TW201101924A - Image display device and organic electroluminescent element - Google Patents

Abstract

Disclosed are an image display device and an organic EL element, each of which involves at least a polyimide film substrate and an ITO electrode formed on the substrate, wherein the ITO electrode is a polycrystalline ITO electrode and the polyimide film contains a repeating unit represented by formula [1] in an amount of at least 10 mol%. Each of the image display device and the organic EL element involves a flexible polyimide film and has excellent element properties including light emission luminance. (In the formula, R1 and R2 independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms; R3, R4 and R5 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a nitril group, or a carboxyl group; and n represents a integer.)

Description

201101924 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to an image display device and an organic electroluminescence device. [Prior Art] In the past, electrical insulating films, organic electroluminescence (hereinafter referred to as organic EL) display substrates, liquid crystal display substrates, 0 electronic paper substrates, and solar cell substrates used in various electronic devices have used glass. However, recently, with the large screen of these devices, there has been a problem of an increase in weight when using a glass substrate, or a film of a display device for a mobile information communication device such as a personal digital assistant such as a mobile phone, an electronic PDA, or a notebook computer. The problem of damage to the glass substrate is severe. Therefore, the use of a plastic substrate which is lightweight and soft, and which is resistant to squeezing, and which is easy to mold, is being demanded. The flexible and tough plastic substrate under transparent can realize flexible display panels that can be bent or curled down. In the field of substrates for organic EL displays, an example of using polyethylene naphthalate (PEN) is known (Patent Document No.). The heat-resistant temperature of PEN is 15 °C. Although it is necessary to form a film at a low temperature, the manufacturing method of this practicality has not been established. The 'polyimine resin' has high mechanical strength and heat resistance 'insulation'. Since it is solvent-resistant, it is widely used as a film for electronic materials, such as a protective material, an insulating material, and a color filter, in a liquid crystal display element or a semiconductor. -5- 201101924 However, the past all-aromatic polyimine resins have to be colored to a solid amber color, which poses a problem for thick films of electronic devices that require high transparency. As one of the methods for achieving transparency, an alicyclic ring such as 3,4-di residue-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (hereinafter abbreviated as TDA) is known. Polycondensation reaction of tetracarboxylic dianhydride with aromatic diamine to obtain a polyimide precursor, and when the precursor is imidized to produce a polyimine, the coloring can be relatively small, and a highly transparent polyimide can be obtained. (Patent Documents 2 and 3). However, these polyimines are suitable for use in a specific field of a liquid crystal alignment film having a thickness of 1 μm or less, so that it is difficult to form a thick film of 1 〇〇 μηι. Further, a TDA-BAPB compound obtained by polycondensation of a TDΑ compound represented by the formula [5] and a substituted bis(aminophenoxy)benzene compound (hereinafter abbreviated as BAPB compound) represented by the formula [6] Although there is no specific description, the physical properties are unknown, and it is unknown how the properties can be exerted on the application surface. [Chemical 1]

(wherein R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and R3' R4 and R5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon. 2 to 5 alkenyl groups, 1 to 5 carbon atoms of alkoxy 201101924, a cycloalkyl group having 3 to 7 carbon atoms, a nitrile group, or a carboxyl group.) Further, it has been reported to have a polyimide substrate and An organic electroluminescence device of a polycrystalline ITO electrode, which has a current density of 100 A/m 2 at a voltage of 14 V and an extremely low luminous efficiency of 1 1 m/W at a current density of 100 A/m 2 , which is a lack thereof. Practicality (Non-Patent Document 1). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-7363 No. [Non-patent literature] [Non-specialized lj document 1] Adv. Mater·, 2002, 14, (18) 127 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 挠性 挠性An image display device and an organic EL device are excellent in element characteristics such as an amine film and a light-emitting luminance. The present inventors have found that a film containing a TDA-BAPB compound polyimine obtained by polycondensation and imidization of a TDA compound represented by the above formula [5] and a BAPB compound represented by the formula [6] is a high gloss. It is used as a substrate (optical film) for an image display device such as an organic EL display or a liquid crystal display, and it is used as a substrate (optical film) such as an organic EL display or a liquid crystal display, but it has flexibility, high heat resistance, high toughness, and flexibility at a low water absorption rate, but it is used in 201101924 (Japanese Patent Application No. 2 08-271947). There is also room for improvement in the characteristics of the components having the film. In order to improve the characteristics of the element of the TDA-BAPB compound polyimide film as a substrate, the inventors of the present invention conducted a detailed review of the characteristics of the device, and the polycrystalline silicon used as an anode was laminated on the substrate. Further, it has been found that the characteristics of the element starting with the luminance of the light are more improved than when the amorphous ITO electrode is used, and the present invention has been completed. That is, the present invention provides a video display device comprising at least a polyimide film substrate and an ITO electrode formed on the substrate, wherein the IT Ο electrode is a polycrystalline IT ◦ electrode, and the concentrating The quinone imine film is a repeating unit represented by the formula [1] containing at least 10 mol% or more; [Chemical 2]

(wherein R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms, and R3, R4 and R5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon. An alkenyl group of 2 to 5, an alkoxy group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, a nitrile group or a carboxyl group, and n is an integer. 2. An image display apparatus according to 1 wherein said polyimine film contains at least 10 moles. /❶ repeating the unit shown in the formula [2]; [Chemical 3]

