. The organic EL layer constituting the ^ portion can be formed by a coating method, and the organic nickel layer is formed by a plate printing method. At this time, it is necessary to design the ink containing the material of the organic EL layer as a fine pattern, so that it is difficult to simply print the ink to selectively distribute the entire rubber I. Note: The position of the pixel and the printing plate in which the printing is =1 as the reference in the center of the column direction is -L: The position of the :: direction is slightly changed by the size of the printing plate. The pixels are inconsistent with the printed version. If you want. In particular, when a large image is applied to an unexpected image, the area to be printed becomes large, and it is more difficult to apply the ink to all the pixels correctly. Thus, the object of the present invention is to provide a coated printing plate. The purpose of the present invention is to provide a high-precision pattern (a means for solving the problem). The embossed glass plate of the present invention and the printing plate of the present invention provided on the glass plate are preferably a composite film. The glass-flexible first film is coated with the glass plate, and the glass plate described in the above (1) is more glass plate. =, in the printing plate of the present invention, it is preferable that the glass plate and the convex portion 1 / the film system β and the convex portion are in contact with each other in the above-mentioned first portion! 322839 4 201213160 Set for film. A printing plate of the present invention is preferably provided with a second film which is more flexible than the glass plate, and the glass plate is disposed between the first film and the front film, and the convex portion is similar. Preferably, in the printing plate of the present invention, the first thin film and the second thin film are made of the same material. The method for producing the film of the present invention preferably uses the foregoing. The printing plate prints the ink on the object to be printed and solidifies it to form a thin enamel.

Further, in the method for producing an organic EL element of the present invention, the organic EL element includes a pair of electrodes and an organic EL layer provided between the electrodes, and the manufacturing method is as follows: a step of forming a pair of electrodes The step of the electrode of one of the electrodes includes a step of printing an organic EL ink which is a material of the organic EL layer, and printing on the electrode of the one using a printing plate; and curing the organic ELHp ink. Forming organically less impurities on one of the electrodes; and forming a further one of the pair of electrodes on the organic EL layer. (Effects of the Invention) According to the present invention, a printing plate which can be applied with high precision can be obtained. [Embodiment] The printing plate of the present invention comprises a glass plate and a convex portion provided on the glass plate. Fig. 1 (d) is a pictorial representation of the present embodiment. The printing plate of the invention can be applied to a letterpress printing plate, and can also be adapted to <

S 322839 201213160 Gravure printing plate, but in the following is a description of the relief printing plate. Further, when the ink remains in the concave portion between the convex portions, and the ink is printed on the convex portion by a doctor blade or the like, the printing plate can also be used as a two-page printing plate. Features. As shown in Fig. 1, the printing plate 101 is provided with a glass plate 1〇2 and a convex 1

103. In the present embodiment, the convex portion 103 is in contact with the glass plate 1〇2. X is formed on the glass plate 102 with a convex portion 1〇3 of a pattern corresponding to the pattern of the film to be formed on the ink of the object to be printed. For example, when a plurality of strip-shaped films are formed on a to-be-printed body, a plurality of convex portions extending in a specific direction are disposed at a predetermined interval so as to correspond to the pattern of the strip-shaped film. printed version. Further, for example, when a film of a plurality of sheets arranged in a matrix is formed, that is, a film of a plurality of sheets arranged at a specific interval in a specific column direction and at a specific interval in a predetermined row direction In the case of a pattern of a film corresponding to the plurality of sheets, a plurality of convex portions arranged in a matrix are provided on the printing plate. The glass plate is not easily changed in size when it is used. By forming the convex portions on such a glass plate, the interval between the convex portions is hardly changed, and as a result, high-precision pattern coating can be performed. The printing plate is pressed against the to-be-printed body at the time of printing, and is deformed by the stress at this time to change the size. For example, a flexographic printing plate or the like which is commonly used in printing plates has a large dimensional change due to stress, but the glass plate is not easily changed in size when used, so that high precision can be achieved compared with the conventional printing plate. Pattern coating. Further, for example, the glass plate has a low coefficient of thermal expansion compared to a metal plate or the like, and 6 322839 201213160. Therefore, even when the temperature is different between the printing plate and the printing plate, the dimensional change of the printing plate due to the temperature difference is small. Further, even for the temperature change of the printing step, the change in the size of the printing plate is small. Therefore, high-precision pattern coating can be performed. In particular, in the present embodiment, the convex portion 103 is directly provided in contact with the glass plate 2 having a small dimensional change, so that the interval between the convex portions 1〇3 is not easily changed, and pattern coating with higher precision can be performed. As will be described later, the printing plate is generally used by being wound around a cylindrical shape (see Fig. 5). Therefore, the printing plate must be curled along the surface of the plate. Although depending on the curvature of the surface of the plate, if the glass plate is too thick, it is difficult to wind the printing plate along the surface of the plate, so the thickness of the glass plate should be thin. The thickness of the glass plate is generally from 10 #m to 200 /zm, preferably from 1 〇//m to 30/zm. The glass plate is composed of, for example, soda-1 ime glass, borosilicate glass, or Vycor (registered trademark) glass. Vycor glass is produced by removing B2〇3 from borosilicate glass (main component: B2〇3/Si〇2), and 96% of the composition is a product of Corning, Inc., which is made of cerium oxide glass. These glasses are inorganic glasses composed of inorganic materials. Further, the linear expansion rate of the glass plate used in the printing plate is generally from 0.5 to 10 x 10-6 to 1 〇χ 1 〇 _6 / Κ, preferably from χ 5 χ 10 - δ to 3 χ 1 (Γ 6 / Κ ° is provided on the glass plate 102 The convex portion 1〇3 is made of, for example, a resin such as an acrylate resin or a polyimide. The convex portion 1〇3 is formed into a specific pattern by a photolithographic method using, for example, a photosensitive resin. Fig. 2 is a view schematically showing a printing of 7 322839 201213160 of another embodiment of the present invention. The printing plate 11 of the present embodiment is provided with a first film which exhibits higher flexibility than the first glass plate 12. 