Patent Grant
8080277
This application is the United States national phase application of International Application PCT/JP2006/303225 filed Feb. 23, 2006.
The present invention relates to a method of forming an organic compound layer of an organic EL element which is applied for such as a plane light source and a display panel, a manufacturing method of an organic EL element and an organic EL element manufactured by said method.
In recent years, an organic EL element utilizing an organic substance has a bright prospect of application as a low priced full color display element having a large area and a light source alley for writing, as a solid emission type, and active research and development thereof is on the way. An organic EL element is a thin film type element which is provided with the first electrode (a cathode or an anode), an organic compound layer (comprising a single layer or plural layers) containing an organic emission substance being accumulated thereon, that is a light emission layer, and the second electrode (a cathode or an anode) accumulated on said light emission layer. When voltage is applied on such an organic EL element, an electron is injected into an organic compound layer from the cathode and a hole is injected from the anode. It is known that said electron and hole are recombined in an emission layer and light emission is obtained by releasing energy as light at the time of an energy level returns to a valence electron band from a conduction band.
As described above, since an organic EL element is a thin film type element, an apparatus equipped with a panel light source can be easily made to be a thin layer type when an organic EL panel, comprising one or plural number of organic EL elements formed on a substrate, is utilized as a plane light source of such as a backlight. Further, when a display device is constituted utilizing an organic EL element panel, in which a predetermined number of organic EL elements as pixels are formed on a substrate, as a display panel, there are advantages such as high visual recognition and no viewing angle dependence, which are not available with a liquid crystal display.
On the other hand, at the time of forming an organic compound layer of an organic EL element, various methods such as an evaporation method, a sputtering method, a CVD, a PVD, a coating method utilizing a solvent, as described in JP-A Nos. 9-102393 and 2002-170676 (hereinafter, JP-A refers to Japanese Patent Publication Open to Public Inspection No.); however, among these, it is known that a wet film forming method such as a coating method is advantageous in view of such as simplification of a manufacturing process, reduction of a manufacturing cost, improvement of a processing property and an application to a flexible element having a large area such as a backlight and an illumination light source. For example, a method to form an organic compound layer on a glass plate of a sheet form by a spin coat method is described in JP-A 2002-170676. A method to successively form organic compound layers on a glass plate of a sheet form by an inkjet method is described in JP-A 2003-142260. In any of these methods, an apparatus becomes large as well as a cost becomes high to manufacture a full color display element having a large area because a sheet form substrate is utilized as a substrate. Therefore, studies are made on a method to manufacture an organic EL element, which has a bright prospect of application as a low priced full color display element having a large area and a light source alley for writing, as a solid emission type. For example, known is a method in which patterning of one or a plural number of emission layers comprising an organic substance and patterning of a cathode are performed by means of a roll to roll method and an evaporation under vacuum method as a method to manufacture an organic EL display in which plastic film is utilized as a transparent substrate and one or a plural number of emission layers comprising an organic substance and an anode layer are provided on this plastic film (for example, refer to patent literature 1).
Since a roll to roll method described in patent literature 1 enable mass production different from a conventional sheet method, manufacturing of an organic EL element is possible at a low cost, however, there are following disadvantages.
1) The using efficiency of an organic substance, which is utilized to form one or a plural number of emission layers comprising an organic substance is low, which is one reason to increase the cost.
2) Since it is a method to form one or a plural number of emission layers comprising an organic substance by an evaporation method, it is difficult to scale up because an evaporation room has to be made large accordingly to require associated equipment having a high capacity, to prepare a display element having a large area.
3) Since it is a method to form one or a plural number of emission layers comprising an organic substance by an evaporation method, it takes long time to form an emission layer resulting in difficulty to increase productivity.
4) Particularly in the case of an organic EL element utilized for an illumination application, it is difficult to form an organic EL element having a large area without unevenness because an organic EL element having a large area has to be formed in an evaporation method.
In view of these situations, desired has been development of a forming method of an organic compound layer for an organic EL element application having high productivity without increasing a cost and having a large area without unevenness, a manufacturing method of an organic EL element utilizing said organic compound layer and an organic EL element.
[Patent Literature 1] PCT International Application Publication No. 01/5194 Pamphlet
The present invention has been made in view of the above-described situation, and an object thereof is to provide a highly productive method of forming an organic compound layer for a high quality organic EL element without increasing the production cost, a method of manufacturing an organic EL element utilizing said organic compound layer and an organic EL element.
The above object of the present invention is achieved by the following structures.
(Embodiment 1)
A method of forming an organic compound layer of an organic EL element, the organic EL element comprising a flexible band substrate having thereon an anode layer comprising a first electrode, the organic compound layer, a cathode layer comprising a second electrode and a sealing layer or a sealing film, in that order, using a manufacturing apparatus comprising a supplying section, a coating•drying section in which the organic compound layer is formed on the anode layer, and a recovery section, coating•drying wherein
flexible band substrate A is supplied to the supplying section as a roll wound on a core, flexible band substrate A comprising the anode layer comprising at least the first electrode;
the coating•drying section comprises a coating section and a drying section to form one unit, wherein, in the coating section, the organic compound layer is formed using a wet coating device for applying an organic compound layer coating liquid under an atmospheric pressure, and, in the drying section, an organic solvent in the organic compound layer is removed under an atmospheric pressure to form the organic compound layer;
the manufacturing apparatus comprises at least one unit of the coating•drying section;
at least one organic compound layer is formed on the anode layer in the coating•drying section to form flexible band substrate B; and
flexible band substrate B is wound on a core to form a roll in the recovery section.
(Embodiment 2)
The method of embodiment 1, wherein flexible band substrate A is subjected to a cleaning-surface modifying treatment before the organic compound layer coating liquid is applied.
(Embodiment 3)
The method of embodiment 2, wherein a means of the cleaning-surface modifying treatment is oxygen plasma or UV irradiation.
(Embodiment 4)
The method of any one of embodiments 1 to 3, wherein flexible band substrate A is subjected to a static elimination treatment using a static eliminating means.
(Embodiment 5)
The method of any one of embodiments 1 to 4, wherein a variation of a conveying speed of flexible band substrate A while the organic compound layer coating liquid is applied is 0.2 to 10% based on an average conveying speed.
(Embodiment 6)
The method of any one of embodiments 1 to 5, wherein the organic compound layer is formed by removing the organic solvent in the organic compound layer by an air drying method in which an air ejection velocity is 0.1 to 5 m/s while a variation of the air ejection velocity in the width direction is 0.1 to 10%, in the drying section.
(Embodiment 7)
The method of any one of embodiments 1 to 6, wherein the organic compound layer coating liquid comprises at least one organic compound material and at least one solvent, and exhibits a surface tension of 15×10−3 to 55×10−3 N/m.
(Embodiment 8)
The method of any one of embodiments 1 to 7, wherein the manufacturing apparatus comprises a heat treating section which follows the drying section.
(Embodiment 9)
The method of embodiment 8, wherein, just after the organic compound layer is formed in the drying section, the organic compound layer is subjected to a heat treatment using a back-surface heat transmission at a heat treatment temperature of −30 to +30° C. based on a glass transition temperature of the organic compound layer, while the heat treatment temperature does not exceed a decomposition temperature of the organic compound layer.
(Embodiment 10)
The method of any one of embodiments 1 to 9, wherein the organic compound layer is formed in an atmosphere having a dew point of −20° C. or lower, a cleanliness class according to JIS B 9920 of class 5 or less, a temperature of 10 to 45° C. excluding the drying section and a heat treatment section, under an atmospheric pressure.
(Embodiment 11)
The method of any one of embodiments 1 to 10, wherein the organic compound layer comprises at least a hole transport layer and an organic light emission layer.
(Embodiment 12)
The method of any one of embodiments 1 to 11, wherein flexible band substrate B is stored under a reduced pressure of 10−5 to 10 Pa.
(Embodiment 13)
A method of manufacturing an organic EL element comprising a flexible band substrate having thereon an anode layer comprising a first electrode, an organic compound layer, a cathode layer comprising a second electrode and a sealing layer, in that order, using a manufacturing apparatus comprising a supplying section, a coating•drying section in which the organic compound layer is formed on the anode layer, a cathode layer forming section in which the cathode layer comprising the second electrode is formed on the organic compound layer, a sealing layer forming section in which a sealing layer I formed on the cathode layer and a recovery section,
wherein
flexible band substrate A is supplied to the supplying section as a roll wound on a core, flexible band substrate A comprising the anode layer comprising at least the first electrode;
the coating•drying section comprises a coating section and a drying section to form one unit, wherein, in the coating section, the organic compound layer is formed using a wet coating device for applying an organic compound layer coating liquid under an atmospheric pressure, and, in the drying section, an organic solvent in the organic compound layer is removed under an atmospheric pressure to form the organic compound layer;
the manufacturing apparatus comprises at least one unit of the coating•drying section;
at least one organic compound layer is formed on the anode layer in the coating•drying section to form flexible band substrate B; and
flexible band substrate B is wound on a core in a first winding section to form a roll;
the cathode layer including the second electrode is formed on the organic compound layer under a reduced pressure, in the coating•drying section, using the roll of flexible band substrate B;
subsequently, the sealing layer is formed on the cathode layer under a reduced pressure in the sealing layer forming section to form the organic EL element; and
the organic EL element is wound on a core to form a roll in the recovery section.
