JP2005078942A - Transfer material and manufacturing method of organic electroluminescent element using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transfer material having a high transfer performance of an organic thin film layer and a manufacturing method of the organic electroluminescent element using the transfer material. <P>SOLUTION: The transfer material comprising at least one layer of organic thin film 14 on a print block 10 has a release layer 15 between a print block 10 and an organic thin film layer 14, and a manufacturing method of an organic electroluminescent element using the same is provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a transfer material for transferring an organic thin film layer and a method for manufacturing an organic electroluminescent element using the transfer material.

  In the conventional printing method, an organic thin film layer is formed on a film formation surface by applying a coating liquid for an organic thin film layer on a plate, transferring the formed coating liquid layer to the film formation surface and drying it. . In this method, however, uniformity is required when the coating solution for organic thin film layer is applied on the plate, and the layer of the coating solution for organic thin film layer is also uniform when transferring to the deposition surface. Therefore, it is difficult to form a highly uniform organic thin film layer on the film formation surface.

  On the other hand, organic light-emitting elements such as organic EL elements have been attracting attention as new optical devices because they can be easily applied to planar light-emitting elements. Specifically, a solid light-emitting type inexpensive large-area full-color display element and a writing light source array are considered promising, and many developments have been made. In general, an organic light emitting device is composed of a light emitting layer and a pair of counter electrodes (back electrode and transparent electrode) sandwiching the light emitting layer. In the organic light emitting device, when an electric field is applied between the pair of counter electrodes, electrons are injected from one electrode into the organic light emitting device and holes are injected from the other electrode. When electrons and holes are recombined in the light emitting layer and the energy level returns from the conduction band to the valence band, energy is released as light and light is emitted.

  Many of organic thin films of organic electroluminescent elements are formed by vapor deposition. When forming a patterned organic thin film layer, a mask having a patterned opening is used. In the case of forming a fine pattern, if the mask is thick, it disturbs a dissipating path, so that a uniform film cannot be formed. For this reason, the mask is designed to be thin using durable metal, glass, ceramic, heat resistant resin, or the like. However, if it is repeatedly used, distortion occurs and the position of the predetermined pattern is shifted, so that productivity is lacking.

  Japanese Patent Laid-Open Nos. 9-167684 and 2000-195665 (Patent Documents 1 and 2) form an organic thin film layer uniformly on a temporary substrate of mica or film in advance by vapor deposition, and then the substrate and the organic thin film layer are formed. Proposes a method of heating and vapor deposition. However, in these methods, a uniform organic thin film layer can be formed in the first vapor deposition, but in the next proximity vapor deposition, there is a problem that uniform vapor deposition is difficult and production efficiency is poor.

  Polyparaphenylene vinylene that emits green light (“Nature”, 347, 539, 1990), poly 3-alkylthiophene that exhibits reddish-blue light (Japanese Journal of Applied Physics, Volume 30, L1938 (1991), polyluminescent fluorene (Japanese Journal of Applied Physics, Volume 30, L1941 (1991)) as a blue light emitting element, and light emitting thin films made of polymers and low molecular compounds. A polymer element using a light-emitting thin film dispersed in a binder resin is also known. These polymer-type devices are advantageous for increasing the area and are expected to be used for flexible displays, but vapor deposition methods cannot be applied to the formation of organic light-emitting thin films. For this reason, a thin film is usually formed directly on a substrate by a wet method, but in the wet method, the film thickness uniformity of the organic thin film becomes insufficient due to the surface tension of the solution, or when organic thin film layers are laminated. There exists a problem that each organic thin film layer will melt | dissolve in an interface. For this reason, the organic electroluminescent element obtained by this method has a problem that it is inferior in luminous efficiency and element durability.

  WO 00/41893 (Patent Document 3) proposes a method of thermal transfer with a laser using a donor sheet having an organic thin film and a photothermal conversion layer. However, in the case of thermal transfer as in WO 00/41893, there is a problem of gas entrainment at the bonding interface of the organic thin film layer. Depending on the state of the interface of the organic thin film layer, the light emission efficiency and durability of the organic electroluminescent device and the uniformity of the light emitting surface are different, and the device function deteriorates if gas is involved in the bonding interface of the organic thin film layer.

  In the case of pattern-shaped thermal writing using a thermal head or a laser used in the printing technology field, a temperature distribution is generated around the pattern due to thermal diffusivity, and the contour of the organic thin film pattern is not cut cleanly from the donor side. For this reason, there are problems in that the amount of emitted light varies, electrical defects and defects due to thin film fragments occur, and durability deteriorates. In addition, there is a problem in yield reduction due to poor alignment between the substrate and the thermal head or laser.

Japanese Unexamined Patent Publication No. 9-67684 JP 2000-195665 A WO 00/41893

  Accordingly, an object of the present invention is to provide a transfer material having a high transferability of an organic thin film layer and a method for producing an organic electroluminescent device using the transfer material.

  As a result of earnest research in view of the above object, the present inventor has obtained a transfer material having an organic thin film layer on the plate, and the contact angle with respect to pure water of the surface of the plate in contact with the organic thin film layer is 50 ° or more. Is excellent in transferability of organic thin film layers, can transfer organic thin film layers with uniform film thickness, and by using this transfer material, it has excellent luminous efficiency and uniformity of light emission and durability. The inventors have found that an electroluminescent device can be produced at low cost and have arrived at the present invention.

  That is, the transfer material of the present invention is a transfer material having at least one organic thin film layer on a plate, and the contact surface of the plate with the organic thin film layer has a contact angle with respect to pure water of 50 ° or more. Features.

  A preferred embodiment of the transfer material of the present invention has at least one surface treatment layer and a release layer between the plate and the organic thin film layer, and at least one layer of the organic thin film layer of the surface treatment layer and the release layer. The contact surface with the pure water has a contact angle with respect to pure water of 50 ° or more.

  The release layer contains a release agent, and the release agent comprises at least one selected from the group consisting of silicon-containing compounds, fluorine-containing compounds, waxes, inorganic fillers, organic fillers, surfactants and metal soaps. Is preferred.

  It is preferable that the surface of the plate has a functional group that reacts with the resin forming the release layer. Further, the maximum surface roughness Rmax (specified by JIS B 0601-1982) of the surface of the plate in contact with the organic thin film layer, that is, the organic thin film layer forming surface is determined when the film thickness of the organic thin film layer is 100. It is preferably 0-50.

  The method for producing an organic electroluminescent element of the present invention uses the transfer material of the present invention to apply the transfer material so that the organic thin film layer side faces the electrode side of the first substrate having electrodes on part or the entire surface. It is characterized by including a step of transferring the organic thin film layer to the electrode side of the first substrate by peeling off the plate after the pressure treatment is repeated.

  After the step of transferring the organic thin film layer to the electrode side of the first substrate, the both substrates are overlapped so that the organic thin film layer faces the electrode side of the second substrate having electrodes on a part or the whole surface. It is preferable to have the process of pressurizing.

  A transfer material having an organic thin film layer on the plate whose contact angle with the pure water on the surface on which the organic thin film layer is formed (the surface in contact with the organic thin film layer) is 50 ° or more. Is excellent. By providing a surface treatment layer and / or a release layer between the plate and the organic thin film layer, the contact angle with pure water can be 50 ° or more.

  In a method for manufacturing an organic electroluminescent device that transfers an organic thin film layer of a transfer material onto a film-forming surface of a substrate, the contact angle between the organic thin film layer forming surface of the plate and pure water is 50 ° or more, The transfer property of the layer onto the substrate is improved, and an organic electroluminescence device having excellent light emission efficiency and uniformity of light emission amount and durability can be produced. The plate of the transfer material can be used repeatedly and does not need to be washed after the transfer process, so that an organic electroluminescent element can be produced at a low cost.

  First, the transfer material of the present invention will be described, then the method for producing the organic electroluminescent device will be described, and finally the organic electroluminescent device will be described.

[1] Transfer material
(1) Structure The transfer material has a plate-like or sheet-like plate and at least one organic thin film layer formed on the plate. When a plurality of organic thin film layers are transferred onto the film formation surface, the organic thin film layers may be formed on the plurality of plates, respectively, or the organic thin film layers may be provided in the surface order on one plate. By using a transfer material having a plurality of organic thin film layers, a multilayer film can be laminated on the film formation surface of the substrate in one transfer step.

  When laminating a plurality of organic thin film layers on a plate, a uniform multilayer film cannot be laminated on the film formation surface unless the interfaces of the laminated organic thin film layers are uniform. For this reason, in order to make the interface uniform, it is necessary to carefully select a film forming method according to the type of the organic thin film layer and the film formation surface. The film forming method is not particularly limited as long as it can form a thin film, and may be a wet method or a dry method such as vapor deposition.

(2) Version (temporary support)
Examples of the plate include a relief plate, a planographic plate, an intaglio plate, and a stencil plate. The plate does not require flexibility. The shape of the plate constituting the transfer material used in the production method of the present invention is not particularly limited, but it is a relief plate having a pattern portion formed in a convex shape and a non-pattern portion located at a position recessed from the pattern portion. More preferred. “Pattern portion” refers to a portion patterned into a shape to be transferred in order to form an organic thin film layer on the surface, and “non-pattern portion” refers to a portion other than the pattern portion. If the plate on which the transfer material is formed is a lithographic plate composed of a lyophilic pattern portion and a water-repellent non-pattern portion, the plate comes into contact with the entire surface to be deposited, so the plate is deposited. Air bubbles easily enter when stacked on the surface. If the surface of the non-pattern part is in the same plane and the pattern part is an intaglio indented from this surface, material loss occurs during production, which is not preferable. Further, in the case of a stencil made of a film or plate having a pattern part penetrating from the front to the back, the organic thin film remains in the hole and material loss occurs, which is not preferable.