14. The curved elastic modulus film 14 is lower than the glass plate 12, and when the force is applied by bending the force between the ends of the glass plate 12 at a unit distance along the plane direction, the first film 14 is the same if the distance and the force are the same. The amount of warpage is larger than the amount of bending of the glass sheet 12. The back surface of the glass sheet 12 is covered by the first film 14. In the present embodiment, the first film 14, the glass sheet 12, and the convex portion 13 are laminated in this order. The first film 14 and the glass plate 12 are bonded via a specific adhesive layer ad The first film 14 is made of, for example, polyethylene terephthalate or polyethylene naphthalate. The thickness of the first film 14 is generally from about 1 Å to about 100 Å, preferably from 10 to 30 Å. Further, the first film 14 exhibits higher flexibility than the glass plate 12, and has a tensile modulus lower than that of the glass plate. For example, the tensile modulus of the quartz glass plate is 7 〇 GPa, but the first The tensile modulus of the film 14 is about 2 to 5 GPa. The adhesive layer AD is made of, for example, an epoxy resin, a polyimide resin, a silicone resin, or a phen〇i resin. It is composed of a polycrystalline epoxy resin or an acrylic resin. The printing plate composed only of the glass plate and the convex portion is in the case of cracking when the plate is attached or moved. Preferably, the first film 14' having a higher flexibility than the glass plate can suppress the occurrence of cracks and improve the operability of the printing plate. Moreover, the glass plate 12 and the convex portion 13 Compared with the glass plate 1〇2 and the convex portion 1〇3 of the embodiment of Fig. 1, the present embodiment is the same as the first embodiment. In the embodiment, the structure is different only in the feature that the first film 14 is provided. 8 322839 201213160 Fig. 3 is a view schematically showing a printing plate according to still another embodiment of the present invention. In the printing plate 21 of the form, the position of the convex portion is different from that of the printing plate of the embodiment shown in Fig. 2, that is, in the embodiment shown in Fig. 2, the convex portion is attached to In the printing plate 21 of the present embodiment, the convex portion 23 is provided in contact with the first film 24, and the first film 24 is provided between the glass plate 22 and the convex portion 23. The glass plate has a low adhesion to other members. For example, there is a case where the adhesion between the convex portion and the glass plate is not high, but the convex portion 23 is formed by being in contact with the first film 24 having higher adhesion than the glass plate 22, thereby improving the adhesion of the convex portion. . Thereby, the durability of the printing plate can be improved. Further, between the first film 24 and the glass plate 22, the adhesive layer AD can be interposed in order to firmly fix the film. The materials of the first film 24, the glass plate 22, the convex portion 23, and the adhesive layer AD are the same as those of the first film 14, the glass plate 12, the convex portion 13, and the adhesive layer AD of the above-described embodiment, and this embodiment is the same. Compared with the second embodiment, the order of the laminates differs in structure. Fig. 4 is a view schematically showing a printing plate according to still another embodiment of the present invention. The printing plate 31 is provided with a second film 35 which exhibits higher flexibility than the glass plate 32. The glass plate 32 is provided between the first film 34 and the second film 35, and the convex portion 33 is provided on the first film 34. In other words, the printing plate 31 is formed by laminating the second film 35, the glass plate 32, the first film 34, and the convex portion 34 in this order. Further, the first film 34 and the glass plate 32 are laminated via the adhesive layer AD1, and the glass plate 32 and the second film 35 are laminated via the adhesive layer AD2. When two sheets of plates with different thermal expansion rates are laminated, the stress of the 322839 201213160 extension of one of the plates is different from the extension of the plate of the other, and the glass plate is made of a glass plate with low thermal expansion rate. In the case of the board, the extension difference also becomes larger. In the present embodiment, the two sheets of film are smashed, and the glass sheets of the first sheet 34 and the glass sheet 32 are produced in the first sheet of the glass sheet 32. The stress is generated between the second film 35 and the glass plate%, and the second stress cancels each other. Therefore, the occurrence of warpage is suppressed. The film 34 and the second film 35 are preferably made of the same material. The first thin medium 34 and the TM =: stress and the second stress cancel each other out more, and are more suppressed. Further, the first film 34 and the second film 35 are preferably composed of the same thickness. . By using the same material film 34 and the second film 35 which are the same as each other, the first stress and the first thinness of the second application are canceled, so that the occurrence of warpage can be further suppressed. The material of the first thin ridge 34 and the adhesive layers ADI and AD2 are the same as those of the slab 32, the first film 24, the glass plate 22, the convex portion 23, and the bonding material. In the first film 34 and the ninth aspect of the present embodiment, the material and the thickness of the ruthenium layer AD are preferably the same as in the embodiment of the present invention. The structure is only the second film. % ' 3 is different. The characteristics are as follows. Next, the method of manufacturing the film using the above printing plate will be described. The printing apparatus having the printing plate described above is schematically shown. The apparatus 41 mainly includes an ink supply source 42 and a front view. The print 42 supplies the ink transfer roller 43 and the above-mentioned printing plate of the ink supplied from the front surface of the table 322839 10 201213160 which is transferred to the front escape e ink supply source p-43 (as pp, representing the flute j η