(Embodiment 14)
A method of manufacturing an organic EL element comprising a flexible band substrate having thereon an anode layer comprising a first electrode, an organic compound layer, a cathode layer comprising a second electrode and a sealing film, in that order, using a manufacturing apparatus comprising a supplying section, a coating•drying section in which the organic compound layer is formed on the anode layer, a cathode layer forming section in which the cathode layer including the second electrode is formed on the organic compound layer, a sealing film adhering section in which a sealing film is adhered on the cathode layer, and a recovery section,
wherein
flexible band substrate A is supplied to the supplying section as a roll wound on a core, flexible band substrate A comprising the anode layer comprising at least the first electrode;
the coating•drying section comprises a coating section and a drying section to form one unit, wherein, in the coating section, the organic compound layer is formed using a wet coating device for applying an organic compound layer coating liquid under an atmospheric pressure, and, in the drying section, an organic solvent in the organic compound layer is removed under an atmospheric pressure to form the organic compound layer;
the manufacturing apparatus comprises at least one unit of the coating•drying section;
at least one organic compound layer is formed on the anode layer in the coating•drying section to form flexible band substrate B;
flexible band substrate B is wound on a core in a first winding section to form a roll;
the cathode layer comprising the second electrode is formed on the organic compound layer under a reduced pressure, in the cathode layer forming section, using the roll of flexible band substrate B to form flexible band substrate C;
flexible band substrate C is wound on a core in a second winding section to form a roll; and
the sealing film is adhered on the cathode layer using the roll of flexible band substrate C in an inert gas atmosphere in the sealing film adhering section to form the organic EL element.
(Embodiment 15)
An organic EL element manufactured by the method of embodiment 13 or 14.
The present invention provides a highly productive method to form an organic compound layer for an organic EL element application having a high quality without increase of a cost, manufacturing method of an organic EL element utilizing said organic compound layer and an organic EL element, and enables to manufacture an organic EL element having a large area which can be primarily utilized as a plane light source for such as an illumination and a backlight.
a) and 1(b) are schematic cross sectional views to show examples of layer constitutions of organic EL elements.
a) and 2(b) are schematic drawings of a process to form until an organic compound layer which is a constituent layer of an organic EL element.
Embodiments to practice the present invention will be explained referring to
A layer constitution of an organic EL element shown in
A layer constitution of an organic EL element shown in
In the drawing, 1b is an organic EL element. Organic EL element 1b is provided with anode layer 102, hole transport layer 103, organic compound layer (emission layer) 104, electron injection layer 105, cathode layer 106, adhesive layer 108 and sealing film 109 in this order on substrate 101. In an organic EL element shown in this drawing, a hole injection layer (not shown in the drawing) may be provided between anode layer 102 and hole transfer layer 103. Further, an electron transfer layer (not shown in the drawing) may be provided between cathode 106 and organic compound layer (emission layer) 104 and electron injection layer 105. In organic EL element 1a and organic EL element 1b, a gas barrier layer (not shown in the drawing) may be provided between anode 102 and substrate 101.
The present invention relates to a method to form organic compound layer (emission layer) 104 and organic compound layer (hole transport layer) 103; a manufacturing method of organic EL element 1a, in which electron injection layer 105, cathode 106 and sealing layer 107 are formed on formed organic compound layer (emission layer) 104 and organic compound layer (hole transport layer) 103, and a manufacturing method of organic EL element 1b, in which electron injection layer 105, cathode 106 and sealing film 109 are pasted up are pasted up on formed organic compound layer (emission layer) 104 sandwiching adhesive layer 108; and organic EL element prepared by these manufacturing methods.
The layer constitution of an organic EL element shown in this drawing is an example, and other typical layer constitutions of an organic EL element include the following constitutions.
(1) substrate/anode/emission layer/electron transport layer/cathode/sealing layer
(2) substrate/anode/hole transport layer/emission layer/hole block layer/electron transport layer/cathode/sealing layer
(3) substrate/anode/hole transport layer (hole injection layer)/emission layer/hole block layer/electron transport layer/cathode buffer layer (electron injection layer)/cathode/sealing layer
A sealing layer utilized in above-described (1)-(4) includes a sealing layer alone, sealing film with intervening adhesive layer, or a combination thereof.
Each layer constituting an organic EL element will be explained later.
In the drawing, 2 is a manufacturing apparatus to form until an organic compound layer which is one of a constitution layer of an organic EL element under an atmospheric pressure condition. Manufacturing apparatus 2 is provided with supply section 201 of a flexible band substrate, washing surface modification treatment section 202 of a flexible band substrate, first coating•drying section 203, first heat treatment section 204, second static elimination treatment section, second coating•drying section 206, second heat treatment section 207, third static elimination treatment section 208 and recovery section 209.
In supply section 201, flexible band substrate A 201a, on which a gas barrier layer and an anode layer including the first electrode have been formed in this order already, being wound on a core to make a roll is supplied.
Washing surface modification treatment section 202 is provided with washing modification surface treatment means 202a to modify the anode layer surface (not shown in the drawing) of flexible band substrate A201b, which is sent from supply section, and first static elimination treatment means 202b, before coating an organic compound layer coating solution. Washing surface modification treatment means 202a includes such as a low pressure mercury lamp, an excimer lamp and a plasma washing apparatus. A condition of washing surface modification treatment by a low pressure mercury lamp includes, for example, a condition to perform washing surface modification treatment by irradiation with a low pressure mercury lamp having a wavelength of 184.2 nm, at irradiation strength of 5-20 mW/cm2 and a distance of 5-15 mm. As a condition of washing surface modification treatment by a plasma washing apparatus, an atmospheric plasma is suitably applied and the washing condition includes, for example, a condition to perform washing surface modification treatment by use of an argon gas containing 1-5 volume % of oxygen at a frequency of 100 kHz-150 MHz, a voltage of 10 V-10 kV and an irradiation distance of 5-20 mm.
First static elimination treatment means 202b includes such as a light irradiation method and a corona discharge method, and may be appropriately selected among them. A light irradiation method generates an air ion by very weak X rays and a corona discharge method generates an air ion by corona discharge. This air ion compensates charges of an opposite polarity to neutralize static electricity. A static elimination by corona discharge and a static elimination by soft X rays can be utilized. Since static elimination of a substrate is promoted by the first static elimination means to prevent adhesion of dust and dielectric breakdown, yield of the element is increased.
First coating•drying section 203 is provided with backup roll 203a to hold flexible band substrate A201b, first wet coater 203b to coat the first organic compound layer coating solution on flexible band substrate A201b held by backup roll 203a, and first dryer 203c to remove a solvent of first organic compound layer 201c formed on the anode layer (not shown in the drawing) on flexible band substrate A201b.
204 is the first heat treatment section and the first heat treatment section is provided with apparatus main body 204a and a plural number of heating rollers 204b to heat first organic compound layer 201c from the back-surface of a flexible band substrate, on which first organic compound layer 201c has been formed, by a back-surface heat transmission method.
First dryer 203c is provided with drying air supply header 203c1, which has ejection outlet 203c3 to eject drying air and supply gate 203c2 of drying air, exhaust gate 203c4 and transport rolls 203c5.
205 is the second static elimination treatment means to perform static elimination of formed first organic compound layer 201c. Herein, in this drawing, the first organic compound layer coating solution is a hole transport layer coating solution, and the first organic compound layer 201c is a hole transport layer.
Second coating•drying section 206 is provided with second wet coater 206b to coat the second organic compound layer coating solution on a flexible band substrate, which is held by backup roll 206c and provided with first organic compound layer (hole transport layer) 201c, and second dryer 206c to dry second organic compound layer 201d having been formed on first organic compound layer (hole transport layer) 201c. Herein, in this drawing, the second organic compound layer coating solution is an emission layer coating solution, and the second organic compound layer 201d is an emission layer.
207 is the second heat treatment section and heat treatment section 207 has the same constitution as first heat treatment section 204 to heat second organic compound layer 201d, which has been formed on first organic compound layer (hole transport layer) 201c, by a back-surface heat transmission method from the back-surface of a flexible band substrate.
208 is the third static elimination means to perform static elimination of formed second organic compound layer (emission layer) 201e. Second dryer 206c has the same constitution as first dryer 203c. First static elimination means 202b, second static elimination means 205 and third static elimination means 208 may be same.
In this drawing, the case that a coating•drying section is provided with two units of first coating•drying section and second coating•drying section is shown, however, the number of the units can be increased when necessary.
A hole transport layer formed by being coated by use of first wet coater 203b is comprised of a hole transport material which has an ability of transporting a hole, and a hole injection layer and an electron block layer are included in a hole transport layer in a broad meaning. A single layer or plural layers of a hole transport layer can be provided. A hole transport material is those having any one of injection or transport ability of a hole, or barrier ability against an electron, and may be either an organic substance or an inorganic substance. For example, listed are triazole derivatives, oxazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino substituted calcon derivatives, oxazole derivatives, styrylanthrathene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline type copolymer, and conductive polymer oligomer, and specifically thiophene oligomer.
