KR20160033921A - A film having a wrinkle structure - Google Patents

Abstract

The present disclosure relates to a film having wrinkle structure, a manufacturing method of the same, a purpose of the film, and a method for controlling a shape of the wrinkle structure of the film. According to an embodiment of the present invention, the film controls thickness of a metal layer deposited on a polymer layer to control the width and height of the wrinkle structure. Accordingly, the film can perform different functions such as external light extraction, internal light extraction, optical anti-resonance, display pixel light extraction, low reflection, flexible light extraction, waterproof coating, and so forth, and be widely used in a different field of industry.

Description

A film having a wrinkle structure < RTI ID = 0.0 >

The present application relates to a film having a wrinkle structure, a method for producing the film, a use of the film, and a method for adjusting the shape of the wrinkle structure of the film.

Films having a wrinkle structure can be used in various fields. For example, such a structure can be used for an organic light emitting diode (OLED). BACKGROUND ART An organic light emitting diode (OLED) is an organic light emitting device that electrically excites an organic light emitting material to emit light. The organic light emitting diode includes a substrate, an anode, a cathode, and an organic light emitting layer formed between the anode and the cathode. Electrons and electrons supplied from the positive and negative electrodes combine in the organic light emitting layer to generate light emitted to the outside.

The organic light emitting diode is an element in which various elements such as a substrate, an organic layer, and a metal thin film are physically stacked. The light generated in the organic light emitting layer becomes visible light when it passes through a material film having a different interface and refractive index between the different materials. The light generated by the mentioned interfaces and the different refractive indexes is photographed or undergoes an internal total reflection process. As a result, about 80% of the light is lost in the conventional thin film laminated structure, and only about 20% of the light is emitted from the OLED device to be visually perceivable light. It is inevitably required to increase the applied voltage in order to secure a luminance higher than a certain level. The applied voltage greatly affects the device in two respects. First, the increase in applied voltage increases energy consumption. Second, when the organic layer is continuously exposed to a high voltage, degradation of the organic layer progresses and the lifetime of the device is shortened. Therefore, in order to save energy and increase the longevity of the device, a technique capable of effectively extracting the generated light is required.

Technological approaches to increase the extraction efficiency of the generated light are collectively referred to as light extraction techniques. Light extraction technology is usually internal light extraction and external light extraction technology. The generated light is partially trapped by the refractive index difference between the transparent anode and the substrate, and is guided through the anode and the substrate to disappear. In order to extract the extinction light, there is a method of patterning irregular irregularities on the substrate so that light scattering can be performed on the substrate, which is called internal light extraction. The light entering the substrate by the internal light extraction method can not escape from the inside of the substrate into the air layer due to the difference in refractive index between the substrate and the air layer as described above, In order to pull out the extinction light out of the air layer, a film with unevenness etched on the opposite surface that is etched by unevenness is attached, which is called external light extraction.

In order to increase the light extraction efficiency, a flip chip structure, a chip shaping, a surface texturing, a patterned sapphire substrate (PSS), a photonic crystal, Technology, and an anti-reflection layer. In addition, Patent Document 1 discloses that a scattering film in the form of a wrinkle structure is formed by UV-curing an organic material to improve the optical quantum efficiency as compared with a device having no existing wrinkle structure. However, The results of research on the ability to control the shape of

Patent Publication No. 2014-0016125

The present application provides a film having a wrinkle structure, a method of producing the film, a use of the film, and a method of adjusting the shape of the wrinkle structure of the film.

The present application relates to a film having a wrinkle structure. The film may comprise, for example, a substrate, a polymer layer present on the substrate, and a metal layer present on the polymer layer. The polymer layer may have a corrugated structure, for example.

The term corrugated structure in this application may mean a concavo-convex structure including, for example, concave and convex regions. The corrugated structure may include a state in which the concave region and the convex region are regularly or irregularly arranged. In one example, a film having a wrinkle structure may have an irregular wrinkle structure when used as a light extracting layer of an optical element, as described later.

The metal layer may be present on the polymer layer, for example, with a continuous corrugation structure formed along the corrugation structure of the polymer layer, or may be dispersed in the form of particles on the corrugated polymer layer . The shape of the metal layer is not particularly limited as long as it can form a corrugated structure in the polymer layer as described later. For example, the thicker the metal layer, the more likely it is to have a continuous corrugated structure. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a substrate 101, a polymer layer 102 present on the substrate and having a corrugated structure, and a continuous corrugated structure 102 disposed on the polymer layer and formed along the corrugation structure of the polymer layer Lt; RTI ID = 0.0 > 103 < / RTI > 2 shows a substrate 101, a polymer layer 102, which is present on the substrate and has a corrugated structure, and a metal layer 104 that is dispersed in the form of metal particles 104 on the polymer layer ≪ / RTI >

A known material can be used for the substrate without any particular limitation. For example, inorganic films such as glass films, crystalline or amorphous silicon films, quartz or indium tin oxide (ITO) films, and plastic films can be used. As the substrate, an optically isotropic substrate such as a substrate or an optically anisotropic substrate such as a retardation layer can be used.