cloth) From the drawings to the middle, the printing plate of any of the embodiments of the drawings). In addition, in the following description, a specific printing apparatus having a printing plate PP is described. However, only the printing plate of each of the above embodiments has no special configuration of the printing device. As described above, the printing plate PP is generally wound around the plate body 44, and for example, when a printing plate pp having a stripe-like convex portion is used, the printing plate PP is used to make it The direction in which the convex portion extends is aligned with the circumferential direction of the plate body 44, or the direction in which the convex portion extends is aligned with the axial direction of the plate body 44, and is wound around the plate body. In the present embodiment, the plate body 44 is rotatably supported by the shaft centering on the center of the center CR1, and is rotated by the driving force from the rotary drive mechanism DRV1. In the figure 5, the (4) 44 series rotates clockwise as indicated by the arrow, and as the plate 44 rotates, the printing plate also rotates. The transfer roller 43 is rotatably supported by the shaft so that the center of the core CR2 is parallel to the axis cri of the body 44, and is rotated by the force (10) originating from the rotary drive mechanism. In the 5th towel, rotate counterclockwise as indicated by the arrow. The transfer roller 43 is made of, for example, chromium, chromium oxide, deoxidized or the like. The transfer crucible 43 may be a so-called anilox roll which is formed with irregularities on the surface, and may be a transfer roller whose surface is flat. The ink supply source 42 accommodates the ink and supplies it to the transfer pro 43. In this embodiment, the slit nozzle 45 is used, and the ink is supplied to the ink 43. Further, in the present embodiment, the printing apparatus 41 is provided with a cleaning mechanism 322839 201213160 46. The cleaning mechanism 46 washes the ink remaining on the transfer roller 43 by transferring the ink by the transfer light 43. For example, odor, = 'make this to the knife to reach _43, and to fall to the residual = 1 h, or use a specific cleaning liquid to wash the transfer ^ printing device 41 with the transfer of the printed body 此 this transfer table The table 48 is kept in the printed body 47, version:. 48. 4, speed, parallel to the tangent direction of the printing plate: the version is horizontally moving. With this transfer table 48~, the σ body also moves in parallel. The heart moves and is printed. The ink supplied from the two ink supply source 42 is inked by the slit nozzle and ink 2: on the roller 43. In this manner, while the ink is supplied from the slit nozzle 45, the transfer roller 43 is rotated to apply the film to the transfer roller and the ink. The surface-printing printing plate is sequentially transferred to the printing plate by the printing ink of the transfer roller 43 that abuts the transfer roller 43; the printing plate is supplied to the printing plate in which the ink is transferred. The ρρ system also rotates in the state of the pressing body 47. The to-be-printed body 47 also moves in parallel at the same time, so that the printing plate 47 is held in the same manner as the rotation of the printing plate ρρ. The convex phase ink is sequentially printed and 'untransferred to the printing plate, and remains in the transfer system, and is removed from the transfer light 43 by the cleaning mechanism 46. ' By using the above steps, the printed body is used. Step 47. Further, the ink can be printed to a film which is formed by curing the printed ink 322839 12 201213160 to form an ink. The curing of the ink can be carried out by removing the solvent. The removal of the solvent is carried out, for example, by natural drying, heat drying, vacuum drying or the like. Further, when the ink contains a material which is hardened by application of light or heat, the ink may be cured by irradiating light or applying heat after the ink is printed by the printing body 47. As described above, since the printing plate PP has a small change in size, the printing variation is small, and the ink can be pattern-coated as intended. By using the printing apparatus described above, a wide variety of films can be formed on the to-be-printed body PP. For example, by appropriately adjusting the ink, an electroconductive thin film having a function as an electrode or a wiring, an active layer of an organic photoelectric conversion element, a semiconductor layer of an organic thin film transistor, and an organic EL layer of an organic EL element to be described later can be formed. Wait. The organic EL element can be formed by using the printing plate PP of each of the above embodiments. In the method of manufacturing an organic EL device of the present embodiment, the organic EL device includes a pair of electrodes and an organic EL layer provided between the electrodes, and the manufacturing method includes the steps of forming a pair of electrodes. a step of forming an electrode of the organic EL layer, which is a material of the organic EL layer, and printing on the electrode of the one using the printing plate; and curing the organic EL ink. a step of forming an organic EL layer on the electrode; and a step of forming the other of the pair of electrodes on the organic EL layer. The organic EL element is used, for example, as a pixel of a display device. In the display device as shown in Fig. 6, a plurality of organic EL elements 1 are provided in a specific arrangement and arranged on the support substrate 6. For example, a plurality of organic 13 322839 201213160 EL elements 1 are arranged in a matrix on the floor substrate 6. In other words, the plurality of organic EL elements 1 are arranged in a specific column direction at a predetermined interval and at a specific interval in a specific row direction. A partition wall IW for distinguishing a plurality of general organic EL elements 1 is provided on the support substrate 6. Then, a plurality of organic EL elements are formed in regions defined by the partition walls IW, respectively. The partition wall IW is δ, for example, striped or lattice-shaped. When the strip-shaped partition wall IW is provided, a plurality of partition walls Iw extending in a specific direction are provided on the substrate at a predetermined interval. Then, each of the organic EL elements J is disposed between the partition walls IW and iw, and is disposed between the partition walls IW and IW at a predetermined interval along the extending direction of the partition wall iw. Further, when the lattice-shaped partition wall iw is provided, each of the organic EL elements 1 is provided in a region which is respectively distinguished by the lattice-shaped partition walls IW. In the present embodiment, a method of producing a plurality of organic EL elements 1 by using the printing plate pp described above on a substrate 6' provided with a stripe-shaped partition wall