As a hole transport material, those described above can be utilized, however, preferably utilized are a porphyrin compound, an aryl tertiary amine compound and a styrylamine compound and specifically preferably an aryl tertiary amine compound. Typical examples of an aryl tertiary amine compound and a styrylamine compound include such as N,N,N′,N′-tetraphenyl-4,4′-diaminophenyl, N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N,N′,N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N′-diphenyl-N,N′-di(4-methoxyphenyl)-4,4′-diaminobiphenyl, N,N,N′,N′-tetraphenyl-4,4′-diaminophenyl ether, 4,4′-bis(diphenylamino)quadoriphenyl, N,N,N-tri(p-tolyl)amine, 4-(di-p-tolylamino)-4′-[4-(di-p-tolylamino)styryl]stilbenezene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4′-N,N-diphenylaminostilben, N-phenylcarbazole, and those having two condensed aryl rings in a molecule which is described in U.S. Pat. No. 5,061,569 such as 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), and such as 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA), in which three of triphenylamine units are connected in a starburst form which is described in JP-A 4-308688.
Further, polymer materials in which these materials are introduced to a polymer chain or these materials constitute a polymer main chain can be also utilized. Further, inorganic compounds such as p-type Si and p-type SiC can be also utilized as a hole injection material or a hole transport material.
Further, so-called p-type hole transport materials such as described in JP-A 11-251067 and a literature by J. Huang et al. (Applied Physics Letters 80 (2002), p. 139) can be also utilized. In the present invention, these materials are preferably incorporated because an emission element having higher efficiency can be prepared.
The layer thickness of a hole transport layer is not specifically limited, however, is generally approximately 5 nm-5 μm and preferably 5-200 nm. This hole transport layer may have a one-layer structure comprising one or at least two types of the above-described materials. Further, a hole transport layer which is doped with impurities and has a high p-property can be also utilized. Such an example includes those described in such as JP-A Nos. 4-297076, 2000-196140 and 2001-102175, and J. Appl. Phys., 95, 5773 (2004). To utilize such a hole transport layer having a high p-property is preferable because an organic EL element exhibiting lower power consumption can be prepared.
In the case that an emission layer formed by second wet coater 206b is comprised of multi layers, a plural number of coating•drying units has to be arranged corresponding to the number of layers to be accumulated. For example, by constituting an emission layer comprising multi layers, preparation of a white emitting element is possible. In the present invention, an emission layer means a blue emission layer, a green emission layer and a red emission layer. The order of accumulation of emission layers in the case of accumulating emission layers is not specifically limited, and further, a non-emission intermediate layer may be provided between each emission layer. In the present invention, at least one blue emission layer is preferably arranged at a position nearest to an anode among all emission layers. Further, when not less than four emission layers are arranged, a blue emission layer, a green emission layer and a red emission layer are preferably accumulated in this order from the nearest to an anode, such as a blue emission layer/a green emission layer/a red emission layer/a blue emission layer, a blue emission layer/a green emission layer/a red emission layer/a blue emission layer/a green emission layer, a blue emission layer/a green emission layer/a red emission layer/a blue emission layer/a green emission layer/a red emission layer, with respect to increasing luminance stability.
The total layer thickness of an emission layer is not specifically limited, however, is selected generally in a range of 2 nm-5 μm and preferably 2-200 nm, in consideration of such as homogeneousness of the film and voltage required for emission. It is furthermore preferably in a range of 10-20 nm. It is preferable that there is an effect to improve stability of emission color against drive current in addition to voltage aspect when the layer thickness is not more than 20 nm. A layer thickness of each emission layer is preferably selected in a range of 2-100 nm and more preferably in a range of 2-20 nm. The relationship among each emission layer of blue, green and red is not specifically limited; however, it is preferable that a blue emission layer (the total when plural layers are present) has the largest layer thickness among three emission layers.
An emission layer contains at least three layers having different emission spectra, the emission maximum wavelengths of which are in a range of 430-480 nm, 510-550 nm and 600-640 nm, respectively. There is no specific limitation provided that not less than three layers present. In the case of not less than 4 layers, there may be plural layers having the same emission spectrum. A layer having an emission maximum wavelength of 430-480 nm is referred to as a blue emission layer; a layer having an emission maximum wavelength of 510-550 nm is referred to as a green emission layer; and a layer having an emission maximum wavelength of 600-640 nm is referred to as a red emission layer. Further, in a range of maintaining the aforesaid maximum wavelength, a plural number of emission compounds may be mixed in each emission layer. For example, in a blue emission layer, a blue emitting compound having a maximum wavelength of 430-480 nm and a green emitting compound having a maximum wavelength of 510-550 nm may be utilized by being mixed.
A material utilized in an emission layer is not specifically limited, and includes various types of materials such as described in Up-to-date Trend of Flat Panel Display; The Present State and Up-to date Technical Trend of EL Display, edited by Toray Research Center Co., Ltd., pp. 228-332.
An organic compound layer (an emission layer), which has been formed by coating an organic compound coating solution by second wet coater 206b followed by being dried, is a layer to emit by recombination of an electron and a hole injected from an electrode, an electron injection layer or a hole injection layer, and the emitting portion may be either the interior of an emission layer or the interface between an emission layer and an adjacent layer.
A drying condition in the first dryer 203c to remove a solvent of a coated film of the first organic compound layer (a hole transport layer) includes air flow drying having an air ejection velocity from an ejection outlet of 0.1-5 m/s and a variation of air ejection velocity in the width direction of 0.1-10%, in consideration of such as drying unevenness and setting mottle of the coated surface. A drying condition to remove a solvent of the second organic compound layer (an emission layer) in the second dryer 206c may be same as the condition in the first dryer 203c.
As a heat treatment condition of the first organic compound layer (a hole transport layer) in first heat treatment section 204, it is preferable to perform heat treatment by means of a back-surface heat transmission method at a temperature of −30-+30° C. based on a glass transition temperature of the first organic compound layer (a hole transport layer) and not to exceed a decomposition temperature of an organic compound constituting the first organic compound layer (a hole transport layer), in consideration of smoothness improvement of the organic compound layer (a hole transport layer), removal of a residual solvent and hardening of the organic compound layer (a hole transport layer).
As a heat treatment condition of the second organic compound layer (an emission layer) in second heat treatment section 207, it is preferable to perform heat treatment by means of a back-surface heat transmission method at a temperature of −30-+30° C. based on a glass transition temperature of the second organic compound layer (an emission layer) and not to exceed a decomposition temperature of an organic compound constituting the second organic compound layer (an emission layer), in consideration of smoothness improvement of the second organic compound layer (an emission layer), removal of a residual solvent and hardening of the second organic compound layer (an emission layer).
A distribution of a transport rate of flexible band substrate A at the time of coating a first organic compound layer (hole transport layer) coating solution by first wet coater 203b and a distribution of a transport rate of flexible band substrate A at the time of coating a second organic compound layer (emission layer) coating solution by second wet coater 206b are preferably 0.2-10% based on a mean transport rate, in consideration of such as emission luminance unevenness which unevenness of a coated layer thickness in the longitudinal direction accompanies.
A first organic compound layer (hole transport layer) coating solution utilized in first wet coater 203b and a second organic compound layer (emission layer) coating solution utilized in second wet coater 206b contain at least one type of an organic compound material and at least one type of a solvent and have a surface tension of 15×10−3-55×10−3 N/m in consideration of such as repellent spots and coating unevenness at the time of coating.
In a process to form the first organic compound layer (a hole transport layer) and the second organic compound layer (an emission layer), which are constituent layers of an organic EL element shown in this drawing, formation is preferably performed under an atmospheric pressure condition having a dewing point of not higher than −20° C., cleanliness, which is measured based on JISB 9920, of not more than class 5, and at 10-45° C. except in the first drying section and the second drying section, in consideration of such as ability maintenance of the first organic compound layer (a hole transport layer) and the second organic compound layer (an emission layer) and prevention of defects which adhesion of foreign matters accompanies. In the present invention, cleanliness of not more than class 5 indicates class 3-class 5.
In recovery section 209, flexible band substrate B201e, on which second organic compound layer (emission layer) 201d has been formed, is wound around a core to be made into a roll form, whereby flexible band substrate B201f of a roll form is prepared. At the time of winding up as a roll form, it is preferable to wind up the substrate sandwiching an interleaf having air permeability or a spacer tape which keeps space on the element surface.
The prepared flexible band substrate B201f of a roll form is preferably stored under a reduced pressure condition of 10−5-10 Pa, in consideration of such as ability maintenance of the first organic compound layer (a hole transport layer) and the second organic compound layer (an emission layer) and non-emission defects. A storing term is preferably 1-200 hours in consideration of removal of oxygen and a slight amount of moisture which may cause deterioration of the first organic compound layer (a hole transport layer) and the second organic compound layer (an emission layer). The substrate may be appropriately stored under a heated environment.