C2] -8 - 201101924 (where η represents the same meaning as described above). 3. An organic EL device characterized by comprising at least a polyimide film substrate and an ITO electrode formed on the substrate, wherein the ITO electrode is a polycrystalline ITO electrode, and the polyimide film contains at least 1〇 More than 5% of the formula Π] repeat unit shown;

[Chemical 4]

[1] (wherein R1 to R5 and η have the same meanings as described above). 4. The organic EL device according to 3., wherein the polyimine film is a repeating unit represented by the formula [2] containing at least 10 mol% or more; [Chemical 5]

η (wherein η represents the same meaning as described above.) 5. The organic EL device according to 3. or 4. wherein the polycrystalline germanium electrode is provided with a hole injection layer, a hole transport layer, and an organic substance. The layers of the light-emitting layer, the electron injecting layer, and the cathode are laminated. 6. The organic EL device according to 5. wherein the hole injection layer contains poly(styrenesulfonate)/poly[2,3-dihydrophene (.3,41〇-1,4-dioxine)' The hole transport layer contains bis[(-naphthyl)-fluorenyl-phenyl]benzidine'. The light-emitting layer and the electron injection layer formed of the above organic substance contain ginseng (8-hydroxyquinoline) aluminum, and the cathode is Al- Laminated electrodes of Li and Α1. The organic EL device of any one of the above-mentioned polycrystalline ITO electrodes, wherein the amorphous ruthenium film is laminated on the polyimine film substrate, and then the amorphous ruthenium film is heat-treated. Formed afterwards. 8. The organic EL device as in 7, wherein the aforementioned heat treatment is at 1〇4~1〇_4

Pa is carried out under reduced pressure. 9. The organic EL device according to 7. or 8. wherein the aforementioned heat treatment is carried out at 100 to 300 °C. 10. The organic EL device according to 9. wherein the aforementioned heat treatment is carried out at 120 to 240 °C. 11. A method of producing an organic EL device according to the invention, characterized in that an amorphous ITO film is laminated on the polyimide film substrate, and the amorphous IT film is heat-treated to form a polycrystalline IT0 electrode. Thereafter, lamination is performed in the order of the hole injection layer, the hole transport layer, the light-emitting layer made of the organic material, the electron injection layer, and the cathode. 12. The method of producing an organic EL device according to 11., wherein the heat treatment is carried out at a pressure of 104 to 1 (T4Pa under reduced pressure. 13. The method for producing an organic EL device according to 1 1 or 12. The heat treatment is carried out at 100 to 300 ° C. 14. The method for producing an organic EL device according to 13., wherein the heat treatment is carried out at 120 to 240 ° C. [Effects of the Invention] The present invention is provided with both A flexible polyimide film and an image display device having excellent device characteristics such as light-emitting luminance and an organic electroluminescence device-10-201101924. MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The polyimine film of the substrate of the element is described. In the present invention, the polyimide film constituting the polyimide film substrate has a repeat of the above formula [1] in which 〇3 has at least ίο mol % or more. In the formula [1], examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 10 carbon atoms may be a straight chain or a branch. Specific examples include methyl and ethyl groups. Η-propyl, i-propyl, η-butyl, i-butyl, s-butyl, t-butyl, η-pentyl, i-pentyl, t-pentyl, ne0-pentyl, Η-hexyl, heptyl, octyl, decyl, decyl, etc. Examples of the alkenyl group having 2 to 5 carbon atoms include a vinyl group, a propenyl hydrazine, a butenyl group, a pentenyl group and the like. The alkoxy group of 1 to 5 may, for example, be a methoxy group, an ethoxy group, a η-propoxy group, an i-propoxy group, an η-butoxy group or an s-butoxy 't-butoxy group. And η-pentyloxy. The cycloalkyl group having a carbon number of 3 to 7 may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group.丨 indicates that 's' indicates that the second 't indicates the third zero. In the present invention, the number average molecular weight of the polyimine is considered to be 5 or more when considering the flexibility when the film is -11 - 201101924. Preferably, it is more preferably 6,000 to 100,000. Therefore, it is preferable that η in the above formulas [1] and [2] is such that the number average molecular weight of the polyimine is 5,000 or more. Specifically, it is 8 to 180. Preferably, it is particularly suitable for 1 〇~1 。. The polyimine film used in the above formula may have a repeating structure of the above formula, and particularly has high heat resistance and transparency, and is intended to be a polyimide film having excellent flexibility. 'The above structure is preferably 50% by mole or more, preferably 70% by mole or more, and most preferably 90% by mole or more. It is represented by the above formulas Π] and [2]. The polyimine of the repeating unit can be obtained by imidating polylysine having a repeating unit represented by the following formulas [3] and [4]. [Chemical 6]

(wherein R1 to R5 and η have the same meanings as described above.) [Chem. 7]