will be described. First, the electrode 2 of each of the organic EL elements 1 is formed on the support substrate 6. That is, the electrode 2 of one of the numbers corresponding to the number of the organic EL elements 1 is formed on the support substrate 6. The electrodes 2 of the plurality of ones are arranged in a matrix in plan view. Then, a striped partition wall IW is formed. The striped partition wall IW is formed between the adjacent electrodes 2, 2. This partition wall IW can be formed, for example, by using a photosensitive resin and by photolithography. Then, an organic EL layer 1 is formed. In the present embodiment, the 14 322839 201213160 organic EL ink containing the material serving as the organic EL layer is supplied between the stripe-shaped partition walls IW and IW, and further formed by solidification to form between the striped partition walls IW and IW. A strip-shaped organic EL layer 10. Further, the organic EL ink is supplied between the striped partition walls IW and IW by a printing method using the printing plate PP described above. In the above printing method, an organic EL ink containing a material which becomes the organic EL layer 10 is used for the ink, and further, in the printing plate PP, a pattern formed between the partition walls IW and IW is used. Corresponding striped printing plate PP. The organic EL ink is supplied between the partition walls IW and IW by the above printing method, and further, by solidifying, the strip-shaped organic EL layer 10 is formed between the partition walls IW and IW. The organic EL ink used in the formation of the organic EL layer 10 has a solid content of usually 0.5 to 3% by weight, and its viscosity is usually about 5 to 100 cP. Since lcP(centipoise, centipoise)=0. OOlPa · sCPascal-second, Pascal seconds), 5cP to 100cP is 0. 005Pa · s to 0. IPa· s. The solvent or dispersion medium of the organic EL ink may be any one which dissolves or disperses the material which becomes the organic EL layer uniformly. A chlorine solvent such as chloroform, dichloromethane or dichloroethane, an ether solvent such as tetrahydrofuran, an aromatic hydrocarbon solvent such as toluene or xylene, a ketone solvent such as acetone or methyl ethyl ketone, or acetic acid can be suitably used. An ester solvent such as ethyl ester, butyl acetate or ethyl cel losolve acetate, or water or the like is used as a solvent or a dispersion medium. The film thickness of the organic EL layer is usually from 30 nm to 120 nm. The pair of electrodes 2 and 5 is not limited to one layer of the organic EL layer, and a plurality of layers of the organic EL layer are provided as needed. Further, the organic EL layer 10 means a layer provided between all of the electrodes 2 and 5 of the pair. 15 322839 201213160 At least one luminescent layer is provided as an organic EL layer between the electrodes of the pair. When a plurality of organic germanium layers are provided, at least one organic EL layer is formed by a printing method using the above printing plate. Further, in the plurality of organic EL layers, the organic EL which can be formed by the coating method is preferably formed by a printing method using the above printing plate. Further, in the case of a color display device, it is necessary to apply an organic EL ink which emits red and green 'blue light, respectively, to a specific partition wall. At this time, the organic EL ink of each color can be dispensed by the pattern of forming the convex portion of the printing plate corresponding to the pattern of the organic EL ink supplied with each color. After the organic EL layer is formed, another electrode is formed on the organic EL layer, thereby forming a plurality of organic EL layers on the substrate.曰πν In the present embodiment, it is explained that a plurality of organic layers are formed on a substrate on which a plurality of organic EL elements are formed on the substrate 6 on which the stripe partition walls IW are formed, === lattice-shaped partition walls: Each of the organic EL element layers was formed by a method. At this time, the printed version of the complex (four) convex portion of the inferior (four) lang S-segment can be used. <Organic EL 7L device> The component system can be composed of various layers. Law. The layer structure of the EL element, the structure of each layer, and the shape 2 of each layer are composed of a pair of electrodes 2, 5 and a layer provided between the electrodes 5 or a plurality of layers of an organic EL layer, and &quot;luminescence The layer has one layer or a plurality of layers, and the layer has a layer of an organic substance or an inorganic layer. 322839 16 201213160 Further, the organic substance constituting the organic layer may be a low molecular compound, a high molecular compound, or a mixture of a low molecular compound and a high molecular compound. The organic layer is preferably a polymer compound, and is preferably a polymer compound having a number average molecular weight of 103 to 100 in terms of polystyrene. The organic EL layer provided between the cathode and the light-emitting layer may, for example, be an electron injection layer, an electron transport layer, a hole barrier layer or the like. When a layer of both an electron injecting layer and an electron transporting layer is provided between the cathode and the light emitting layer, a layer close to the cathode is referred to as an electron injecting layer, and a layer close to the emitting layer is referred to as an electron transporting layer. The organic EL layer provided between the anode and the light-emitting layer may, for example, be a hole injection layer two-hole transport layer or an electron barrier layer. When a layer of both the hole injection layer and the hole transport layer is provided, the layer close to the anode is referred to as a hole injection layer, and the layer close to the light-emitting layer is referred to as a hole transport layer. The organic EL element may have a specific layer in addition to the light-emitting layer between the electrodes of the pair as described above. The organic layer 10 formed between the electrode (anode) 2 and the electrode (cathode) 5 formed on the support substrate 6 can be, for example, the following configuration. The structure of the organic EL element can be such that, as shown in FIG. 7, the organic layer γ is interposed between the electrode (anode) 2 and the light-emitting layer 4, and the organic layer is interposed between the electrode (the cathode and the precursor layer 4). Structure of X. The structure of the organic EL element can be such that, as shown in Fig. 8, the organic layer γ is interposed between the electrode (anode) 2 and the light-emitting layer 4, and the electrode 5 is directly formed on the light-emitting layer 4. Structure: The structure of the organic EL element can be interposed between the electrode (cathode) 5 and the light-emitting layer 4 as shown in Fig. 9, and the vertical light-emitting layer 4 is directly connected to the electric 曰s 17 