Plastic substrates include TAC (triacetyl cellulose); A cycloolefin copolymer (COP) such as a norbornene derivative; Poly (methyl methacrylate), PC (polycarbonate), polyethylene (PE), polypropylene (PVP), polyvinyl alcohol (PVA), diacetyl cellulose (DAC), polyacrylate (PAC), polyether sulfone (PES) (PPS), polyarylate (PAR), amorphous fluorine resin, or the like can be used as the substrate, but it is possible to use a substrate such as PPS (polyphenylsulfone), PEI (polyetherimide), PEN (polyethylenemaphthatate) A coating layer of a silicon compound such as gold, silver, silicon dioxide or silicon monoxide, or a coating layer such as an antireflection layer may be present on the substrate.

The wrinkle structure formed in the polymer layer may have an average height in the range of, for example, 50 nm to 300 nm, and may have a width in the range of 500 nm to 3000 nm. The wrinkle structure may also be such that the average spacing between wrinkles is within the range of 500 nm to 3000 nm. The height, width, or spacing of the wrinkle structure can be adjusted by adjusting the thickness of the metal layer present on the polymer layer as described below.

As the polymer layer, for example, acrylic, urethane, ester, isocyanate, olefin, amide, cellulose or imide polymer layers can be used. As a specific example of the polymer layer, an acrylic polymer layer can be used, and more specifically, a butyl acrylate polymer layer can be used. The acrylic polymer layer can be obtained, for example, by providing a (meth) acrylic acid ester monomer and a crosslinkable functional group The copolymerizable monomers may be included in polymerized form.

The alkyl (meth) acrylate monomer having an alkyl group having 1 to 14 carbon atoms may be used, for example, in consideration of desired physical properties and the like, Acrylate may be used. Examples of such alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, Acrylate, lauryl (meth) acrylate, and tetradecyl (meth) acrylate. One or more of these may be polymerized in the polymer layer. As specific examples of the (meth) acrylic ester monomers, butyl (meth) acrylate can be used, but it is not limited thereto.

The copolymerizable monomer providing the crosslinkable functional group can provide a crosslinkable functional group capable of reacting with the polyfunctional crosslinking agent in the polymer layer. Examples of such a crosslinkable functional group include a hydroxy group, a carboxyl group, a nitrogen-containing group, an epoxy group or an isocyanate group, and specific examples thereof include a hydroxyl group and a carboxyl group. In the production of acrylic polymers, various copolymerizable monomers capable of providing such crosslinkable functional groups to the resin are known, and in the present application, such monomers can be used without limitation. Examples of the copolymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) Hydroxyethyl (meth) acrylate, 2-hydroxypropyleneglycol (meth) acrylate, and 2-hydroxypropyleneglycol (meth) Examples of the copolymerizable monomer include (meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyric acid, dimer ), Itaconic acid, maleic acid, or maleic anhydride, but not limited thereto

The ratio of the (meth) acrylic acid ester monomer in the acrylic polymer and the copolymerizable monomer that provides the crosslinkable functional group can be appropriately controlled within a range that does not impair the desired physical properties. The acrylic polymer may include, for example, from 90 parts by weight to 99.9 parts by weight of a (meth) acrylic acid ester monomer and from 0.1 part by weight to 10 parts by weight of a copolymerizable monomer which provides a crosslinkable functional group. In the present application, the unit " parts by weight " may mean a weight ratio.

In the present application, the acrylic polymer as described above may be used in a conventional polymerization system of this field, for example, solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization (Emulsion polymerization), or the like, preferably by a solution polymerization method.

In the present application, the acrylic polymer as described above may exist in a crosslinked state by, for example, a polyfunctional crosslinking agent. That is, the acrylic polymer layer may further include, for example, a multifunctional crosslinking agent for crosslinking the acryl-based polymer. The kind of the crosslinking agent that can be used in the present application is not particularly limited, and for example, an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, or the like can be used. Considering the kind of the crosslinkable functional group contained in the resin And one or more kinds of crosslinking agents may be appropriately selected.

Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and naphthalene diisocyanate, An addition reaction product of an isocyanate compound and a polyol, and the like. As the polyol, trimethylolpropane or the like may be used. Examples of the epoxy compound include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylol propane triglycidyl ether, N, N, N'N'-tetraglycidylethylenediamine, glycerin diglycidyl ether, etc. And aziridine compounds include N, N'-toluene-2,4-bis (1-aziridine carboxamide), N, N'- -Bis (1-aziridine carboxamide), triethylene melamine, bisisopropanoyl-1- (2-methyl aziridine), or tri-1-aziridinyl phosphine oxide . As the metal chelate compound, there can be used a compound in which the polyvalent metal exists in a state of being poured into acetylacetone, ethyl acetate or the like. As the polyvalent metal, there can be used aluminum, iron, zinc, tin, , Magnesium or vanadium, and the like.

In the present application, the content of the polyfunctional crosslinking agent can be suitably selected within a range that does not impair the desired physical properties. For example, the multifunctional crosslinking agent may be included in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic polymer, but is not limited thereto.

The thickness of the polymer layer can be suitably selected within a range that does not impair the desired physical properties, for example. The thickness of the polymer layer may be, for example, in the range of 10 nm to 1 cm. When the thickness of the polymer layer is within the above range, a corrugated structure can be formed by vapor deposition of a metal layer, and a film including the polymer layer can be applied to an optical element to exhibit excellent light extraction performance.

The metal layer may be formed of at least one selected from the group consisting of Ir, Pt, Au, Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Al, Se, Te, V, Cr, Mn, , Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, La, Hf, Ta, W and Os or metal oxides thereof. As a specific example, a metal layer containing Ir may be used, but is not limited thereto.

The thickness of the metal layer can be suitably selected within a range that does not impair the desired physical properties, for example. The thickness of the metal layer may be, for example, in the range of 0.1 nm to 50 nm. When the thickness of the metal layer is within the above range, a wrinkle structure can be formed by vapor deposition of a metal layer, and in the case of controlling the thickness of the metal layer, the shape of the wrinkle structure can be adjusted.

The refractive index of the film having the wrinkle structure can be suitably selected within a range that does not impair the desired physical properties. The film may have a refractive index, for example, in the range of 1.4 to 1.8. Such a refractive index may be, for example, a value measured with respect to light having a wavelength of 580 nm. Films having a refractive index in this range can be obtained, for example, by adjusting the thickness of the metal layer to adjust the shape of the wrinkle structure or by adding suitable scattering particles in the film. When the film has a refractive index in the above range, it can be applied to, for example, an optical element to exhibit excellent light extraction performance.

The haze of the film having the wrinkle structure can be suitably selected within a range that does not impair the desired physical properties. The film may have, for example, a haze in the range of 10% to 95%. Films having haze in this range can be obtained, for example, by adjusting the thickness of the metal layer to adjust the shape of the wrinkle structure or by adding suitable scattering particles in the film. When the film has a haze in the above range, it can be applied to, for example, an optical element to exhibit excellent light extraction performance.

The present application also relates to a method for producing a film having a wrinkle structure. A film having a wrinkle structure can be produced, for example, by depositing a metal layer on a polymer layer formed on a substrate to form a corrugated structure in the polymer layer. In the above, the substrate, the polymer layer, and the metal layer may be equally applied to the description of the film having the corrugated structure.

The polymer layer can be formed, for example, by laminating a polymer layer on a substrate or by coating a coating liquid containing a polymer. The method of coating the coating liquid is not particularly limited and a roll coating, a printing method, an inkjet coating, a slit nozzle method, a bar coating, a comma coating, a spin coating, a spray coating or a gravure coating may be used.

The metal layer can be deposited, for example, on the polymer layer in a vacuum state. The vacuum state in the present application may mean, for example, a pressure condition of 1 Torr or less. Further, the lower the pressure condition, the more appropriate the vacuum condition can be maintained. The lower limit of the pressure condition is not particularly limited, but may be 10-7 Torr or higher, 10-6 Torr or 10-5 Torr or higher, for example. The metal layer may also be deposited on the polymer layer at room temperature, for example, at a temperature condition within the range of 10 < 0 > C to 35 < 0 > C. The method of depositing the metal layer is not particularly limited, and a known vacuum deposition method can be used. The metal layer can be deposited by, for example, a sputtering method or an e-beam method. The metal layer may also be deposited on the polymer layer to a thickness in the range of 0.1 nm to 50 nm, as described above. When a metal layer is deposited on the polymer layer in the above thickness range, for example, a wrinkle structure having an average height in the range of 50 nm to 300 nm and an average width in the range of 500 nm to 3000 nm can be formed in the polymer layer.

The present application also relates to a method of adjusting the shape of the wrinkle structure of a film having a wrinkle structure. An exemplary method can adjust the shape of the wrinkle structure of the polymer layer by depositing a metal layer on the polymer layer formed on the substrate to a thickness such that a wrinkle structure can be formed in the polymer layer. The substrate, the polymer layer, and the metal layer in the above-described method can be applied equally to the description of the manufacturing method of the film having the wrinkle structure.