[4] The polylysine represented by the above formulas [3] and [4] can be synthesized by the polycondensation of the TD oxime compound represented by the formula [5] and the hydrazine compound represented by the formula [6] as described above. In the present invention, as the TDA compound, 3,4-dicarboxy--12-201101924 1.2.3.4-tetrahydro-1-naphthalene succinic dianhydride (but 0 person), 2-methyl-3, 4 may be mentioned. -Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride '2-ethyl-3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene amber Acid dianhydride, 2-11-propyl-3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 2-11-butyl-3,4-dicarboxyl - 1.2.3.4- Tetrahydro-naphthalene succinic dianhydride, 2-11-pentyl-3,4-dicarboxy- 1.2.3.4-tetrahydro-naphthalene succinic dianhydride, 5-methyl-3, 4-Dicarboxy-1.2.3.4- Tetrahydro-1-naphthalene succinic dianhydride, 6-methyl-3,4-dicarboxy- 0 1,2,3,4-tetrahydro-1-naphthalene succinic acid Anhydride, 7-methyl-3,4-dicarboxy- 1.2.3.4-tetrahydro-1-naphthalene succinic dianhydride, 8-methyl-3,4-dicarboxy-1,2,3,4·4 Hydrogen-1-naphthalene succinic dianhydride, 5,8-dimethyl-3,4-dicarboxy- 1.2.3.4-tetrahydro-1-naphthalene succinic dianhydride, 5-chloro-3,4-dicarboxyl -1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 6-chloro-3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, etc. . Among them, TD A is preferred from the viewpoint of easy availability. On the other hand, examples of the BAPB compound include 1,3-bis(4-aminoindenyloxy)benzene (hereinafter abbreviated as 1,3-BAPB) and 1,4-bis(4-aminophenoxyl). Benzene, 1,3-bis(4-amino-3-methylphenoxy)benzene, 1,3-bis(4-aminophenoxy)-5-methylbenzene, 3-bis(4-aminobenzene) Oxy)-5-mercaptobenzene, 1,3-bis(4.aminophenoxy)-5-eicosylbenzene, 3-bis(4-amino-3-dodecylphenoxy)- 5-Benzene, 1,3-bis(4-aminophenoxy)-5-cyanobenzene, 1,3-bis(4-aminophenoxy)-5-chlorobenzene, 1,3-double (4 -aminophenoxy)_5_mercaptobenzene, 1,3-bis(4-aminophenoxy)-5-methoxybenzene, 1,3-bis(4-aminophenoxy)-5-ethylene Benzobenzene, 1,3-bis(4-aminophenoxy)-5-allylbenzene, 1,3-bis(4-aminophenoxy)-5-carboxybenzene, 1,3-double (4 -aminophenoxy)-5-cyclo-13- 201101924 propylbenzene, 3-bis(4-aminophenoxy)_5-cyclohexylbenzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-amino-4-methylphenoxy)benzene, 3-bis(3-aminophenoxy)-5-A Benzobenzene, 1,3-bis(3-aminophenoxy)-5-mercaptobenzene, 1,3-bis(3-aminobenzene) )-5-Eicosylbenzene, 3-bis(3-amino-4-dodecylphenoxy)-5-benzene, 1,3-bis(3-aminophenoxy)_5-cyano Benzene, 1,3-bis(3-aminophenoxy)-5-chlorobenzene, 3-bis(3-aminophenoxy)-5-mercaptobenzene, 1,3-bis(3-aminobenzene) Oxy)-5-methoxybenzene, 1,3-bis(3-aminophenoxy)-5-vinylbenzene, I,3-bis(3-aminophenoxy)-5-allylbenzene 1,3 -bis(3-aminophenoxy)-5-carboxybenzene, 1,3-bis(3-aminophenoxy)-5-cyclopropylbenzene, 3-bis(3-aminobenzene) Oxygen)-5-cyclohexylbenzene and the like. Among them, 1 , 3 - B A P B is preferred from the viewpoint of the physical properties of the obtained film. Further, the polyimine film used in the present invention contains 10 mol% or more of any of the above repeating units of the formulae [] and [2], and does not affect the obtained polyimide film. Under the physical properties, the tetracarboxylic acid compound and its derivative used in the synthesis of a general polyimine other than the above TD A compound can be used at the same time. Specific examples of this include 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 1,2,4,5-cyclohexane acid, and 3 , 4-dicarboxy-1-cyclohexyl succinic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3.3.0]octane-2,4, An alicyclic tetracarboxylic acid such as 6,8-tetracarboxylic acid, and these dianhydrides and these dicarboxylic acid diacid halides. Further, pyroic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-decanetetracarboxylic acid, l,2,5,6- -14 - 201101924 恵tetraresidic acid, 3,3 ',4,4 '-biphenyltetrahydro acid, 2,3 , 3 ',4-diphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4- Dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-di Carboxyphenyl)propylidene, bis(3,4-dicarboxyphenyl)dimethyloxane, bis(3,4-dimercaptophenyl)diphenylnonane, 2,3,4,5-pyridine tetra An aromatic tetracarboxylic acid such as a carboxylic acid or a 2,6-bis(3,4.di residue phenyl)pyridine; and these acid dianhydrides, and these dicarboxylic acid diacid halides. Further, these tetracarboxylic acid compounds may be used singly or in combination of two or more kinds. On the other hand, when the diamine contains at least 1% by mole of the repeating unit of the above formulas [1] and [2], the above properties may not be affected by the physical properties of the obtained polyimide film. Other diamine compounds other than the BAPB compound. Specific examples of this include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, and 4,4,-diamino group. Biphenyl hydrazine, 3,3 dimethyl-4,4'-diaminobiphenyl, 