  The letterpress includes a pattern portion formed so that the upper surface is flush with the non-pattern portion that is recessed from the upper surface of the pattern portion. The relief pattern portion is in contact with the film formation surface, but the non-pattern portion is not in contact with the film formation surface. There are two types of relief printing plates, one produced mechanically and one produced chemically. The letterpress plates that are mechanically produced include original plates that use letterpress (typesets with typesetting, photographs that are incorporated into letterpresses) themselves, lead plates that are made by casting an alloy into the original plate, wood plates, plastic plates, Examples include rubber plates. Examples of the chemically produced relief include those produced from an original plate using electroplating. A line drawing letterpress is used for printing a line drawing without gradation, and a mesh letterpress or an electronic engraving letterpress is used for printing an image with gradation such as a photograph.

  FIG. 1 shows an example of the transfer material of the present invention. As shown in FIGS. 1A and 1B, the relief plate 10 has a plate-like main body portion 11, and a plurality of convex pattern portions 12 are formed on the main body portion 11. The surface on the pattern portion 12 side of the relief plate 10 is an organic thin film layer forming surface 13, and the organic thin film layer 14 is formed on the organic thin film layer forming surface 13. In this example, the organic thin film layer 14 is formed on the entire organic thin film layer forming surface 13, but the present invention is not limited to this, and the relief plate 10 has the organic thin film layer 14 only on the upper surface 120 of the pattern portion 12. You may do it.

  The pattern portion 12 is arranged so that the organic thin film layer 14 to be transferred has a desired pattern. In this example, the pattern portion 12 has a rectangular cross section, but the present invention is not limited to this, and the cross section of the pattern portion 12 may be a square or a trapezoid. The height of the pattern portion 12 is preferably 0.5 to 50 μm. If the height of the pattern portion 12 is less than 0.5 μm, the organic thin film layer 14 may be transferred to a portion other than the pattern. If the height of the pattern portion 12 is more than 50 μm, it is not preferable because the pattern portion 12 is easily broken.

  The shape, structure, size and the like of the plate 10 are not particularly limited, and can be appropriately selected according to the use, purpose, etc. of the organic electroluminescent element to be produced. Generally, it is roll shape, plate shape, or sheet shape. The plate is preferably transparent or translucent. When the plate is transparent or translucent, patterning can be aligned by observing from the plate side in a state where the plate is overlaid on the substrate.

  Since the pattern portion of the lithographic plate is treated with a lyophilic solution and the non-patterned portion is treated with a liquid repellent treatment, an organic thin film having a desired pattern on the lithographic plate is applied when a coating liquid for forming an organic thin film layer is applied to the plate. A layer can be formed.

  As a method for producing a lithographic plate, a method of chemically treating the surface of a plate-like plate can be mentioned. For example, a lyophilic treatment is performed on the plate so as to form a predetermined pattern, and the lyophilic treatment is performed on the surface other than the lyophilic portion, and the lyophilic treatment pattern portion and the surface subjected to the lyophobic treatment. And a non-patterned portion can be formed.

  As the lithographic plate, a lithographic plate mainly composed of calcium carbonate, a metallic lithographic plate made of zinc or aluminum, etc., a multi-layer lithographic plate in which a plate material composed of two different metals in layers is provided on a supporting plate, and gelatin is a main component. As an example, there is a collotype in which a non-patterned portion is formed by absorbing or swelling the coating solution for an organic thin film layer in a portion that is not cured to use a cured portion.

  The intaglio has a structure in which the upper surface of the non-pattern part is in the same plane and the pattern part is depressed more than this surface. In the case of an intaglio, an organic thin film layer is formed on the entire surface of the intaglio, and the non-patterned organic thin film layer is wiped or scraped off, leaving a predetermined pattern portion in the depressed portion. The intaglio is produced by mechanical engraving on a copper plate or the like, or chemically by etching produced by corroding a predetermined pattern portion using a chemical solution. There is a gravure plate that forms a photographic layer by corroding a copper plate or a copper cylindrical surface, and an electronic engraving gravure that is produced by electronic and / or mechanical engraving.

  The pattern portion of the stencil is a film or plate having holes penetrating from the front to the back. An organic thin film layer is formed by filling the hole with a coating solution and drying. As the stencil, there are a copying plate, a wire mesh used for silk screen printing, a silk mesh, and the like.

  The material of the plate is not particularly limited as long as it is chemically and thermally stable. Specifically, metal foil such as glass plate, aluminum foil, copper foil, stainless steel foil, gold foil, silver foil, polyimide, liquid crystalline polymer, fluororesin [for example, tetrafluoroethylene resin (PTFE), trifluorochloroethylene resin (PCTFE)], polyester (for example, polyethylene terephthalate, polyethylene naphthalate (PEN)), polycarbonate, polyethersulfone (PES), polyolefin (for example, polyethylene, polypropylene), polyarylate, a sheet made of plastic such as hard vinyl chloride, or These laminated bodies can be mentioned. Among these, an aluminum foil, a copper foil, a stainless steel foil, a glass plate or a laminate thereof is preferable from the viewpoint of ease of processing and cost. For example, it is preferable to use white plate glass. In the present invention, “white plate glass” means a glass having less iron content and less bluish than soda lime glass. Soda lime glass is a common glass used for window glass.

  The thickness of the plate is not particularly limited, but is preferably thicker for repeated use, and is appropriately selected according to the specifications incorporated in the production facility. Typical plate thickness is 0.5 μm to 5 m. The structure and size of the plate are not particularly limited, and can be appropriately selected according to the specifications and purpose of the production equipment.

  The contact angle with the pure water on the surface in contact with the organic thin film layer, that is, the organic thin film layer forming surface of the plate is preferably 50 ° or more, more preferably 60 ° or more, and 70 ° or more. Is particularly preferred. The contact angle between the organic thin film layer forming surface and pure water is an angle formed between the organic thin film layer forming surface and a tangent drawn from the contact point of pure water to the surface of the water droplet. The measuring method is not particularly limited as long as it is a general contact angle measuring device that measures a water droplet that has been allowed to stand immediately after dropping. Specifically, it can be measured with model number CA-X manufactured by Kyowa Interface Science Co., Ltd. The measurement is preferably performed under constant conditions of a temperature of 21 to 24 ° C. and a relative humidity of about 45 to 55%. If the contact angle with pure water is less than 50 °, the organic thin film layer is too close to the support and / or the plate, so that the transferability is excessively deteriorated.

  When an organic thin film layer is provided on a plate by a coating method, it depends on the composition of the coating solution, but if the contact angle exceeds 90 °, the solution becomes uneven, which is not preferable. When the organic thin film layer is provided by a dry method such as a vacuum film forming method or a transfer peeling method, there is no such problem, and there is no particular upper limit.

  FIG. 3 shows a side view of the droplet formed on the plate. In order to obtain the contact angle θ, a straight line 26 is drawn from the top 23 of the droplet 22 dropped on the organic thin film layer forming surface 21 of the plate to the contact point 25 between the plate and pure water, and this straight line 26 and the organic thin film layer forming surface are drawn. Measure the angle α with 21. The contact angle θ, which is the angle formed between the plate and the tangent line 24 of the droplet 22, is twice as large as α.

In order to set the contact angle to 50 ° or more, it is preferable to provide a surface treatment layer (water-repellent treatment layer) on the surface of the plate. The surface treatment layer may be provided at least on the organic thin film layer forming surface. For example, in the case of a relief plate, a surface treatment layer may be provided at least on the upper surface of the protrusion. Examples of the method for forming the surface treatment layer (surface water repellency treatment) include fluorination treatment, corona discharge treatment, plasma treatment, ozone treatment, flame treatment, and glow discharge treatment. As the fluorination treatment, a plasma treatment using a fluorocarbon gas (CF ₄ gas or the like) or a method of exposing to a vapor of a fluorine alkyl coupling agent (for example, perfluoroalkyl functional silane, preferably perfluoroalkyltrimethoxysilane). Etc.

  Prior to the water repellent treatment, an undercoat layer may be provided on the plate. By providing the undercoat layer, the surface water-repellent effect can be improved.

(3) Release layer The transfer material preferably has a release layer on the surface on which the organic thin film layer is formed, and the release layer preferably contains a component having a release effect (release agent). The mold release effect is an effect in which the organic thin film layer is not fused to the plate side when the transfer material is heated and / or pressurized while being superimposed on the substrate and peeled off, and is efficiently transferred to the substrate.

  FIG. 2 shows a transfer material having a release layer 15. The release layer 15 is uniformly formed on the surface on the pattern portion 12 side. The surface of the release layer 15 is an organic thin film layer forming surface 130, and the organic thin film layer 14 is uniformly formed on the organic thin film layer forming surface 130. The thickness of the release layer 15 is preferably 0.5 nm to 50 μm. If the thickness is less than 0.5 nm, it is difficult to obtain a sufficient release effect.

  Materials for forming the release layer include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and vinyl chloride. Vinyl acetate copolymers, vinyl resins such as polyacrylates, polystyrene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, copolymers of olefins such as ethylene and propylene and other vinyl monomers, Examples include cellulose resins such as ionomers, ethyl cellulose, and cellulose acetate, polycarbonate resins, and phenoxy resins. Of these, vinyl resins and polyester resins are preferred. These resins may be used alone or in combination of two or more.

  The release layer may contain a release agent. Examples of the mold release agent include silicon-containing compounds, fluorine-containing compounds, waxes, inorganic fillers, organic fillers, surfactants, metal soaps, and the like. The silicon-containing compound is preferably at least one selected from the group consisting of a silane compound, silicone oil, silicone rubber, and silicone resin. The fluorine-containing compound is preferably at least one selected from the group consisting of fluorine-based surfactants, fluorine-based oils, fluorine rubber, and fluorine resins. These release agents may be used alone or in combination of two or more.