The corrugation structure of the polymer layer can be specifically shaped by adjusting the thickness of the metal layer deposited on the polymer layer. The thickness of the metal layer can be adjusted, for example, within the range of 0.1 nm to 50 nm. In this case, the wrinkle structure can be adjusted within an average height range of 50 to 300 nm and an average width of 500 to 3000 nm. Also, in this case, as the thickness of the metal layer increases, the width and height of the wrinkle structure may tend to increase.

The present application also relates to the use of a film having said wrinkle structure. The present application relates to an organic electronic device comprising, for example, a film having the corrugation structure. The organic electronic device may include, for example, a substrate, an electrode layer formed on the substrate, a functional organic layer formed on the electrode layer, and an electrode layer formed on the functional organic layer. Hereinafter, an electrode layer formed on a substrate for the purpose of distinction is referred to as a first electrode layer, and an electrode layer formed on the functional organic layer is referred to as a second electrode layer. The film having the corrugated structure may be formed on one side of the substrate or the second electrode, for example.

As the substrate, a glass substrate or a plastic substrate can be used. As the glass substrate, a suitable material can be used without any particular limitation. For example, a substrate layer such as soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, But is not limited thereto. Examples of the plastic substrate include TAC (triacetyl cellulose); A cycloolefin copolymer (COP) such as a norbornene derivative; Poly (methyl methacrylate), PC (polycarbonate), polyethylene (PE), polypropylene (PVP), polyvinyl alcohol (PVA), diacetyl cellulose (DAC), polyacrylate (PAC), polyether sulfone (PES) (PPS), polyarylate (PAR), amorphous fluororesin, or the like may be used as the base layer, but it is possible to use a base layer containing at least one selected from the group consisting of PPS (polyphenylsulfone), PEI (polyetherimide), PEN (polyethylenemaphthatate) The substrate may be, for example, transparent, but may be opaque if it is an upper light emitting device.

The organic layer may include a light emitting layer. For example, if the first electrode layer is transparent and the second electrode layer is a reflective electrode layer, the bottom emission type device can emit light emitted from the light emitting layer of the organic layer to the substrate side.

The organic electronic device may be, for example, an organic light emitting device (OLED). In the case of an organic light emitting device, the organic electronic device may have, for example, a structure in which an organic layer including a light emitting layer is interposed between a hole injection electrode layer and an electron injection electrode layer. For example, if the electrode layer included in the substrate is a hole injection electrode layer, the second electrode layer is an electron injection electrode layer, and conversely, if the electrode layer included in the substrate is an electron injection electrode layer, the second electrode layer may be a hole injecting electrode layer.

The organic layer present between the electron and hole injecting electrode layers may include at least one luminescent layer. The organic layer may include a plurality of light emitting layers of two or more layers. When two or more light emitting layers are included, the light emitting layers may have a structure in which the light emitting layers are divided by an intermediate electrode layer having charge generating characteristics, a charge generating layer (CGL) or the like.

The light-emitting layer can be formed, for example, by using various fluorescent or phosphorescent organic materials known in the art. Examples of the material of the light-emitting layer include tris (4-methyl-8-quinolinolate) aluminum (III) (aluminum (III)) (Alg3), 4-MAlq3 or Gaq3 Alq series materials, C-545T (C ₂₆ H ₂₆ N ₂ O ₂ S), DSA-amine, TBSA, BTP, PAP-NPA, Spiro-FPA, Ph ₃ Si (PhTDAOXD), PPCP , 4,5-pentaphenyl-1,3-cyclopentadiene), cyclopenadiene derivatives such as 4,4'-bis (2,2'-diphenylyinyl) -1,1'-biphenyl, Benzene or a derivative thereof or DCJTB (4- (Dicyanomethylene) -2-tert-butyl-6- (1,1,7,7, -tetramethyljulolidyl-9-enyl) -4H-pyran), DDP, AAAP, NPAMLI; Or Firpic, m-Firpic, N- Firpic, bon 2 Ir (acac), (C 6) 2 Ir (acac), bt 2 Ir (acac), dp 2 Ir (acac), bzq 2 Ir (acac), bo _{2 Ir (acac), F 2} Ir (bpy), F 2 Ir (acac), op 2 Ir (acac), ppy 2 Ir (acac), tpy 2 Ir (acac), FIrppy (fac-tris [2- ( 4,5-difluorophenyl) pyridine-C'2, N] iridium (III)) or Btp ₂ Ir (acac) ') iridium (acetylacetonate)), and the like, but the present invention is not limited thereto. The light emitting layer may contain the above material as a host and may also include perylene, distyrylbiphenyl, DPT, quinacridone, rubrene, BTX, ABTX or DCJTB. And may have a host-dopant system including a dopant.