3,3,-dimethoxy-4,4'-diaminobiphenyl, diaminodi Phenylmethane, diaminodiphenyl ether, 2,2,-diaminodiphenylpropane, bis(3,5-diethylaminophenyl)methane, diaminodiphenylphosphonium, two Aminobenzophenone, diaminonaphthalene, i,4_bis(4-aminophenoxy)benzene, I,4-bis(4-aminophenyl)benzene, 9,1〇_double (4_ Aminophenyl)anthracene, 13-bis(4-aminophenoxy)benzene, 4,4,_bis(4-aminophenoxy)diphenylanthracene, 2,2-bis[4-(4- Aromatic diamines such as aminophenoxy)phenyl]propane, 2,2'-trifluoromethyl-4,4,-diaminobiphenyl; bis(4-aminocyclohexyl)methane, bis (4) _Amino-3_methylcyclohexyl)methane, -15- 201101924 4,4'-extended methyl bis(2-methylcyclohexylamine) and other alicyclic diamine compound tetramethylamine, six Some diamine compounds such as methyl diamine and other aliphatic diamine compounds can be used alone. The ratio of the total tetracarboxylic dianhydride compound to the molar ratio of the total diamine compound in the case of using one or two or more kinds of the above polyfluorene to form the carboxylic acid compound/diamine = 0.8 to 1.2 is preferred. As in the case of the general polycondensation reaction, the closer to 1, the greater the degree of polymerization of the resulting polymer. When the degree of polymerization is increased, the strength of the polyimide film is insufficient, and the degree of polymerization is too high, and the workability at the time of formation of the polyimide film may be deteriorated. Therefore, the degree of polymerization of the product in the present reaction is 0.5% to 5.0 dl/g (concentration of 0.5% in N-methyl-2-alkanone at 30 ° C) in terms of polyphosphoric acid-reducing viscosity. g/dl) is better. Examples of the solvent used for the synthesis of polylysine include m-, N-methyl-2-pyrrolidone (NMP), hydrazine, hydrazine-dimethylformamide ( ), hydrazine, hydrazine-dimethyl methacrylate. Ethyl amide (DMAc), N-methyl caprolactam methyl flavonoid, tetramethyl urea, pyridine, dimethyl milling, hexamethylphosphine, r-butyrolactone, and the like. These can be used singly or in combination. Even if it is a solvent which does not dissolve polyamic acid, it can be used together with the above solvent in a uniform solution. The temperature of the polycondensation reaction is -2 0 to 150 ° C, preferably any temperature selected from I00 ° C. The polyimine used in the present invention can be obtained by synthesizing lysine as shown above by heating, followed by dehydration ring closure (thermal imidization). And the use of the auricular compound to the ear of the small molar solution of pyrrole cresyl DMF decylamine and the range of -5 to the poly, this -16,019,019,24 can also convert the poly-proline to the solvent The imine is used as a solvent-soluble polyimine. Further, a method of chemically ring-closing using a known dehydration ring-closing catalyst can also be employed. The heating can be carried out at any temperature of 100 to 300 ° C, preferably 120 to 2501. The chemical ring closure method can be carried out, for example, in the presence of pyridine or triethylamine or the like in the presence of acetaldehyde anhydride, and the temperature at this time can be selected from any of _2 Torr to 200 °C. The polyimine solution thus obtained may also be used as it is, or may be precipitated by adding a poor solvent such as methanol or ethanol, and the separated polyimine may be used as a powder' or the polyimine powder may be dissolved. Re-use in a suitable solvent. The solvent for re-dissolution is not particularly limited as long as it can dissolve the obtained polyimine, and examples thereof include m-cresol, 2-pyrrolidone, NMP, N-fluorenyl-2-pyrrolidone, and N- Vinyl-2-pyrrolidone 'DMAc, DMF, γ-butyrolactone, and the like. Further, even if it is a solvent which cannot dissolve polyimine in a single unit, it can be used by adding the above solvent in a range which does not impair the solubility. As such a specific example, ethyl sirolius, butyl siroliol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy- 2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, 'propylene glycol monoacetate, propylene glycol diacetate, Propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- -17- 201101924 (2-ethoxypropoxy) propyl Alcohol, methyl lactate, ethyl lactate, η-propyl lactate, η-butyl lactate, isoamyl lactate, and the like. The polyimine film used in the present invention can be coated on the glass by a polylysine solution obtained by polymerization or an organic solvent solution of the polyimine obtained by chemically imidating it. It is produced by evaporating a solvent on a substrate such as a plate. In this case, it is preferably carried out at a temperature of 50 to 100 ° C for 1 to 5 hours after the preliminary calcination at a pressure of 〜Pa under reduced pressure of 〇〇〇Pa, by using at a temperature exceeding 1 ° C to 160 ° C. ~5 hours, followed by a multi-stage heating method of 1 to 5 hours