  The release layer may have a functional group that reacts with the surface of the plate and / or the resin that forms the release layer. For example, a resin having a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an acrylic group, or a methacryl group is used as a resin for forming a surface layer and / or a release layer of the plate. The release layer can be fixed to the plate by reacting a silicon-containing compound having a functional group such as a carboxyl group, a hydroxyl group, an amino group, an epoxy group, or an isocyanate group, or a fluorine-containing compound. In addition, a resin having a reactive group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an acrylic group, or a methacryl group is used as a resin for forming a release layer, and a silicon-containing compound, a fluorine-containing compound, or the like having the above functional group And may be reacted in the release layer. By crosslinking within the release layer, the release layer is cured and the release effect can be enhanced. The release agent having a functional group may react with both the surface of the plate and the resin forming the release layer.

  The reactive group (hydrophilic group such as hydroxyl group) on the plate surface may be formed by activation treatment such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, glow discharge treatment and the like. The reaction between the release agent having a functional group and the resin forming the surface of the plate and / or the release layer can be performed by heat, light, or the like. Therefore, after forming the release layer on the plate, the reaction can be advanced by a heating and drying process.

  As the release agent having a functional group, modified silicones such as epoxy modification, vinyl modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy / polyether modification, polyether modification, etc. Examples thereof include oil, modified silicone resin, modified fluororesin, and modified fluororubber.

Hereinafter, the release agent used for the release layer will be described in more detail.
(A) Silicon-containing compound
(a) Silane compounds Silane compounds include Si (OCH ₃ ) ₄ , CH ₃ Si (OCH ₃ ) ₃ , HSi (OCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , CH ₃ SiH (OCH ₃ ) ₂ , C ₆ H ₅ Si (OCH ₃ ) ₃ , Si (OC ₂ H ₅ ) ₄ , CH ₃ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₂ Si (OC ₂ H ₅ ) ₂ , H ₂ Si (OC ₂ H ₅ ) ₂ , C ₆ H ₅ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₂ CHCH ₂ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₁₇ Si (OC ₂ H ₅ ) ₃ , (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , [(CH ₃ ) SiNH] ₂ CO, tert-C ₄ H ₉ (CH ₃ ) ₂ SiCl, HSC ₃ H ₆ Si (OCH ₃ ) ₃ , silane coupling agents, fluorine-containing silane compounds, isocyanate silane compounds, and their hydrolysates And partial hydrolysates. Among these, fluorine-containing silane compounds include CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , C ₆ F ₁₃ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₇ F ₁₅ CONH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , C ₈ F ₁₇ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₈ F ₁₇ C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ , C ₈ F ₁₇ C ₂ H ₄ Si [ ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , C ₉ F ₁₉ C ₂ H ₄ Si (OCH ₃ ) ₃ , C ₉ F ₁₉ C ₂ H ₄ Si (NCO) ₃ , (NCO) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (NCO) ₃ , C ₉ F ₁₉ C ₂ H ₄ Si (C ₂ H ₅ ) (OCH ₃ ) ₂ , (CH ₃ O) ₃ SiC ₂ H ₄ C ₈ F _{16 C 2 H 4 Si (OCH 3} ) 3, include _{(CH 3 O) 2 (CH} 3) SiC 9 F 18 C 2 H 4 Si (CH 3) (OCH 3) 2 and the like. As isocyanate silane compounds, (CH ₃ ) ₃ SiNCO, (CH ₃ ) ₂ Si (NCO) ₂ , CH ₃ Si (NCO) ₃ , vinylsilyl triisocyanate, C ₆ H ₅ Si (NCO) ₃ , Si ( NCO) ₄ , C ₂ H ₅ OSi (NCO) ₃ , C ₈ H ₁₇ Si (NCO) ₃ , C ₁₈ H ₃₇ Si (NCO) ₃ , (NCO) ₃ SiC ₂ H ₄ (NCO) ₃ .

(b) Silicone rubber Silicone rubber includes millable silicone rubber (dimethyl, methyl vinyl, methyl phenyl vinyl, methyl fluoroalkyl, etc.) and liquid silicone rubber (condensation silicone rubber, addition silicone rubber, ultraviolet rays) Curable silicone rubber). These silicone rubbers may be modified silicone rubbers such as epoxy-modified, vinyl-modified, amino-modified, carboxyl-modified and alcohol-modified.

(c) Silicone Resin Generally, the silicone resin includes a silicone resin having a high degree of polymerization and a silicone varnish having a relatively low molecular weight. Examples of the silicone varnish include silicone alkyd varnish, silicone epoxy varnish, silicone polyester varnish, modified varnish obtained by reacting these with acrylic resin, phenol resin, polyurethane, melamine resin and the like. The silicone resin may be a modified silicone resin such as epoxy modification, vinyl modification, amino modification, carboxyl modification, alcohol modification and the like.

(d) Silicone oil Examples of the silicone oil include dimethylpolysiloxane and methylphenylpolysiloxane type silicone oils, methylhydrogen silicone oils, and modified silicone oils in which a reactive group is introduced into the molecule.

  As the modified silicone oil, modified silicone oils such as carboxyl modification, amino modification, epoxy modification, polyether modification, and alkyl modification can be used. For example, the modified silicone oil described in pages 6 to 18B of “modified silicone oil” technical data (published by Shin-Etsu Silicone Co., Ltd.) can be given. When adding to an organic solvent-based release layer forming resin, an amino-modified silicone oil having a group capable of reacting with a reactive group (for example, isocyanate) of the resin is preferable, and when adding by emulsifying and dispersing in a water-soluble resin Is preferably a carboxyl-modified silicone oil (for example, trade name X-22-3710 manufactured by Shin-Etsu Silicone Co., Ltd.). Examples of the modified silicone oil include the following skeleton structures and compounds thereof.

(B) Fluorine-containing compound The fluorine-containing compound may have a low molecular weight or a high molecular weight. Examples of low molecular weight fluorine-containing compounds include U.S. Pat.No. 3,775,126, U.S. Pat.No. 3,589,906, U.S. Pat.No. 3,798,265, U.S. Pat. No. 3,779,768, U.S. Pat. 48-87826, JP 49-10722, JP 49-46733, JP 50-16525, JP 50-113221, JP 50-161236, JP 50- 99525, JP 50-160034, JP 51-43131, JP 51-106419, JP 51-7917, JP 51-32322, JP 51-151125 JP-A-51-151126, JP-A-51-151127, JP-A-51-129229, JP-A-52-127974, JP-A-52-80023, JP-A-53-84712, Kaisho 53-146622, JP 54-14224, JP 54-48520, JP 55-7762, JP 56-55942, JP 56-114944, JP Examples thereof include compounds described in 56-114945, JP-B 57-8456, JP-B 57-12130, JP-B 57-12135, and JP-B 58-9408. Examples of the polymer fluorine-containing compound include U.S. Pat.No. 4,175,969, U.S. Pat.No. 4087394, U.S. Pat.No. 4016125, U.S. Pat.No. 3,676,123, U.S. Pat. Kaisho 54-158222, JP 55-57842, JP 57-11342, JP 57-19735, JP 57-179837, “Chemical Review No. 27, New Fluorine Chemistry” (The Chemical Society of Japan, 1980), “Functional fluorine-containing polymers” (edited by Nikkan Kogyo Shimbun, 1982), and the like. These fluorine-containing compounds can be produced by the methods described in the above-mentioned related documents, and can also be synthesized by fluorination of corresponding hydrocarbons. Fluorination of hydrocarbons is described in “New Experimental Chemistry Course” Vol. 14 [I] (Maruzen, 1977), pages 308-331 can be used.

Preferred examples of the fluorine-containing compound used in the present invention are shown below.
(a) Fluorosurfactant

  In addition, Dainippon Ink Mfg. F-171 to 173, F-141 to 144, F170 to 173, F-180 to 184, F-192 to 195, F-522; manufactured by Asahi Glass Co., Ltd. Surflon S-111 to 113, S-131 to 133, S-141, S-101, S-105, S-381, S-382; Neos Corporation's Footgent 400S, etc. are mentioned. Among these, betaine surfactants are preferably used.

(b) Fluorine oil (or grease)
Examples of the fluorinated oil include compounds having the following structure. The fluorinated oil may be a modified product such as isocyanate modified or carboxyl modified. For example, when it has OCN-C ₆ H ₃ (CH ₃ ) NHCO— at the end of the molecule, it is an isocyanate-modified product, and when it has —COOH, it is a carboxyl-modified product, —CH ₂ OH, —CF ₂ CH ₂ When it has (OCH ₂ CH ₂ ) nOH (n represents a natural number), etc., it is an alcohol-modified product, and when it has —COOR (R: an alkyl group), it is an ester-modified product.

(c) Fluororesin Fluororesin includes fluoroethylene resin (tetrafluoroethylene resin, ethylene trifluoride resin, ethylene difluoride resin, etc.), tetrafluoroethylene telomer, ethylene trifluoride chloride resin, fluoride Vinylidene resin, propylene hexafluoride-tetrafluoroethylene copolymer, copolymer of tetrafluoroethylene and perfluoroalkoxyethylene, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene tetrafluoride and ethylene Examples include copolymers and modified fluororesins.

  The modified fluororesin is reactive with the main chain or side chain of the polymer by copolymerizing a functional group-containing or polyfunctional comonomer (vinyl compound, etc.) at the time of synthesis of each of the above fluororesins, or by graft copolymerization, substitution reaction, etc. This is a modification in which the original properties of the fluororesin are not impaired by introducing a functional group having a valence. Examples of the functional group having reactivity include a carboxyl group, an acid anhydride, an epoxy group, a hydroxyl group, a chloromethyl group, an isocyanate group, an amino group, and an aldehyde group. Of these, from the viewpoint of easy introduction of functional groups and reactivity with amino groups, modified fluororesins such as carboxyl-modified and epoxy-modified are preferred.