A flexible band substrate utilized for a flexible band substrate, on which an anode layer including the first electrode have been already formed, according to the present invention includes transparent resin film. Resin film includes polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyethylene; polypropylene; cellophane; cellulose esters such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof; polyvinylidene chloride; polyvinyl alcohol; polyethylene vinylalcohol; syndiotactic polystyrene; polycarbonate; norbornene resin; polymethylpenetene; polyether ketone; polyimide; polyether sulfone (PES); polyphenylene sulfide; polysulfones; polyether imide, polyether ketone imide; polyamide; fluorine-contained resin; nylon; polymethyl methacrylate; acryls or polyallylates; and cycloolefin type resin such as Arton (product name, manufactured by JSR Co., Ltd.) or Apel (product name, manufactured by Mitsui Chemicals, Inc.).
As an anode, those employing a metal, an alloy, a conductive compound and a mixture thereof having a large work function (not less than 4 eV) as an electrode substance are preferably utilized. As specific examples of such an electrode substance, a metal such as Au and a conductive transparent material such as CuI, indium tin oxide (ITO), SnO2 and ZnO. Further, a material capable of forming amorphous and transparent conductive film such as IDIXO (In2O3.ZnO) may be also utilized. As an anode, a pattern of a desired form may be formed by a photolithographic method after forming thin film by a method such as evaporation or sputtering, or the pattern may be formed through a mask of a desired form at the time of evaporation or sputtering of the above-described electrode substance in the case of patterning precision being not much required (approximately not less than 100 μm). Further, in the case of utilizing a substance capable of being coated such as an organic conductive compound, a wet film forming method such as a printing method and a coating method can be also utilized. When emission is taken out from this anode, the transparency is desirably made to be not less than 10%, and a sheet resistance as an anode is preferably not more than a few hundreds Ω/□. Further, a layer thickness depends on a material, however, is selected in a rage of generally 10-1,000 nm and preferably 10-200 nm.
Between an anode and an organic compound layer (an emission layer) or a hole transport layer, a hole injection layer (an anode buffer layer) may be provided. An injection layer is a layer provided between an electrode and an organic layer in order to decrease driving voltage and improve emission efficiency, and is detailed in 2nd volume 2nd chapter “Electrode Material” (pp. 123-166) of “Organic EL Element and Front of Industrialization Thereof (Published by N. T. S. Co., Ltd., Nov. 30, 1998)”.
An anode buffer layer (a hole injection layer) is detailed in such as JP-A Nos. 9-45479, 9-260062 and 8-288069, and specific examples include a phthalocyanine buffer layer represented by copper phthalocyanine, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, a polymer buffer layer utilizing conductive polymer such as polyaniline (emeraldine) and polythiophene. An anode buffer layer (a hole injection layer) is preferably very thin film and the layer thickness, although depends on materials, is preferably in a range of 1 nm-5 μm.
Gas barrier film is appropriately formed on the surface of resin film utilized as a flexible band substrate. Gas barrier film includes film of an inorganic substance, an organic substance or hybrid film of the both. As the characteristic of gas barrier film, a water vapor permeability is preferably not more than 0.01 g/m2·day·atm. Further, film having a high barrier capability of an oxygen permeability of not more than 10−3 ml/m2/day and a water vapor permeability of not more than 10−5 g/m2/day is preferable.
As a material to form barrier film, a material provided with a function to restrain invasion of such as moisture and oxygen, which may induce deterioration of an element, is preferable and such as silicon oxide, silicon dioxide and silicon nitride can be utilized. Further, to overcome brittleness of said film, it is more preferable to provide an accumulation structure comprising an inorganic layer and a layer comprising an organic material. The order of accumulation of an inorganic layer and an organic layer is not specifically limited; however, it is preferable to alternately accumulate the both in plural times. A forming method of barrier film is not specifically limited, and such as a vacuum evaporation method, a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method and a coating method can be utilized, however, an atmospheric pressure plasma polymerization method such as described in JP-A 2004-68143 is specifically preferable.
As a wet coater utilizable as first wet coater 203b and second wet coater 206b, for example, a coater of such as a die coat method, a screen printing method, a flexography method, an inkjet method, a wire-bar method, a cap coat method, a spray coat method, a cast method, a roll coat method and a gravure coat method can be utilized. Utilization of these wet coaters can be suitably selected depending on a material of an organic compound layer.
A forming method of an organic compound layer, in which flexible band substrate A, on which an anode layer including the first electrode has been formed, is utilized to be made into flexible band substrate B by forming the first organic compound layer (a hole transport layer) and the second organic compound layer (an emission layer) on the anode layer, then the flexible band substrate B is wound on a core to be made into flexible band substrate B of a roll-form, can achieve the following effects compared to the evaporation method.
1) It becomes possible to depress a cost because using efficiency of an organic compound, which is utilized to form one or a plural number of emission layers comprising an organic compound, is high.
2) Formation of a large area organic compound layer, which is required to form a large area organic EL element, becomes easy.
3) Improvement of a rate of operation is possible because organic compound layer can be formed in a short time.
4) Formation of a large area organic compound layer, which is required to form a large area organic EL element, becomes easy.
In the drawing, 3 is a manufacturing apparatus to prepare an organic EL element. Manufacturing apparatus 3 is provided with a coating•drying section (same as coating•drying section 203 shown in
In manufacturing apparatus 3 shown in this drawing to prepare an organic EL element, transport of an object is performed always in a roll form throughout each of coating•drying section 2—sealing film paste up section 5, and the object is recovered as a roll form wound on a core also in a recovery section. Herein, the object, after having been pasted up with sealing film, may be cut into a sheet form to be recovered.
Cathode layer forming section 4 is provided with material supply section 401, first cathode forming section 402, second cathode forming section 403 and second windup section 404, and the operation is continuously performed under a reduced pressure condition from supply section 401 until recovery section 404. In material supply section 401, flexible band substrate B201f of a roll form, which is comprised of an anode, a hole transport layer and an organic compound layer (an emission layer) formed on a flexible band substrate and has been wound up on a core, and which is prepared in manufacturing apparatus 2, is supplied.
Electron injection layer 201g is formed on the organic compound layer (the emission layer) of flexible band substrate B201f having an organic compound layer (an emission layer) unwound from supply section 401 in first cathode layer forming section 402. 402a is an evaporation apparatus and 402b is an evaporation source container.
In second cathode layer forming section 403, cathode layer 201h, which is the second electrode, is formed on electron injection layer 201g in second cathode layer forming section 403. 403a is an evaporation apparatus and 403b is an evaporation source container.
Flexible band substrate C201i, on which cathode layer 201h, which is the second electrode, is formed in second cathode layer forming section 403, is wound up on a core to be flexible band substrate C201j of a roll form.
In this drawing, the case of first cathode layer forming section 402 and second cathode layer forming section 403 being an evaporation apparatus is shown, however, a cathode layer forming method is not specifically limited and such as a sputtering method, a reactive sputtering method, a molecular beam epitaxy method, a cluster ion beam method, an ion plating method, a plasma polymerization method, an atmospheric pressure plasma polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method and a coating method can be utilized.
Sealing film paste up section 5 is provided with material supply section 501, paste up section 502 and recovery section 503, and the operation can be continuously performed under an atmospheric pressure condition from supply section 501 until recovery section 6. In supply section 501, flexible band substrate C201j of a roll form, which is comprised of an anode, a hole transport layer, an organic compound layer (an emission layer), an electron injection layer and a cathode layer formed on flexible band substrate C201i and has been wound up on a core, and which is prepared in cathode layer forming section 4, is supplied. Herein, sealing film paste up process 5 is preferably performed under an inert gas environment to prevent deterioration of an organic compound layer (an emission layer).
Paste up section 502 is provided with coating apparatus 502a to coat an adhesive on a cathode layer of flexible band substrate C201i which is fed from supply section 501, sealing film supply section 502b, press roll 502c and curing treatment section 502d. 502b1 is sealing film of a roll form having been wound up on a core.
Flexible band substrate C201i unwound from supply section 501, after having been coated with an adhesive on the cathode layer of said substrate C201i in a coating apparatus 502a, is continuously pasted up with sealing film and passed through press roll 502c, whereby sealing film is continuously pasted up on a cathode layer sandwiching an adhesive. A curing treatment of paste up of sealing film is performed after sealing film 502b2 has been pasted up sandwiching an adhesive. An organic EL element protected with sealing film 502b2 is prepared at the stage of finishing the curing treatment of an adhesive, and is wound on a core to make a roll form in recovery section 6 to complete preparation of organic EL element 601 of a roll form protected with sealing film. In this case, after pasting up sealing film, organic EL element may be cut into a sheet form without being wound. Other symbols are identical with those in
An electron injection layer formed in first cathode forming section 402 is comprised of a material having a function to transport an electron and is included in an electron transport layer in a broad meaning. An electron injection layer is a layer provided between an electrode and an organic layer to decrease drive voltage and improve emission luminance, and is described in detail in 2nd volume 2nd chapter “Electrode Material” (pp. 123-166) of “Organic EL Element and Front Line of Industrialization Thereof (published by N. T. S. Corp., Nov. 30, 1998)”. An electron injection layer (a cathode buffer layer) is detailed in JP-A Nos. 6-325871, 9-17574 and 10-74586, and specifically includes such as a metal buffer layer represented by such as strontium and aluminum, an alkali metal compound buffer layer represented by lithium fluoride, an alkaline earth metal compound buffer layer represented by magnesium fluoride, and an oxide buffer layer represented by aluminum oxide. The above-described buffer layer (an injection layer) is desirably very thin film, and preferably has a layer thickness in a range of 1 nm-5 μm although it depends on a material. An electron transport material (also functions as a hole block material) utilized in an electron transport layer adjacent to the cathode side is provided with a function to transmit an electron injected from a cathode to an emission layer, and a material utilized can be arbitrary one selected among conventionally known compounds and includes such as nitro substituted fluorene derivatives, diphenyl quinone derivatives, thiopyrandoxide derivatives, carbodiimide, fluorenylidene methane derivatives, anthraquinone dimethane and anthrone derivatives and oxadiazole derivatives. Further, thiadiazole derivatives in which an oxygen atom of an oxadiazole ring is substituted by a sulfur atom in the above described oxadiazole derivatives, and quinoxaline derivatives which has a quinoxaline ring known as an electron attractive group, can be utilized as an electron transport material. Further polymer material in which these materials are introduced in a polymer chain or utilized as a polymer main chain can be also utilized.