at a temperature exceeding 1600 ° C to 200 ° C for 1 to 5 hours, and further at 200 ° C to 300 ° C for 1 to 5 hours. It is possible to produce a polyimide film having less coloration and high surface smoothness. The polyimide film thus produced has a film thickness of 5 Å to 50,000 μm and a light transmittance of 70% or more at 400 nm. 10% by weight of temperature above 300 °C, water absorption of 1% or less, Young's modulus of 1.5GP a or more, maximum elongation of 5% or more, high transparency, high mechanical strength, high heat resistance, low water absorption, And both soft. The polyimide film can be used as a substrate for an image display device such as a substrate for an organic EL display or a substrate for a liquid crystal display. Since the image display device and the organic EL device of the present invention have such a feature as a polycrystalline ITO electrode which is used as the polyimide film and the anode, the other constituent members may be appropriately selected and used by a person skilled in the past. As a representative example, an application example to an organic EL display device as described below. -18-201101924 The organic EL device of the present invention is a substrate having the above polyimide film and a polycrystalline ITO electrode formed on the substrate, and as an example of the specific configuration, On the amine film substrate, a polycrystalline ITO electrode (anode), a hole injection layer, a hole transport layer, a light-emitting layer made of an organic substance, an electron injection layer, and a transparent cathode are laminated in this order. The polycrystalline ITO electrode is not particularly limited, but in the present invention, 'on the polyimide film substrate, once the amorphous ITO film is laminated, the amorphous ITO film is heat-treated to form ITO. The latter is preferred for polycrystallization. Wherein 'as the heat treatment temperature, if it is considered to increase the degree of crystallization more', the final temperature is preferably 10 to 300 ° C, preferably 1 2 0 to 2 70 t: to 1 2 0~2 4 (TC is better. The heat treatment time is at the above final temperature to 〇. 1~30 hours is better, and 0 · 2~2 0 hours is better. Also 'heat treatment at 104~l ( It is preferable to carry out the pressure reduction under the pressure of T4Pa. The amorphous IT0 film can be produced by a general sputtering method or an ion plating method. Examples of the material constituting the hole injection layer include C up c and H2Pc. Isobaric cyanine material; 4, 4, 4,, _ gin [N-( 3_methylphenyl)-N — phenyl phenyl group] bis-fee (m-MTDATA), TPTE, FTPD1 ~7, OTPAC1~5, OTCAC6 and other aromatic amine materials, poly(styrenesulfonate)/poly[2,3-hydropheno(3,4^)-1,4-dioxine) (PEDOT- PSS) such as a molecular material or the like 'But in the present invention, pED〇T-PSS is particularly preferred. -19-201101924 As a material constituting the above-mentioned hole transport layer, for example, bis[N-(1-naphthyl)-N-phenyl]benzidine (NPB) can be cited [alias: 4, 4, - double [N] -(p-naphthyl)-N-phenyl-amino]-biphenyl](α-NPD)], TPD, 2Me-TPD, ARA, TPAC, PAA, Diamine, TPM, etc. In particular, NPB is preferred in the invention. As the organic material constituting the light-emitting layer, any of a low molecular light-emitting material and a polymer light-emitting material can be used. The low molecular luminescent material' may be either a fluorescent material or a calendering material. Examples of the fluorescent material ' include argon (8-hydroxysallium) aluminum (A1 q 3 ), ginseng (4-methyl-8-hydroxyquinoline) aluminum (Almq3), Bebq2, DPVBi, H2Pc, and N, N'-bis(2,5-di-t-butylphenyl)-3,4,9,10-decanedicarboxyimine (BPPC), QD, 4-(dicyanomethyl)-2 - -6-(p-dimethylaminostyryl)_4H-pyran (Dcm), (1,1〇-phenanthroline)-para-(4,4,4-trifluoro-1-( 2 -Thienyl)-butane _ 丨, 3 - diacid) 铕 [Eu(TTA) 3 (Phen)], ppCp, erythritol, Zn (BQ 〇 EH) and the like. Examples of the calendering material include fac _ ginseng (2 _phenyl b b ding) f (III) (Ir (ppy) 3), I r (pp y) 3 ( acac), and I r (Fp py). 3 (ac ac), btp2Ir (acac), FIrpic, Gllr, PtOEP, etc. On the other hand, examples of the polymer light-emitting material include polyparaphenylene-extended vinyl materials such as PPV and MEH-PPV, and polyphenylene-based materials such as ppp and R〇_ppp, PAT, PCHMT, and pdcHT. , P0PT and other materials such as polystyrene materials such as PDAF and PFBT; polydecane-based materials such as pMp; and other materials such as PVK. -20- 201101924 Among them, in particular, A1 q3 is preferred in the present invention. Examples of the material constituting the electron injecting layer include 2—(4—biphenyl)-5-(4-t-butylphenyl)oxadiazine (pBD), BND, BMD, MBSQ, MBDQ, BDD, BBOT, BAPD, Alq3, etc. In the present invention, in particular, Alq3 which exhibits the performance of a light-emitting material is particularly preferable.