The light-emitting layer can be formed by suitably employing a kind that exhibits luminescence characteristics among electron-accepting organic compounds or electron-donating organic compounds described below.

The organic layer may be formed with various structures, including various other functional layers known in the art, as long as the layer includes a light emitting layer. Examples of the layer that can be included in the organic layer include an electron injecting layer, a hole blocking layer, an electron transporting layer, a hole transporting layer, and a hole injecting layer.

The electron injection layer or the electron transport layer can be formed using, for example, an electron accepting organic compound. As the electron-accepting organic compound in the above, any known compound can be used without any particular limitation. Examples of such organic compounds include polycyclic compounds or derivatives thereof such as p-terphenyl or quaterphenyl, naphthalene, tetracene, pyrene, coronene, ), Polycyclic hydrocarbon compounds or derivatives thereof such as chrysene, anthracene, diphenylanthracene, naphthacene or phenanthrene, phenanthroline, Heterocyclic compounds or derivatives thereof such as bathophenanthroline, phenanthridine, acridine, quinoline, quinoxaline, or phenazine may be exemplified. It is also possible to use at least one of fluoroceine, perylene, phthaloperylene, naphthaloperylene, perynone, phthaloferrinone, naphthoferrinone, diphenylbutadiene ( diphenylbutadiene, tetraphenylbutadiene, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, and the like. Oxine, aminoquinoline, imine, diphenylethylene, vinyl anthracene, diaminocarbazole, pyrane, thiopyrane, polymethine, Quinacridone or rubrene or derivatives thereof, Japanese Patent Application Laid-Open No. 1988-295695, Japanese Patent Application Laid-Open No. 1996-22557, Japanese Patent Application Laid-Open No. 1996-81472, Japanese Patent Application Laid-Open No. 1993-009470 or Japanese Patent Application Laid- For example, tris (8-quinolinolato) aluminum, a metal chelated oxanoid compound, bis (8-quinolinolato) aluminum, Bis (benzo (f) -8-quinolinolato] zinc}, bis (2-methyl-8-quinolinolato) aluminum, Tris (8-quinolinolato) indium], tris (5-methyl-8-quinolinolato) aluminum, 8- quinolinolato lithium, tris (5- Quinolinolato) gallium, bis (5-chloro-8-quinolinolato) calcium and the like, metal complexes having at least one of 8-quinolinolato or a derivative thereof as an arbiter, Japanese Patent Laid- Oxadiazole compounds disclosed in Japanese Patent Application Laid-Open Nos. 1995-179394, 1995-278124, and 1995-228579, Stilbene derivatives, distyrylarylene derivatives, and the like disclosed in Japanese Patent Application Laid-Open (kokai) No. 1994-132080 Styryl derivatives disclosed in JP-A-1994-88072 and the like, diolefin derivatives disclosed in JP-A-1994-100857 and JP-A-1994-207170, and the like; Fluorescent brightening agents such as benzooxazole compounds, benzothiazole compounds or benzoimidazole compounds; Bis (4-methylstyryl) benzene, distyrylbenzene, 1,4-bis (2-methylstyryl) benzene, Bis (2-methylstyryl) benzene, 1,4-bis (3-ethylstyryl) benzene, Methylstyryl) -2-ethylbenzene, and the like; Bis (4-methylstyryl) pyrazine, 2,5-bis (4-methylstyryl) pyrazine, 2,5- Bis [2- (4-biphenyl) vinyl] pyrazine such as bis (4-methoxystyryl) pyrazine, 2,5-bis [2- Distyrylpyrazine compounds, 1,4-phenylenedimethylidene, 4,4'-phenylenedimethylidyne, 2,5-xylenedimethylidyne, 2,6-naphthylenedimethylidyne, 1,4-biphenylene dimethyl (9,10-anthracenediyldimethylidine) or 4,4 '- (2,2-di-t-butylphenylvinyl) biphenyl , Dimethylidine compounds such as 4,4- (2,2-diphenylvinyl) biphenyl or derivatives thereof, silanamine disclosed in Japanese Patent Application Laid-Open No. 1994-49079 or Japanese Patent Laid-Open Publication No. 1994-293778 silanamine derivatives, Japanese Patent Application Laid-Open No. 1994-279322 or Japanese Patent Application Laid-Open No. 1994-279323 Oxadiazole derivatives disclosed in Japanese Patent Laid-Open Publication No. 1994-109264, Japanese Patent Laid-Open Publication No. 1994-206865 and the like, an anthracene compound disclosed in Japanese Patent Oxynate derivatives disclosed in JP-A-1994-145146 and the like, tetraphenylbutadiene compounds disclosed in JP-A-1992-96990 and the like, organic trifunctional compounds disclosed in JP-A-1991-296595, A coumarin derivative disclosed in JP-A-1990-191694, a perylene derivative disclosed in JP-A-1990-196885, a naphthalene derivative disclosed in JP-A-1990-255789, Phthaloperynone derivatives disclosed in JP-A No. 1990-289676 or JP-A No. 1990-88689 or a derivative of phthaloperynone derivatives disclosed in JP-A No. 1990-25029 Styrylamine derivatives disclosed in, for example, Japanese Patent Laid-open Publication No. 2 (1990) can also be used as electron-accepting organic compounds contained in the low refractive layer. In addition, the electron injection layer may be formed using a material such as LiF or CsF.