322839 201213160 2. The structure of the contact layer. The organic layer X may be composed of two or more organic layers XI and X2 as shown in Fig. 10, and the organic layer Y may be composed of two or more organic layers Y1 as shown in Fig. 11 . The structure of the organic EL element may be such that, as shown in Fig. 14, only the light-emitting layer 4 is formed between the anode 2 and the cathode 5. The layer X provided between the cathode 5 and the light-emitting layer 4 may be For example, an electron injection layer, an electron transport layer, a hole barrier layer, etc. are provided between the cathode 5 and the light-emitting layer 4 as shown in FIG. When the electron injection layer XI and the electron transport layer X2 are both layers, the layer in contact with the cathode is referred to as an electron injection layer XI, and the layer from which the electron injection layer XI is removed is referred to as an electron transport layer X2. The electron injection layer has an improvement source The function of electron injection efficiency from the cathode. The electron transport layer has a function of improving electron injection from a layer contacting the surface of the cathode side. The hole barrier layer has a function of preventing transport of holes. When the injection layer and/or the electron transport layer have a function of preventing the hole transport, the layers also serve as a hole barrier layer. The hole barrier layer has a function of preventing the transport of the hole, and can be produced, for example, by The effect of the blocking is confirmed by the reduction of the current value of the element in which the current of the current flows only. The layer Y provided between the anode 2 and the light-emitting layer 4 may be, for example, a hole injection layer, a hole transport layer, or an electron. a barrier layer, etc. As shown in Fig. 11, when a layer of both the hole injection layer Y1 and the hole transport layer Y2 is provided between the anode 2 and the light-emitting layer 4, the layer connected to the anode is called a hole. Inject layer Y1 to remove this hole Y1 layer into the layer is called Y2. 18 322839 201213160 of the hole injection layer, hole transport function. Lines with the electron barrier layer to prevent transport of electrons

Less and confirm the effect of blocking. =:=:===:::

An example of this. a) Anode 2 / luminescent layer 4 / cathode 5 (refer to Fig. 14) b) Anode 2 / hole injection layer Y / luminescent layer 4 / cathode 5 (refer to Fig. 8) c) Anode 2 / hole injection layer Y / luminescent layer 4 / electron injection layer χ / cathode 5 (refer to Figure 7) d) anode 2 / hole injection layer Υ / luminescent layer 4 / electron transport layer χ / cathode 5 (Figure 7) e) anode 2/ hole injection layer 发光/light-emitting layer 4/electron transport layer χ2/electron injection layer XI/cathode 5 (refer to Fig. 7 and Fig. 10) f) anode 2/hole transport layer Y/light-emitting layer 4/cathode 5 (Refer to Fig. 8) g) Anode 2/hole transport layer Y/light-emitting layer 4/electron injection layer X/cathode 5 (refer to Fig. 7) h) Anode 2/hole transport layer Y/light-emitting layer 4/ Electron transport layer X/cathode 5

S 322839 19 201213160 Photo 7) i) Anode 2 / hole transport layer γ / luminescent layer 4 / electron transport layer X2 / electron injection layer XI / cathode 5 (refer to Figures 7 and 10) j) Anode 2 / Hole injection layer γΐ/hole transport layer Y2/Light-emitting layer 4/Cathode 5 (Refer to Fig. 8 and Fig. 11) k) Anode 2/hole injection layer γι/hole transport layer Y2/light-emitting layer 4/ Electron injection layer X/cathode 5 (refer to Fig. 7 and Fig. 11) l) Anode 2/hole injection layer γι/hole transport layer Y2/light emitting layer 4/electron transport layer X/cathode 5 (refer to Fig. 7) And Fig. 11) m) Anode 2/hole injection layer Y1/hole transport layer Y2/light-emitting layer 4/electron transport layer X2/electron injection layer XI/cathode 5 (refer to Fig. 7, Fig. 10 and Fig. 11) Fig. η) Anode 2 / luminescent layer 4 / electron injection layer X / cathode 5 (refer to Fig. 9) 〇) Anode 2 / luminescent layer 4 / electron transport layer X / cathode 5 (refer to Fig. 9) 阳极) Anode 2 / luminescent layer 4 / electron transporting layer / 2 / electron injecting layer XI / cathode 5 (refer to Fig. 9 and Fig. 1) (here, the symbol "/" means that each layer of the stagnation mark "/" is adjacent to each other and laminated. The same applies to the above) The organic EL device of the present embodiment may have two or more layers. Floor. In the layer structure of the above-mentioned a) to Ρ), when the layered body held by the anode and the cathode is used as the "structural unit A", the structure of the organic EL element having two light-emitting layers can be used. For example, a layer configuration as shown in the following Q) is given. Further, the layer constitutions of the two (structural unit A) may be identical to each other' or may be different. 20 322839 201213160 . q) Anode 2 / (structural unit AV charge generation layer Z / (structural unit A) / cathode. 5 (refer to Fig. 12) Further, "(structural unit A) / charge generation layer" is used as "( In the case of the structural unit B", the composition of the organic germanium element having three or more light-emitting layers may be, for example, a layer configuration as shown in the following r): r) anode 2 / (structural unit B) x / (structural unit) A) / cathode 5 (refer to Fig. 13) Further, the apostrophe "X" indicates an integer of 2 or more, and (structural unit Β) χ indicates a laminated body in which the X segment of the layer is accumulated by the structural unit. Further, the plurality of (structural unit 的) layer constitutions may be the same or different. Here, the charge generating layer Ζ refers to a layer which generates a hole and an electron by applying an electric field, and generates a layer system such as oxidized hunger, indium tin oxide (abbreviated as ΙΤ0), molybdenum oxide, or the like. The film formed. The organic EL element is generally provided on a support substrate. Regarding the organic EL element, the anode in the pair of electrodes formed by the anode and the cathode can be disposed on the support substrate at a position closer to the support substrate than the cathode, and the cathode can be disposed closer to the support than the anode. The substrate is provided on the support substrate. For example, in the configuration of the above-mentioned 〇 to r), the organic EL element having a structure in which the layers are laminated on the support substrate from the right side may be used, or the organic EL element may be formed by laminating the layers on the support substrate from the left side. . The order of the layers of the laminate, the number of layers, and the thickness of each layer can be appropriately set in consideration of luminous efficiency or component life. Next, the materials and formation methods of the respective layers constituting the organic EL element will be described more specifically.