(d) Fluororubber Fluororubber includes copolymer of vinylidene fluoride and perfluoropropene (FKM), copolymer of vinylidene fluoride and ethylene trifluoride chloride, alternating of tetrafluoroethylene and propylene. And a copolymer, a copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether (FFKM), and the like. The fluororubber may be a modified fluororubber in which a reactive functional group is introduced into the main chain or side chain of the polymer.

(C) Wax Examples of the wax include microcrystalline wax, carnauba wax, paraffin wax, Fischer-Tropsch wax, montan wax, sazol wax, various low molecular weight polyethylene, wood wax, beeswax, whale wax, ibota wax, wool wax, shellac wax, Examples include candelilla wax, petrolactam, polyester wax, partially modified wax, fatty acid ester, fatty acid amide, polyethylene wax, polypropylene wax, and sterol wax.

(D) Inorganic filler and organic filler Examples of the inorganic filler include silica, colloidal silica, alumina, kaolin, clay, calcium carbonate, talc, and titanium dioxide. Examples of the organic filler include fillers made of an organic resin such as a fluororesin such as tetrafluoroethylene resin and ethylene-tetrafluoroethylene copolymer, a polyethylene resin, a polystyrene resin, an acrylic resin, a polyamide resin, and a benzoguanamine resin. . The average particle size of the inorganic filler and the organic filler is preferably 0.1 to 10 μm. If the average particle size is less than 0.1 μm, a sufficient releasing effect cannot be obtained, and if it exceeds 10 μm, transfer unevenness occurs.

(E) Surfactant Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a fluorosurfactant. In particular, it is preferable to use an activator that is liquid at room temperature, such as the above-mentioned fluorosurfactant and phosphate ester surfactant.

(F) Metal soap Metal soap is a non-alkali metal long chain fatty acid salt, such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, strontium stearate, barium stearate, lithium stearate, 12 -Lithium hydroxystearate, zinc laurate, calcium laurate, barium laurate, lead benzoate, zinc paratertiary butylbenzoate, barium paratertiary butylbenzoate, sodium stearate, potassium stearate, sodium oleate, etc. Is mentioned. In addition, as the phosphate metal salt, stearyl acid phosphate, magnesium stearyl acid phosphate, aluminum stearyl acid phosphate, calcium stearyl acid phosphate, zinc stearyl acid phosphate, barium stearyl acid phosphate, zinc behenyl acid phosphate Can be used.

  The content of the release agent is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass with respect to the resin forming the release layer. If the content is too large, the release agent may be deposited to deteriorate the film quality, and if the content is too small, the transfer rate is lowered. The release layer may contain other components as long as the effects of the present invention are not hindered. The release layer is preferably formed by a wet method. For this, the release layer material is dissolved in an organic solvent at a desired concentration, and the resulting solution is applied to a plate. The coating method is not particularly limited as long as a uniform film thickness distribution can be obtained. Spin coating method, gravure coating method, dip coating method, cast method, die coating method, roll coating method, bar coating method, extrusion coating method And an inkjet coating method.

  The surface of the release layer preferably has a maximum surface roughness Rmax specified in JIS B 0601-1982 of 0 to 50 when the film thickness of the organic thin film layer of the transfer material is 100, and 0 to 25 Is more preferable, and 1 to 10 is particularly preferable. If it exceeds 50, the film quality of the release layer is deteriorated due to a decrease in film forming property, film strength, etc., and the transfer rate is unfavorable.

  Examples of the method for measuring the maximum surface roughness Rmax include atomic force microscopy, confocal microscopy, stylus method, optical microscopic interference method, multiple interference method, optical cutting method, and atomic force microscopy. And preferably by confocal microscopy.

(4) Patterning The organic thin film layer is preferably formed uniformly on the organic thin film layer forming surface of the plate. The organic thin film layer may be formed on one surface of the organic thin film layer forming surface, or the organic thin film layer may be formed by patterning. For example, when an organic thin film layer is formed on a relief plate, the organic thin film layer may be formed on the surface of the convex pattern portion and the non-pattern portion at a position recessed from the pattern portion, or the upper surface of the pattern portion. Only the organic thin film layer may be formed.

  It is preferable that the convex pattern portion of the relief plate and the concave pattern portion of the intaglio plate are tapered so that a predetermined pattern can be accurately created. When the organic thin film layer is transferred a plurality of times, the plate may be marked for alignment. As the marking method, a general method can be appropriately used.

(5) Organic layer An organic layer is a layer sandwiched between a pair of electrodes in an organic electroluminescent device, and is a layer having a function as an organic electroluminescent device. Examples of the organic thin film layer of the organic electroluminescence device include a light emitting organic thin film layer, an electron transporting organic thin film layer, a hole transporting organic thin film layer, an electron injection layer, and a hole injection layer according to their respective characteristics. In addition, various layers for improving color developability can be exemplified. Specific examples of the compound used for each layer are described in, for example, “Monthly Display”, October 1998 issue “Organic EL Display” (Techno Times).

  The glass transition temperature of the organic thin film layer and / or components of the organic thin film layer is preferably 40 ° C. or higher and transfer temperature + 40 ° C. or lower, more preferably 50 ° C. or higher and transfer temperature + 20 ° C. or lower, and 60 ° C. or higher and transfer temperature or lower. Particularly preferred. The flow start temperature of the organic thin film layer and / or organic thin film layer component of the transfer material is preferably 40 ° C. or higher and the transfer temperature + 40 ° C. or lower, more preferably 50 ° C. or higher and the transfer temperature + 20 ° C. or lower, 60 ° C. or higher and The transfer temperature or lower is particularly preferable. The glass transition temperature can be measured by a differential scanning calorimeter (DSC). The flow start temperature can be measured using, for example, a flow tester CFT-500 manufactured by Shimadzu Corporation.

(a) Luminescent organic thin film layer The luminescent organic thin film layer contains at least one luminescent compound. The light emitting compound is not particularly limited, and may be a fluorescent light emitting compound or a phosphorescent light emitting compound. Further, a fluorescent compound and a phosphorescent compound may be used at the same time. In the present invention, it is preferable to use a phosphorescent compound from the viewpoint of light emission luminance and light emission efficiency.

  Fluorescent compounds include benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxalates. Diazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, styrylamine derivatives, aromatic dimethylidene compounds, metal complexes (metals of 8-quinolinol derivatives) Complexes, rare earth complexes, etc.), polymer light-emitting compounds (polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polymers) Fluorene derivatives etc.) and the like can be used. These may be used alone or in admixture of two or more.

  The phosphorescent compound is preferably a compound that can emit light from triplet excitons, and orthometalated complexes and porphyrin complexes are preferable. Of the porphyrin complexes, a porphyrin platinum complex is preferred. The phosphorescent compounds may be used alone or in combination of two or more.

  The ortho-metalated complex used in the present invention is “A foundation and application of organometallic chemistry” written by Akio Yamamoto, p. 150 and p. 232, “Hana Yashin” (1982), “Photochemistry and Photophysics of Coordination Compounds” by H. Yersin. 71-77 and 135-146, Springer-Verlag (1987), etc. The ligand forming the orthometalated complex is not particularly limited, but 2-phenylpyridine derivative, 7,8-benzoquinoline derivative, 2- (2-thienyl) pyridine derivative, 2- (1-naphthyl) pyridine derivative or A 2-phenylquinoline derivative is preferred. These derivatives may have a substituent. Moreover, you may have another ligand other than these essential ligands for ortho metalation complex formation. As the central metal forming the orthometalated complex, any transition metal can be used. In the present invention, rhodium, platinum, gold, iridium, ruthenium, palladium and the like can be preferably used. An organic compound layer containing such an orthometalated complex is excellent in light emission luminance and light emission efficiency. Specific examples of ortho-metalated complexes are described in Japanese Patent Application No. 2000-254171.

  The orthometalated complexes used in the present invention are Inorg. Chem., 30, 1685, 1991, Inorg. Chem., 27, 3464, 1988, Inorg. Chem., 33, 545, 1994, Inorg. Chim. Acta, 181. , 245, 1991, J. Organomet. Chem., 335, 293, 1987, J. Am. Chem. Soc., 107, 1431, 1985, and the like.

  Although content in particular of the luminescent compound in a luminescent organic thin film layer is not restrict | limited, For example, it is preferable that it is 0.1-70 mass%, and it is more preferable that it is 1-20 mass%. If the content of the luminescent compound is less than 0.1% by mass or exceeds 70% by mass, the effect may not be sufficiently exhibited.

  The light-emitting organic thin film layer may contain a host compound, a hole transport material, an electron transport material, an electrically inactive polymer binder, and the like as necessary. Note that the functions of these materials may be achieved simultaneously by one compound. For example, a carbazole derivative not only functions as a host compound but also functions as a hole transport material.

  A host compound is a compound that causes energy transfer from its excited state to the luminescent compound, and as a result, causes the luminescent compound to emit light. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide oxide Derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, and heterocyclic tetra Rubonic anhydride, phthalocyanine derivatives, metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes with benzoxazole, benzothiazole, etc. as ligands, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers , Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like. A host compound may be used independently or may use 2 or more types together. The content of the host compound in the light-emitting organic thin film layer is preferably 0 to 99.9% by mass, and more preferably 0 to 99.0% by mass.

  The hole transport material is not particularly limited as long as it has any one of the function of injecting holes from the anode, the function of transporting holes, and the function of blocking electrons injected from the cathode. Or a polymer material. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidene compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline copolymers, Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorenes Derivatives and the like. These may be used alone or in combination of two or more. The content of the hole transport material in the light-emitting organic thin film layer is preferably 0 to 99.9% by mass, and more preferably 0 to 80.0% by mass.