The hole blocking layer is a layer which can prevent the injected holes from entering the electron injecting electrode layer through the light emitting layer to improve the lifetime and efficiency of the device. If necessary, the hole blocking layer can be formed using a known material, As shown in FIG.

The hole injecting layer or the hole transporting layer may include, for example, an electron donating organic compound. Examples of the electron donating organic compound include N, N ', N'-tetraphenyl-4,4'-diaminophenyl, N, N'- N, N ', N'-tetra-p-tolyl-4,4'-diaminobiphenyl, Phenyl, N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N'- (N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadriphenyl] 4-N, N-diphenylaminostilbene, N-phenylcarbazole, 1,1-bis (4-methoxy- Bis (4-dimethylamino-2-methylphenyl) phenylmethanesulfonate, 1,1-bis (4-di- N, N, N-tri (p-tolyl) amine, 4- (di-p- tolylamino) -4 ' N ', N'-tetraphenyl-4,4'-diaminobis N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, Phenylamino] biphenyl, 4,4'-bis [N- (3-acenaphthenyl) -N (2-naphthyl) Phenylamino] biphenyl, 1,5-bis [N- (1-naphthyl) -N-phenylamino] naphthalene, 4,4'- Bis [N- (2-phenanthryl) -biphenylphenylamino] biphenyl, 4,4'-bis [N- N-phenylamino] biphenyl, 4,4'-bis [N- (2-pyrenyl) - N-phenylamino] biphenyl, 4,4'-bis [N- (1-choronenyl) - N-phenylamino] biphenyl), 2,6-bis (di-p-tolylamino) naphthalene, 2,6-bis (1-naphthyl) amino] naphthalene, 2,6-bis [N- (1-naphthyl) Bis [N, N-di (2-naphthyl) amino] terphenyl, 4,4'-bis { Bis [N, N-di- (2-naphthyl) amino] fluorene or 4,4'-bis (N, N-di-p-tolylamino) terphenyl and bis (N-1-naphthyl) (N-2-naphthyl) amine and the like are exemplified. It is not.

The hole injecting layer or the hole transporting layer may be formed by dispersing an organic compound in a polymer or by using a polymer derived from the organic compound. Further, a hole-transporting non-conjugated polymer such as a? -Conjugated polymer, poly (N-vinylcarbazole), or a? -Conjugated polymer of a polysilane, such as polyparaphenylenevinylene and its derivatives, .

The hole injection layer may be formed by using a metal phthalocyanine such as copper phthalocyanine, a nonmetal phthalocyanine, a carbon film and an electrically conductive polymer such as polyaniline, or by reacting the arylamine compound with an Lewis acid using the arylamine compound as an oxidizing agent You may.

Illustratively, the organic light emitting device includes (1) a form of a hole injection electrode layer / an organic light emitting layer / electron injecting electrode layer formed sequentially; (2) a form of a hole injection electrode layer / a hole injection layer / an organic light emitting layer / an electron injection electrode layer; (3) a form of a hole injection electrode layer / an organic light emitting layer / an electron injection layer / an electron injection electrode layer; (4) a form of a hole injection electrode layer / a hole injection layer / an organic light emitting layer / an electron injection layer / an electron injection electrode layer; (5) a form of a hole injection electrode layer / an organic semiconductor layer / an organic light emitting layer / an electron injecting electrode layer; (6) the form of the hole injection electrode layer / organic semiconductor layer / electron barrier layer / organic light emitting layer / electron injection electrode layer; (7) Forms of hole injecting electrode layer / organic semiconductor layer / organic light emitting layer / adhesion improving layer / electron injecting electrode layer; (8) Forms of hole injecting electrode layer / hole injecting layer / hole transporting layer / organic light emitting layer / electron injecting layer / electron injecting electrode layer; (9) Forms of hole injecting electrode layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (10) Forms of hole injecting electrode layer / inorganic semiconductor layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (11) Forms of hole injecting electrode layer / organic semiconductor layer / insulating layer / organic light emitting layer / insulating layer / electron injecting electrode layer; (12) Hole injection electrode layer / Insulation layer / Hole injection layer / Hole transport layer / Organic light emitting layer / Insulation layer / Electron injection electrode layer or (13) Hole injection electrode layer / Insulating layer / Hole injection layer / Hole transport layer / The light emitting layer may have a shape of an injection layer / electron injecting electrode layer, and in some cases, at least two light emitting layers may be disposed between the hole injecting electrode layer and the electron injecting electrode layer as an intermediate electrode layer or a charge generating layer (CGL) But the present invention is not limited thereto.