S 322839 21 201213160 &lt;Anode&gt; When the organic EL element _ is configured to emit light emitted from the light-emitting layer through the anode to the outside of the element, the anode is an electrode exhibiting light transmittance. As the electrode which exhibits light transmittance, a film of a metal oxide, a metal sulfide, or a metal can be used, and a conductivity and a light transmittance are preferably used. Specifically, the use of oxidized steel, zinc oxide, tin oxide, indium tin oxide (lndiuro h 〇 Xlde: 1T0), indium zinc oxide (Indium Zinc Oxide: ΙΖ0), gold, platinum, silver, and copper, etc. A film composed of ITG, IZG, or tin oxide is preferably used as the winter film. The method for producing the anode may, for example, be a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, or polythiophene or a derivative thereof may be used. The thickness of the anode is appropriately set in consideration of the characteristics required for the film thickness or the ease of the film formation step, and is, for example, 1 〇 nm to 1 〇 #m, preferably 2 〇 nm to 丄 quot quot, more preferably 50 nm to 500 nm. . &lt;Curtain injection layer&gt; The hole injection layer material constituting the hole injection layer may, for example, be an oxide such as oxidized sharp, oxidized key, cerium oxide, or aluminum oxide, or a stupid amine system or a starburst. Type amines, phthalocyanine systems, amorphous slaves, polyanilines, and polyphene derivatives. The film formation method of the hole injection layer can be carried out, for example, by a solution containing a hole injection material. For example, a solution containing a hole injecting material can be applied to a film by a specific coating method, and a hole injection layer can be formed by curing it. 22 322839 201213160, the cloth method can be, for example, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a bar coating method, and a dip coating. Coating method, spray method, screen printing method (flexographic printing mei; h〇 (i), brushing (〇 ffset printing method), inkjet printing method, etc.: Chengli. 'It is preferable to set the thickness required for the film thickness of the layer by the printing method using the printing plate described above, 简易 the ease of film formation of the burdock, etc., for example, lnra to 5 〇〇 nm, more preferably 5 nm to 200 nm. and 2 nm to &lt;cavity transport layer&gt;: The transport material is, for example, a polygala sylvestre sulphate, a J-key primary bond, a stilbene street organism. , Linhe bio, arylamine-derived organisms, polythiophene or smuggling soil, amines, organisms, polyaniline or its derivatives or its derivatives, knots (thermal + polyarylamine or its derivatives, poly-transfer Stretching the street creatures, or gathering them in the 'holes to send materials to gather money or its derivatives, in the _2 women's base bite or The derivative-based polymethane riding bio-bond has an aromatic amination derivative, a polyarylamine or its derivative, its street organism, polystimulus or its derivative, or poly(2,5-(tetra)指^/(#伸phenyl-extended women's base) polymer hole-wheeling material, soil vinyl) or its derivatives, etc.

S 322839 23 201213160 ==It: ΐ物' is a polyamine having an aromatic amine in the side chain or main chain =1. When the material of the second sub-conductor is transported, it should be dispersed in a high-molecular binder. Electricity: The film formation method of the transport layer is not particularly limited, but if it is a low molecular material '__, if it is formed by a polymer containing polymer and a hole material: a mixed liquid, if it is a polymer hole The transport material may be formed, for example, by a solution containing a hole transport material. : Dissolution: The method of forming a film is, for example, the same coating method as the film formation method of the above-described hole injection layer. The juice 匕 σ knives should be a non-extremely impeding charge transporter. Suitable for those with weak absorption of visible light, such as polycarbonate, polyacrylic acid vinegar, polyacrylic acid vinegar, polymethyl methacrylate Polystyrene, polyglycolized ethylene, polyoxyalkylene, and the like. The thickness of the electric/conveying layer is set by taking into consideration the characteristics obtained by the measurement or the simplicity of the film forming step, and is, for example, _ to _, preferably - to 5 〇〇 nm, more preferably 5 nm to 200 η π ^ &lt; Light-emitting layer &gt; The light-emitting layer is generally formed mainly by an organic substance that emits fluorescence and/or phosphorescence, or an organic substance and a dopant thereof. The dopant is used, for example, to increase the luminous efficiency or to change the wavelength of the light. Further, the organic substance constituting the light-emitting layer may be a low molecular compound or a polymer compound. When the light-emitting layer is formed by a coating method, the light-emitting layer preferably contains a polymer compound. The polystyrene-equivalent number average molecular weight of the polymer compound constituting the light-emitting layer is, for example, about 1 to 3 Å. The luminescent material constituting the luminescent layer can be exemplified by the following pigment-based materials and dopant materials. y, metal complex material, polymer system (pigment material), biological color = ϋ 糸, for example, cycl〇pendamine derivative compound, triphenylamine derivative, phenyl derivative And two (stupidated derivatives, bis(styrene porphin ring compound 1 carboxylic acid derivative, scale derivative, ^, perinone derivative, violent thiophene) a derivative, a quinone dimer, a ratio (4) (pyrazol.^^^, a ruthenium derivative, etc. (a metal complex material) η2 +1: a material, for example, a central metal having Tb, Eu, IS = i sitting, nitrazine, phenyl benzimidazole, quinoline structural metal complex, which case domain complex, homozygous to have a luminescent metal origin derived from the state of double money Compound, (4) (10) complex, benzopyrene, oxime complex, ke. zinc complex, benzoic conjugate, azomethyl zinc complex, bismuth zinc complex, morphine (phenanthroline europium) complex or the like. (Polymer-based material) The polymer-based material may, for example, be a poly-p-phenylene-based derivative, polybenz derivative , derivatives of derivatives, poly-wei derivatives, poly-b-derivatives, scented objects, polyethylene-corrected organisms, the above-mentioned colors 322839 25 201213160 elemental materials or gold secrets (4) orders for the above-mentioned luminescent materials, 3 a &amp; _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ "H poly-p-phenylene derivative, polyvinyl-based carbazole derivative of poly-derivative 4-door knives, poly-p-extension-based derivatives, and derivative. The sound-two green-emitting chair material can be cited, for example, seven. Anthrone derivative, coumarin = polymer, poly-p-phenylene derivative, polyfluorene derivative, etc. Among them, the cargo helmet one (10), the bio-base derivative, the «derivative (four) two-molecule material For the chair material which is red-emitting, the phenylene derivative, the porphin=== and the polymer, the poly-p-phenylene derivative (10)-based derivative, the polythiophene