  The electron transport material is not particularly limited as long as it has any one of the function of injecting electrons from the cathode, the function of transporting electrons, and the function of blocking holes injected from the anode. Specific examples thereof include, for example, triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, Stylylpyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, metal complexes such as phthalocyanine derivatives and 8-quinolinol derivatives, metal complexes having metallophthalocyanine, benzoxazole and benzothiazole ligands, and aniline copolymers , Conductive polymers such as thiophene oligomers and polythiophenes, polythiophene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polyfluorene derivatives, and the like. These may be used alone or in combination of two or more. The content of the electron transport material in the light-emitting organic thin film layer is preferably 0 to 99.9% by mass, and more preferably 0 to 80.0% by mass.

  As polymer binder, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, Polyurethane, melamine resin, unsaturated polyester, alkyd resin, epoxy resin, silicone resin, polyvinyl butyral, polyvinyl acetal, etc. can be used. These may be used alone or in combination of two or more. The light-emitting organic thin film layer containing a polymer binder can be easily applied and formed in a large area by a wet film forming method.

  The thickness of the luminescent organic thin film layer is preferably 10 to 200 nm, more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the drive voltage may increase. On the other hand, if it is less than 10 nm, the organic electroluminescent device may be short-circuited.

(b) Hole-transporting organic thin film layer The organic electroluminescent device may have a hole-transporting organic thin-film layer made of the hole-transporting material, if necessary. The hole transporting organic thin film layer may contain the polymer binder. The thickness of the hole transporting organic thin film layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the organic electroluminescent element may be short-circuited.

(c) Electron transporting organic thin film layer The organic electroluminescent element may have an electron transporting organic thin film layer made of the electron transporting material, if necessary. The electron transporting organic thin film layer may contain the polymer binder. The thickness of the electron transporting organic thin film layer is preferably 10 to 200 nm, and more preferably 20 to 80 nm. When the thickness exceeds 200 nm, the driving voltage may increase. When the thickness is less than 10 nm, the organic electroluminescent element may be short-circuited.

  When the organic thin film layer is formed by a wet film forming method, the solvent used when adjusting the coating liquid by dissolving the material forming the organic compound layer is not particularly limited, and the hole transport material, It can be appropriately selected according to the type of orthometalated complex, the host material, the polymer binder and the like. Examples of the solvent include halogen solvents such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, cyclohexanone, benzene, toluene, Aromatic solvents such as xylene, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, ester solvents such as diethyl carbonate, ether solvents such as tetrahydrofuran and dioxane, Examples include amide solvents such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide, and water.

  In addition, the solid content amount with respect to the solid content solvent in the coating solution is not particularly limited, and the viscosity can be arbitrarily selected according to the coating method.

  When forming a plurality of organic thin film layers, in addition to the peeling transfer method of the present invention, dry film forming methods such as vapor deposition and sputtering, dipping, spin coating, dip coating, casting, die coating, and roll coating Further, wet film forming methods such as bar coating method and gravure coating method, printing methods and the like can be used in combination.

(6) Formation of Organic Thin Film Layer on Plate In the formation of the organic thin film layer of the present invention, a preferable method differs depending on whether it contains a high molecular compound or a low molecular compound.

  When the organic thin film layer is made of a low molecular weight compound, there is no particular limitation as long as the dry film thickness of the organic thin film layer is 200 nm or less and a uniform film thickness distribution can be obtained. Methods and vapor deposition methods can also be used. For example, physical vacuum deposition methods include vacuum deposition, electron beam deposition, laser ablation MBE, MOMBE, reactive deposition, ion plating, cluster ion beam, glow discharge sputtering, ion beam A sputtering method, a reactive sputtering method, etc. can be mentioned. Examples of the chemical vacuum film forming method include a thermal CVD method, a MOCVD (MOVPE) method, an RF plasma CVD method, an ECR plasma CVD method, a photo CVD method, a laser CVD method, and a mercury sensitization method. Of these, vacuum deposition is preferred. Details of these methods are described in the [Surface] Thin Film Technology edited by the Surface Science Society of Japan.

  When the organic thin film layer contains a polymer compound as a binder, it is preferably formed on the plate by a wet method. For this purpose, the organic thin film layer material is dissolved in an organic solvent at a desired concentration, and the obtained solution is applied onto the plate. The coating method is not particularly limited as long as the organic thin film layer has a dry film thickness of 200 nm or less and a uniform film thickness distribution can be obtained. Spin coating method, gravure coating method, dip coating method, casting method, die coating method, roll Examples thereof include a coating method, a bar coating method, an extrusion coating method, and an ink jet coating method. Among these, the roll-to-roll extrusion coat method is preferable.

  The transfer material is preferably used repeatedly for transferring the organic thin film layer. When repeatedly used, washing may be performed after each use or after a plurality of uses. A general method can be used for the cleaning, and is not particularly limited. However, a method using a solvent is preferable because the predetermined pattern provided on the plate is not damaged. The solvent is not particularly limited and may be appropriately selected depending on the type of the organic thin film layer provided on the plate. For example, a halogen-based solvent such as chloroform, carbon tetrachloride, dichloromethane, 1,2-dichloroethane, chlorobenzene, etc. , Ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, cyclohexanone, aromatic solvents such as benzene, toluene, xylene, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl propionate, Examples thereof include ester solvents such as ethyl propionate, γ-butyrolactone and diethyl carbonate, ether solvents such as tetrahydrofuran and dioxane, amide solvents such as dimethylformamide and dimethylacetamide, dimethyl sulfoxide and water. The solvent may be sprayed or sprayed on the plate, or the plate may be immersed in the solvent. In order to promote dissolution in a solvent, ultrasonic treatment or heating treatment may be performed.

[2] Method for Producing Organic Electroluminescent Element The method for producing an organic electroluminescent element of the present invention comprises producing a transfer material by forming at least one organic thin film layer on a plate, and the organic thin film layer side is the first substrate. The organic thin film layer is transferred to the film formation surface of the substrate by peeling the plate with a transfer material superimposed on the substrate so as to face the film formation surface and heating and / or pressurizing. One type of transfer material may be used, or two or more types of organic thin film layers having the same or different compositions may be used.

  In the peeling transfer method, the organic thin film layer is softened by heating and / or pressurizing the transfer material and adhered to the film forming surface of the substrate, and then the plate is peeled to form only the organic thin film layer. This is a method of leaving the film surface (peeling transfer method). As the heating and / or pressurizing means, generally known methods can be used. For example, a laminator, an infrared heater, a thermal head, a hot plate, a press machine or the like can be used. As the laminator, for example, First Laminator VA-400III (manufactured by Taisei Laminator Co., Ltd.), a thermal head for thermal transfer printing, a hot plate press machine, or the like can be used.

  The temperature at which the organic thin film layer is transferred to the substrate is not particularly limited and can be changed depending on the material of the organic thin film layer and the heating member, but is generally preferably 40 to 250 ° C, more preferably 50 to 200 ° C, 60-180 degreeC is especially preferable. However, the preferable range of the transfer temperature is related to the heat resistance of the heating member, the transfer material, and the substrate, and changes as the heat resistance is improved. When two or more transfer materials are used, the transfer temperature of the transfer material to be transferred first is equal to or higher than the transfer temperature of the transfer material to be transferred next, and the transfer material having two or more organic thin film layers is used. In this case, it is preferable that the transfer temperature of the organic thin film layer to be transferred first is equal to or higher than the transfer temperature of the organic thin film layer to be transferred next.

The pressure at the time of transferring the organic thin film layer to the substrate is not particularly limited and can be changed depending on the material of the organic thin film layer and the pressure member, but is generally preferably 0 to 10 t / cm ^{2, and} more preferably 0 to 5 t. / cm ² is preferable, and 0 to 2 t / cm ² is particularly preferable. However, the preferable range of the transfer pressure is related to the pressure resistance of the pressure member, the transfer material, and the substrate, and changes as the pressure resistance improves.

  The glass transition temperature or flow start temperature of the organic thin film layer or the polymer component thereof is preferably 40 ° C. or higher and the transfer temperature + 40 ° C. or lower. Two or more organic thin film layers to be transferred may contain at least one common component.

  Prior to transfer, the substrate and / or transfer material may be preheated. The preheating temperature of the substrate and / or the transfer material is preferably 30 ° C. or higher and the transfer temperature + 20 ° C. or lower. The temperature at which the plate is peeled off is preferably −50 ° C. or higher and the transfer temperature or lower. The transferred organic thin film layer may be heated again after peeling the plate.

  When the transfer material is superimposed on the substrate and heated so that the organic thin film layer faces the deposition surface of the substrate, pressurization may also be performed.

  When the transfer material is stacked on the substrate so that the organic thin film layer faces the film-forming surface of the substrate, it is preferable to increase the angle of entry of the transfer material with respect to the substrate, because entrainment of bubbles and the like is reduced. Further, when peeling the plate from the organic thin film layer transferred onto the substrate, it is preferable to increase the peeling angle of the plate with respect to the organic thin film layer.

  The organic thin film layer preferably has a light emitting organic compound and / or a carrier transporting organic compound. A plurality of organic thin film layers can be laminated on the substrate by repeating the transfer process. The plurality of organic thin film layers may be the same or different. In the case of the same composition, there is an advantage that it is possible to prevent the layer from coming off due to transfer failure or peeling failure. When different layers are provided, the function can be separated to improve the light emission efficiency. For example, a transparent conductive layer / luminescent organic thin film layer / electron transporting organic thin film layer / electron injection layer / back electrode, transparent conductive layer / hole injection layer / hole transporting organic thin film layer / The light emitting organic thin film layer / electron transporting organic thin film layer / electron injection layer / back electrode can be laminated in this order or in the reverse order.