In this field, various materials for forming a hole or electron injection electrode layer and an organic layer such as a light emitting layer, an electron injection or transport layer, a hole injection or transport layer, and a forming method thereof are known. All of the same methods can be applied.

The organic electronic device may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture, oxygen and the like from being introduced into the organic layer of the organic electronic device. The sealing structure may be a can structure such as a glass can or a metal can, or may be a film structure covering the entire surface of the organic layer. The film-shaped encapsulation structure may be formed by applying a liquid material which is cured by irradiation with heat or ultraviolet (UV), such as epoxy resin, and curing it, or by using the epoxy resin or the like, And the upper substrate may be laminated using an adhesive sheet or the like.

Figures 3-5 illustrate an exemplary organic electronic device comprising a film (1) having a pleated structure. An exemplary organic tram device includes a structure in which a substrate 201, a first electrode 202, an organic layer 203, and a second electrode 204 are sequentially stacked, as shown in Fig. 3, The first electrodes 1a and 1b may be formed on one surface of the substrate 201 or one surface of the second electrode 204 to function as a light extracting layer. The exemplary organic electronic device may be a bottom emission organic electronic device as shown in Figs. 4 to 5, and the films 1a and 1b having a corrugated structure may be formed on one surface of the substrate 201, The second electrode may be formed on one surface of the first electrode 204 to function as a light extracting layer.

The present application also relates to the use of the method for adjusting the shape of the wrinkle structure. The method can control the height and width of the corrugation structure by adjusting the thickness of the metal layer deposited on the polymer layer. For example, the method of adjusting the shape of the wrinkle structure can be used to increase the surface area by forming a wrinkle structure on the polymer layer. For example, the adhesive layer tends to have improved adhesion as the surface area increases. Accordingly, when the metal layer is vapor-deposited on the adhesive layer to an appropriate thickness to form a wrinkle structure, the surface area can be increased, and the adhesive force of the adhesive layer can be improved. Such a method of increasing the surface area is not particularly limited as long as the method for adjusting the shape of the wrinkle structure is applied, and can be suitably applied when it is necessary to increase the surface area of the polymer layer.

Since the height and width of the corrugated structure can be controlled by adjusting the thickness of the metal layer deposited on the polymer layer, the film of the present application can be used for external light extraction, internal light extraction, optical antireflection, It has various functions such as anti-reflection function, flexible light extraction function, water-repellent film coating function, and can be used in various industrial fields.

Fig. 1 exemplarily shows a film having a wrinkle structure.
Figures 3-5 illustrate exemplary organic electronic devices.
Figs. 6 to 9 show the wrinkle structure of the films of Examples 1 to 4. Fig.

Hereinafter, the film will be described in more detail through the examples according to the present application, but the scope of the present application is not limited by the following embodiments.

Example  One.

Manufacture of film with wrinkle structure

(Butyl Acrylate: Hydroxy butyl acrylate = 99: 1 part by weight and an isophoronediisocyanate based isocyanate curing agent: 0.1 part by weight, Mw (weight average molecular weight): 1.8 million, G ' ): 4.5 x 10 < 4 > Pa) at a temperature of 25 DEG C and a vacuum of 1 Torr or less to form a film having a corrugated structure. The wrinkle structure of the film prepared in Example 1 is shown in Fig. 6, and a three-dimensional topography image was obtained in a tapping mode using an Atomic Force Microscopy (Veeco, Dimension 3100) apparatus. The height and width of the wrinkle structure were measured As a result, the average height was 50 nm to 100 nm and the average width was 500 nm to 700 nm.

Example  2.

A film having a corrugated structure was prepared in the same manner as in Example 1, except that the thickness of the deposited metal layer was changed to 0.5 nm. The wrinkle structure prepared in Example 2 is shown in Fig. 7, and the wrinkle structure had an average height of 100 nm to 150 nm and an average width of 800 nm to 1100 nm.

Example  3.