Further, metal complexes of an 8-quinolinol derivative such as tris(8-quinolinol)aluminum (Alq), tris(5,7-dichloro-8-quinolinol)aluminum, tris(5,7-dibromo-8-quinolinol)aluminum, tris(2-methyl-8-quinolinol)aluminum, tris(5-methyl-8-quinolinol)aluminum and bis(8-quinolinol)zinc (Znq), and in addition to these, metal complexes in which the central metal of these metal complexes is replaced by In, Mg, Cu, Ca, Sn, Ga or Pb can be also utilized as an electron transport material. Further, a distyrylpyradine derivative can be also utilized as an electron transport material, and similar to the cases of a hole injection layer and a hole transport layer, inorganic semiconductors of such as n-type Si and n-type SiC can be also utilized as an electron transport material. The layer thickness of an electron transport layer is not specifically limited; however, is generally approximately 5 nm-5 μm and preferably 5-200 nm. An electron transport layer may have one layer structure comprising one or at least two types of the above-described materials. Further, an electron transport layer which is doped with impurities to have a high n-property may be also utilized. Such examples includes those described in such as JP-A Nos. 4-297076, 10-270172, 2000-196140 and 2001-102175, and J. Appl. Phys., 95, 5773 (2004). To utilize such an electron transport layer having a high n-property is preferred because an element exhibiting low power consumption can be prepared. An electron transport layer can be also formed by making the above-described electron transport material into a thin film by a method well known in the art such as a wet coating method and a vacuum evaporation method. In the present invention, for example, an electron transport layer can be also formed by arranging second coating•drying section 206 and second heat treatment section 207 after third static elimination means 208.
As a cathode, those comprising a metal having a small work function (not more than 4 eV) (referred to as an electron injecting metal), an alloy, an electric conductive compound and a mixture thereof as an electrode substance are utilized. Specific examples of such an electrode substance include such as sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium/copper mixture, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, indium, a lithium/aluminum mixture and a rare earth metal. Among them, preferable is a mixture of an electron injecting metal and the second metal, which has a work function larger than said metal and is stable, such as a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al2O3) mixture, a lithium/aluminum mixture and aluminum are preferable. A cathode can be prepared by making these electrode substances into thin film by means of evaporation or sputtering. Further a sheet resistance as a cathode is not more than a few hundreds Ω/□, a layer thickness is generally selected in a range of 10 nm-5 μm and preferably in a range of 50-200 nm. Herein, to transmit emitted light, it is convenient to improve emission luminance provided that either one of an anode or a cathode of an organic EL element is transparent or translucent.
Further, after a cathode has been prepared with the above-described metal at a layer thickness of 1-20 nm, by forming a conductive transparent material, which was described in the explanation of an anode, thereon, it is possible to prepare a transparent or translucent cathode, whereby an element, the both an anode and an cathode of which provided with transparency, can be prepared.
As sealing film, barrier film made of the same material as gas barrier film, and metal thin film can be employed. An adhesive specifically includes photo-curing and thermal-curing type adhesive having a reactive vinyl group such as acrylic acid type oligomer and methacrylic acid type oligomer; an adhesive of a moisture-curing type such as 2-cyanoacrylic acid ester; a thermal and photo-curing type adhesive such as an epoxy type; a hot melt type adhesive such as a polyamide type, a polyester type and a polyolefin type; and an ultraviolet curing type epoxy resin adhesive of a cationic curing type.
Herein, since an organic compound layer may be deteriorated by a heat treatment, adhesion and curing is preferably performed from room temperature to 80° C. Further, a drying agent may be dispersed in the aforesaid adhesives. To coat an adhesive on the sealing portion, a die coat method and a printing method can be employed.
As shown in this drawing, a process to coat by a wet coating method under atmospheric pressure to form coated film for an organic compound layer, a process to form an electron injection layer and a cathode layer on the organic compound layer under a reduced pressure condition, and a process to paste up sealing film on the cathode layer under atmospheric pressure are provided, transfer of an object between each process being performed in a roll form, and organic EL element is prepared via each process thereof, whereby the following effects can be obtained in addition to the effect of organic compound layer forming method shown in
1) By separating a coating•drying process to form an organic compound layer, a cathode layer forming process to form an cathode layer including the second electrode and a sealing film paste up process, optimization in each process becomes easy to enable achievement of stable quality as well as improvement of productivity.
2) Using efficiency of an organic compound utilized to form one or a plural number of emission layers comprising an organic substance is high resulting in depression of a cost.
In the drawing, 7 is a manufacturing apparatus to prepare an organic EL element. Manufacturing apparatus 7 is provided with a coating•drying section (identical with coating•drying section 203 shown in
Cathode layer•sealing layer forming section 8 is provided with supply section 801, first cathode layer forming section 802, second cathode layer forming section 803, sealing layer forming section 804 and recovery section 9, and the process is continuously performed under a reduced pressure condition from material supply section 801 until recovery section 9. In material supply section 801, flexible band substrate B201f of a roll form, which is prepared in manufacturing apparatus 2, and which is comprised of an anode, a hole transport layer and an organic compound layer are formed on a flexible band substrate to be wound on a core, is supplied.
Electron injection layer 201i is formed on an organic compound layer (an emission layer) of flexible band substrate B201f, which is provided with an organic compound layer (an emission layer) and unwound from supply section 801, in first cathode layer forming section 802. 802a is an evaporation apparatus and 802b is an evaporation source container.
In second cathode layer forming section 803, cathode layer 201j is formed on electron injection layer 201i which has been formed in first cathode layer forming section. 803a is an evaporation apparatus and 803b is an evaporation source container. In sealing layer forming section 804, a sealing layer is formed on a cathode layer to prepare an organic EL element protected with a sealing layer, which is wound on a core in recovery section 9 to be made into a roll form, whereby preparation of organic EL element 901 of a roll form protected with sealing film is completed. Other symbols are identical those in
In sealing layer forming section 804 shown in this drawing, preferable is a method to provide inorganic and organic layers on the outside of a cathode layer to form sealing film. In this case, a film forming material is a material provided having a function to restrain invasion of matters which may cause deterioration of an element such as moisture and oxygen, and such as silicon oxide, silicon dioxide and silicon nitride can be utilized.
As shown in this drawing, a process to coat and form coated film for an organic compound layer by a wet coating method under atmospheric pressure, a process to form an electron injection layer, a cathode layer and a sealing layer on the organic compound layer under a reduced pressure condition are provided, transfer of an object between each process being performed in a roll form, and organic EL element is prepared via each process thereof, whereby the following effects can be obtained in addition to the effect of organic compound layer forming method shown in
1) By separating a coating•drying process to form an organic compound layer, a cathode layer forming process to form an cathode layer including the second electrode and a sealing film paste up process, optimization in each process becomes easy to enable achievement of stable quality as well as improvement of productivity.
2) Using efficiency of an organic compound utilized to form one or a plural number of emission layers comprising an organic substance is high resulting in depression of a cost.
In S1, flexible band substrate 201a, on which an anode layer including the first electrode having been formed, of a roll form is provided to a supply section. Flexible band substrate 201n shown in this drawing is already in a state of first electrode layer 201o having been formed thereon. First electrode layer 201o has been formed on the barrier layer of flexible band substrate 201n continuously along the longitudinal direction at a predetermined size and an interval. Herein, a barrier layer may be provided between flexible band substrate 201n and first electrode layer 201o. In this case a barrier layer is formed all over the surface of flexible band substrate 201n. Flexible band substrate 201a of a roll form is in a state of having been wound making first electrode layer 201o inside.
In S2, a washing surface modification treatment of a flexible band substrate, which has been unwound from a substrate supply section is carried out, at a washing surface modification treatment section.
In S3, a first organic compound layer (a hole transport layer) coating solution is coated by a wet coater at first coating section under atmospheric pressure. At this time, a first organic compound layer (a hole transport layer) coating solution is coated except on the edge portion 201o1 of first electrode layer 201o. After coating, drying is carried out by the first dryer in the first dryer section to form first organic compound layer (hole transport layer) 201c. Successively, a heat treatment of the first organic compound layer (hole transport layer) is carried out by the first heating treatment apparatus. Then, static elimination treatment of the surface of the formed hole transport layer is carried out by a static elimination means.