Examples of the material constituting the cathode include, for example, A1 - L i, A1 - L i F Ο , AUCe, A1, Mg-Ag, etc. In the present invention, a laminate of Al-Li and A1 is particularly preferable. The above-mentioned respective layers can be produced by any conventional method, and a general sputtering method or an ion plating method can be used. Further, the hole injection layer can also be produced by a coating method such as a spin coating method using a solution or a dispersion. The hole injection layer, the hole transport layer, the light-emitting layer made of an organic substance, and the electron injection layer are laminated on the polycrystalline ITO anode and the cathode, and are formed in a matrix on the polyimide film substrate. A voltage is applied between the anode and the cathode to inject a current into the organic EL layer to cause the pixel to emit light. The generated light is taken out from the anode electrode side to the outside. [Embodiment] [Examples] Hereinafter, the present invention will be further described by way of Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. The measurement device for each physical property in the examples is as follows. -21 - 201101924 [1]Molecular weight Device: Normal temperature GPC measuring device (SSC-7200, (share) Senshu science system)

Dissolved solution: DMF

[2] TG/DTA (differential thermal heat simultaneous measuring device) Device: Thermoplus TG8120 ((stock) physics electrical mechanism)

[3]FT-IR

Device: NICOLET 5700 ( Thermo ELECTRON CORPORATION

[4] Film thickness measuring device: Micrometer (manufactured by Santop) [5] UV-Vis spectroscopy device: UV-VIS-NIR SCANNING SPECTROPHOTOMETER (self-recording spectrophotometer) (manufactured by Shimadzu Corporation) [6] X Line diffraction device: RINT-2000 (manufactured by Rigaku Co., Ltd.) [7] Conductive device: Loresta-GP MCP-T610 (manufactured by Mitsubishi Chemical Corporation) -22- 201101924 [Manufacturing example 1] TDA/1,3-BAPB Synthesis of polyaminic acid and polyimine, and production of polyimine film [Chemical 8]

TDA / 1,3-BAPB Polyamic acid +

TDA 1,3>BAPB

The 1,3-BAPB was dissolved in DMAc in a 50 mL four-port reaction flask equipped with a stirrer in a 25 t water bath, and charged with 1,3 BAPB 1.95 g (7_0 mmol) and DMACl 6.0 g. While stirring the solution, TDA2.10 g (7.0 mmol) was dissolved and gradually added. Next, polymerization was carried out by stirring at 26 ° C for 24 hours to obtain a polyamine solvent solution having a solid content of 20% by mass. 〇The solution was cast onto a 75 mm x 100 mm glass plate, placed in a vacuum dryer (pressure 1 0 OP a ), and subjected to 80 ° C / 4 hours, 140 ° C / 1.5 hours, 190 ° C/1.5 hours and 24 (TC/2 hours of stepwise firing. Thereafter, the glass substrate with the film was immersed in a 80 °C soup bath for 1 hour, and the film was peeled off from the glass plate. The peeled film was peeled off. The film was again placed in a vacuum dryer and dried at 100 ° C for 2 hours under reduced pressure. The obtained film was a film having less coloration, high transparency, flexibility, and excellent toughness and smoothness, and the physical properties were as follows. Μιη Film thickness: 101 -23- 201101924 Light transmittance (400 nm): 75% 5% weight reduction temperature (T d 5 :. (:): 374.4 [Comparative Example 1] Production and evaluation of organic EL device Production example 1 The produced D-80/1,3-6 octa-8-polyimine film was used as a substrate to produce a polymer-type organic EL device under the following conditions. The IT0 produced in the following anode film formation step was completed. After the film is not fired at a high temperature, the film is formed into an amorphous film under a low temperature and low damage process. (a) Washing step: UV ozone washing (b) Anode film forming step device: RF conical target sputtering (manufactured by ALS Technologies) Substrate temperature: room temperature (2 5 °C) Reaching degree of vacuum: S5.0xl (T4Pa film forming vacuum: Sl.OxlOdpa Output: 2 0 0 W Pre-sputtering time: 5min. Sputtering time: 120min. Gas flow rate: Ar ( lO.Osccm) (c) Organic vapor deposition film step Vacuum: $ 7.0x1 0_4Pa Evaporation speed: S〇.2nm /sec -24- 201101924 (d) Cathode film formation conditions Vacuum degree: S 7.0x1 (T4Pa evaporation rate: S 0.7 nm / sec (e) Organic EL element structure film substrate / ITO (300 nm) / PEDOT-PSS ( 70 nm) / NPB (30 nm) / Alq3 (40 nm) / Al-Li (40 nm) / A1 (1 〇〇 nm) 0 and PEDOT-PSS (manufactured by Aldrich) was formed by a spin coating method. Conditions: 2750 rpm, 30 sec. Drying conditions after film formation: At room temperature, firing temperature: 200 ° C, firing time: 10 minutes, and the crystallization peak of ITO was not observed in the firing conditions of this step. [Example 1 T The TDA/1,3-BAPB polyimide film produced in Production Example 1 was used as a substrate, and the ITO produced in the anode film formation step of Comparative Example 1 (b) was subjected to the following conditions. An organic EL device was produced under the same conditions as in Comparative Example 1, except that heat treatment was carried out. <heat treatment conditions> The polyimide substrate having the amorphous ITO film produced in the anode film formation step was placed in a vacuum (continuous exhaust gas under a rotary pump to a pressure of 4 〇 Pa) In the furnace core tube, heat treatment was carried out under the following conditions to crystallize non--25-201101924 crystal IΤ0. Room temperature to 200 ° C (2_3 ° c / min) 200 ° (: ~ 250 ° (: (1.3 ° (: / min) 2 5 0 ° C (1 2 0 min hold) 2 5 0 ° C ~ room temperature (Μ, 、, and natural cooling) The 1 Τ 0 film produced in the above-mentioned Example 1 and Comparative Example 1 was measured and evaluated for crystallization, light transmittance, and conductivity by enthalpy diffraction (CuKα). The X-ray diffraction pattern is as shown in Fig. 1. The UV _ V1 S spectrum (light transmittance) is shown in Fig. 2. As shown in Fig. 1, the amorphous state is shown in the amorphous ITO element produced in Comparative Example 1. (The regular sequence of the lattices) 'but no steep peaks were observed. Only the amorphous mountain peaks unique to the amorphous side were observed on the low angle side, and it is clearly shown that the germanium is amorphous. On the other hand, in the first embodiment The enthalpy diffraction pattern after the heat treatment was observed, and the distinct peaks (2 2 2 ), (400), (440), and (622) inherent to I τ 观测 were observed, which clearly showed that the ΙΤΟ was crystallized. These sheet resistances are about 150 Ω/□ under amorphous ΙΤΟ (before heating) and about 30 Ω / □' under polycrystalline I Τ (after heating) by applying heat Further, as shown in Fig. 2, the average transmittance was 82% on the polyimide substrate and 68% in the amorphous τ0 of Comparative Example 1 'under the polycrystal 1τ of Example 1. It is 5 5 %.