A film having a corrugated structure was prepared in the same manner as in Example 1, except that the thickness of the deposited metal layer was changed to 1.5 nm. The wrinkle structure of the film produced in Example 3 is shown in Fig. 8, and the wrinkle structure has an average height of 50 nm to 100 nm and an average width of 1200 nm to 1600 nm.

Example  4.

A film having a wrinkle structure was produced in the same manner as in Example 1 except that the thickness of the deposited metal layer was changed to 2.5 nm. The wrinkle structure of the film produced in Example 4 is shown in Fig. 9, and the wrinkle structure has an average height of 50 nm to 100 nm and an average width of 1800 nm to 2100 nm.

Example  5.

As the polymer layer, a butyl acrylate polymer layer (Butyl Acrylate: Aacrylic acid = 94: 6 parts by weight and Mw: 1.8 million, G ': 7 x 10 4 Pa) containing 0.02 part by weight of an epoxy curing agent was used , A film having a wrinkle structure was produced. It was confirmed that the wrinkle structure of the film produced in Example 5 had an average height and width similar to those of Example 1. [

Example  6.

A film having a wrinkle structure was produced by following the same procedure as in Example 5, except that the thickness of the deposited metal layer was changed to be 0.5 nm. It was confirmed that the wrinkle structure of the film produced in Example 6 had an average height and width similar to those of Example 2. [

Example  7.

A film having a wrinkle structure was prepared in the same manner as in Example 5 except that the thickness of the deposited metal layer was changed to 1.5 nm. It was confirmed that the wrinkle structure of the film produced in Example 7 had an average height and width similar to those of Example 3. [

Example  8.

A film having a wrinkle structure was produced by following the same procedure as in Example 5 except that the thickness of the deposited metal layer was changed to 2.5 nm. It was confirmed that the wrinkle structure of the film produced in Example 7 had an average height and width similar to those of Example 4. [

1, 1a, 1b: a film having a pleated structure
101: substrate
102: polymer layer
103: metal layer
104: metal particles
201: substrate
202: first electrode
203: organic layer
204: second electrode

Claims (20)

A film having a pleated structure comprising a substrate, a polymer layer present on the substrate and having a pleated structure, and a metal layer present on the polymer layer. The film according to claim 1, wherein the substrate is an inorganic film containing glass or silicon, or a plastic film comprising PET (polyethyleneterephtalate). The film according to claim 1, wherein the polymer layer has a wrinkle structure in which a wrinkle structure having an average height within a range of 50 nm to 300 nm and an average width within a range of 500 nm to 3000 nm is formed. The film according to claim 3, wherein the average wrinkle interval of the wrinkle structure is in the range of 500 nm to 3000 nm. The film according to claim 1, wherein the polymer layer has a wrinkle structure comprising an acrylic, urethane, ester, isocyanate, olefin, amide, cellulose or imide polymer. The film of claim 1, wherein the polymer layer has a pleated structure having a thickness in the range of 10 nm to 1 cm. The method of claim 1, wherein the metal layer is selected from the group consisting of Ir, Pt, Au, Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, Al, Se, Te, V, Cr, Mn, At least one metal selected from the group consisting of Ni, Cu, Zn, Ga, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, In, La, Hf, Wherein the film has a wrinkle structure. The film according to claim 1, wherein the metal layer has a pleated structure having a thickness in the range of 0.1 nm to 50 nm. The film according to claim 1, having a pleated structure having a refractive index in the range of 1.4 to 1.8. The film according to claim 1, wherein the film has a wrinkle structure with a haze within a range of 10% to 95%. And depositing a metal layer on the polymer layer formed on the substrate to form a corrugated structure in the polymer layer. 12. The method of claim 11, wherein the polymer layer has a pleated structure comprising forming a pleated structure having an average height in the range of 50 nm to 300 nm and an average width in the range of 500 nm to 3000 nm. The method for producing a film according to claim 11, wherein the film has a wrinkle structure for depositing a metal layer at a pressure of 1 Torr or less. The method for producing a film according to claim 11, wherein the film has a wrinkle structure for depositing a metal layer at a temperature within a range of 10 캜 to 35 캜 12. The method of claim 11, wherein the film has a wrinkle structure for depositing a metal layer in a thickness ranging from 0.1 nm to 50 nm. And depositing a metal layer on the polymer layer formed on the substrate to a thickness at which a wrinkle structure can be formed in the polymer layer. 17. The method of claim 16, comprising adjusting the thickness of the metal layer to within the range of 0.1 nm to 50 nm. The method of claim 17, wherein the wrinkle structure of the polymer layer is shaped to have an average height in the range of 50 to 300 nm and an average width in the range of 500 to 3000 nm. An organic electronic device comprising a film having the pleated structure of claim 1. A method of increasing the surface area of a polymer layer using the method of claim 16.

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