In S4, a second organic compound layer (emission layer) coating solution is coated on formed first organic compound layer (hole transport layer) 201c by a wet coater in the second coating section under atmospheric pressure and drying is carried out by the second dryer in the second drying section resulting in formation of second organic compound layer (emission layer) 201d. Successively, a heat treatment of second organic compound layer (emission layer) 201e is carried out by the second heat treatment apparatus. Second organic compound layer (emission layer) 201d is coated at the same coating width as first organic compound layer (hole transport layer) 201c. Herein, in the case of a plural number of second organic compound layers (emission layers) being provided, accumulated second organic compound layers (emission layers) are formed by repeating coating•drying•heat treatment corresponding to the number of second organic compound layers (emission layers) to be accumulated. Then, static elimination of the formed second organic compound layer (emission layer) 201e is carried out by a static elimination means.
In S5, a flexible band substrate having the second organic compound layer (emission layer) is kept, until being transferred to the next process, under a reduced pressure condition of 10−5-10 Pa as a form of flexible band substrate 201h of a roll form wound on a core making the second organic compound layer (emission layer) inside.
In S′1, flexible band substrate provided with second organic compound layer (emission layer) 201e shown in S5 of
In S′2, electron injection layer (LiF layer) 201g having a thickness of 0.5 nm is formed on the second organic compound layer (emission layer) 201e of a flexible band substrate by an evaporation method under a reduced pressure condition of 5×10−4 Pa. Formation of an electron injection layer is carried out in a state of arranging a mask so as not to cover the one edge portion 201o1 of first electrode layer 201o at the time of evaporation.
In S′3, electron injection layer 201i and second electrode layer (aluminum layer) 201h having a thickness of 100 nm are formed on formed electron injection layer 201g by an evaporation method under a reduced pressure condition of 5×10−4 Pa. The second electrode layer is formed so as to make the edge portion opposite to one edge portion 201o1 broader than the width of the electron injection layer and on flexible band substrate 201n.
In S′4, a flexible band substrate, on which a cathode layer including the second electrode (electron injection layer 201g and second electrode layer 201h) has been formed, is wound on a core under a reduced pressure condition to be flexible band substrate 201j of a roll form, which is transferred to the next process.
In S′5, adhesive 201p is coated under atmospheric pressure so as to cover a cathode layer including the second electrode except one edge portion 201o1 of the first electrode layer and edge portion 201h1 of the cathode layer including the second electrode. As an adhesive, for example, UV curable epoxy resin (UV Resin NXR5570-B1, manufactured by Nagase Chemtex Co., Ltd) was coated by a die coater. Successively, sealing film 502b2, which is supplied from sealing film supply portion, is pasted up to meet the area of the coated adhesive, being pressed by a press roll, and a curing treatment is carried out by irradiation from the cathode side with an UV lamp, whereby a flexible band substrate on which an organic EL element is formed (an organic EL element protected by sealing film) is prepared. Herein, epoxy resin of an adhesive may be a heat-curable type. In this case, heat press is carried out by being passed between heat rolls at the time of paste up.
In S′6, a flexible band substrate (an organic EL element protected by sealing film) is wound up on a core to make a roll form, whereby preparation of organic EL element 601 of a roll form protected by seal film is completed. Herein, the finished substrate may be appropriately cut into a sheet form corresponding to the size of the first electrode layer. In the case of being cut, an adhesive is preferably applied only on the outer circumference of organic compound layer (emission layer) by means of such as a dispenser or a screen printing method.
In S″1, a flexible band substrate provided with second organic compound layer (emission layer) shown in S5 of
In S″2, electron injection layer (LiF layer) 201g having a thickness of 0.5 nm is formed on the second organic compound layer (emission layer) 201e of a flexible band substrate by an evaporation method under a reduced pressure condition of 5×10−4 Pa. Formation of an electron injection layer is carried out in a state of arranging a mask so as not to cover the one edge portion 201o1 of first electrode layer 201o at the time of evaporation.
In S″3, second electrode layer (aluminum layer) 201h having a thickness of 100 nm is formed on formed electron injection layer 201g by an evaporation method under a reduced pressure condition of 5×10−4 Pa. The second electrode layer is formed so as to make the edge portion opposite to one edge portion 201o1 broader than the width of the electron injection layer and on flexible band substrate 201n.
In S″4, successively on formed electron injection layer (cathode layer) 201h, sealing layer 201q is formed under a reduced pressure condition so as to cover second electrode layer 201j except one edge portion 201o1 of first electrode layer (anode layer) 201o and one edge portion 201h1 of second electrode layer (cathode layer) 201h, whereby a flexible band substrate, on which an organic EL element has been formed, is prepared.
In S″5, a flexible band substrate (an organic EL element protected by sealing film) is wound up on a core to make a roll form, whereby preparation of organic EL element 601 of a roll form protected by seal film is completed. Herein, the finished substrate may be appropriately cut into a sheet form corresponding to the size of the first electrode layer. In the case of being cut, an adhesive is preferably applied only on the outer circumference of organic compound layer (emission layer) by means of such as a dispenser or a screen printing method.
Thereafter, the finished substrate may be continuously cut into a sheet form corresponding to the size of the first electrode layer, or may be once wound on a core to be a roll form.
Next, other constituent materials utilized to constitute an organic EL element according to the present invention will be explained. A layer arranged adjacently to an organic compound layer (emission layer) includes a block layer. A block layer includes a hole block layer and an electron block layer. A block layer is appropriately arranged in addition to basic constituent layers of organic compound thin film. For example, listed is a hole block layer described in such as JP-A Nos. 11-204258 and 11-204359 and p. 237 of “Organic EL Element and Front Line of Industrialization Thereof (published by N. T. S Corp., Nov. 30, 1998)”. A hole block layer has a function of an electron transport layer in the broad meaning, being comprised of a material, which has a function to transport an electron but has very little ability to transport a hole, and capable of improving recombination probability of an electron and a hole by blocking a hole while transporting an electron. Further, a constitution of an electron transport layer, which will be described later, may be appropriately utilized as a hole block layer according to the present invention, and a hole block layer is preferably arranged adjacently to an organic compound layer (emission layer).
When an organic compound layer (emission layer) is comprised of a plural number of emission layers of different emission colors, an emission layer, an emission maximum wavelength of which is shortest, is preferably arranged nearest to an anode among the all emission layers, however, in such a case, a hole block layer is preferably additionally arranged between said shortest wavelength layer and an emission layer second nearest to an anode. Further, not less than 50 weight % of a compound contained in a hole block layer arranged at said position has a larger ionization potential by not less than 0.3 eV against a host compound of the aforesaid shortest wavelength layer.
An ionization potential is defined by an energy required to release an electron existing on the HOMO (highest occupied molecular orbit) level to a vacuum level, and for example, can be determined according to the following method. (1) By use of Gaussian 98 (Gaussian 98, Revision A. 11. 4, M. J. Frisch, et al, Gaussian, Inc., Pittsburgh Pa., 2002), which is a molecular orbit calculation software manufactured by Gaussian, Inc., USA; a value calculated by performing structural optimization (converted value of eV unit), the second place of decimals of which is rounded off, is defined as an ionization potential. (2) An ionization potential can be also determined by being directly measured by means of photoelectron spectroscopy. Foe example, a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd., or a method known as ultraviolet photoelectron spectroscopy can be preferably utilized.
On the other hand, an electron block layer has a function of a hole transport layer in the broad meaning, being comprised of a material which has a function to transport a hole but has very little ability to transport an electron, and capable of improving recombination probability of an electron and a hole by blocking an electron while transporting a hole. Further, a constitution of a hole transport layer, which will be described later, may be appropriately utilized as an electron block layer. The layer thickness of a hole block layer and an electron transport layer, according to the present invention, is preferably 3-100 nm and more preferably 5-30 nm.
In an organic compound layer (emission layer) constituting an organic EL element of the present invention, a host compound well known in the art and a phosphorescent compound (also referred to as a phosphorescence emitting compound) well known in the art are preferably incorporated to increase emission efficiency of an organic compound layer (emission layer).
A host compound is defined as a compound, which occupies not less than 20 weight % in the layer based on a weight ratio among compounds contained in an emission layer and has a phosphorescence quantum efficiency of phosphorescent emission at room temperature (25° C.) of less than 0.1. The phosphorescence quantum efficiency is preferably less than 0.01. Plural types of host compounds may be utilized together. By utilizing plural types of host compounds, it is possible to control charge transfer and to prepare an organic EL having high efficiency. Further, by utilizing plural types of phosphorescent compounds, it becomes possible to mix different emission resulting in enabling to obtain an arbitrary emission color. By adjusting a type and a doping amount of a phosphorescent compound, it is possible to obtain white emission, which can be applied for illumination and backlight.
As these host compounds, preferable is a compound which has hole transport ability and electron transport ability, as well as prevents emission from going to a longer wavelength and further has a high Tg (glass transition temperature). Host compounds well known in the art include compounds described in such as JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357977, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227, 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084 and 2002-308837.