  It is preferable to reheat and / or repressurize the organic thin film layer transferred to the substrate or the new organic thin film layer transferred to the previously transferred organic thin film layer as necessary. By reheating and / or repressurization, the organic thin film layer is more closely attached to the substrate or the previously transferred organic thin film layer. The temperature at the time of reheating is preferably in the range of the transfer temperature ± 50 ° C. The pressure during re-pressurization is preferably in the range of ± 100% of the original pressurization.

  In order to prevent the previous transfer layer from being reversely transferred to the next transfer layer, a surface treatment may be performed between the previous transfer process and the next transfer process so as to improve the adhesion force on the film formation surface. Examples of such surface treatment include activation treatment such as corona discharge treatment, flame treatment, glow discharge treatment, and plasma treatment. When the surface treatment is used in combination, the transfer temperature of the previous transfer material may be lower than the transfer temperature of the next transfer material unless reverse transfer is performed.

  An apparatus for manufacturing an organic electroluminescent element is a device that feeds a transfer material in which an organic thin film layer is formed on a plate by a wet method or the like, and presses the transfer material against a deposition surface of the substrate while heating and / or pressing the transfer material. Accordingly, it is preferable to have an apparatus for transferring the organic thin film layer to the film formation surface of the substrate and an apparatus for peeling the plate from the organic thin film layer after the transfer.

  It is preferable to have means for preheating the transfer material and / or the substrate prior to delivery to the transfer apparatus. Moreover, you may have a cooling device in the back | latter stage of a transfer apparatus.

  An entrance angle adjustment unit that increases the entrance angle of the transfer material with respect to the substrate may be provided on the front surface of the transfer device, and the back surface of the transfer device or the cooling device is provided with a release that increases the release angle with respect to the organic thin film layer of the plate. An angle adjustment unit may be provided.

  Details of the method and apparatus for producing the organic electroluminescent element described above are described in JP-A No. 2002-260854, Japanese Patent Application No. 2001-089663, and the like.

[3] organic electroluminescent devices
(1) Configuration The organic electroluminescent element of the present invention is composed of at least a transparent substrate, a transparent electrode layer, at least one organic thin film layer, a transparent or opaque electrode layer, and a transparent or opaque substrate in this order. At least one of the organic thin film layers is preferably a light-emitting organic thin film layer. Further, the overall configuration of the organic electroluminescent device is as follows: transparent conductive layer / luminescent organic thin film layer / back electrode, transparent conductive layer / luminescent organic thin film layer / electron transporting organic thin film layer / back electrode, transparent conductive layer / Hole transporting organic thin film layer / Luminescent organic thin film layer / Electron transporting organic thin film layer / Back electrode, Transparent conductive layer / Hole transporting organic thin film layer / Luminescent organic thin film layer / Back electrode, Transparent conductive layer / Luminescent property Organic thin film layer / Electron transporting organic thin film layer / Electron injection layer / Back electrode, Transparent conductive layer / Hole injection layer / Hole transporting organic thin film layer / Luminescent organic thin film layer / Electron transporting organic thin film layer / Electron injection layer / A structure in which the back electrode and the like are laminated in this order, a structure in which a substrate is further provided thereon and an organic thin film layer is sandwiched between the substrates, or a structure in which these are laminated in reverse may be employed. The luminescent organic thin film layer contains a fluorescent luminescent compound and / or a phosphorescent luminescent compound, and light emission is usually extracted from the transparent conductive layer. Specific examples of the compound used for each layer are described in, for example, “Monthly Display”, October 1998 issue “Organic EL Display” (Techno Times).

(2) Substrate The substrate is made of zirconia stabilized yttrium (YSZ), inorganic materials such as glass, polyester such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate , Polyimide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, Teflon (registered trademark), polytetrafluoroethylene? It may be made of a polymer material such as a polyethylene copolymer. The substrate may be formed of a single material or two or more materials. Among them, a polymer material is preferable for forming a flexible organic electroluminescence device, and is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation and workability, and has low air permeability and low moisture absorption. Polymer materials containing fluorine atoms such as polyester, polycarbonate, polyethersulfone, polychlorotrifluoroethylene, Teflon (registered trademark), and polytetrafluoroethylene-polyethylene copolymer are more preferable.

  The shape, structure, size and the like of the substrate can be appropriately selected according to the use and purpose of the organic electroluminescence device. The shape is generally a plate or continuous web. The structure may be a single layer structure or a laminated structure. The substrate may be formed of a single member or two or more members. The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the light-emitting organic thin film layer.

  A moisture permeation preventing layer (gas barrier layer) may be provided on the surface of the substrate support on the electrode side, the surface opposite to the electrode, or both. As a material constituting the moisture permeation preventing layer, it is preferable to use an inorganic material such as silicon nitride or silicon oxide. The moisture permeation preventing layer can be formed by a high frequency sputtering method or the like. The substrate support may be provided with a hard coat layer or an undercoat layer as necessary.

  Either the transparent conductive layer or the back electrode can be used as the cathode or the anode, and either one is determined by the composition constituting the organic electroluminescent element.

  The anode usually has a function as an anode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc. Accordingly, it can be appropriately selected from general electrodes.

  Suitable materials for the anode include, for example, metals, alloys, metal oxides, organic conductive compounds, or mixtures thereof, and materials having a work function of 4.0 eV or more are preferred. Specific examples include semiconductive metal oxides such as tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) doped with antimony or fluorine. Metals such as gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, the semiconductive metal oxides or Examples thereof include dispersions of metal compounds, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO.

  The anode is, for example, a printing method, a wet method such as a coating method, a vacuum evaporation method, a sputtering method, a physical method such as an ion plating method, a chemical method such as CVD or a plasma CVD method, and the like. It can be formed on the substrate according to a method appropriately selected in consideration of the suitability of the above. For example, when ITO is selected as the material of the anode, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like. Further, when an organic conductive compound is selected as the material of the anode, it can be carried out according to a wet film forming method.

  The patterning of the anode layer may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like, or may be performed by vacuum deposition or sputtering with a mask overlapped. Alternatively, the lift-off method or the printing method may be used.

  The thickness of the anode layer can be appropriately selected depending on the material and cannot be generally defined, but is usually 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ⁶ Ω / □ or less, more preferably 10 ⁵ Ω / □ or less. In the case of 10 ⁵ Ω / □ or less, a large area light emitting device with excellent performance can be obtained by installing a bus line electrode.

  The anode may be colorless and transparent, colored and transparent, or opaque. However, when the anode is a transparent anode and light emission is extracted from the transparent anode side, the transmittance is 60% or more. Preferably, 70% or more is more preferable. This transmittance can be measured according to a known method using a spectrophotometer. As the transparent anode, an electrode described in detail in “New development of transparent conductive film” (supervised by Yutaka Sawada, published by CMC, 1999) can be applied to the present invention. In particular, when using a plastic substrate support having low heat resistance, it is preferable to use ITO or IZO as the transparent conductive layer material and to form a film at a low temperature of 150 ° C. or lower.

(3) Cathode The cathode usually has a function as a cathode for injecting electrons into the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., and the use of the light emitting device Depending on the purpose, it can be appropriately selected from general electrodes.

  Examples of the material of the cathode include simple metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof, and those having a work function of 4.5 eV or less are preferable. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium- Examples include rare earth metals such as silver alloys, indium, and ytterbium. These may be used alone, but are preferably used in combination of two or more from the viewpoint of achieving both stability and electron injection.

  Among these, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injection properties, and materials mainly composed of aluminum are preferable from the viewpoint of excellent storage stability.

  Examples of the material mainly composed of aluminum include aluminum alone, or an alloy or mixture of aluminum and 0.01 to 10% by mass of an alkali metal or alkaline earth metal (for example, a lithium-aluminum alloy, a magnesium-aluminum alloy). It is done.

  When light is extracted from the cathode side, the transparent cathode only needs to be substantially transparent to light (a state in which the amount of light when observing reaches a necessary amount). In order to achieve both the electron injecting property and the transparency, it is possible to take a two-layer structure of the thin metal layer and a transparent conductive layer. The material of the thin film metal layer is described in detail in Japanese Patent Laid-Open Nos. 2-15595 and 5-111172. The thickness of the metal layer of the thin film is preferably 1 nm or more and 50 nm or less. When the thickness is 1 nm or less, it is difficult to form a thin film layer uniformly. On the other hand, if it is thicker than 50 nm, the light transmittance is deteriorated.

  The material used for the transparent conductive layer in the case of the two-layer structure is not particularly limited as long as the material has conductivity and semiconductivity and is transparent. The materials described for the anode can be suitably used. Among them, for example, tin oxide doped with antimony or fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO).

  The thickness of the transparent conductive layer is preferably 30 nm or more and 500 nm or less. If it is thinner than this, conductivity and semiconductivity will be inferior, and if it is thicker than this, productivity will be worse.

  The method for forming the cathode is not particularly limited, and can be performed according to a general method, but is preferably performed in a vacuum apparatus. For example, physical methods such as vacuum deposition, sputtering, and ion plating, and chemical methods such as CVD and plasma CVD can be used. Among these methods, it is preferable to select a forming method in consideration of suitability for the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like. In the case of using an organic conductive material, a wet film forming method may be used.

  Cathode patterning may be performed by chemical etching such as photolithography, physical etching using a laser, or the like, or may be performed by vacuum deposition or sputtering with a mask overlapped. Alternatively, the lift-off method or the printing method may be used.

  A dielectric layer made of a fluoride of the alkali metal or the alkaline earth metal or the like may be inserted between the cathode and the organic compound layer with a thickness of 0.1 to 5 nm. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

(4) Other layers As a layer constituting the organic electroluminescent element, it is preferable to provide a protective layer or a sealing layer in order to prevent deterioration of the light emitting performance. Furthermore, if the transfer material does not affect the light emission performance, a release layer is provided between the plate and the organic thin film layer to improve transferability, or an adhesive layer is provided between the organic thin film layer and the film formation surface. Also good.