Next, the characteristics of the organic EL elements produced in the above-mentioned Example 1 and Comparative Example 1 were measured using an organic EL luminous efficiency measuring apparatus (ELI 003 ' PRECISE -26-201101924 GAUGES Co., Ltd.), and these properties were evaluated. [Evaluation Result] (1) Appearance of Element The illuminating state when the brightness of the element produced in Example 1 was measured is shown in Fig. 3. The brightness is 2,000 cd/m2. 〇 ( 2 ) Luminance brightness - voltage characteristics Luminous brightness - voltage relationship is shown in Figure 4. The luminance of the element of Comparative Example 1 was 610 cd/m2 at a voltage of 10 V, and the luminance of the element of Example 1 was 2, 〇〇〇cd/m2. (3) Current density-voltage characteristics The relationship between current density and voltage is shown in Fig. 5. The current density of Comparative Example 1 was 1 1 mA/cm 2 at a voltage of 10 V, and the current density 〇 of the element of Example 1 was 70 μm/cm 2 . (4) Luminous efficiency - current density characteristics The relationship between luminous efficiency and current density is shown in Fig. 6. The luminous efficiency of the element of Comparative Example 1 having a current density of 10 mA/cm 2 was 5.7 cd/A'. The luminous efficiency of the element of Example 1 was 4.0 cd/A. Further, the luminous efficiency of the element of Comparative Example 1 at a current density of 20 mA/cm 2 was 4.2 cd/A, and the luminous efficiency in the element of Example 1 was 4.5 cd/A. -27-201101924 [Example 2] An amorphous ITO was crystallized in the same manner as in Example 1 except that the heat treatment was carried out under the following conditions to produce an organic EL device. Room temperature to 200 ° C (2.3 ° C / min) 200 ° C ~ 240 ° C (1.3 ° C / min) 240 ° C (120 min hold) 240 ° C ~ room temperature (8 hours, natural cooling) For the above The I Τ film made in Example 2 was measured and evaluated for light transmittance. The UV-VIS spectrum (light transmittance) is shown in Figure 2. As shown in Fig. 2, in the polycrystalline ITO of Example 2, the average transmittance was 80%. Next, the properties of the organic EL device produced in the above Example 2 were measured and evaluated in the same manner as described above. [Evaluation Result] (Appearance of η Element The illuminating state at the time of measuring the luminance of the element produced in Example 2 is as shown in Fig. 7. (2) Light-emitting luminance, voltage characteristic, luminance, and voltage are as shown in Fig. 8. The luminance at a voltage of 10 V is 2,000 cd/m 2 . (3 ) Current density - voltage characteristic -28 - 201101924 The relationship between current density and voltage is shown in Fig. 9. The current density between voltages 8 8 to 2 V is about 4 mA. /cm2, the current density at a voltage of 10 V reaches about 7 Om A/cm 2 . (4 ) Luminous efficiency - current density characteristic The relationship between luminous efficiency and current density is shown in Fig. 1. At a current density of 15 mA/cm 2 , The luminous efficiency is 5 cd/A. For example, in the elements of Examples 1 and 2 using a polycrystalline I Τ electrode, a high luminance of 2,000 cd/m 2 at a voltage of 10 V can be achieved, and a voltage of 10 V is 70 mA/cm 2 ( Example 1) High current density of about 4 mA/cm 2 (Example 2) between voltages of 0.8 to 2 V, and high luminous efficiency of 4.5 cd/A at a current density of 20 mA/cm 2 (Example 1) or current density High luminous efficiency of 5 cd/A at 15 mA/cm 2 (Example 2), and the element of Comparative Example 1 using an amorphous ITO electrode Compared with the 2,000 cd/m2 which has excellent performance, especially the highest luminous brightness, it is particularly excellent. ❹ [Simplified description of the drawing] [Fig. 1] shows the polyfluorene produced in the first embodiment and the comparative example 1. The X-ray diffraction pattern of ITO on the imide substrate. [Fig. 2] Fig. 2 is a graph showing the light transmittance of ITO on the polyimide substrates prepared in Examples 1 and 2 and Comparative Example 1. [Fig. 3] The light-emitting luminance-voltage characteristic diagram of the organic EL element produced in the first embodiment and the comparative example 1 is shown in Fig. 4, and Fig. 4 is a graph showing the light-emitting luminance-voltage characteristics of the organic EL element -29-201101924 produced in the first embodiment and the comparative example 1. ♦ indicates the result of the first embodiment, and 〇 indicates the result of the comparative example 1. [Fig. 5] shows a current density-voltage characteristic diagram of the organic EL element produced in the first embodiment and the comparative example 1 As a result, the results of Comparative Example 1 were reduced. [Fig. 6] Fig. 6 is a graph showing the luminous efficiency-current density characteristic of the organic EL device produced in Example 1 and Comparative Example 1, wherein Lu indicates the result of Example 1, and 〇 indicates The result of the comparative example 1. [Fig. 7] shows the organic EL element produced in Example 2. [Fig. 8] Fig. 8 is a graph showing the light-emitting luminance-voltage characteristics of the organic EL device produced in Example 2. [Fig. 9] shows the current density-voltage characteristics of the organic EL device fabricated in Example 2. Fig. 10 is a graph showing the luminous efficiency-current density characteristics of the organic EL device produced in Example 2. -30-