In the case that an organic compound layer (emission layer) is provided with a plural number of emission layers, it is preferable that not less than 50 weight % of host compounds of these layers are the same compound with respect to easily achieving a homogeneous film properties all over the organic layer, and it is further preferable that a phosphorescence emission energy of a host compound is not less than 2.9 eV because it is advantageous to efficiently restrain energy transfer from a dopant and to obtain high luminance. Phosphorescent emission energy refers to a peak energy of the 0-0 band of phosphorescence emission when a photoluminescence is measured by forming an evaporated film of a host compound having a thickness of 100 nm.
A host compound preferably has a phosphoresce emission energy of not less than 2.9 eV and Tg of not lower than 90° C. in consideration of such as deterioration of an organic EL element at aging (luminance decrease, deterioration of film properties) and market needs as a light source. That is, to satisfy the both of luminance and durability, those having phosphorescence emission energy of not less than 2.9 eV and Tg of not lower than 90° C. are preferable. Tg is furthermore preferably not lower than 100° C.
A phosphorescent compound (phosphorescence emitting compound) is a compound in which emission from an exited triplet state is observed and which emits phosphorescence at room temperature (25° C.), and is a compound having a phosphorescence quantum yield at 25° C. of not less than 0.01. By utilizing a phosphorescent compound together with a host compound explained before, an organic EL element having further higher emission efficiency can be prepared.
A phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of not less than 0.1. The above-described phosphorescence quantum yield can be measured by a method described at p. 398 of Spectroscopy II of the 4th edition Experimental Chemistry Course 7 (Maruzen, 1992). A phosphorescence quantum yield in a solution can be measured employing various types of solvents; however, it is preferred that a phosphorescent compound utilized in the present invention achieves the above-described phosphorescence quantum yield in any one of arbitrary solvents.
A principle of emission of a phosphorescent compound includes two types; one is an energy transfer type in which recombination of a carrier is caused on a host compound, which transport a carrier, to generate an exited state of a host compound and this energy is transferred to a phosphorescent compound resulting in obtaining emission from the phosphorescent compound, and the other is a carrier trap type in which a phosphorescent compound functions as a carrier trap to cause recombination of a carrier on a phosphorescent compound resulting in obtaining emission; however, in either case, it is necessary that energy of an exited state of a phosphorescent compound is lower than energy of an exited state of a host compound.
A phosphorescent compound can be utilized by being appropriately selected among those well known in the art and utilized in an emission layer of an organic EL element. A phosphorescent compound is preferably a complex type compound containing a metal of the 8-10th groups of the periodic table of elements, more preferably an iridium compound, an osmium compound, a platinum compound (a platinum complex type compound) or a rare earth compound, and most preferably among them an iridium compound.
In the present invention, the phosphorescence emission maximum wavelength of a phosphorescent compound is not specifically limited, and the emission wavelength obtained can be principally varied by selecting the central metal, the ligand and the substitution position of the ligand.
Color of emission from an organic EL element of the present invention and from a compound according to the present invention is determined by a color when a measured result by use of Spectral Radiation Luminance Meter CS-1000 (manufactured by Konicaminolta Sensing Corp.) according to p. 108, FIG. 4.16 in “New Edition Color Science Handbook” (Edited by Japan Color Society, Tokyo University Publishing Association, 1985) is applied into CIE chromaticity coordinates.
A white element in the present invention refers that chromaticity in CIE 1931 color specification system at 1,000 Cd/m2, when a front luminance at 2° viewing angle is measured by the above-described method, is within a region of X=0.33±0.07, Y=0.33±0.07.
Take out efficiency of an organic EL element of the present invention at room temperature is preferably not less than 1%, and more preferably not less than 5%. Herein, take out quantum efficiency (%)=a number of photons emitted outside of an organic EL element/a number of electrons flown in an organic EL element×100.
Further, a hue improving filter such as a color filter may be utilized together, and a color conversion filter, which converts emission color from an organic EL element into multicolor by use of a fluorescent substance, may be also utilized together. In the case of utilizing a color conversion filter, λmax of emission of an organic EL element is preferably not more than 480 nm.
In a gap between a sealing member (a sealing layer or sealing film shown in
An organic EL element of the present invention preferably employs together the following method to efficiently take out light generated in an emission layer. In an organic EL element, it is generally said that emission is generated at the inside of a layer having a refractive index higher than air (refractive index of approximately 1.7-2.1) and only 15-20% of light generated in an emission layer can be taken out. This is because light incident into the interface at an angle θ over the critical angle causes total reflection to unable to be taken out of an element, and because light causes total reflection between a transparent electrode or an emission layer and a transparent substrate to be guided through the transparent electrode or the emission layer resulting in making light escape to the side surface direction of an element.
As a method to improve this take out efficiency of light includes, for example, a method roughness is formed on the transparent substrate surface to prevent total reflection at the interface of a transparent substrate and air (U.S. Pat. No. 4,774,435), a method to improve the efficiency by providing a substrate with a condensing property (JP-A 63-314795), a method to form a reflective plane on such as the side surface of an element (JP-A 1-220394), a method to introduce a flat layer having an intermediate refractive index between a substrate and a fluorescent substance to form anti-reflection film (JP-A 62-172691), a method to introduce a flat layer having a refractive index lower than that of a substrate between a substrate and a fluorescent substance (JP-A 2001-202827), and a method to form a diffraction grating at the interlayer of any one of a substrate, a transparent electrode and an emission layer (including the interface between a substrate and the outside) (JP-A 11-283751).
In the present invention, these methods can be utilized in combination with an organic EL element, however, a method to introduce a flat layer having a refractive index lower than that of a substrate between a substrate and a fluorescent substance or a method to form a diffraction grating at the interlayer of any one of a substrate, a transparent electrode and an emission layer (including the interface between a substrate and the outside) is preferably utilized. In the present invention, by combining these methods, an element having further high luminance or excellent durability can be prepared.
In the case that a medium having a low refractive index is formed between a transparent electrode and a transparent substrate at a thickness of longer than a wavelength of light, light emitted from the transparent electrode has the higher efficiency of taking out when a refractive index of a medium is the lower. A low refractive index layer includes such as aerogel, porous silica, magnesium fluoride and fluorine-containing polymer. Since a refractive index of a transparent substrate is generally approximately 1.5-1.7, a low refractive index layer preferably has a refractive index of approximately not more than 1.5 and more preferably of not more than 1.35. A thickness of a low refractive index layer is preferably at least twice of a wavelength in the medium. This is because an effect of a low refractive index layer will be decreased when a thickness of a low refractive index becomes approximately as large as a wavelength of light making electromagnetic waves bleeding out by evanescent to invade into a substrate. A method to introduce a diffraction grating to the interface or either medium which causes total reflection is characterized by a high improvement effect of taking out of light. In this method, by utilizing a property to change the direction of light into a specific direction different from refraction by so-called Bragg's diffraction such as primary diffraction and secondary diffraction, light which cannot go out due to such as total reflection between layers among light generated from an emission layer is made to be diffracted by introduction of a diffraction grating to any of inter-layers or in a medium (such as a transparent substrate or a transparent electrode), whereby light will be taken out. A diffraction grating introduced is preferably provided with a two dimensional periodic refractive index. This is because light emitted in an emission layer will be randomly generated in all directions and only light advancing a specific direction is diffracted by an ordinary one-dimensional diffraction grating, which has a diffractive index distribution only in a certain direction, resulting in not so much increase of taking out efficiency of light. However, by making the refractive index distribution two-dimensionally, light advancing all directions will be diffracted to increase taking out efficiency of light.
The position to introduce a diffraction grating may be either any one of inter-layers or in media (in a transparent substrate or in a transparent electrode), however, is desirably the neighborhood of an organic emission layer where light is generated. In this case, the period of a diffraction grating is preferably approximately ½-3 times of a wavelength of light in the medium. The arrangement of a diffraction grating is preferably those in which an arrangement is repeated two dimensionally such as a square lattice form, a triangle lattice form and a honeycomb lattice form.
Further, an organic EL element of the present invention can be made to have higher luminance in a specific direction by such as processing to provide a structure of a micro-lens form on the light take out side of a substrate, or by such as condensing light to the front direction against an element emission plane. As an example of a micro-lens alley, a square pyramid is arranged two-dimensionally so as to make one edge of 30 μm and the peak angle of 90 degree on the light take out side of a substrate. One edge is preferably 10-100 μm. An effect of diffraction will generate to cause coloring when it is not more than this, while it is not preferable to increase thickness when it is excessively large.
As a condenser sheet, for example, those practically employed in practice as an LED backlight of a liquid crystal display can be utilized. As such a sheet, for example, brightness enhancing film (BEF) manufactured by Sumitomo 3M Ltd. can be utilized. As a form of a prism sheet, for example, employed may be a form in which a stripe of a triangle form having a peak angle of 90 degree and a pitch of 50 μm are formed on a substrate, a form having a rounded peak angle, a form having randomly varying pitches or other forms. Further, a light scattering plate-film to control the light emission angle from an emission element may be utilized together. For example, Diffusion Film (Light Up) manufactured by Kimoto Co., Ltd. can be utilized.
In the following, specific effects will be shown referring to examples; however, embodiments of the present invention are not limited thereto.