(a) Protective layer The organic electroluminescent device is a protective layer described in JP-A-7-85974, JP-A-7-192866, JP-A-8-22891, JP-A-10-275682, JP-A-10-106746. You may have. The protective layer is formed on the uppermost surface of the organic electroluminescent element. Here, the uppermost surface represents the outer surface of the back electrode when, for example, a substrate support, a transparent conductive layer, an organic compound layer, and a back electrode are laminated in this order, and the substrate support, back electrode, organic compound layer, and transparent When the conductive layers are laminated in this order, the outer surface of the transparent conductive layer is represented. The shape, size, thickness and the like of the protective layer are not particularly limited. The material of the protective layer is not particularly limited as long as it has a function of suppressing intrusion or permeation of an element that can deteriorate the organic electroluminescent element such as moisture or oxygen into the element. Silicon oxide, silicon dioxide, germanium monoxide, germanium dioxide and the like are preferable.

  The method for forming the protective layer is not particularly limited. For example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, plasma CVD method, laser CVD method Thermal CVD method, coating method, etc. can be applied.

(b) Sealing layer The organic electroluminescent element is preferably provided with a sealing layer for preventing moisture and oxygen from entering. As a material for forming the sealing layer, a copolymer of tetrafluoroethylene and at least one comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, polyethylene, polypropylene, polymethyl methacrylate, polyimide, Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, chlorotrifluoroethylene or a copolymer of dichlorodifluoroethylene and other comonomers, water-absorbing substance with a water absorption of 1% or more, water absorption of 0.1% the following proof materials, metal (in, Sn, Pb, Au , Cu, Ag, Al, Ti, Ni , etc.), metal oxides _{(MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, _{BaO, Fe 2 O 3, Y} 2 O 3, TiO 2 , etc.), metal fluorides _{(MgF 2, LiF, AlF 3} , CaF 2 , etc.), liquid fluorinated carbon (perfluoroalkane, perfluoro amine Perfluoro ether), such as those in the liquid fluorinated carbon was dispersed adsorbent moisture or oxygen can be used.

  In order to block moisture and oxygen from the outside, it is preferable to seal the organic compound layer with a sealing member such as a sealing plate or a sealing container. Even if it installs a sealing member only in the back electrode side, you may cover the whole light emitting laminated body with a sealing member. The shape, size, thickness, and the like of the sealing member are not particularly limited as long as the organic compound layer can be sealed and external air can be blocked. As a material used for the sealing member, glass, stainless steel, metal (aluminum, etc.), plastic (polychlorotrifluoroethylene, polyester, polycarbonate, etc.), ceramic, or the like can be used.

  When installing the sealing member on the light emitting laminate, a sealing agent (adhesive) may be used as appropriate. When covering the whole light emitting laminated body with a sealing member, you may heat-seal sealing members without using a sealing agent. As the sealant, an ultraviolet curable resin, a thermosetting resin, a two-component curable resin, or the like can be used.

  Further, a water absorbent or an inert liquid may be inserted into the space between the sealing container and the organic electroluminescent element. Specific examples of moisture absorbers include barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride, cesium fluoride, niobium fluoride, Examples thereof include calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide. As the inert liquid, paraffins, liquid paraffins, fluorinated solvents (perfluoroalkane, perfluoroamine, perfluoroether, etc.), chlorinated solvents, silicone oils, and the like can be used.

  The organic electroluminescence device emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 40 volts) or a direct current between the anode and the cathode. Can do.

Regarding the driving of the light emitting device of the present invention, JP-A-2-48689, JP-A-6-301355, JP-A-5-29080, JP-A-7-13558, JP-A-8-234685, JP-A-8-241047 No. 5, U.S. Pat. No. 5,828,429, U.S. Pat. No. 6023308, and Japanese Patent No. 2784615 can be used.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1
(a) Preparation of plate A plate A1 was prepared by applying the release layer coating solution 1 to one side of a 1 mm thick stainless steel plate with a bar coater and vacuum drying at 80 ° C. for 2 hours. The dry film thickness of the release layer was 3 μm. The contact angle of the plate surface with pure water was measured by CZ-X manufactured by Kyowa Interface Science Co., Ltd. The results are shown in Table 1.

  Plates A2 to A10 and A13 were prepared in the same manner as the plate A1, except that the thickness of the substrate, the release layer coating solution, and the release layer were as shown in Table 1. A plate A12 was prepared in the same manner as the plate A1, except that the coating solution 10 for the release layer was applied to the substrate and irradiated with a 100 W high pressure mercury lamp for 5 minutes from a distance of 5 cm.

A white plate glass having a thickness of 5 mm was subjected to a surface water-repellent treatment with a plasma gas of CF ₄ and fluorocarbon to obtain a plate A11. The carrier gas was helium, and the distance between the plate and the electrode was 1 mm. In the same manner as the plate A1, the contact angle between the surface of the plate A11 and pure water was measured. The results are shown in Table 1.

  Plates A14 and 15 were prepared in the same manner as the plate A1, except that the plate, release layer coating solution, release layer thickness and plasma gas were as shown in Table 1.

Release layer coating solution 1:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C, softening point 95 ° C): 30 parts by mass Silicone-modified acrylic resin solution (manufactured by Toagosei Chemical Co., Ltd., US-3700): 10 parts by mass Methyl ethyl ketone: 30 parts by mass Toluene: 30 parts by mass

Release layer coating solution 2:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP301, glass transition temperature 62 ° C., softening point 105 ° C.): 18 parts by mass Silicone that reacts with the release layer forming resin (Matsumoto Kosho, Olga Tix SI220): 2 parts by mass Methyl ethyl ketone: 40 parts by mass Toluene: 40 parts by mass

Release layer coating solution 3:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C, softening point 95 ° C): 17 parts by mass Silcorn oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF54): 3 parts by mass methyl ethyl ketone: 40 masses Part toluene: 40 parts by mass

Release layer coating solution 4:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP301, glass transition temperature 62 ° C, softening point 105 ° C): 15 parts by weight vinyl-modified silicone (Toshiba Silicone, XF40-A1987): 5 parts by weight Platinum catalyst: 0.01 parts by weight Methyl ethyl ketone: 40 parts by mass Toluene: 40 parts by mass

Release layer coating solution 5:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP301, glass transition temperature 62 ° C., softening point 105 ° C.): 16 parts by mass epoxy-modified silicone (Toshiba Silicone, XF42-A4439): 4 parts by mass methyl ethyl ketone: 40 parts by mass toluene : 40 parts by mass

Release layer coating solution 6:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C., softening point 95 ° C.): 30 parts by mass fluoric mold release agent (manufactured by Mitsui Fluorochemical Co., Ltd., FC430): 1 part by mass methyl ethyl ketone: 35 parts by mass Toluene: 35 parts by mass

Release layer coating solution 7:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C., softening point 95 ° C.): 30 parts by mass Carnauba wax: 3 parts by mass Methyl ethyl ketone: 35 parts by mass Toluene: 35 parts by mass

Release layer coating solution 8:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C., softening point 95 ° C.): 30 parts by mass Fischer Tropsch wax (manufactured by Sazol, H1): 3 parts by mass Methyl ethyl ketone: 35 parts by mass Toluene: 35 Parts by mass

Release layer coating solution 9:
Polyester resin (manufactured by Nippon Synthetic Chemical Co., Ltd., HP320, glass transition temperature 62 ° C., softening point 95 ° C.): 30 parts by mass Sterol wax: 3 parts by mass Methyl ethyl ketone: 35 parts by mass Toluene: 35 parts by mass

Release layer coating solution 10:
UV curable resin liquid (Aronix M-450, manufactured by Toagosei Co., Ltd.): 100 parts by mass Photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 651): 10 parts by mass

(b) Preparation of transfer material On the prepared plates A1 to 15, a tris (2-phenylpyridyl) iridium complex as a phosphorescent material and an 4,4'-N, N'-di as a host material. Carbazole biphenyl was co-deposited at a rate of 0.1 nm / second and 1 nm / second, respectively, by a vacuum deposition method to form a 40 nm thick light-emitting organic thin film layer, which was designated as transfer materials A ₁ 1-15.

(c) Preparation of laminate a (substrate / anode / hole transportable organic thin film layer) White glass (0.5 mm (thickness) x 2.5 cm x 2.5 cm) is placed in a vacuum chamber and the SnO ₂ content is 10 mass. % ITO target (indium: tin = 95: 5 (molar ratio)) and DC magnetron sputtering (conditions: substrate temperature 250 ° C., oxygen pressure 1 × 10 ⁻³ Pa) with a thickness of 0.2 μm ITO A transparent electrode made of a thin film was formed. The surface resistance of the ITO thin film was 10Ω / □. An aluminum lead wire was connected to the transparent electrode (ITO) to form a laminated structure. The glass plate on which the transparent electrode was formed was placed in a cleaning container and cleaned with isopropyl alcohol (IPA), and then oxygen plasma treatment was performed. The surface of the treated transparent electrode was spin-coated with an aqueous dispersion of polyethylene dioxythiophene / polystyrene sulfonic acid (BAYER, Baytron P: solid content 1.3% by mass), and then vacuum-dried at 150 ° C. for 2 hours to obtain a thick layer. A hole-transporting organic thin film layer having a thickness of 100 nm was formed.

(d) Transfer of organic thin film layer [production of laminate b (substrate / anode / hole transporting organic thin film layer / luminescent organic thin film layer)]
The hole-transporting organic thin film layer of layered product a and the organic thin film layer of transfer material A ₁ 1 are stacked, and 0.1 m / min between a pair of rollers with a pressure of 0.3 MPa (each roller heated to 160 ° C) Heating and pressurization were performed by passing at a speed of Next, by peeling off the plate, a light emitting organic thin film layer was formed on the laminate a composed of the substrate, the anode, and the hole transporting organic thin film layer to obtain a laminate b.