v. Polyfluorene derivative poly-p-phenylene-extension derivative μ v 生物 biological, polythiophene derivative, polyfluorene derivative (Doping material) The material of the foreign matter may, for example, be a flower derivative, a coumarin derivative, a red camp thin (on the (10)) derivative, a ruthenium derivative, a squaraine (s ryiium), a living organism, ° brunin derivative, phenyl biphenyl pigment, tetrazide derivative, (tetra) linketone (py-e) derivative, decacyciene derivative phenophene (% qi (xQxaZQne) derivative, etc. The thickness of such a light-emitting layer is generally about 2 nm to 200 nm. The film formation method of the light-emitting layer is, for example, a method of forming a film from a solution, a vacuum deposition method, a transfer method, etc. 322839 26 201213160 When film formation from a solution The method of applying the solution may, for example, spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire coating, dip coating, slit coating Coating methods such as a capillary coating method, a spray coating method, and a nozzle printing method, and a coating method such as a gravure printing method, a screen printing method, a flexographic printing method, a lithography method, a reverse printing method, or an inkjet printing method, In one embodiment, it is preferable to form it by a printing method using the aforementioned printing plate. &lt;Electron transport layer&gt; The electron transport material constituting the electron transport layer may be a known one, and may, for example, be an oxadiazole derivative, onion dimethane or a derivative thereof, benzoquinone or a derivative thereof, or naphthalene; or a derivative thereof, onion I, or a derivative thereof, tetracyanoquinone dimethane or a derivative thereof, a ketone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative, or 8 a metal complex of hydroxy phthalocyanine or a derivative thereof, polyphosphonium or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and the like. Among these, the electron transport layer material is preferably an oxadiazole derivative, benzoquinone or a derivative thereof, onion or a derivative thereof, or a metal complex of 8-meridene or a derivative thereof, polyquine Or a quinone or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, more preferably 2-(4-biphenyl)-5-(4-t-butylphenyl)-1, 3,4-曙2α sitting, benzene g Kun, Hui brewing i, three (8-喧琳纷) Ming, Ju Yulin. The film formation method of the electron transport layer is not particularly limited. However, if it is a low molecular weight electron transport material, for example, a vacuum deposition method using a powder or a film formation in a molten state or a molten state may be used. Polymer Electron 27 322839 201213160 The transport material can be formed, for example, from a solution or a molten state. Further, when a film is formed from a solution or a molten state, a polymer binder may be used in combination. The method of forming the electron transporting layer into a film from a solution may, for example, be the same as the method of forming a film by injecting a hole into a film from a solution. The film thickness of the electron transporting layer is appropriately set in consideration of the characteristics required for the film formation step, the ease of the film forming step, and the like, and is, for example, from 1 nm to 2 nm to 500 nm', more preferably from 5 nm to 200 nm. &lt;Electron injection layer&gt; The material constituting the electron injection layer is appropriately selected according to the type of the light-emitting layer, and examples thereof include an alkali metal, an alkaline earth metal, and an alloy containing at least one of an alkali metal and an alkaline earth metal. An oxide, a halide, a carbonate, or a mixture of such substances of an alkali metal or an alkaline earth metal. Examples of the alkali metal, the alkali metal oxide, the tooth compound, and the carbonate salt include lithium, sodium, potassium, gamma, annihilation, oxidization, fluorination, sodium oxide, gasification, oxidation, potassium fluoride, Oxidation surface, fluorination surface, oxidation planer, gasification, lithium carbonate, etc. Examples of the alkaline earth metal, the alkaline earth metal oxide, the halide, and the carbonic acid include magnesium m, magnesium oxide, magnesium oxide, oxidized dance, calcium fluoride, cerium oxide, cerium fluoride, cerium oxide, cerium fluoride, and magnesium carbonate. Wait. The in-layer layer may be composed of a laminate having two or more layers, and examples thereof include m F/Ca and the like. The electron injecting layer can be formed by a vapor deposition method, a sputtering method, a printing method, or the like. The film thickness of the electron injection layer should be about lmn to 1/W &lt;cathode&gt; The material of the tower is suitable for the work function, and the electronic charge is applied to the first layer. Material 322839 28 201213160 In the organic EL pieces, in order to reflect the light emitted from the light-emitting layer to the anode side, the material of the cathode is preferably a material having a high visible light reflectance. Cathode, transition metal and 13th gold of the periodic table • Clock 'nano, unloading, surface, absolute, key'

a metal such as ruthenium or iridium, or an alloy of two or more of the above metals, one or more of the above metals, and gold, silver, copper, lanthanum, titanium, lanthanum, nickel, crane, and, for example, a gold layer and an alkaline earth metal. , transitional affiliation, etc. Examples of the material of the cathode include an alloy of one or more kinds of lithium, magnesium, calcium, pin, bismuth, aluminum, and tin, or a graphite or graphite intercalation compound. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-niobium alloy, calcium-aluminum alloy I, and cathode. A transparent conductive electrode composed of a conductive metal oxide and a conductive organic substance is used. Specifically, the conductive metal oxide may, for example, be indium oxide, zinc oxide, tin oxide or antimony. The conductive material may, for example, be polyaniline or a derivative thereof or a poly. ^ phenotype or its derivatives. Further, the cathode may be composed of a laminate having two or more layers. Further, there is also a case where an electron injecting layer is used as a cathode. The film thickness of the cathode is appropriately determined depending on the characteristics required for the film formation or the ease of the film formation step, and the like, for example, 10 nm to 10 &quot; m, preferably 20 nm to 1 &quot;ffl, more preferably 50 nm to 500 nm. * The method for producing the cathode may, for example, be a vacuum deposition method, a sputtering method, or a lamination method in which a metal thin film is thermocompression bonded. EXAMPLES (Letter Printing) The letterpress printing plate uses a ribbed bend made by Microtechnology Research Institute. 