(Preparation of Flexible Band Substrate Provided with Gas Barrier Layer and First Electrode Layer in this Order)
A gas barrier layer and the first electrode layer were formed by the following method on polyether sulfone having a thickness of 200 μm (film manufactured by Sumitomo Bakelite Co., Ltd., hereinafter referred to as PES), which was wound on a core to be a roll from, whereby a flexible band substrate provided with a gas barrier layer and the first electrode layer in this order was prepared.
(Formation of Transparent Gas Barrier Layer)
A transparent gas barrier layer having a thickness of approximately 90 nm was formed on the prepared PES by an atmospheric pressure discharge treatment method. Water vapor permeability was measured by a method based on JISk-7129B to be not more than 10−3 g/m2/day. Oxygen permeability was measured by a method based on JISk-7126B to be not more than 10−3 g/m2/day.
(Formation of First Electrode Layer)
ITO (indium tin oxide) having a thickness of 120 nm was patterned by an evaporation method on the formed barrier layer, whereby the first electrode layer was formed.
(Formation of Organic Compound Layer (Emission Layer))
By utilizing a process shown in
Before coating a hole transport layer coating solution, a washing surface modification treatment of a flexible band substrate was carried out by use of a low pressure mercury lamp having a wavelength of 184.9 nm at an irradiation strength of 15 mW/cm2 and a distance of 10 mm. A static elimination treatment was carried out by use of a charge neutralizer employing very weak X rays.
A hole transport layer coating solution was coated so as to make a dry layer thickness of 50 nm. An organic compound layer coating solution was coated so as to make a dry layer thickness of 100 nm. Herein, transport speed was 2 m/min.
Preparation of Hole Transport Layer Coating Solution
A solution of polyethylene dioxythiophene•polystyrene sulfonate (PEDOT/PSS, Bytron P AI 4083, manufactured by Bayer Corp.), which had been diluted by 65% of pure water and 5% of methanol, was prepared as a hole transport layer coating solution. A surface tension of a hole transport layer coating solution was 0.04 Nm (Surface Tension Meter CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd.).
Preparation of Organic Compound Layer Coating Solution
Polyvinylcarbazole as a host material and 5 weight % of dopant material Ir(ppy)3 were dissolved in 1,2-dichloroethane to make a 10% solution, whereby a organic compound layer coating solution was prepared. A surface tension of an organic compound layer coating solution was 0.032 Nm (Surface Tension Meter CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd.). A glass transition temperature of an organic compound layer was 225° C. Herein, in this example, a material having green emission, however, a white emission organic EL element can be prepared by further accumulating layers employing blue and red materials together with a dopant material.
Drying and Heat Treatment Conditions
After coating a hole transport layer coating solution, by use of the first dryer and the first heat treatment apparatus shown in
After coating an organic compound layer (emission layer) coating solution, by use of the second dryer and the second heat treatment apparatus shown in
Coating Condition
A temperature at the time of coating a hole transport layer coating solution was 25° C. and a temperature at the time of coating an organic compound layer coating solution was 25° C., under atmospheric environment. Herein a wet coating process was kept at a dew point of −20° C. and a cleanliness class of not more than 5 (JIS B 9920).
Evaluation
With respect to prepared sample Nos. 101-108, emission luminance unevenness was evaluated based on the following evaluation ranks and the result is shown in table 1.
Measurement Method of Emission Luminance Unevenness
Emission luminance was measured by use of CS-1000, manufactured by Konicaminolta Corp. when direct current voltage of 10 V was applied, and unevenness was determined by the following equation.
Emission luminance unevenness (%)=(maximum emission luminance−minimum emission luminance)/maximum emission luminance×100
Evaluation Ranks of Emission Luminance Unevenness
Herein, sample No. 101 showed an excellent evaluation result in emission luminance unevenness, however, since it is effective to increase a mean transport speed to restrain a distribution of a transport speed, a transport speed is increased to make drying apparatus large resulting in possible decrease of energy efficiency. Effectiveness of the present invention has been proved.
An organic compound layer was formed in a similar manner to preparation of sample No. 103 in example 1 except that a drying condition (an air ejection velocity, a variation of air ejection velocity in the coated film width direction of an organic compound layer) after an organic compound layer coating solution having been coated was changed as shown in table 2, being cooled down to room temperature, the resulting substrate was wound on a core to make a roll form, whereby sample Nos. 201-214 were prepared. Herein, an air ejection velocity was measured by hot air anemometer Model 6113, manufactured by Kanomax Co., Ltd., and a wind velocity distribution in the width direction was calculated by the following equation.
Wind velocity distribution=(maximum wind velocity−minimum wind velocity)/mean wind velocity×100
Evaluation
With respect to prepared sample Nos. 201-214, the state of a coated surface was visually evaluated and the evaluation result based on the following evaluation ranks is shown in table 2.
A: No unevenness and no mottle, of the coated layer surface, are observed.
B: Slight unevenness and mottle, of the coated layer surface, which is not problematic in practical use, are partly observed.
C: Unevenness and mottle, of the coated layer surface, are observed all over the surface.
The effectiveness of the present invention has been proved.
An organic compound layer was formed in a similar manner to preparation of sample No. 103 in example 1 except that a surface tension of an organic compound layer coating solution was changed as shown in table 3, being cooled down to room temperature, the resulting substrate was wound on a core to make a roll form, whereby sample Nos. 301-307 were prepared. Herein, a surface tension was measured by surface tension meter CBVP-A3, manufactured by Kyowa Interface Science Co., Ltd.
Evaluation
With respect to prepared sample Nos. 301-307, the state of a coated surface was visually evaluated and the evaluation result based on the following evaluation ranks is shown in table 2.
A: No unevenness and no mottle, of the coated layer surface, are observed.
B: Slight unevenness and mottle, of the coated layer surface, which is not problematic in practical use, are partly observed.
C: Unevenness and mottle, of the coated layer surface, are observed all over the surface.
The effectiveness of the present invention has been proved.
An organic compound layer was formed in a similar manner to preparation of sample No. 103 in example 1 except that a heat treatment condition, after an organic compound layer coating solution having been coated and dried, was changed as shown in table 3, being cooled down to room temperature, the resulting substrate was wound on a core to make a roll form, whereby sample Nos. 401-308 were prepared.
Evaluation
With respect to sample Nos. 401-408, a lifetime of an organic compound layer (emission layer) was evaluated, and the result is shown in table 4. Herein, as for a lifetime of an organic compound layer (emission layer), time required to decrease luminance when the sample was driven at a constant current of 2.5 mA/cm2 to the half was employed as an index and evaluation was carried out based on the relative value when a lifetime of a sample without a heat treatment was set to 100. The heat treatment temperature is shown as a temperature based on a glass transition temperature (225° C.) of an organic compound layer (emission layer).
The effectiveness of the present invention was proved.
An organic compound layer (emission layer) was formed by processing under identical conditions with preparation of sample No. 103 in example 1, except that an environmental condition, from coating of a hole transport layer coating solution and an organic compound layer (emission layer) coating solution until forming a hole transport layer and an organic compound layer (emission layer), was changed as shown in table 5, being cooled down to room temperature, the resulting substrate was wound on a core to make a roll form, whereby sample Nos. 501-507 were prepared. Herein, cleanliness is shown by a value measured based on JISB 9920, and cleanliness was changed by varying a filter. Further, since the coating temperature of a hole transport layer coating solution and an organic compound layer (emission layer) coating solution was 25° C., processes other than a dryer and a heat treatment apparatus was carried out at a temperature of 25° C. under an atmospheric condition.
Evaluation
With respect to prepared sample Nos. 501-507, a non-emission defect was visually confirmed and the evaluation result based on the following ranking is shown in table 5.
Confirmation Method of Non-emission Defect
After the prepared sample having been stored in a thermostat of 80° C. for 1 week, presence of a non-emitting point was visually confirmed when the sample was driven at a constant current of 2.5 mA/cm.
Evaluation Rank of Non-emission Defect
A: No non-emission defect is recognized.
B: A slight non-emission defect, which is not problematic in practical use, is recognized.
C: A few non-emission defects, which are problematic in practical use, are observed.
It is estimated that sample No. 501 caused a non-emission defect due to moisture content in a sample and sample No. 504 caused a non-emission defect due to adhered foreign matters. The effectiveness of the present invention has been proved.
Sample Nos. 601-606 were prepared in identical conditions with sample No. 103 prepared in example 1 except the storing condition was changed as shown in table 6. Herein, the storing term was set to 5 days.
Evaluation
With respect to sample Nos. 601-606, the evaluation item same as that of example 4 was measured by the same measuring method and the result is shown in table 6. Herein, a life time (relative value) is a relative value against a life time when a storing condition is 10−5 Pa.
Sample No. 606 showed an excellent lifetime (a relative value), however, the equipment becomes excessively large to keep a high vacuum considering the obtained effects, resulting in anxiety of maintenance and control of equipment and cost up. The effectiveness of the present invention has been proved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2005-079146 | Mar 2005 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2006/303225 | 2/23/2006 | WO | 00 | 9/13/2007 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2006/100868 | 9/28/2006 | WO | A |
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