Claims (1)

201101924 VII. Patent application scope: 1. An image display device comprising at least a polyimide film substrate and an ITO electrode formed on the substrate, wherein the ITO electrode is a polycrystalline ιτο electrode, and the poly The amine film contains at least 重复ο mol % or more of the repeating unit represented by the formula [1]; 〇[Chemical 1] [1] The alkyl group of R5, R1, R2 and R3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. A group, a cycloalkyl group having a carbon number of 3 to 7, a nitrile group or a carboxyl group, and η represents an integer). The image display device of claim 1, wherein the polyimine film contains at least 10 mol% of a repeating unit represented by the formula [2] [2] An organic electroluminescence device comprising at least a polyimide film substrate and an I Τ 0 electrode formed on the substrate, wherein the 2 IT 0 electrode is a polycrystalline ruthenium electrode, and the concentrating The quinone imine film is a repeating unit represented by the formula [1] containing at least 3 10 mol% or more; 201101924 (wherein R1 and R2 each independently represent a hydrogen atom, a halogen atom' or an alkyl group having 1 to 5 carbon atoms, and R3, R4 and R5 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and carbon. The alkenyl group of 2 to 5, the alkoxy group having 1 to 5 carbon atoms, the cycloalkyl group having 3 to 7 carbon atoms, the nitrile group, or the carboxyl group 'η represents an integer. 4. The organic electroluminescent device of claim 3, wherein the polyimine film is a repeating unit of the formula [2] containing at least 10 mol% or more; [Chemical 4] - 〇 - [2] . η (where η represents the same meaning as described above). 5. The organic electroluminescence device according to claim 3, wherein the polycrystalline germanium electrode has a hole injection layer, a hole transport layer, and an organic material laminated in the following order. A light emitting layer, an electron injecting layer, and a cathode. 6. The organic electroluminescent device according to claim 5, wherein the hole injection layer contains poly(styrenesulfonate)/poly[2,3-dihydrophene (3,41〇-1,4) - Dioxin), the hole transport layer contains bis [NU-naphthyl]-fluorenyl phenyl]benzidine, and the light-emitting layer and the electron injection layer made of the organic substance contain ginseng (8-hydroxyquinoline) aluminum, the aforementioned The cathode is a laminated electrode of A1-Li and Α1. The organic electroluminescent device of any one of the above-mentioned items of the present invention, wherein the polycrystalline ITO electrode is laminated on the polyimine film substrate to form an amorphous IΤ Ο After the film, the amorphous I τ film is formed by heat treatment. 8. The organic electroluminescence device according to claim 7, wherein the heat treatment is performed under a reduced pressure of 1〇4 to 1〇4Pa. 9. The organic electroluminescent device according to claim 7 or 8, wherein the heat treatment is carried out at 100 to 300 °C. 10. The organic electroluminescence device according to claim 9, wherein the heat treatment is carried out at 120 to 240 °C. 1 1 _ A method for producing an organic electroluminescence device according to claim 5, characterized in that an amorphous ITO film is laminated on the polyimide film substrate, and the amorphous ITO film is heat-treated After the polycrystalline ITO electrode is produced, the laminate is laminated in the order of the hole injection layer, the hole transport layer, the light-emitting layer made of the organic material, the electron injection layer, and the cathode. Ο 12. The method for producing an organic electroluminescence device according to claim 11, wherein the heat treatment is carried out under a reduced pressure of 10 to 4 Å to 4 Pa, as described in the patent application. The method for producing an organic electroluminescence element according to item i, wherein the heat treatment is performed at 1 〇〇 to 3 〇〇 ° c. A method of producing an organic electroluminescence device according to claim 3, wherein the heat treatment is carried out at 120 to 24 Torr. -33-