29 322839 201213160 Curved glass. Here, in the curved glass to which the ribs are attached, a PEN (polyethylene naphthalate) film is adhered to the back surface of the glass plate with an adhesive, and a polyester resin is used as the photosensitive property on the surface of the glass plate. The resin is formed on the glass plate by a photolithography method from which ribs functioning as convex portions. The thickness of the PEN film was 丨25//111, the thickness of the glass plate was 15 〇 from m, and the thickness of the other layer was 25 cm. The glass material is s〇da glass. A plurality of convex portions extending in parallel with each other are disposed on the glass plate at a predetermined interval. That is, a strip-shaped convex portion is formed. The width of each convex portion is 6 〇/zm, the height is 5 〇//m, and the interval between adjacent convex portions is 24 〇μιη (that is, the pitch is 35 〇em) 〇 (preparation of the substrate) Preparation 200 mm ( Vertical) x2 〇〇 mm (horizontal) x 〇. A 7 mm (thick) transparent glass plate is used as the object to be coated. (Preparation of organic EL ink) A mixed solvent composed of 90 parts by weight of anisole and 1 part by weight of cyclohexylbenzene was prepared, and the organic light-emitting material was dissolved in a concentration of 丨% by weight in the mixed solvent to prepare an organic solvent. EL ink. As the organic light-emitting material, a Southern molecular light-emitting material (manufactured by Summation, trade name: rGreen 1300) was used. The prepared organic EL ink has a viscosity of 25 cp (〇. 〇25 Pa · s). (Printing) Printing was carried out using a "printing test apparatus" manufactured by Dainippon Screen Manufacturing Co., Ltd., which operates in the same manner as the printing apparatus schematically shown in Fig. 5. The printed version uses the prepared printing plate described above. The printing plate is placed on the plate body such that the direction in which the convex portion 322839 30 201213160 extends is aligned with the circumferential direction of the plate body. As described earlier, the organic EL ink is formed on the surface of the transfer roller by using a slit nozzle (the slit width is 220 mm, and the slit gap 50 is supplied to the transfer roller composed of chrome oxide on the surface). Further, in order to push the convex portion of the printing plate into a state of 20 /zm with respect to the transfer roller, the printing plate is pressed against the transfer roller, and the organic EL ink is transferred from the transfer roller to the printing plate. The convex portion. Secondly, the printing plate is pressed against the glass substrate in a state where the convex portion of the printing plate is pushed 20/m with respect to the glass substrate. Thereafter, the organic 1 EL ink is dried to obtain a plurality of bands. Further, the length of each film in the extending direction was 80 mm. (Measurement of Size) Among the plurality of strip-shaped films, the center of the width of one film at one end and the other end of the film were measured. The distance between the center positions of the strips in the width direction (hereinafter referred to as "intercenter distance"). The measurement system uses a length measuring machine (AMIC-300 manufactured by Sokkia). In the above printing, the design is such that the distance between the centers is 145 mm. Printed version. The formed film The distance between the centers covers the direction in which the film extends, and is controlled in the range of 145/zm to ±3 vm, and good results are obtained. (Comparative Example) The printing plate is different only from the embodiment, and is the same as in the first embodiment. The operation is to form a plurality of strip-shaped films. The printing plate uses a flexographic printing plate (material: polyester resin). Further, the design of the pattern of the convex portions is the same as that of the embodiment. (Measurement of dimensions) 31 322839 201213160 In the same manner, the distance between the centers was measured in the same manner. The distance between the centers was 20 μm wider than the set value of 145 mm. [Brief Description] Fig. 1 is a view schematically showing a printing plate according to one embodiment of the present embodiment. Fig. 3 is a view schematically showing a printing plate according to still another embodiment of the present invention. Fig. 4 is a view schematically showing the present invention. Fig. 5 is a view schematically showing a printing apparatus 41 including a printing plate. Fig. 6 is a longitudinal sectional view of a display device including an organic EL element. Have Fig. 8 is a longitudinal sectional view of an organic EL element. Fig. 9 is a longitudinal sectional view of an organic EL element. Fig. 10 is a longitudinal sectional view of an organic EL element. Fig. 11 is an organic EL Fig. 12 is a longitudinal sectional view of an organic EL element. Fig. 13 is a longitudinal sectional view of an organic EL element. Fig. 14 is a longitudinal sectional view of an organic EL element. EL element 322839 32 201213160 2 electrode 4 light-emitting layer 5 electrode 6 support substrate 10 organic EL layer 11 printing plate 12 glass plate 13 convex portion 14 film 21 printing plate 22 glass plate 23 convex portion 24 film 31 printing plate 32 glass plate 33 convex portion 34 film 35 film 41 printing device 42 ink supply source 43 transfer roller 44 plate 45 slit nozzle 46 cleaning mechanism 201213160 47 printed body 48 table 101 printing plate 102 glass plate 103 convex portion A structural unit A AD Agent layer ADI Adhesive layer AD2 Adhesive layer B Building unit B CR1 Axis CR2 Axis DRV1 Rotary drive mechanism DRV2 Rotary drive mechanism IW Partition PP Printing plate X Organic layer XI organic layer X2 organic layer Y organic layer Y1 organic layer Y2 organic layer Z charge generation layer

Claims (1)

201213160 VII. Patent Application Range: 1. A printing plate comprising: a glass plate and a convex portion provided on the glass plate. 2. The printing plate according to claim 1, further comprising a first film which exhibits higher flexibility than the glass plate, and the glass plate is covered by the first film. 3. The printing plate according to claim 2, wherein the first film is provided between the glass plate and the convex portion, and the convex portion is provided in contact with the first film. 4. The printing plate according to claim 2 or 3, further comprising a second film which exhibits higher flexibility than the glass plate, wherein the glass plate is provided on the first film and the second film The convex portion is provided on the first film between the films. 5. The printing plate according to claim 4, wherein the first film and the second film are made of the same material. A method of producing a film according to any one of claims 1 to 5, wherein the ink is printed on the object to be printed, and then cured to form a film. 7. A method of producing an organic EL device comprising: a pair of electrodes and an organic EL layer provided between the electrodes; the manufacturing method comprising the steps of: forming an electrode of one of the pair of electrodes And an organic EL ink containing the material of the organic EL layer, which is printed on the electrode of one of the above, using the printing plate according to any one of claims 1 to 5; a step of curing the organic EL ink to form an organic EL layer on the electrode of the one of the electrodes, and a step of forming the other of the pair of electrodes on the organic EL layer. 322839