(e) Fabrication of the device On the light-emitting organic thin film layer side of the laminate b, an electron transporting organic material having the following structure is formed by vapor deposition to a film thickness of 36 nm to form an electron transporting organic layer. Next, LiF is vapor-deposited to a thickness of 3 nm, and aluminum (cathode) is laminated to a thickness of 250 nm by vapor deposition. Then, an aluminum lead wire is connected to both electrodes, and the organic electroluminescent element A ₂ 1

A light-emitting organic thin film layer of the transfer material A ₁ 2 to 15 in the same manner as the organic electroluminescent element A ₂ 1 except that the transfer to the laminate a, to manufacture an organic electroluminescent element A ₂ 2 to 15.

(f) Evaluation Each organic electroluminescent element was evaluated by the following method. Transferability was evaluated according to the following criteria by observing an area of 2 mm ² of the transferred light-emitting organic thin film layer using a fluorescence microscope. The results are shown in Table 2.
When 95% or more of the light-emitting organic thin film layer is transferred: A
When the transfer of the light-emitting organic thin film layer is 80% or more and less than 95%: B
When the transfer of the light-emitting organic thin film layer is less than 80%: C

Using a KEITHLEY source measure unit type 2400, a direct current voltage was applied to each organic electroluminescent element to emit light. The organic electroluminescence device which was made to emit light at 200 cd was observed with a 50 × microscope, and the light emission unevenness was evaluated according to the following criteria. The results are shown in Table 2.
When 90% or more emit light uniformly: A
If light emission is dark and light, but 70% or more emits uniformly: B
When there is light and dark emission, and less than 70% of the light emitted uniformly: C

Example 2
As shown in the following (g), organic electroluminescent elements B ₂ 1 to 15 were prepared in the same manner as in Example 1 except that transfer materials B _{11 to} 15 were prepared and the organic thin film layers were transferred using the transfer materials. 15 was produced.

(g) Preparation of transfer material On plates A1-15, the following composition:
Polyvinylcarbazole (Mw = 63000, manufactured by Aldrich): 40 parts by mass Polyvinyl butyral (Mw = 140000, manufactured by Sekisui Chemical Co., Ltd., ESREC BX-5): 25 parts by mass Tris (2-phenylpyridine) iridium complex (ortho Metallic complex): 1 part by weight Dichloroethane: A luminescent organic thin film layer having a thickness of 40 nm is formed by applying a coating solution for a luminescent organic thin film layer having 4500 parts by weight using a bar coater and drying at room temperature. As a result, transfer materials B ₁ 1 to 15 were obtained.

(h) Evaluation In the same manner as in Example 1, the organic electroluminescent elements B ₂ 1 to 15 were evaluated. The results are shown in Table 3.

Example 3
The laminate c as shown in the following (i), except that an electron-transporting organic layer and the cathode in the stack c, in the same manner as in Example 1 to prepare an organic electroluminescent element C ₂ 1 to 15 .

(i) Production of laminate c (substrate / anode / hole transportable organic thin film layer) White glass (0.5 mm (thickness) x 2.5 cm x 2.5 cm) was placed in a vacuum chamber and the SnO ₂ content was 10% by mass. ITO target (indium: tin = 95: 5 (molar ratio)) and DC magnetron sputtering (conditions: substrate temperature 250 ° C., oxygen pressure 1 × 10 ⁻³ Pa) with a thickness of 0.2 μm ITO thin film A transparent electrode was formed. The surface resistance of the ITO thin film was 10Ω / □. An aluminum lead wire was connected to the transparent electrode (ITO) to form a laminated structure. The glass plate on which the transparent electrode was formed was placed in a cleaning container and cleaned with isopropyl alcohol (IPA), and then oxygen plasma treatment was performed. On the surface of the treated transparent electrode, the following composition:
Polymer compound represented by the following structural formula (Et-PTPDEK): 40 parts by mass

Additive (TBPA) represented by the following structural formula: 10 parts by mass

Dichloroethane: A hole transporting organic thin film layer having a thickness of 40 nm is coated on the anode by applying a coating liquid for hole transporting organic thin film layer having 3500 parts by mass using an extrusion type coating machine and drying at room temperature. Formed.

(j) Evaluation The obtained organic electroluminescent elements C ₂ 1 to 15 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 4
In the same manner as in Example 1 except for attaching a laminate e shown below in the laminate b, to manufacture an organic electroluminescent element D ₂ 1 to 15.

(k) Preparation of laminate d (first substrate / cathode / electron transporting organic thin film layer) Polyimide (50μ Upilex 50s, manufactured by Ube Industries) was used as an adhesive on both sides of a 30μ thick aluminum foil. The release layer coating solution 14 was applied with a bar coater to a dry film thickness of 3 μm, and irradiated with light from a 5 W high-pressure mercury lamp for 5 minutes from a distance of 5 cm to form a first substrate.

  Al was vapor-deposited on the first substrate so as to have a film thickness of 250 nm (cathode). Next, an aluminum lead wire is connected to the cathode, and the deposition rate of each material is adjusted so that LiF is 10% by weight with respect to the electron transporting organic material having the following structure so that the film thickness becomes 36 nm. A mixed layer was laminated, and a laminate d in which a cathode and an electron-transporting organic thin film layer were sequentially laminated on the first substrate was obtained.

(l) Transfer of organic thin film layer [production of laminate e (first substrate / cathode / electron transporting organic thin film layer / luminescent organic thin film layer)]
The transfer material is stacked on the electron transporting organic thin film layer of the laminate d so that the light emitting organic thin film layer faces, and heated for 20 seconds by a pair of hot press plates (heating each press plate to 110 ° C) with a pressure of 0.03 MPa. Thus, heating and pressurization were performed. Next, by peeling off the plate from the transfer material, a laminate e in which the cathode, the electron transporting organic thin film layer, and the light emitting organic thin film layer were laminated in this order on the first substrate was obtained.

(m) Fabrication of device Laminate e (first substrate / cathode / electron transporting organic thin film layer / luminescent organic thin film layer) laminated so that the luminescent organic thin film layer faces the luminescent organic thin film layer side. The organic electroluminescent device was fabricated by stacking the bodies b and passing between a pair of rollers with a pressure of 0.3 MPa (each roller was heated to 160 ° C.) at a speed of 0.1 m / min.

(n) Evaluation The obtained organic electroluminescent elements D ₂ 1 to 15 were evaluated in the same manner as in Example 1. The results are shown in Table 5.

Example 5
Other than using a substrate with a 20 mm x 20 mm convex pattern (pattern part: 100 µm x 50 µm, between pattern parts: 25 µ) in the center of a 50 mm x 50 mm aluminum plate or white plate glass as the substrate for the transfer material In the same manner as in Examples 1 to 4, organic electroluminescent elements were produced.

  When each obtained organic electroluminescent element was observed similarly to Example 1 and the transferability and the light emission unevenness were evaluated, the same results as in Examples 1 to 4 were obtained.

Next, (1) the organic thin film layer that was transferred after repeatedly using and transferring 20 times while washing the plate for each transfer, and (2) the organic film that was transferred after transferring 20 times without washing the plate The thin film layer was observed. Cleaning was performed by immersing the plate in dichloroethane and irradiating with ultrasonic waves for 15 minutes, and the organic thin film layer was transferred onto the same film formation surface. There was no change in the transferability and light emission unevenness depending on whether or not the plate was washed.

It is a figure which shows an example of the transfer material of this invention, (a) is a top view, (b) is a side view. . It is a figure which shows another example of the transfer material of this invention, (a) is a top view, (b) is a side view. . It is a side view which shows the droplet formed on the plate.

Explanation of symbols

10 ... Letterpress
11 ... Main body
12 ... Pattern part
13, 130 ... Organic thin film layer forming surface
14 ... Organic thin film layer
15 ... Peeling layer
21 ... Organic thin film layer formation surface
22 ... Droplet
23 ... The top of the droplet
24 ... tangent
25 ... Contact point of pure water with plate
26 ... straight line drawn from the apex to the contact point θ ... contact angle α ... angle formed by the straight line drawn from the apex to the contact point and the organic thin film layer formation surface

Claims (7)

  A transfer material having at least one organic thin film layer on a plate, wherein the surface of the plate in contact with the organic thin film layer has a contact angle with pure water of 50 ° or more.   A transfer material having at least one organic thin film layer on a plate, and having at least one of a surface treatment layer and a release layer between the plate and the organic thin film layer, the surface treatment layer and the release layer A transfer material characterized in that at least one of the surfaces in contact with the organic thin film layer has a contact angle with pure water of 50 ° or more.   The release layer contains a release agent, and the release agent comprises at least one selected from the group consisting of silicon-containing compounds, fluorine-containing compounds, waxes, inorganic fillers, organic fillers, surfactants and metal soaps. The transfer material according to claim 1 or 2, wherein   The transfer material according to claim 2 or 3, wherein the surface of the plate has a functional group that reacts with a resin forming the release layer.   The maximum surface roughness Rmax (specified by JIS B 0601-1982) of the surface of the plate in contact with the organic thin film layer is 0 to 50 when the film thickness of the organic thin film layer is 100. The transfer material according to claim 1.   Using the transfer material according to any one of claims 1 to 5, the electrode side of the first substrate having an electrode on a part or the entire surface of the transfer material on the organic thin film layer side was subjected to pressure treatment. Then, the organic electroluminescent element manufacturing method comprising the step of transferring the organic thin film layer to the electrode side of the first substrate by peeling off the plate. After the step of transferring the organic thin film layer to the electrode side of the first substrate, the organic thin film layer side of the first substrate and the electrode side of the second substrate having electrodes on a part or the entire surface are made to face each other. The method for producing an organic electroluminescent element according to claim 6, further comprising a step of applying pressure treatment.

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